A non-topcoat (non-TC) resist is a photoresist that contains a hydrophobic additive, which segregates to the surface and
forms a layer to minimize surface free energy. The improvement of surface hydrophobicity and the suppression of resist
component leaching were confirmed by using this segregation layer. Compared to conventional topcoat process, it is
speculated that the use of non-TC resist will reduce the cost of lithographic materials, improve throughput, and will be
compatible for the scanning speed improvement of immersion scanners. One issue for the non-TC resist is the possibility
of increased defect generation compared to processes using topcoats. It is assumed that the high resist surface
hydrophobicity and the developer insolubility of the hydrophobic additive are main factors causing the increase in defect.
Therefore, it is important to work out solutions for reducing these defects to realize the non-TC resists. A process of
selectively removing the hydrophobic additive between exposure and development process for the purpose of defective
reduction of non-TC resist was investigated. Specifically, wet processing was performed to the wafer after exposure
using an organic solvent to dissolve the hydrophobic additive. As a result, defect count was reduced to less than 1/1000
with the effective removal of the segregation layer without affecting pattern size. These results prove the effectiveness of
the proposed process named 'selective segregation removal (SSR)' treatment in reducing defects for non-TC resists.
In this study, we focus on the controllability of a wafer bevel from adhesion and hydrophobicity viewpoints in order to
solve the problems of film peeling and microdroplet formation around wafer bevels, which result in pattern defects.
Hexamethyldisilazane (HMDS) treatment is a common solution to these problems. We examine a novel wafer bevel
treatment utilizing silane coupling agents (SCAs) for obtaining high adhesion and hydrophobicity. SCAs comprise
trimethoxysilanol and organic functional groups. These groups react with inorganic substrates and films just over the
surface subjected to a novel chemical treatment (NCT), respectively. Several organic functional groups both with and
without fluorine are examined. The hydrophobicity is estimated from the static and receding contact angles of water.
The adhesion strength is measured from the stress required for pulling the topcoat film away from the substrate subjected
to the NCT. The coating performance of chemicals on the surface by the NCT and the aging stability of the formulated
solution of the SCAs are examined for optimizing the composition of the NCT solution. Further, we verify the film
peeling behavior and water leakage in wafers having a topcoat, ArF resist, and bottom antireflective coating (BARC)
using a quasi-immersion exposure stage.
A new technology called the double patterning (DP) process with ArF immersion lithography is one of the candidate
fabrication technologies for 32 nm-node devices. Over the past few years, many studies have been conducted on
techniques for the DP process. Among these technologies, we thought that the double Si hard mask (HM) process is the
most applicable technology from the viewpoint of high technical applicability to 32 nm-node device fabrication.
However, this process has a disadvantage in the cost performance compared with other DP technologies since these HMs
are formed by the chemical vacuum deposition (CVD) method.
In this paper, we studied the DP process using a dual spin-on Si containing layer without using the CVD method to
improve process cost and process applicability. Perhydropolysilazane (PSZ) was used as one of the middle layers (MLs).
PSZ changes to SiO2 through the reaction with water by the catalytic action of amine in the baking step. Using PSZ and
Si-BARC as MLs, we succeeded in making a fine pattern by this novel DP technique. In this paper, the issues and
countermeasures of the double HM technique using spin-on Si containing layers will be reported.
A dynamic receding contact angle (RCA) is a well-known guideline to estimate the degree of watermark (WM)
defects, which shapes circle and bridges inside of the defect and reduces with enlarging the RCA of topcoat (TC).
However, our recent investigation revealed the occurrence of the circular shape defects in spite of using the TC with a
large RCA, bringing about a change of line and space pattern pitch. In this paper, we clarify the origin of these defects
and propose a new key factor of the dynamic surface properties of immersion-specific defects. It was found that the
pitch-change defect is caused by the lens effect of the air bubbles embedded between advancing water meniscus and the
TC. To well understand generation of the bubble defects, we defined the "effective" hysteresis (EH) as the hysteresis of
dynamic contact angle taken the effects of water-absorption into account. An analysis with the EH indicates that the
bubble defect arises from not only to the large ACA but also small amount of water uptake and the amount of
water-absorption could be substituted by the dissolution rate of TC. It was demonstrated that the EH proposed is a new
key factor for estimating the number of bubble defects. The EH is very useful for analyzing the bubble defects in
immersion lithography. The characteristics of the bubble defect are also discussed with a focus on the structure of the
polymer attached to water.
