Weiming Qiu

Novel hydrofluorocarbon polymers for use as pellicles in 157 nm semiconductor photolithography: fundamentals of transparency

With the advent of 157 nm as the next photolithographic wavelength, there has been a need to find transparent and radiation durable polymers for use as soft pellicles. Pellicles are � 1 mm thick polymer membranes used in the photolithographic reproduction of semiconductor integrated circuits to prevent dust particles on the surface of the photomask from imaging into the photoresist coated wafer. Practical pellicle films must transmit at least 98% of incident light and have sufficient radiation durability to withstand kilojoules of optical irradiation at the lithographic wavelength. As exposure wavelengths have become shorter the electronics industry has been able to achieve adequate transparency only by moving from nitrocellulose polymers to perfluorinated polymers as, for example, Teflon 1 AF 1600 and Cytop TM for use in 193 nm photolithography. Unfortunately, the transparency advantages of perfluorinated polymers fail spectacularly at 157 nm; 1 mm thick films of Teflon 1 AF 1600 and Cytop TM have 157 nm transparency of no more than 38 and 2%, respectively, with 157 nm pellicle lifetimes measured in millijoules. Polymers such as ‐[(CH2CHF)xC(CF3)2CH2]y‐, or ‐(CH2CF2)x[2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole]y‐ with chains that alternate fluorocarbon segments with either oxygen or hydrocarbon segments frequently show >98% transparency at 157 nm, if amorphous. These polymers are made from monomers, such as vinylidene fluoride (VF2) and hexafluoroisobutylene, which themselves exhibit good alternation of CH2 and CF2 in their structures. In addition, we find that ether linkages also can serve to force alternation. In addition, we find that fluorocarbon segments shorter than six carbons, and hydrocarbon segments less than two carbons or less than three carbons if partially fluorinated also promote 157 nm transparency. We also find that even with these design principles, it is advantageous to avoid small rings, as arise in the cyclobutanes. These results suggest a steric component to transparency in addition to the importance of alternation. Upon irradiation these polymers undergo photochemical darkening and therefore none has demonstrated the kilojoule radiation durability lifetimes required to be commercially attractive. This is likely because these exposure lifetimes require every bond to absorb � 10 photons, each photon having an energy roughly twice common bond energies. We have studied intrinsic (composition, molecular weight) and extrinsic (trace metals, impurities, environmental contaminants, oxygen, water) contributions to optical absorption and photochemical darkening in these polymers. Studies of photochemical darkening in model molecules illustrate the dynamics of photochemical darkening and that appreciable lifetimes can be achieved in fluorocarbons. To a first approximation the polymers that have lower 157 nm optical absorbance also tend to show the longest lifetimes. These results imply that quantum yield, or the extent to which the polymer structure can harmlessly dissipate the energy, can be important as well. # 2003 Elsevier Science B.V. All rights reserved.

Second generation fluids for 193nm immersion lithography

Water is the first generation immersion fluid for 193 nm immersion lithography. With a fluid refractive index of 1.436 and an optical absorbance of 0.01/cm at 193 nm, water immersion technology can enable optical lithography for the ITRS’ 65 nm half-pitch node. However, to achieve numerical apertures above 1.35 and to go beyond the 45 nm node, low absorbance fluids with indices higher than 1.6 are needed for the second generation of immersion lithography. We have developed a number of Gen. 2 high index fluids for immersion lithography at 193 nm. These highly transparent fluids have 193 nm indices up to 1.67. 32 nm 1:1 line space imaging has been demonstrated using two of our Gen 2 candidate fluids, representing major advance in optical lithography. To understand the behavior and performance of different fluid classes, we use spectral index measurements to characterize the index dispersion, coupled with Urbach absorption edge analysis, and Lorentz oscillator modeling.

Optical Properties and van der Waals–London Dispersion Interactions of Polystyrene Determined by Vacuum Ultraviolet Spectroscopy and Spectroscopic Ellipsometry

The interband optical properties of polystyrene in the vacuum ultraviolet (VUV) region have been investigated using combined spectroscopic ellipsometry and VUV spectroscopy. Over the range 1.5–32 eV, the optical properties exhibit electronic transitions we assign to three groupings, E1 ,E 2, and E3, corresponding to a hierarchy of interband transitions of aromatic (π → π*), non-bonding (n → π*, n → σ*), and saturated (σ → σ*) orbitals. In polystyrene there are strong features in the interband transitions arising from the side-chain π bonding of the aromatic ring consisting of a shoulder at 5.8 eV (E � ) and a peak at 6.3 eV (E1), and from the σ bonding of the C–C backbone at 12 eV (E � ) and 17.1 eV (E3). These E3 transitions have characteristic critical point line shapes associated with one-dimensionally delocalized electron states in the polymer backbone. A small shoulder at 9.9 eV (E2) is associated with excitations possibly from residual monomer or impurities. Knowledge of the valence electronic excitations of a material provides the necessary optical properties to calculate the van der Waals–London dispersion interactions using Lifshitz quantum electrodynamics theory and full spectral optical properties. Hamaker constants and the van der Waals–London dispersion component of the surface free energy for polystyrene were determined. These Lifshitz results were compared to the total surface free energy of polystyrene, polarity, and dispersive component of the surface free energy as determined from contact angle measurements with two liquids, and with literature values. The Lifshitz approach, using full spectral Hamaker constants, is a more direct determination of the van der Waals–London dispersion component of the surface free energy of polystyrene than other methods.

