Dry-developable positive resist

Details Dry-developable positive resist Dry-developable positive resist

1996-11-25

1998-03-31

Baxter, Janet C.

Radiation imagery chemistry: process, composition, or product th

Imaging affecting physical property of radiation sensitive...

Radiation sensitive composition or product or process of making

4302811, 430914, G03C 173

Patent

active

057337063

DESCRIPTION:

BRIEF SUMMARY
BACKGROUND OF THE INVENTION

The invention relates to a dry-developable, positively acting TSI resist.
In photolithographic structure production, dry-developable TSI single layer resists (TSI=Top Surface Imaging) demonstrate a number of advantages, such as suppression of reflections and reduction of topography effects. A detailed description of such systems is found in "introduction to Microlithography," ACS Symposium Series 219 (1983), pages 287 to 350.
TSI resists are known both in the form of positively acting and in the form of negatively acting dry-developable single layer systems. In contrast to negatively acting systems, positively acting TSI systems are much better suited for applications in the contact hole planes, which are very critical, because of their lesser defect density.
Dry-developable single layer systems function according to the following principle: causing the resist--in the exposed areas (negative resist) or in the non-exposed areas (positive resist)--to become resistant to dry developing, particularly in an oxygen plasma;
This number of process steps should not be exceeded in production, if possible.
A high-resolution TSI system which is well suited for production should furthermore satisfy the following requirements: mentioned above result in higher costs, with the additional costs being caused by investments for additional equipment and/or reagents, and by the additional process steps. throughput of the expensive exposure equipment (steppers), and therefore the higher the costs. A high level of sensitivity in the DUV range (DUV=deep UV) is particularly important. treated with the metallization agent is important for a high process latitude in dry developing.
In order to solve the problem of low DUV sensitivity of photoresists, resist systems were developed which have tert. butyl ester or tert. butoxy carbonyloxy groups in the basic polymer (see in this regard EP-OS 0 102 450 and 0 161 476, i.e. the corresponding U.S. Pat. Nos. 4,491,628 and 4,552,833). When exposed in the presence of a strong acid former, for example a Crivello salt, carboxyl groups or phenolic OH groups are formed, with a single proton splitting off several groups, according to the principle of so-called "chemical amplification" (see, for example, "J. Electrochem. Soc.," Vol. 136 (1989), pages 1453 to 1456).
Cationic polymerization or crosslinking can also be carried out by catalysis with strong acids; these are suitable for use in resist systems with high DUV sensitivity. A negative TSI resist which is very sensitive in the DUV range and functions according to the principle of acid-catalyzed polymerization is described, for example, in EP-OS 0 192 078, i.e. in the corresponding U.S. Pat. No. 4,551,418. Reports about the use of acid-catalyzed crosslinking in photoresist systems, for example by means of etectrophilic substitution on activated aromatics in the presence of Crivello salts, were presented at the 8th international Conference on Photopolymers, Ellenville, N.Y. (1988) (see Conference report: pages 63 to 72).
Also, several positively acting TSI systems have already become known, but they do not fully meet the above requirements in each instance: produced with UV light or with electron beams. A disadvantage is the need for special apparatus (for vacuum) as well as the requirement of metallization with corrosive or toxic gases, such as B.sub.2 H.sub.6, SiCl.sub.4, and TiCl.sub.4, which is not very suitable for production. permeability of the resist relative to the metallization agent is changed by the exposure. Disadvantages of this system in the positive mode are a low level of DUV sensitivity (50 to 300 mJ/cm.sup.2) and the requirement of silylation with hexamethyl cyclotrisilazane in o-xylene at 65.degree. C., for which special apparatus is required, resulting in low line compatibility. amplification and has a high level of DUV sensitivity (approximately 6 mJ/cm.sup.2). However, two additional process steps are needed, namely metal-free treatment with methyl isocyanate, in a vacuum oven, as well as flood

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Gogolides, E. et al., "Wet Silyation and Dry Development with the AZ 5214.TM. Photoresist," J. Vac. Sci. Technol. B. (1992), pp. 2610-2614.

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