Top coat process is required for immersion lithography in order to prevent both the chemical contamination of scanner optics with eluted chemicals from resist material and the formation of residual droplet under the immersion exposure with high scanning speed. However, defect density of ArF immersion lithography with alkaline developer soluble type top coat material is much higher than that of ArF dry lithography. Mimic immersion experiments comprised of soaking of exposed conventional dry ArF resist with purified water followed by drying step were performed in order to study the immersion specific defects. It was suggested that the origin of immersion specific defects with alkaline developer soluble type top coat was the remaining water on and in the permeable top coat layer that might interfere the desired deprotection reaction of resist during post exposure bake (PEB). Therefore, application of post exposure rinse process that can eliminate the impact of the residual micro water droplets before PEB is indispensable for defect reduction. Post exposure rinse with optimized purified water dispense sequence was noticed to be valid for defect reduction in mimic immersion lithography, probably in actual immersion lithography.
In the past several years, ArF immersion lithography has been developed rapidly for practical applications. One of the most important topics is the elucidation of a mechanism and its solution of immersion specific defects. In this paper, we report several analytical results of immersion specific defects. First, we classify several possible origins of specific defects that are proposed based on our experiment on the actual immersion process and previous literature. We focused on a droplet of immersion water that was the origin of circular and deformed circular-type defects. Further, a watermark (WM) was created on some types of film stacks with or without the topcoat (TC) on the resist. We observed that all samples exhibited the trace of the WM. From chemical surface analyses, we obtained different types of components in the residue of the WM, which dried spontaneously. These components depended on the tested film stack. Some types were not always derived from leaching materials in the resist. Some components in the residue appeared to be airborne contaminants that were unregulated in machines used in the photolithography process. Based on the results of these tests, we discussed some methods for avoiding defects according to the droplet WM.
We have developed a new ArF-RELACS (Resolution Enhancement Lithography Assisted by Chemical Shrink) material called AZ-LExp.R720. The principle and process procedure of LExp.R720 are almost identical to those previously developed with KrF lithography. The extent of crosslinking reactions and the mobility balance of chemical components at the boundary between resist and the RELACS film is adjusted to ArF resist chemistry. LExp.R720 can vary shrinkage from 10 to 40nm by controlling the process conditions, mainly the mixing bake temperature. The amount of shrinkage is independent of pattern pitch and focus. We confirmed that pattern profile, lithography margin, CD uniformity, etching resistance, and pattern defects were not deteriorated by the RELACS process with deionized water development. L.ExpR720 was able to get an amount of shrinkage with several of ArF resists, which has commercial applications. In conclusion, we believe that LExp.R720 is extremely useful for 65 nm node and next generation devices.
A chemical shrink technology, RELACS (Resolution Enhancement Lithography Assisted by Chemical Shrink), utilizes the cross linking reaction catalyzed by the acid component existing in a predefined resist pattern. This “RELACS” process is a hole shrinking procedure that includes simple coating, baking, and rinsing applied after conventional photolithography. Our target is realize of sub-70nm hole pattern formation by using new RELACS for ArF resist. At present, RELACS process is introduced to mass production of KrF lithography by using AZ R200 (Product name of Clariant) mainly. Then first of all we reported process performance of conventional RELACS material, AZ R200 with ArF resist. However AZ R200 does not show satisfactory shrinkage on ArF resist. Thereupon, we started on the development of new RELACS corresponding to ArF resist. As the result, we developed new RELACS material including Cross Linking Accelerator (CLA). It was found that CLA is able to improve reactivity of RELACS with ArF-resist. By using this new RELACS, It is Realized sub-70nm hole pattern formation with ArF-Ex lithography and It is able to Control of hole size by mixing bake (MB) temperature and additive ratio of CLA. Moreover this process was realized that thickness of shrunk hole is increased.