Optical metasurfaces, planar sub-wavelength nano-antenna arrays with the singular ability to sculpt wave front in almost arbitrary manners, are poised to become a powerful tool enabling compact and high-performance optics with novel functionalities. A particularly intriguing research direction within this field is active metasurfaces, whose optical response can be dynamically tuned post-fabrication, thus allowing a plurality of applications unattainable with traditional bulk optics. The efforts to date, however, still face major performance limitations in tuning range, optical quality, and efficiency especially for non-mechanical actuation mechanisms. In this paper, we introduce an active metasurface platform combining phase tuning covering the full 2π range and diffraction-limited performance using an all-dielectric, low-loss architecture based on optical phase change materials (O-PCMs). We present a generic design principle enabling binary switching of metasurfaces between arbitrary phase profiles. We implement the approach to realize a high-performance varifocal metalens. The metalens is constructed using Ge2Sb2Se4Te1 (GSST), an O-PCM with a large refractive index contrast and unique broadband low-loss characteristics in both amorphous and crystalline states. The reconfigurable metalens features focusing efficiencies above 20% at both states for linearly polarized light and a record large switching contrast ratio (CR) close to 30 dB. We further validate aberration-free and multi-depth imaging using the metalens, which represents the first experimental demonstration of a non-mechanical active metalens with diffraction-limited performance.
The development of low-loss optical phase change materials (O-PCMs) promises to enable a plethora of nonvolatile integrated photonic applications. However, the relatively large optical constants change between different states of calls for a set of new design rationales. Here we report a non-perturbative design that enables low-loss device operation beyond the traditional figure-of-merit limit. The basic design rationale is to engineer the light propagation path through the OPCMs when it is in the low-loss amorphous state, and divert light away from the lossy crystalline state leveraging the large mode modification induced by the O-PCM phase transition. Following this approach, we demonstrate broadband photonic switches with significantly enhanced performances compared to current state-of-the-art.
We have already successfully employed the Generalized Dispersion Material (GDM) technique to include optical dispersion of different materials in the multiphysics time domain methods implementing the GDM model with various Auxiliary Differential Equation (ADE) and Recursive Convolution (RC) schemes. So far, we have demonstrated that the approach works efficiently to model the optical dispersion of metals, and to characterize the multivariate tunable dispersion of graphene. In this paper, we apply the GDM model to two emerging fields in the time-domain computational photonics.
In the first part, we further extend the GDM model to the Bi-Anisotropic (BA) case, where a full BA material tensor comes from homogenization procedure in the frequency domain. Conventional BA homogenization is a powerful multiscale technique for rapid prototyping and optimization of metasurfaces. With a new extension, the BA-GDM model characterizes artificial dispersion obtained from the mathematical equivalence of physical effects and enables the multiscale modeling of metasurfaces in the time domain.
Part 2 deals with new use of the GDM model in temperature-dependent time-domain simulations of phase change materials (PCMs). Optical PCMs, such as GST/GSST, are of critical utility in applications including, e.g., programmable metasurfaces, and nonvolatile memory. Typically, dispersions of amorphous and crystalline phases of PCMs are fitted separately in the frequency domain with a combination of the Tauc-Lorentz and Gauss terms, while Bruggeman’s mixing rule describes the transition states. Significantly advancing the-state-of-the-art, our GDM characterization describes dependency on temperature and crystallization levels explicitly and enables full wave modeling of PCMs in the time domain.
Optical phase change materials (O-PCMs) are a unique class of materials which exhibit extraordinarily large optical property change (e.g. refractive index change > 1) when undergoing a solid-state phase transition. Traditional O-PCMs suffer from large optical losses even in their dielectric states, which fundamentally limits the performance of optical devices based on the materials. To resolve the issue, we have recently demonstrated a new O-PCM Ge-Sb-Se-Te (GSST) with broadband low loss characteristics. In this talk, we will review an array of reconfigurable photonic devices enabled by the low-loss O-PCM, including nonvolatile waveguide switches with unprecedented low-loss and high-contrast performance, free-space light modulators, bi-stable reconfigurable metasurfaces, and transient couplers facilitating waferscale device probing and characterizations.
The dramatic optical property change of optical phase change materials (O-PCMs) between their amorphous and crystalline states potentially allows the realization of reconfigurable photonic devices with enhanced optical functionalities and low power consumption, such as reconfigurable optical components, optical switches and routers, and photonic memories. Conventional O-PCMs exhibit considerable optical losses, limiting their optical performance as well as application space. In this talk, we present the development of a new group of O-PCMs and their implementations in novel meta-optic devices. Ge-Sb-Se-Te (GSST), obtained by partially substituting Te with Se in traditional GST alloys, feature unprecedented broadband optical transparency covering the telecommunication bands to the LWIR. A drastic refractive index change between the amorphous and crystalline states of GSST is realized and the transition is non-volatile and reversible.
Optical metasurfaces consist of optically-thin, subwavelength meta-atom arrays which allow arbitrary manipulation of the wavefront of light. Capitalizing on the dramatically-enhanced optical performance of GSST, transparent and ultra-thin reconfigurable meta-optics in mid-infrared are demonstrated. In one example, GSST-based all-dielectric nano-antennae are used as the fundamental building blocks for meta-optic components. Tunable and switchable metasurface devices are developed, taking advantage of the materials phase changing properties.
