In immersion lithography, high index fluids are used to increase the numerical aperture (NA) of the imaging system and
decrease the minimum printable feature size. Water has been used in first generation immersion lithography at 193 nm to
reach the 45 nm node, but to reach the 38 and 32 nm nodes, fluids and resists with a higher index than water are needed.
A critical issue hindering the implementation of 193i at the 32 nm node is the availability of high refractive index (n >
1.8) and low optical absorption fluids and resists. It is critical to note that high index resists are necessary only when a
high refractive index fluid is in use. High index resist improves the depth of focus (DOF) even without high index fluids.
In this study, high refractive index nanoparticles have been synthesized and introduced into a resist matrix to increase the
overall refractive index. The strategy followed is to synthesize PGMEA-soluble nanoparticles and then disperse them
into a 193 nm resist. High index nanoparticles 1-2 nm in diameter were synthesized by a combination of hydrolysis and
sol-gel methods. A ligand exchange method was used, allowing the surface of the nanoparticles to be modified with
photoresist-friendly moieties to help them disperse uniformly in the resist matrix. The refractive index and ultraviolet
absorbance were measured to evaluate the quality of next generation immersion lithography resist materials.
A critical issue preventing the implementation of 193nm immersion lithography (193i) to the 32nm node is the
availability of high refractive index (n > 1.8) and low optical absorption fluids. To overcome these issues, we have
synthesized high refractive index nanoparticles and introduced them into the immersion fluid to increase the refractive
index. Hydrolysis and sol-gel methods have been implemented to grow high refractive index nanoparticles with diameters of 3-4nm. Depending on the synthetic route, it is possible to produce stable suspensions of nanoparticles in either aqueous or organic solvents, making it possible to synthesize a stable high-index immersion fluid.
Generation-three (Gen-3) immersion lithography offers the promise of enabling the 32nm half-pitch node. For Gen-3
lithography to be successful, however, there must be major breakthroughs in materials development: The hope of
obtaining numerical aperture imaging ≥ 1.70 is dependent on a high index lens, fluid, and resist. Assuming that a fluid
and a lens will be identified, this paper focuses on a possible path to a high index resist. Simulations have shown that
the index of the resist should be ≥ 1.9 with any index higher than 1.9 leading to an increased process latitude.
Creation of a high index resist from conventional chemistry has been shown to be unrealistic. The answer may be to
introduce a high index, polarizable material into a resist that is inert relative to the polymer behavior, but will this too
degrade the performance of the overall system? The specific approach is to add very high index (~2.9) nanoparticles
to an existing resist system. These nanoparticles have a low absorbance; consequently the imaging of conventional
193nm resists does not degrade. Further, the nanoparticles are on the order of 3nm in diameter, thus minimizing any
impact on line edge roughness (LER).
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.