Directed self-assembly (DSA) of block copolymers is proving to be an interesting and innovative method to make three-dimensional periodic, uniform patterns useful in a variety of microelectronics applications. Attributes critical to acceptable DSA performance of block copolymers include molecular weight uniformity, final purity, and reproducibility in all the steps involved in producing the polymers. Reversible Addition Fragmentation Chain Transfer (RAFT) polymerization technology enables the production of such materials provided that careful process monitoring and compositional homogeneity measurement systems are employed. It is uniquely suited to construction of multiblocks with components of widely divergent surface energies and functionality. We describe a high chi diblock system comprising partially fluorinated methacrylates and substituted styrenics. While special new polymer separation strategies involving controlled polymer particle assembly in liquid media are required for some monomer systems and molecular weight regimes, we have been able to demonstrate high yield and compositionally homogeneous diblocks of lamellar and cylindrical morphology with polydispersities < 1.1. During purification processes, these diblock materials undergo assembly processes in liquid media, and with appropriate controls, this allows for removal of soluble homopolymer contaminants. SAXS analyses of solid polymer samples provide estimates of lamellar d-spacing, and a good correlation with molecular weight is shown. This system will be described.
Reversible Addition Fragmentation Chain Transfer (RAFT) polymerization technology enables the production of
polymers possessing low polydispersity (PD) in high yield for many applications. RAFT technology also enables control
over polymer architecture. With synthetic control over these polymer characteristics, a variety of polymers can be
designed and manufactured for use in advanced electronic applications. By matching the specific RAFT reagent and
monomer combinations, we can accommodate monomer reactivity and optimize acrylate or methacrylate
polymerizations (193 and 193i photoresist polymers) or optimize styrenic monomer systems (248 nm photoresist
polymers) to yield polymers with PD as low as 1.05. For 193i lithography, we have used RAFT technology to produce
block copolymers comprising of a random "resist" block with composition and size based on conventional dry
photoresist materials and a "low surface energy" block The relative block lengths and compositions may be varied to
tune solution migration behavior, surface energy, contact angles, and solubility in developer. Directed self assembly is
proving to be an interesting and innovative method to make 2- and even 3-dimensional periodic, uniform patterns. Two
keys to acceptable performance of directed self assembly from block copolymers are the uniformity and the purity of the
materials will be discussed.
Optical immersion lithography using fluids with refractive indices greater than that of water (1.436) can enable numerical apertures of 1.55 or above for printing sub-45-nm lines. Two second-generation immersion fluid candidates, IF132 and IF169, both have indices above 1.64 and have been optimized to absorb less than 0.1 cm−1 at 193.4 nm. These fluids, although meeting the requirements of index and absorption, must also be compatible with current resists and processes to image the required fine line patterns. Results of fluid-resist interactions, with water and high-index fluids on four commercial resists, are shown. Photoacid generator (PAG) leaching measurements reveal much less leaching into both high-index fluids than into water, and in two water-immersion dedicated resists, no leaching is detected with the high-index immersion fluids. Little resist thickness change and swelling is detected by a quartz crystal microbalance (QCM) on contact with the fluids. Resist profile and line height changes due to pre- and postexposure fluid contact varies from one resist to the next, but overall the changes are minimal. Misting defects from high-index fluid-resist contact show lower counts than for water, and imaging on an immersion interference printer produces 36-nm half-pitch lines. We find no serious impediments to the use of high-index liquids based on these results.
Roger French, Hoang Tran, Doug Adelman, Nyrissa Rogado, Mureo Kaku, Michael Mocella, Charles Chen, Eric Hendrickx, Freida Van Roey, Adam Bernfeld, Rebekah Derryberry
We have performed high-index immersion fluid studies to define the levels of both soluble and insoluble impurities
present. These studies have also revealed the importance of process materials' purity in fluid contact. Fluid interactions
with resist, leading to both surface and imaging defects, can be minimized by proper resist selection. Our Active Recycle
Package technology can greatly extend the useful life of both the fluid itself, as well as the final lens element.
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.
Our studies of second generation immersion fluid candidates are moving beyond the discovery phase, and into addressing issues for their commercial application. Thus, we continue work to examine and fundamentally understand fluid transparency and refractive index, to fully optimize these properties. At the same time, we are now examining other process concerns, including index variation with temperature, new imaging performance studies, fluid handling considerations, and fluid property maintenance with active recycle during lithographic exposure. The systems and procedures we have developed in these areas continue to show our fluids' promise for sub-45nm immersion lithography applications.
Michael Crawford, William Farnham, Andrew Feiring, Jerald Feldman, Roger French, Kenneth Leffew, Viacheslav Petrov, Weiming Qiu, Frank Schadt, Hoang Tran, Robert Wheland, Fredrick Zumsteg
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.
KEYWORDS: Diffusion, Polymers, Glasses, Photoresist materials, Molecules, Adaptive optics, Temperature metrology, Systems modeling, Chemical reactions, Chemical analysis
In a chemically amplified resist the exposure energy is used to generate a catalytic species, which promotes a solubility-switching reaction during a post exposure processing step. Using an absorbed photon to generate a catalyst, instead of using it to directly cause a solubility-switching photochemical reaction, allows for much lower exposure doses to be used for patterning since the catalytic species can eventually promote multiple solubility-switching events instead of just one. Some level of catalyst mobility is necessary to achieve the amplification effect as the catalyst must move from reaction site to reaction site, but any catalyst mobility creates the possibility of movement from exposed regions into unexposed regions causing image blur or line width spreading. As the catalyst diffuses in the resist, it promotes chemical reactions; these chemical reactions complicate analyses of catalyst diffusion by changing the chemical environment of the diffusant. Thus, the material properties of the surrounding resin are changing, sometimes drastically, as the catalyst diffuses. In addition to simple changes in material type, the chemical reaction also generates a transient material state as reaction by-products either remain in the resist film or desorb. The variation in lifetime of this transient state is another factor that must be considered in a full analysis. This work reports a method to separate reaction effects from catalyst diffusion effects. Acid diffusion in polymers which are close structural analogues to poly(4-t-butyloxycarbonyloxystrene) (TBOCST), while being unreactive to diffusing acidic molecules, was studied. Specifically, the diffusion properties of photogenerated perfluorobutanesulfonic acid in the unreactive TBOCST analogues poly(4-isopropyloxycarbonyloxystyrene) and poly(4-neopentyloxycarbonyloxysytrene) are reported. Measuring and understanding diffusion in these analogue polymers provides insight into the more complicated, and more important, reaction-diffusion processes of TBOCST.