The dramatic optical property change of optical phase change materials (O-PCMs) between their amorphous and crystalline states potentially allows the realization of reconfigurable photonics devices with low power consumption, such as optical switches and routers, reconfigurable meta-optics, displays, and photonic memories. However, conventional O-PCMs, such as VO2 and Ge2Sb2Te5, are inherently plagued by their excessive optical losses even in dielectric states, limiting their optical performance and hence application space. In this talk, we present the development of a new group of O-PCMs and their implementations in novel photonic devices. Ge-Sb-Se-Te (GSST), obtained by partially substituting Te with Se in traditional GST alloys, feature unprecedented broadband optical transparency covering the telecommunication bands to LWIR. Capitalizing on the dramatically-enhanced optical performance, novel non-volatile, reconfigurable on-chip photonics devices and architectures are demonstrated. GSST-integrated Si photonics based on the material innovation and novel “non-perturbative” designs exhibit significantly improved switching performance over state-of-the-art GST-based approaches. The technology is further scalable to realize non-blocking matrix switches with arbitrary network complexity, paving the path towards high performance reconfigurable photonics chips.
Optical phase change materials (O-PCMs) are a unique class of materials which exhibit extraordinarily large optical property change (e.g. refractive index change > 1) when undergoing a solid-state phase transition. These materials, exemplified by Mott insulators such as VO2 and chalcogenide compounds, have been exploited for a plethora of emerging applications including optical switching, photonic memories, reconfigurable metasurfaces, and non-volatile display. These traditional phase change materials, however, generally suffer from large optical losses even in their dielectric states, which fundamentally limits the performance of optical devices based on traditional O-PCMs. In this talk, we will discuss our progress in developing O-PCMs with unprecedented broadband low optical loss and their applications in novel photonic systems, such as high-contrast switches and routers towards a reconfigurable optical chip.
Lightweight, portable solar blankets, constructed from thin film photovoltaics, are of great interest to
hikers, the military, first responders, and third-world countries lacking infrastructure for transporting
heavy, brittle solar cells. These solar blankets, as large as two square meters in area, come close to
satisfying specifications for commercial and military use, but they still have limited absorption due to
insufficient material efficiency, and therefore are large and too heavy in many cases.
Metasurfaces, consisting of monolayers of periodic and semi-random plasmonic particles patterned in
a scalable manner, are explored to enhance scattering into thin photovoltaic films (currently of
significant commercial and military value), in order to enhance absorption and efficiency of solar
blankets. Without nano-enhancement, absorption is limited by the thickness of the thin photovoltaic
active layer in the long-wavelength region. In this study, lithographically patterned, periodic Al
nanostructure arrays demonstrate experimentally a large absorption enhancement, resulting in a
predicted increase in short-circuit current density of at least 35% and as much as 70% for optimized
arrays atop 200-nm amorphous silicon thin films. Optimized arrays extend thin-film absorption to the
near infrared region. This impressive absorption enhancement and predicted increase in short-circuit
current density may significantly increase the efficiency and reduce the weight of solar blankets,
enabling their use for commercial and military applications.
In recent years, optical super-resolution by microspheres and microfibers emerged as a new paradigm in nanoscale label-free and fluorescence imaging. However, the mechanisms of such imaging are still not completely understood and the resolution values are debated. In this work, the fundamental limits of super-resolution imaging by high-index barium-titanate microspheres and silica microfibers are studied using nanoplasmonic arrays made from Au and Al. A rigorous resolution analysis is developed based on the object’s convolution with the point-spread function that has width well below the conventional (~λ/2) diffraction limit, where λ is the illumination wavelength. A resolution of ~λ/6-λ/7 is demonstrated for imaging nanoplasmonic arrays by microspheres. Similar resolution was demonstrated for microfibers in the direction perpendicular to the fiber axis with hundreds of times larger field-of-view in comparison to microspheres. Using numerical solution of Maxwell’s equations, it is shown that extraordinary close point objects can be resolved in the far field, if they oscillate out of phase. Possible super-resolution using resonant excitation of whispering gallery modes is also studied.
Vanadium oxide (VO2) is known to undergo a semiconductor-to-metal transition at 68°C. Therefore, it can be used as a tunable component of an active metamaterial. The lamellar metamaterial designed and studied in this work is composed of subwavelength VO2 and Au layers and is predicted to have the temperature controlled transition from the hyperbolic phase to the metallic phase. The VO2 films and VO2/Au lamellar metamaterial stacks have been fabricated and studied in the electrical conductivity as well as optical (transmission, reflection) experiments. The temperature depended changes in the absorption and transmission spectra of metamaterials and films have been observed experimentally and compared with the theory predictions.
Nanoparticles and nanostructures with plasmonic resonances are currently being employed to enhance the efficiency of solar cells. 1-3 Ag stripe arrays have been shown theoretically to enhance the short-circuit current of thin silicon layers. 4 Monolayers of Ag nanoparticles with diameter d < 300 nm have shown strong plasmonic resonances when coated in thin polymer layers with thicknesses < d.5 We study experimentally the diffuse vs. specular scattering from monolayer arrays of Ag nanoparticles (spheres and prisms with diameters in the range 50 – 300 nm) coated onto the front side of thin (100 nm < t < 500 nm) silicon films deposited on glass and flexible polymer substrates, the latter originating in a roll-to-roll manufacturing process. Ag nanoparticles are held in place and aggregation is prevented with a polymer overcoat. We observe interesting wavelength shifts between maxima in specular and diffuse scattering that depend on particle size and shape, indicating that the nanoparticles substantially modify the scattering into the thin silicon film.
