Manipulation of dissolution properties by changing organic solvent developer and rinse material provides a novel
technology to obtain fine pattern beyond the limitation of imaging system based on alkaline developer. QCM study
showed no swelling character in negative-tone imaging (NTI) process even for current developer of n-butyl acetate
(nBA). Actually, NTI process has shown advantages on resolution and line-width roughness (LWR) in loose pitch
around 30 ~ 45 nm hp as a consequence of its non-swelling character. On the other hand, bridge and collapse limited its
resolution below 20 nm hp, indicating that non-negligible amount of swelling still exists for tight pitch resolution. We
investigated effects of solubility parameter of organic solvents on resolution below 20 nm hp. A bridge was reduced with
a decrease in the solubility parameter dp from nBA. On the other hand, much lower dp caused film remaining due to its
extremely slow Rmax. Based on these results, we newly developed FN-DP301 containing organic solvent with smaller
dp than nBA. Although rinse solvent gave negligible effects on bridge, there is a clear improvement on pattern collapse
only in case of using new rinse solvent of FN-RP311.
Lithographic performances of NTI process using nBA and FN-DP301 together with the other organic solvents were
described in this paper under exposures with an E-beam and a EUV light. It is emphasized that 14 nm hp resolution was
obtained only using FN-DP301 as a developer and FN-RP311 as a rinse under E-beam exposure. NTI showed 43% faster
photospeed in comparison with PTI at 16 nm hp, indicating that NTI is applicable to obtain high throughput with
maintaining resolution. In addition, sub-20 nm trench was obtained using NTI without bridge under EUV exposure, all of
which are attributed to the low swelling character of NTI process. Similarly, NTI was able to print 20 nm dots using
NXE:3100 with only a little peeling. Conversely CH patterning was significantly worse with NTI compared to PTI, that
is, only 36 nm contacts with 60 nm pitch was resolved under EUV exposure.
An effective filter start-up method has been required by device manufacturers, mainly in order to reduce waste volume of
lithography process chemicals, which become more expensive as lithography technology advances. Remaining air was
monitored during static-pressure-driven filter start-up. As a result, 3500 ml of the resist was needed to eliminate
remaining air. For improvement, cyclohexanone pre-wetting was applied prior to the resist introduction. As a result, the
resist volume needed for the solvent displacement was 1900 ml, approximately half the volume required for staticpressure-
driven start-up. Other solvents were evaluated for the pre-wetting start-up method. Results, in descending
order of performance were PGME (best) < PGMEA = IPA < cyclohexanone (worst). Moreover, air displacement
performance strongly correlated with Hansen solubility parameter distance between each solvent and nylon 6,6 material.
Transparency of the resist film at exposure wavelength affects lithographic performances, such as sensitivity, profile and resolution. Not only binder polymer, but also photo acid generator (PAG) itself has a significant impact on transparency of the formulated resist. Triphenylsulfonium salt (TPS) or Diphenyliodonium salt (DPI) have been widely used as PAGs in DUV chemically amplified (CA) resists, however, aromatic groups there have strong absorption at 193nm and thereby these PAGs have to suffer from low transparency. In this paper, we will report a novel class of transparent enone sulfonium salt PAGs(ENS-PAG), which we believe useful for 193nm resist. The ENS-PAGs do not have any aromatic groups but have an α,β-unsaturated ketone structure for the absorbing moiety in the backbone. These PAGs showed excellent transparency, thermal stability, and demonstrated an advantage in the line edge roughness (LER).
Physical and lithographic properties of functionalized acetal- based polymers, newly designed bulky acetals, were investigated for the use of KrF DUV resist. The key structural design was to incorporate some functional groups into the acetal moieties in the polymers through an ether or ester linkage. The polymers were synthesized by reacting poly p- hydroxy styrene (PHS) with variety of functionalized vinyl ethers that were prepared with substitution reaction of chloroethyl vinyl ether. By selecting large moieties in size for the functional group, the polymers showed good lithographic performance even with a low level of the acetal blocking. This was advantageous for minimizing the defects that could generally be formed in image development and also for improving dry etch resistance of the resist. The ester- linked polymers showed a high dissolution discrimination which could be accounted for with dissolution inhibition induced by a molecular interaction of the ester group with photo acid generator (PAG) in the resist composition. A new class of acetal polymers having additional another acid-decomposable group in the functional group is also proposed for achieving a further improvement in lithographic property.
A study for a new organic bottom antireflective coating (BARC) composition is described. A structural design of a light-absorbing dye was most important because dye structure not only plays a role in eliminating reflection from a substrate but also shows influence on dry etch rate of BARC material to a considerable extent. For example, an anthracene moiety with large absorption at 248 nm had undesirable dry etch resistance. 3-Hydroxy-2-naphthoic acid moiety was found to be one of suitable dyes for KrF BARC compositions, and the polymer bearing the dye showed enough absorbance and good erodability in dry etch. The BARC polymer was eroded as one and a half times faster than a novolak resin, and a little faster than an anthracene incorporated polymer. The result was discussed from the concepts of Ohnishi parameter and the ring parameter for dry etch durability of resist materials. BARC polymer should be thermoset by hard bake to eliminate intermixing with resist compositions. The BARC polymer bearing hydroxy group which is useful for a crosslinking reaction was thermoset in the presence of melamine-formaldehyde crosslinker and an acid catalyst after baking over 200 degrees C.
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