Fluorocarbon based polymers have been identified as promising resist candidates for 157nm material design because of their relatively high transparency at this wavelength. This paper reports our recent progress toward developing 157nm resist materials based on transparent dissolution inhibitors. These 2 component resist systems have been prepared and preliminary imaging studies at 157nm are described. Several new approaches to incorporating these transparent monomers into functional polymers have been investigated and are described. The lithographic performance of some of these polymers is discussed.
The synthesis and characterization of several new fluoropolymers designed for use in the formulation of photoresists for exposure at 157 nm will be described. The design of these resist platforms is based on learning from previously reported fluorine-containing materials. We have continued to explore anionic polymerizations, free radical polymerizations, metal-catalyzed addition polymerizations and metal-catalyzed copolymerizations with carbon monoxide in theses studies. The monomers were characterized by vacuum-UV (VUV) spectrometry and polymers characterized by variable angle spectroscopic ellipsometry (VASE). Resist formulations based on these polymers were exposed at the 157 nm wavelength to produce high-resolution images. The synthesis and structures of these new materials and the details of their processing will be presented.
Fluorocarbon polymers and siloxane-based polymers have been identified as promising resist candidates for 157 nm material design because of their relatively high transparency at this wavelength. This paper reports our recent progress toward developing 157 nm resist materials based on the first of these two polymer systems. In addition to the 2-hydroxyhexafluoropropyl group, (alpha) -trifluoromethyl carboxylic acids have been identified as surprisingly transparent acidic functional groups. Polymers based on these groups have been prepared and preliminary imaging studies at 157 nm are described. 2-Trifluoromethyl-bicyclo[2,2,1] heptane-2-carboxylic acid methyl ester derived from methyl 2-(trifluoromethyl)acrylate was also prepared and gas-phase VUV measurements showed substantially improved transparency over norbornane. This appears to be a general characteristic of norbornane-bearing geminal electron-withdrawing substituents on the 2 carbon bridge. Unfortunately, neither the NiII nor PdII catalysts polymerize these transparent norbornene monomers by vinyl addition. However, several new approaches to incorporating these transparent monomers into functional polymers have been investigated. The first involved the synthesis of tricyclononene (TCN) monomers that move the bulky electron withdrawing groups further away from the site of addition. The hydrogenated geminally substituted TCN monomer still has far better transparency at 157 nm than norbornane. The second approach involved copolymerizing the norbornene monomers with carbon monoxide. The third approach involved free-radical polymerization of norbornene monomers with tetrafluoroethylene and/or other electron-deficient comonomers. All these approaches provided new materials with encouraging absorbance at 157 nm. The lithographic performance of some of these polymers is discussed.
Top surface imaging (TSI) has had an interesting history. This process showed great promise in the late 1980's and several attempts were made to introduce it to full-scale manufacturing. Unfortunately, defect density problems limited the process and it fell from favor. TSI emerged again as an important part of the EUV and 193 nm strategies in the early stages of those programs because it offered a solution to the high opacity of common resist materials at both wavelengths. A flurry of research in both areas identified the seemingly insurmountable problem of line edge roughness than typical single layer resist systems. This has largely been due to the development of polymers specifically tailored for this end use. The optimum materials must be moderately transparent and have high Tg's in the silylated state. The 157nm program has much in common with the early stages of the 193nm program. The optical density of even 193nm resist materials at 157nm is far too high to allow their use in single layer applications. The less stringent optical density of even 193nm resist materials at 157nm is far too high to allow their use in single layer applications. The less stringent optical density requirements of TSI make it a potentially viable imaging scheme for use at 157nm. Various TSI materials, including the traditional poly(t-BOC- hydroxystyrene), as well as novel aliphatic cyclic polymers bearing bis-trifluoromethyl carbinol substituents, have been investigated for use at 157 nm, and smooth high-resolution images have been generated.
The migration of acid catalyst molecules from exposed regions into unexposed regions in chemically amplified photoresists and the resulting image blur, has long been recognized as an important topic requiring close study. A fuller understanding of acid transport mechanisms occurring during the post exposure bake is important to help guide the development and formulation of photoresists capable of reliably resolving the increasingly small features required by the semiconductor industry. This paper reports the direct measurement of diffusion coefficients for perfluorobutane sulfonic (nonaflate) acid in poly(4-hydroxystyrene) at several elevated temperatures. These results show that the Fickian diffusion coefficient for nonaflate acid in poly(4-hydroxystyrene) is too small, at typical post exposure bake temperatures, to account for observed isofocal bias. Also reported is a new technique for investigating acid transport properties of photoresist films. This method uses selective silylation to decorate cleaved resist film stacks, so that the extent of acid catalyst migration can be measured directly by scanning electron microscope (SEM). Acid transport distances from the SEM method are compared to those obtained from infrared (IR) spectroscopic techniques.
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