Tunable, narrow-wavelength spectral filters with a ms response in the mid-wave/long-wave infrared (MW/LWIR) are an enabling technology for hyperspectral imaging systems. Few commercial off-the-shelf (COTS) components for this application exist, including filter wheels, movable gratings, and Fabry-Perot (FP) etalon-based devices. These devices can be bulky, fragile and often do not have the required response speed. Here, we present a fundamentally different approach for tunable reflective IR filters, based on coupling subwavelength plasmonic antenna arrays with liquid crystals (LCs). Our device operates in reflective mode and derives its narrow bandwidth from diffractive coupling of individual antenna elements. The wavelength tunability of the device arises from electrically-induced re-orientation of the LC material in intimate contact with antenna array. This re-orientation, in turn, induces a change in the local dielectric environment of the antenna array, leading to a wavelength shift. We will first present results of full-field optimization of micron-size antenna geometries to account for complex 3D LC anisotropy. We have fabricated these antenna arrays on IR-transparent CaF2 substrates utilizing electron beam lithography, and have demonstrated tunability using 5CB, a commercially available LC. However, the design can be extended to high-birefringence liquid crystals for an increased tuning range. Our initial results demonstrate <60% peak reflectance in the 4- 6 μm wavelength range with a tunability of 0.2 μm with re-orientation of the surface alignment layers. Preliminary electrical switching has been demonstrated and is being optimized.
As next generation immersion lithography, combined with double patterning, continues to shrink feature sizes, the
industry is contemplating a move to non-chemically amplified resists to reduce line edge roughness. Since these resists
inherently have lower sensitivities, the transition would require an increase in laser exposure doses, and thus, an increase
in incident laser fluence to keep the high system throughput.
Over the past several months, we have undertaken a study at MIT Lincoln Laboratory to characterize performance
of bulk materials (SiO2 and CaF2) and thin film coatings from major lithographic material suppliers under continuous
193-nm laser irradiation at elevated fluences. The exposures are performed in a nitrogen-purged chamber where samples
are irradiated at 4000 Hz at fluences between 30 and 50 mJ/cm2/pulse. For both coatings and bulk materials, in-situ laser
transmission combined with in-situ laser-induced fluorescence is used to characterize material performance. Potential
color center formation is monitored by ex-situ spectrophotometry. For bulk materials, we additionally measure spatial
birefringence maps before and after irradiation. For thin film coatings, spectroscopic ellipsometry is used to obtain
spatial maps of the irradiated surfaces to elucidate the structural changes in the coating.
Results obtained in this study can be used to identify potential areas of concern in the lens material performance if
the incident fluence is raised for the introduction of non-chemically amplified resists. The results can also help to
improve illuminator performance where such high fluences already occur.
For several years, SEMATECH has invested significant effort into extending 193 nm immersion lithography by
developing a set of high index materials. For high index immersion lithography (HIL) to enable 1.70NA imaging, a
high index lens element with an absorbance < 0.005/cm, a fluid with an index of ≥ 1.80, and a resist with an index >1.9
are needed. This paper reviews the success or failure of various HIL components and presents the top final material
prospects and properties in each category.
Since this abstract was submitted, the industry has decided to cease any effort in HIL, not because of fundamental
showstoppers but because of timing. This choice was made even though the only currently available technology the can
enable 32 nm and 22 nm manufacturing is double patterning. This may represent a paradigm shift for the semiconductor
industry and lithography. It may very well be that using lithography as the main driver for scaling is now past. Due to
economic forces in the industry, opportunity costs will force performance scaling using alternative technology.
The need to extend 193nm immersion lithography necessitates the development of a third generation (Gen-3) of
high refractive index (RI) fluids that will enable approximately 1.7 numerical aperture (NA) imaging. A multi-pronged
approach was taken to develop these materials. One approach investigated the highest-index organic thus far
discovered. The second approach used a very high refractive index nanoparticle to make a nanocomposite fluid.
This report will describe the chemistry of the best Gen-3 fluid candidates and the systematic approach to their
identification and synthesis. Images obtained with the Gen-3 fluid candidates will also be presented for a NA ≥ 1.7.
An extension of water-based immersion lithography involves replacing water with a higher index transparent oil.
Understandably, potential lens contamination is a major concern for an all-organic immersion fluid. We have
constructed an experimental system for controlled irradiation of high index fluids, including capabilities for in-situ
cleaning of potential deposits. We present results of laser-irradiation of several high index immersion fluid candidates.
Using properly developed exposure metrics, we discuss implications for fluid lifetimes in an immersion system, with and
without in-situ purification. Using our in-situ metrology, we are able to decouple bulk fluid degradation from window
photocontamination for several fluids. We find a significant variation in optics contamination rate depending on the fluid
tested. Even the slowest observed contamination rates would require some remediation strategies to remove the built-up
deposit from the final element surface. We also present results of irradiation of model hydrocarbon compound fluids.
