In the past several years, ArF immersion lithography has been developed rapidly for practical applications. ArF
immersion lithography is now researched actively and developed for the purpose of implementing the 45-nm technology
node. For the device designs involved immersion lithography, line width roughness (LWR) and film wettability are very
important criteria to control in the point of high resolution and defectivity.
Free radical polymerization in the presence of thiocarbonylthio compounds of general structure Z-C(=S)S-R provides
living polymers of predetermined molecular weight and narrow molecular weight distribution by a process of reversible
addition-fragmentation chain transfer (RAFT). A rationale for selecting the most appropriate thiocarbonylthio
compounds for a particular monomer type is presented with reference to the polymerization of methacrylates, styrenes,
acrylates, acrylamides, and vinyl acetate.
In this study, resist polymers with narrow polydispersity (PD) and controlled molecular structure were prepared using
controlled radical polymerization techniques, such as RAFT polymerization. PD index of polymers showed between
about 1.2 to 1.4 and in some instances, between about 1.1 to 1.2 or less. Additionally, each polymer chain has a RAFT
end group. That is the resulting polymer contains a chain transfer agent (CTA) moiety at each terminal end of polymer
backbone. It is possible that hydrophobic CTAs can be used to decrease the hydrophilicity of resist film.
ArF Immersion lithography is the most promising technology for 45nm node and possibly beyond. However, serious
issues in ArF immersion lithography for semiconductor mass production still exist. One of the issues is immersion
specific defects, which are caused by photoresist component leaching and residual water droplets. In order to minimize
immersion specific defects, preventing water penetration into the resist film is regarded as an important factor. Several
research groups have reported that higher receding contact angle reduced defectivity. High receding contact angle of
film surface prevent water penetration into the resist film due to the hydrophobic nature. Resist component leaching
phenomenon also can be caused by the water penetration into the film, so hydrophobic resist can reduce leaching
In this paper, to investigate chemical leaching from resist surface, we evaluated the leaching value of PAG anion and
contact angles of various polymers according to their hydrophobicity. Hydrophilicity of a polymer was changed by the
degree of hydrophobic group substitution to polymer chain. We measured receding contact angle with four different
resists composed of water-repellent functiona group. Receding contact angle of resist surface increased as the portion of
water-repellent functional group increased. Also, the leaching amount of PAG anion decreased as the receding contact
angle of film surface increased. We expect that higher receding contact angle prevents chemical leaching from resist film
by repelling water at the surface. We will report detailed results in this paper.
Immersion materials have to overcome immersion-issues for successful wet process introduction to semiconductor
mass production. Component-leaching issue is one of the most influential wet process huddles, which is related to
immersion-liquid and projection lens contamination as well as resist patterning performances. In this paper, we will
introduce our experimental results of leaching blocking effects resulted from the modification of polymer and additive
structures and from the application of top surface blocking layers. PAG-leaching level of resist film formed of low Tg
resin shows the highest meanwhile that of high Tg resin is the smallest leaching value. The interaction forces between
additives and resin platforms are the most important to prevent additives leaching to immersion liquid.
We have tested 3 different types of resin structures to modify the interaction forces between resin platform and resist
components especially PAG molecules and photo-generated acid molecules. We changed 2-hydroxyethyl
methacrylate(2-HEMA) contents to be 5, 10, 15% in our base resin, COMA-acrylate hybrid system to modify the
hydrophilicity of resist platforms. By mimicking immersion process to obtain wet-performance of their resists we have
obtained relative value of component-leaching. Interaction-force between resist platform and PAG was seemed to be
largest when resist component-leaching is least so that the pattern profiles become to be vertical. It was appeared that
the 5% 2-HEMA containing resin and TPS-Nonaflate PAG system showed the best performance because of its low
leaching resulted from their strong interaction forces.