Imaging of 32-nm 1:1 lines and spaces using 193-nm immersion interference lithography with second-generation immersion fluids to achieve a numerical aperture of 1.5 and a k 1 of 0.25

Water-based immersion lithography using ArF illumination is able to provide optical solutions as far as the 45-nm node, but is not able to achieve the 38- or 32-nm nodes as currently defined. Achieving these lithographic nodes will require new, higher refractive index fluids to re- place the water used in first-generation immersion systems. We have developed a number of such second-generation high-index fluids for im- mersion lithography at 193 nm. These highly transparent fluids have 193-nm indices up to 1.664. To understand the behavior and perfor- mance of different fluid classes, we use spectral index measurements to characterize the index dispersion, coupled with Urbach absorption edge analysis and Lorentz Oscillator modeling. Interference imaging printers have long been available, and they now have a new use: a rapid, cost- effective way to develop immersion lithography, particularly at extremely high resolutions. Although interference printers will never replace classi- cal lens-based lithography systems for semiconductor device production, they do offer a way to develop resist and fluid technology at a relatively low cost. Their simple image-forming format offers easy access to the basic physics of advanced imaging. Issues such as polarization of the image-forming light rays, fluid/resist interaction during exposure, topcoat film performance, and resist line edge roughness LER at extremely high resolutions, can all be readily studied. 32-nm 1:1 line/space L/S imaging is demonstrated using two of the second-generation fluids. These resolutions are well beyond current lens-based system capabili- ties. Results on the performance of various resists and topcoats are also reported for 32-nm L/S features.

Materials design and development of fluoropolymers for use as pellicles in 157-nm photolithography

The introduction of 157 nm as the next optical lithography wavelength has created a need for new soft (polymeric) or hard (quartz) pellicle materials optimized for this wavelength. Materials design and development of ultra transparent fluoropolymers suitable for 157 nm soft pellicle applications has produced a number of promising candidate materials with absorbances below 0.03/micrometer as is necessary to achieve pellicle transmissions above 95%. We have developed 12 families of experimental TeflonAFR (TAFx) materials which have sufficient transparency to produce transmissions above 95%. For the successful fabrication of 157 nm pellicles from these materials, the fluoropolymers must have appropriate physical properties to permit the spin coating of thin polymer films and their lifting and adhesive mounting to pellicle frames, the processes which produce free standing pellicle membranes of micron scale thickness. Relevant physical properties include molecular weight, glass transition temperature, and mechanical strength and toughness. We have successfully developed various of the ultra transparent TAFx polymer families with these physical properties. Upon irradiation these 157 nm pellicle polymers undergo photochemical darkening, which reduces the 157 nm transmission of the material. Measurements of the photochemical darkening rate allow the estimation of the pellicle lifetime corresponding to a 10% drop in 157 nm transmission. Increasing the 157 nm lifetime of fluoropolymers involves simultaneous optimization of the materials, the pellicle and the end use. Similar optimization was essential to achieve the desired radiation durability lifetimes for pellicles successfully developed for use with KrF (248 nm) and ArF (193 nm) lithography.

Single layer fluropolymer resists for 157-nm lithography

We have developed a family of 157 nm resists that utilize fluorinated terpolymer resins composed of 1) tetrafluoroethylene (TFE), 2) a norbornene fluoroalcohol (NBFOH), and 3) t-butyl acrylate (t-BA). TFE incorporation reduces optical absorbance at 157 nm, while the presence of a norbornene functionalized with hexafluoroisopropanol groups contributes to aqueous base (developer) solubility and etch resistance. The t-butyl acrylate is the acid-catalyzed deprotection switch that provides the necessary contrast for high resolution 157 nm imaging. 157 nm optical absorbances of these resists depend strongly upon the amount of t-BA in the polymers, with the TFE/NBFOH dipolymers (which do not contain t-BA) exhibiting an absorbance lower than 0.6 μm-1. The presence of greater amounts of t-BA increases the absorbance, but also enhances the dissolution rate of the polymer after deprotection, yielding higher resist contrast. Formulated resists based upon these fluorinated terpolymer resins have been imaged at International Sematech, using the 157 nm Exitech microstepper with either 0.6 NA or 0.85 NA optics. We have carefully explored the relationship between imaging performance, resist contrast, optical absorbance, and t-BA content of these terpolymer resist resins, and describe those results in this contribution.

157-nm pellicles: polymer design for transparency and lifetime

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.