Irradiation of these materials leads to fundamental understanding of underlying photochemistry, and also provides
guidance in designing future generation high index fluids.
R. French, V. Liberman, H. Tran, J. Feldman, D. Adelman, R. Wheland, W. Qiu, S. McLain, O. Nagao, M. Kaku, M. Mocella, M. Yang, M. Lemon, L. Brubaker, A. Shoe, B. Fones, B. Fischel, K. Krohn, D. Hardy, C. Chen
To identify the most practical and cost-effective technology after water immersion
lithography (Gen1) for sub-45 nm half pitches, the semiconductor industry continues to
debate the relative merits of water double patterning (feasible, but high cost of
ownership), EUV (difficulties with timing and infrastructure issues) and high index
immersion lithography (single-exposure optical lithography, needing a suitable high
index last lens element [HILLE]). With good progress on the HILLE, high index
immersion with numerical apertures of 1.55 or above now seems possible. We continue
our work on delivering a commercially-viable high index immersion fluid (Gen2). We
have optimized several fluids to meet the required refractive index and absorbance
specifications at 193 nm. We are also continuing to examine other property/process
requirements relevant to commercial use, such as fluid radiation durability, last lens
element contamination and cleaning, resist interactions and profile effects, and particle
contamination and prevention. These studies show that both fluid handling issues, as well
as active fluid recycling, must be well understood and carefully managed to maintain
optimum fluid properties. Low-absorbing third generation immersion fluids, with
refractive indices above 1.7 (Gen3), would further expand the resolution of singleexposure
193 nm lithography to below 32 nm half pitch.
Leaching of resist components into water has been reported in several studies. Even low dissolution levels of photoacid generator (PAG) may lead to photocontamination of the last optical surface of the projection lens. To determine the impact of this phenomenon on optics lifetime, we initiate a set of controlled studies, where predetermined amounts of PAG are introduced into pure water and the results monitored quantitatively. The study identifies the complex, nonlinear paths leading to photocontamination of the optics. We also discover that spatial contamination patterns of the optics are strongly dependent on the flow geometry. Both bare SiO2 surfaces as well as coated CaF2 optics are studied. We find that for all surfaces, at concentrations typical of leached PAG, below 500 ppb, the in situ self-cleaning processes prevent contamination of the optics.
Leaching of resist components into the water has been reported in several studies. Potential effects of photo-acid generator (PAG) dissolved in water include photocontamination of the last optical surface and the formation of particulate defects on the wafer surface. In order to determine the impact of these phenomena on lithographic performance, such as optics lifetime and yield, we have initiated a set of controlled studies, where predetermined amounts of PAG were introduced into pure water and the results monitored quantitatively. One set of studies identified the complex, nonlinear paths leading to photocontamination of the optics. At concentrations typical of leached PAG, below 500 ppb, the in-situ self-cleaning processes prevent contamination of the optics. On the other hand, initial experiments with a nano-dropper show that micron-scale particles from the dissolved PAG are formed on the wafer surface when water evaporates. This phenomenon requires further systematic studies both at the fundamental science and the engineering levels.
The final projection lens element in a 193-nm immersion-based lithographic tool will be in direct contact with water during irradiation. Thus, any lifetime considerations for the lens must include durability data of lens materials and thin films in a water ambient. We have previously shown that uncoated CaF2 is attacked by water in a matter of hours, as manifested by a substantial increase in AFM-measured surface roughness.1 Thus, CaF2 lenses must be protected, possibly by a thin film, and the coatings tested for laser durability in water. To address the above lifetime concerns, we have constructed a marathon laser-irradiation system for testing thin film exposure to water under long-term laser irradiation. Coated substrates are loaded into a custom water cell, made of stainless steel and Teflon parts. Ultrapure water is delivered from a water treatment testbed that includes particle filtration, deionization and degassing stages. In-situ metrology includes 193-nm laser ratiometry, UV spectrophotometry and spectroscopic ellipsometry, all with spatial profiling capabilities. In-situ results are coupled with off-line microscopy, AFM measurements and spatial surface mapping with spectroscopic ellipsometry at multiple incidence angles. A variety of laser-induced changes have been observed, from complete adhesion loss of protective coatings to more subtle changes, such as laser-induced index changes of the thin films or surface roughening. Implications of the study on expected lifetimes of the protective coatings in the system will be discussed.
In liquid immersion lithography the last optical element is in intimate contact with the liquid for extended periods of time, and therefore is at risk of being contaminated by impurities in the liquid. The purity of the liquid must be kept under stringent control compared to "dry" lithography, since the density of liquid is ~ 1000 times higher than that of gas. Thus, 1 part per billion contaminant in the liquid may have an equivalent effect on the optics to 1 part per million in gas. The risk is that the combination of high contaminant density, short wavelength, and large laser dose will conspire to contaminate the optics, change its transmission, and possibly cause increased flare. In order to clarify the potential for such effects, we have begun a set of experiments with controlled contamination. In these studies, a 193-nm laser irradiates a sample in the presence of flowing clean water into which controlled amounts of contaminant have been injected. The sample is either bare fused silica or calcium fluoride protected with thin films. Results will be presented with organic contaminants such as isopropanol and acetone. These results will include an analysis on the implications for controlling water purity.