Another polymer parameter to determine the component-diffusivity is glass transition temperature, Tg. Low Tg
means high mobility of resin by small thermal energy due to high free volume contents inside of the resist film which
can act as diffusion pathways of resist components. 10% MA resin system shows the lowest Tg, around 140 degrees C and the
most serious T-topping profiles.
Defectivity issue becomes more important in immersion process, which is most related to the partial leaching by
residual water and resulted in watermark defects. We evaluated the relative easiness of watermark formation on
different resist films by correlations between static and dynamic contact angles. We made 2 different resist films
composed of 2 different water-repellent functional group monomers. Static contact angles of developer as well as DI
water were measured. It was found indirectly that amphiphilicity of resist film surface makes positive effect on
watermarks formation, that is, more hydrophobic and more developer-philic resist film remains less residual water
As the device design rule is continuously shrinking, line end shortening (LES) has grown to be one of the critical problems in 193 nm photolithography. Among several factors causing LES, diffusivity of photo-generated acid seems to have the most profound effect. Also, diffusivity of base quencher produces equivalent effects on LES, but in the reversed way. Besides, post-exposure bake (PEB) condition is another key factor by affecting diffusion length of photo-generated acid. Low LES can be achieved by lowering PEB temperature or shortening its time. In this paper, we will discuss our experimental results to assess the determining factors of LES and suggest controllability of LES in ArF lithographic process.
Sensitivity and resolution capability of photoresist depend on various parameters, such as efficiency of photoacid generation, base strength, types and concentration of protection groups on a polymer, as well as lithographic process condition. We have prepared polymers containing different protecting groups and investigated their effects on the sensitivity, and eventually, on ArF resist photolithographic behavior. Also, several different photoacid generators (PAGs) and bases were employed to study the influence of them on the resist sensitivity. We have changed process condition, especially, bake condition to discuss the role of bake temperature on the photochemical efficiency of the resist. It was found that the diffusion of the photogenerated acid and bases is the most significant factor to determine resist sensitivity than others. The detailed results will be discussed in this paper.
Hydrophilicity of a resist film is a major property to determine the compatibility of resist film and substrates. By incorporation of polar groups in the side chain of polymer, the hydrophilicity of polymer, eventually, the hydrophilicity of a resist film can be modified. Since most developer for photoresist is aqueous alkaline solution, the polar side groups control not only interaction with a substrate but also dissolution rate of the resist film. We have synthesized model polymers having various polar groups, and investigated the effect of the polarity on the 193nm resist photographic behavior. Acid, lactone, ether, and alcohol were selected as polar groups. Among them, various lactone and alcohol functional groups were selected for further study on the effect of the side group bulkiness. Hydrophilicity of each functional group was estimated by Log P, which can be calculated using simulation program. From the calculation, aliphatic alcohol and lactone have the highest polarity and ether has the lowest. However, the bulkiness of alcohol increases, the polarity is getting lower than that of ether. Polarity and bulkiness of the polar monomers (acid, lactone, ether, and alcohol group) affect wettability against developer, collapse in 1:1 L/S patterns and adhesion to substrates. The resist films have different contact angles by polarity, bulkiness and content of these monomers in polymer. The polymer including lactone group shows excellent lithographic performance and minimizes pattern collapse in 1:1 L/S. Furthermore, we investigated contrast, pattern profile and process margin of 193nm resist according to the polymer polarity.
We have been interested in the effect of the residual solvent on lithographic performance. The concentration distribution of solvent molecules along the film depth and the amount of residual solvents depend on their physical properties: evaporation rate, boiling point, viscosity, and so on. Since fast-evaporating solvent can make a dense skin-like layer at the top of the resist film, faster evaporation rate of solvent makes thicker film, while slow rate results in thinner film. And the amount of residual solvent is dependent of the evaporation rate of the casting solvent. The amount of residual solvent was verified by TGA method. It was found that the amount of residual solvent is a major parameter to determine film thickness, stiffness of resist pattern, acid diffusion length, and pattern profile shape.