Pellicle materials for use at 157 nm must display sufficient transparency at this wavelength and adequate lifetimes to be useful. We blended a leading candidate fluoropolymer with silica nanoparticles to examine the effect on both the transparency and lifetime of the pellicle. It is anticipated that these composite materials may increase the lifetime by perhaps quenching reactive species and/or by dilution, without severely decreasing the 157-nm transmission. Particles surface-modified with fluorinated moieties are also investigated. The additives are introduced as stable nanoparticle dispersions to casting solutions of the fluoropolymers. The properties of these solutions, films, and the radiation-induced darkening rates are reported. The latter are reduced in proportion to the dilution of the polymer, but there is no evidence that the nanoparticles act as radical scavengers.
The photo-induced degradation of 157-nm anti-reflective (AR) coatings, and the role of water vapor in the ambient, have been studied with in-situ spectroscopic ellipsometry, atomic force microscopy (AFM), and x-ray photoelectron spectroscopy. Using ellipsometric techniques, we find that MgF2 thin films develop a surface roughness layer under laser irradiation at an incident dose of ~0.1 MJ/cm2. These thin film changes occur well before any changes in 157-nm transmission are observed. The findings are confirmed by ex-situ post-irradiation AFM measurements. LaF3 does not exhibit this effect. Addition of ppm-levels of moisture suppresses surface roughness formation, suggesting that the surface roughness growth may be a precursor to the transmission degradation of full AR stacks that had been observed earlier.
Successful insertion of 157-nm lithography into production requires that materials comprising the optical train meet the lifetime requirements of the industry. At present, no degradation of bulk fluoride materials has been observed for at least up to 109 pulses. However, last year we reported on the surface damage to fluoride materials that appeared after 3-4x109 pulses at moderate fluences of 3-4 mJ/cm2/pulse2. This damage manifested itself as a precipitous transmission drop of up to 50% at 157 nm and was accompanied by the formation of a porous rough surface layer about 0.20 μm thick. Understanding this surface damage is important for the durability of laser windows and beam delivery optics, and it may also help elucidate fundamental 157-nm photophysics of fluoride surfaces. To understand the underlying phenomena, we have designed and constructed a new accelerated damage test chamber. The chamber utilizes 157-nm light from a lithography-grade laser operating at 1000 Hz. Inside the chamber, light is focused onto the sample to a submillimeter spot size. The chamber allows us to test in-situ transmission of multiple spots on a given sample over a range of fluences up to 140 mJ/cm2/pulse without breaking purge. We have used this chamber to understand the scaling of the damage mechanism for both uncoated and antireflectance (AR) -coated CaF2 samples as a function of laser repetition rate and fluence. Substrate damage appears to be governed by a complex set of mechanisms, both thermal and non-thermal in origin. Preliminary damage studies of AR-coated substrates show that AR-coating related degradation occurs well before the onset of the substrate surface damage.
Photo-induced contamination rates on 157-nm optical surfaces have been studied in controlled experiments with contaminants containing fluorocarbon, sulfur and iodine. The compounds investigated represent species generated in controlled outgassing studies of common construction materials and photoresists used in 157 nm steppers. No photocontamination was measured for highly fluorinated alkanes and ethers on an anti-reflective coating, at levels exceeding 10 ppm. Photocontamination with sulfur based compounds was similar to the behavior observed with hydrocarbon based derivatives. Sulfur containing residues, even from oxidized precursors, are fully cleanable in oxygen, with cleaning rates scaling proportionally with the level of oxygen. In contrast, at elevated levels of oxygen, non-volatile iodate complexes can form from iodine based contaminants. Sulfonium salts should therefore be considered over iodonium species in photoacid generators in 157 nm photoresists. In addition to studying these new classes of compounds, cleaning rates of hydrocarbon residues in trace levels of water were also studied.
We present results of the durability of antireflectance (AR) coatings under laser irradiation with emphasis on the interplay between coating materials and ambient. We find that introducing ppm-levels of water has a dramatic impact on the performance of certain coatings. In particular, no significant degradation of a coating was observed for up to 1MJ/cm2 dose in the presence of ~20 ppm H2O, whereas linear transmission drop of several percent was observed when irradiating a coating of similar design in <0.1 ppm H2O but under 1.5 ppm O2. Cycling water concentration on and off leads a corresponding cycling of transmission of the coatings. Adding water vapor to the ambient has a much greater benefit to coating durability than adding corresponding amounts of gas phase oxygen. In a series of experiments involving the same coating stack with different degrees of porosity of the outer layer, moisture was found to have the greatest impact on the most porous coating.
We present the methodology and recent results on the long-term evaluation of optical materials for 157-nm lithographic applications. We review the unique metrology capabilities that have been developed for accurately assessing optical properties of samples both online and offline, utilizing VUV spectrophotometry with in situ lamp-based cleaning. We describe ultraclean marathon testing chambers that have been designed to decouple effects of intrinsic material degradation from extrinsic ambient effects. We review our experience with lithography-grade 157-nm lasers and detector durability. We review the current status of bulk materials for lenses, such as CaF2 and BaF2, and durability results of antireflectance coatings. Finally, we discuss the current state of laser durability of organic pellicles.
Photodeposition rates for ten hydrocarbon species have been measured on CaF2 substrates under 157-nm irradiation in the presence of ppm scale levels of oxygen. The species are representative of hydrocarbon based compounds observed in outgassing studies of common build materials used in 157-nm based lithographic systems. Photodeposition rates have also been measured for a subset of the hydrocarbon species on a MgF2 thin film, six anti-reflective dielectric stacks, and fluorine doped fused silica for comparison with the results on CaF2 substrates. Two contamination processes are observed. One is the formation of an equilibrium layer on the surfaces. The other is a quasi-permanent contamination which is most pronounced at elevated levels of contaminant.
Long-term durability tests of optical thin films and thin films designed for attenuating phase shifters have been performed in a chamber, which stresses clean protocols to eliminate extraneous effects of surface contamination. Most anti-reflective coatings tend to degrade several percent in transmission within 1 MJ/cm2 total dose. Attenuating phase
shifting materials usually show an increase in transmission during 6 kJ/cm2. In both types of films there are exceptions, indicating that there are no fundamental causes that would limit the performance of such films. A new phenomenon of laser-induced surface damage in calcium fluoride has been observed, and is being studied.
Transmission loss during irradiation remains the critical limitation for polymer pellicle materials at 157 nm. In this work we establish a framework for calculating the necessary pellicle lifetime as well as a test methodology for evaluating the laser durability of candidate polymer films. We examine the role of key extrinsic environmental variables in determining film lifetime. Oxygen concentration affects pellicle lifetime, but there is not an oxygen level that effectively balances pellicle perforation and cleaning against the onset of photochemical darkening. Neither moisture level nor 172-nm UV lamp pre-cleaning were found to have a significant impact on pellicle lifetime.
An attenuating phase shifting mask has been designed, fabricated, and tested at 157 nm. It consists of two layers, a metal attenuator and a transparent phase shifter. The metal, platinum, was chosen for its chemical and radiation stability. The phase shifter was a commercial spin-on glass. A single step of pattern transfer has been implemented, which significantly simplifies the fabrication process of the mask. The lithographic advantage in increased depth of focus was demonstrated for 130-nm spaces and contacts, and it was found to agree with numerical simulations.
The introduction of 157 nm as the next optical lithography wavelength has created a need for new soft (polymeric)
or hard (quartz) pellicle materials. Pellicles should be > 98% transparent to incident 157 nm light and, ideally, sufficiently
resistant to photochemical damage to remain useful for an exposure lifetime of 7.5 kJ/cm2.
The transparency specification has been met. We have developed families of experimental Teflon™AF (TAFx)
polymers with > 98% transparency which can be spin coated and lifted as micron-scale, unsupported membranes. Still higher
transparencies should be possible once optimization of intrinsic (composition, end groups, impurities, molecular weight) and
extrinsic (oxygen, absorbed hydrocarbons, contaminants) factors are completed. The measured transparencies of actual
pellicle films, however, are affected by many factors other than absorption. Film thickness must be precisely controlled so as
to allow operation at the fringe maxima for the lithographic wavelength. Roughness and thickness uniformity are also
critical. An important part of our program has thus been learning how to spin membranes from the solvents that dissolve our
pellicle candidates.
Meeting the durability specification at 157 nm remains a major concern. The 157 nm radiation durability lifetime of
a polymer is determined by two fundamental properties: the fraction of 157 nm radiation absorbed and the fraction (quantum
efficiency) of this absorbed radiation that results in photochemical darkening. Originally it was assumed that lifetime
increases uniformly with increasing transparency. We now have cases where materials with very different absorbances
(TAFx4P and 46P) have similar lifetimes and materials with similar absorptions (TAFx46P and 2P) have very different
lifetimes. These findings demonstrate the importance of the relative quantum efficiencies as the 157 nm light energy
distributes itself along degradative versus non-degradative pathways. In an effort to identify chemical and structural features
that control lifetime, we have been studying model molecular materials, some quite similar to the monomer units used to
make our pellicle candidates. Several of these models have shown transparencies much higher and lifetimes far longer than
our best pellicle candidates to date.
We determined the damage thresholds and lifetimes of several materials using 157- and 193-nm excimer lasers and a beam profile technique similar to that described in ISO 11254-2. We made these measurements to select an appropriate absorbing material for use in our primary standard laser calorimeter for 157-nm excimer laser energy measurements. The materials we tested were nickel-plated sapphire, chemically-vapor-deposited silicon carbide (CVD SiC), nickel-plated copper, and polished copper. Applied pulse energy densities (or dose) ranged from 80 to 840 mJ/cm2. We determined the applied dose from a series of laser beam profile measurements. Silicon carbide had the highest damage threshold: 730 mJ/cm2 per pulse. For this reason, and because of its high thermal and electrical conductivities, we have chosen silicon carbide as the absorber material for the 157-nm calorimeter. We also conducted long-term exposure studies in cooperation with MIT Lincoln Laboratory at a pulse energy density of 5 mJ/cm2 to simulate typical calorimeter operating conditions. No aging effects or other surface changes were observed at these dose levels after 500 million pulses, corresponding to a projected calorimeter lifetime of 50 years.
Contamination rates of CaF2 substrates in the presence of trace levels of toluene vapor and oxygen under 157-nm irradiation have been studied to determine conditions which prevent contamination films from depositing on optical elements in lithographic projection systems. A 2 - 3 monolayer thick deposit, causing a 1 - 2% transmission drop per surface, can readily form over a range of contaminant levels in the sub-ppm range and typical background oxygen levels. In addition, stable partial surface coverage can be supported with either lower concentrations of contaminant or conversely much higher levels of oxygen. Contamination rates are also higher at lower fluences, and thus contamination effects are expected to impact the projection optics more severely than beam delivery and illumination components. Finally, a permanent degradation in transmission of coated optics has been observed on anti-reflective coatings exposed to sub-ppm levels of toluene. Taken together, the results suggest that even with hydrocarbon based contaminants, where oxygen can be introduced into the beam-line in trace levels (i.e. hundreds of ppb) without significantly degrading transmission, toluene contaminant levels will have to be maintained in the ppb range or below.
A UV-lamp-based cleaning station, serving as a load-lock to a VUV spectrometer, has been used to evaluate the cleaning of hydrocarbon residues on 157-nm reticles. UV lamp based cleaning is found to be an effective tool to remove both nanometer scale layers of physisorbed and significantly more resilient highly conjugated 'graphitized' layers on the mask substrate. Slight changes in reflectance and surface roughness are observed on the chromium absorber indicating some degree of photo-oxidation is occurring during lamp cleaning.
In this work we present progress on the long-term evaluation of optical materials for 157-nm lithographic applications. We review the unique metrology capabilities that have been developed for accurately assessing optical properties of samples both online and offline, utilizing VUV spectrophotometry with in-situ lamp-based cleaning. We review the current status of bulk materials for lenses, such as CaF2 and BaF2, and durability results of antireflectance coatings. Finally, we describe progress on materials testing of organic pellicles, both with 172-nm lamps as well as under 157-nm laser irradiation.
A number of fluoro-functionalized poly(4-hydroxystyrene) derivatives, consisting of both blocked and unblocked hexafluoroisopropanol-substituted stryrenes, were prepared and their vacuum-ultraviolet absorption spectra were measured. From our efforts, we find that a wide range of synthetic flexibility exists and allows for a variety of fluorinated analogs of APEX-like and ESCAP-like copolymers and terpolymers with 157nm absorption coefficients less than 4.0micrometers . From these findings, we conclude that facile routes to high-performance 157nm resins are possible with optimum imaging thicknesses of 100 to 130nm.
In-situ laser cleaning is shown to be an effective tool for removal of organic contaminants on CaF2 windows. To study laser cleaning in a controlled fashion, CaF2 substrates were pre-contaminated with 5 to 10 nm of poly(methyl methacrylate), poly(4-hydroxy styrene), poly(norbornene), and poly((beta) -pinene) thin films. Irradiation of all the polymer films showed similar trends. Initially, a high rate of material removal occurs, which depends on the chemistry of the polymer. During this period, the material also undergoes significant bond rearrangement, forming a more tightly bound highly conjugated network. Removal of this residual 'graphitized' film is significantly more difficult, but can be accelerated by the presence of modest levels of oxygen. For oxygen concentrations between 10-1000 ppm, the measured removal rate is approximately 3 nm/(kJ/cm2) ppm oxygen. No effect on removal rate was observed as pulse energy or purge gas flow rate was varied over ranges expected to be used in practical systems.
Photolithography utilizing 157-nm excimer lasers is a leading candidate technology for the post-193-nm generation. A key element required for successful insertion of this technology is the near-term performance and long-term reliability of the components of the optical train, including transparent bulk materials for lenses, optical coatings, photomask substrates, and pellicles. For instance, after 100 billion pulses at an incident fluence of 0.5 mJ/cm2/pulse optical materials, of which the primary candidate is calcium fluoride, should have an absorption coefficient of less than 0.002 cm-1, and antireflective layers should enable transmission of 98.5 percent for a two-sided coated substrate. Modified fused silica has emerged as a viable option as a transparent photomask substrate, and several approaches are being explored for transmissive membranes to be used as pellicles.
Photodeposition of organic films on transparent substrates irradiated in the presence of trace levels of hydrocarbons has been experimentally investigated and a model is presented that describes the film growth behavior. The efficacy of a given organic precursor at forming a deposit is proportional to the product of its surface coverage and by its photon absorption cross section. These measurement are important in predicting the transmission characteristics of lithographic optics operating at 157-, 193-, and 248-nm wavelength. For example, a lens element irradiated continuously for one year in the presence of 1 part per billion of t-butyl benzene would exhibit a transmission of approximately 87 percent at 193 nm. The effects of oxygen- containing ambients are also documented, and methods for elimination and/or prevention of organic contamination are suggested.
Photolithography using 157-nm pulsed F2 lasers has emerged as the leading candidate technology for the 0.1 micrometer lithography node for the post-193-nm generation. The extension of operating wavelength to the VUV range presents new challenges for thin film metrology tools, such as ellipsometers and spectrophotometers, most of which have not yet shown robust performance at high accuracy at wavelengths below 193 nm. Knowledge of material optical properties near 157 nm is essential for several areas of microlithography, such as (1) optimization of resist and bottom antireflectance coating (BARC) and lithographic performance modeling; (2) development of thin dielectric layers for lens coatings, including antireflectance, beamsplitter and high reflectance designs; and (3) development of resolution enhancement techniques, such as attenuating phase shifting masks. In this work we review our experience with VUV spectrophotometers, as well as techniques for obtaining stable reflection and transmission measurements necessary for deriving optical constants of thin films. In particular, we find that reliably accurate reflection data can be obtained only using absolute reflectance methods. Extraction of optical constants is performed utilizing global optimization methods with a commercially available software package. Kramers-Kronig- consistent dispersion relations are used to describe the material dielectric constants. We will present real and imaginary refractive index values of various thin films, as determined from reflection/transmission data into the deep UV wavelengths to as low as 140 nm. A separate study designed to understand scatter losses of materials at 157 nm will also be described. We have constructed a 157-nm laser-based scatterometer for obtaining bidirectional reflection distribution function (BRDF) measurements. By correlating scatter signals with total transmission losses, we are able to separate absorption from scatter effects.
We have completed a comprehensive evaluation of bulk materials designed for 193-nm lithographic applications. These studies are performed at realistic fluences and pulse counts in excess of 6 X 109. The outcome of the study shows that most calcium fluoride materials should meet the industry lifetime targets for use in lens applications. Some fused silica material also appears to meet lifetime expectations of the industry; however, large grade-to-grade variability in both absorption and laser-induced densification has been observed. We also report on the impact of transient absorption in fused silica on lithographic dose control.
We update previously reported results on the absorption of optical materials and coatings for use in 157 nm based optical projection system. New results include the transmissions spectrum of a modified from of fused silica with suitable initial transmission for use as a mask substrate. We also report on a more systematic study of the effects of surface contaminants on optical components at 157 nm. We have modified our vacuum spectrometer to allow in- situ cleaning to enable a closer examination of purging requirements and cleaning procedures.
We have undertaken a systematic evaluation of both bulk material sand optical coatings designed for 193-nm lithographic applications. These studies are performed at realistic fluences and pulse counts in excess of 109. Measurements of absorption is fused silica show a large variation in performance for different samples in both initial and laser-induced absorption. Calcium fluorides samples show less variation in laser-induced absorption and appear to be more stable under irradiation of 0.2-1 billion pulses. Laser-induced densification of fused silica appears to follow an empirical power law; however, an order of magnitude spread in densification is observed among grades. For optical antireflectance coatings, we have characterized the initial 'laser-cleaning' phenomenon for various coatings. We have observed that laser-cleaned coatings deposited on CaF2 substrates exhibit higher initial optical losses at 193 nm than their counterparts on SiO2 substrates. However, the losses for coatings on CaF2 substrates are reduced over irradiation times of 0.2-1 billion pulses to final values comparable to their SiO2 counterparts. Finally, we have characterized various catastrophic failures of coating material, such as induced losses, adhesion failure and laser-induced thinning.
We present an assessment of bulk fused silica and calcium fluoride, and of antireflective coatings for 193-nm lithographic applications. In the course of extensive marathon studies we have accumulated 1-5 billion laser pulses on over 100 bulk material samples at fluences from 0.2 to 4 mJ/cm2/pulse. The result show large variation in both initial and induced absorption of fused silica and in densification of fused silica. For antireflective coatings, there are samples that undergo no appreciable degradation when irradiated for > 1 billion pulses at 15 mJ/cm2/pulse. However, initial losses in some coatings may be unacceptably high for lithographic applications.
We investigated laser-induced damage of pellicles for 193-nm lithography. We surveyed 193-nm-optimized material from three pellicle suppliers. Pellicles were irradiated under realistic reticle plane conditions (0.04 mJ/cm2/pulse - 0.12 mJ/cm2/pulse for up to 100 million pulses). Pellicles from two suppliers were found to meet lifetime requirements of the industry. Pellicles from the third supplier do not appear to meet the lifetime requirements. We present fluence scaling of pellicle damage and discuss effects of the ambient on pellicle degradation rates. We present results of the outgassing studies of pellicle material under irradiation using a separate gas chromatograph-mass spectrometer-based detection apparatus. From the results of these studies, we suggest possible photochemical pathways for pellicle degradation as a function of ambient.
We present an assessment of antireflective coatings for 193-nm lithography. Coatings from nine suppliers were exposed in a nitrogen ambient for up to 1.5 billion pulses at 15 mJ/cm2/pulse at 400 Hz. Sensitive metrology, developed for this study, included reflectance/transmittance measurements, in-situ ratiometric transmission measurements, and interferometric calorimetry for absorption measurements. The coatings from at least two suppliers withstood greater than 1 billion pulses with no observable degradation. Catastrophic damage observed on some samples included blistering and a dramatic transmission drop. Such damage occurred rather early (less than 100 million pulses).
We investigate the effect of 193-nm radiation on commercially available pellicles for 248-nm lithography. Pellicles from two suppliers were irradiated at a realistic reticle plane fluence (0.1 mJ/cm2/pulse) for 50 million pulses. Analysis of transmission spectra revealed loss of pellicle material, decreased refractive index and increased absorption in various combinations depending on pellicle type and ambient. Although one of the two materials may be suitable for use at 193 nm, the other showed unacceptable degradation. We also quantified outgassing rates of organic species during irradiation, and observed greatly accelerated material loss in a pure nitrogen ambient compared with air. Yield rates of perfluorinated fragments and polymer product exhibited two-photon scaling behavior.
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