Kyle Patterson

157 nm resist materials: Progress report

Many semiconductor device manufacturers plan to make products with 157 nm lithography beginning in 2004. There is, at this time, no functional photoresist suitable for 157 nm exposure. Developing resist materials for 157 nm lithography is particularly challenging since water, oxygen, and even polyethylene are strongly absorbing at this wavelength. A modular approach to the design of a single layer resist for 157 nm has been undertaken. In this approach, the resist has been conceptually segmented into four functional modules: an acidic group, an acid labile protecting group, an etch resistant moiety, and a polymer backbone. Each of these modules has an assigned function and each must be transparent at 157 nm. Progress has been made toward finding candidate structures for each of these modules. We have demonstrated that acidic bistrifluoromethylcarbinols are very transparent at 157 nm and function efficiently in chemically amplified resists with both high and low activation energy protecting groups. Judicious incorporation of fluorine in acrylates and alicyclics has provided etch resistant polymers with greatly improved transparency at 157 nm. In particular, esters of poly(α-trifluromethylacrylic acid) are far more transparent than their protio analogs. The Diels–Alder adducts derived from reaction of these and other fluorinated alkenes with cyclopentadiene offer a route to a wide range of alicyclic monomers that show great promise as transparent, etch resistant platforms for the design of 157 nm resists. Polymers of this sort with absorbance below 2 per micrometer are reported.

Organic imaging materials: a view of the future

Over the last half century, the world semiconductor industry has provided phenomenal increases in computing power while simultaneously lowering production costs. This achievement is largely the result of the industry being able to print smaller and smaller features using photolithographic techniques. The organic imaging materials used in the photolithography (generally known as photoresists) have undergone many changes over the industrys history, and if the increases in computing speeds and decreases in costs are to continue in the future, more changes are necessary. This paper discusses the current generation of photoresists and the on-going development of future generation photoresist technologies. Copyright

Study of the fundamental contributions to line edge roughness in a 193 nm, top surface imaging system

Top surface imaging systems based on vapor phase silylation have been investigated for use at a variety of wavelengths. This approach to generating high aspect ratio, high resolution images held great promise particularly for 193 nm and EUV lithography applications. Several 193 nm top surface imaging (TSI) systems have been described that produce very high resolution (low k factor) images with wide process latitude. However, because of the line edge roughness associated with the final images, TSI systems have fallen from favor. In fact, TSI does not appear in the strategy or plan for any imaging technology at this time. Most of the 193 nm TSI systems that have been studied are based on poly(p-hydroxystyrene) resins. These polymers have an unfortunate combination of properties that limit their utility in this application. These limiting properties include (1) high optical density, (2) poor silylation contrast, and (3) low glass transition temperature of the silylated material. These shortcomings are relate...

Improving the performance of 193-nm photoresists based on alicyclic polymers

This paper reports our work on a series of alicyclic polymer-based photoresist platforms designed for 193 nm lithography. The polymers described here were prepared from derivatives of norbornene and appropriate co-monomers by either free radical or ring opening metathesis polymerization methods. A variety of techniques were explored as a means of enhancing the lithographic, optical, dissolution, and mechanical properties of photoresists formulated from these alicyclic polymers. Recent studies designed to improve the lithographic performance of photoresists formulated with these materials are described.

Polymers for 157-nm photoresist applications: a progress report

Finding materials that offer the all of the characteristics required of photoresist matrix resin polymers while trying to maintain a high level of transparency at 157 nm is a daunting challenge. To simplify this task, we have broken the design of these polymers down into subunits, each of which is responsible for a required function in the final material. In addition, we have begun collecting gas-phase VUV spectra of these potential subunits to measure their individual absorbance contributions. Progress on developing materials for each of these subunits are presented along with plans for future studies.

Dissolution behavior of fluoroalcohol substituted polystyrenes

(alpha) -Fluoroalcohols have been proposed as transparent, base-soluble functional groups for use in the design of new 157 nm photoresist polymers. The two most common and easily prepared fluoroisopropanol groups are bis-trifluoromethyl carbinols (hexafluoroalcohol) and methyl-trifluoromethyl carbinols (trifluoroalcohol). This paper describes studies designed to assess the suitability of both of these functionalities as acidic groups. Dissolution rate studies were carried out on polystyrene films that incorporate these groups. The dissolution rates of the sample polymers were compared to that of poly(hydroxystyrene) (PHOST) to provide a reference for the measurements. It was found that the trifluoroalcohol polymers do not exhibit any solubility in basic media, while the hexafluoroalcohol polymers dissolve rapidly relative to PHOST in 0.13N TMAH. Further, it was found that the two fluoroalcohol polymers can be blended to adjust the inherent dissolution rate of the resin and that the hexafluoroalcohol polymer is sensitive to incorporation of classical dissolution inhibitors. The study concludes that hexafluoroalcohol is a promising candidate for incorporation into the design of 157 nm photoresists.

Positive- and negative-tone water-processable photoresists: A progress report

This paper presents the progress we have made toward the development of fully water processable, negative and positive tone I-line resist systems. The negative tone system is based on styrene copolymers bearing pendant ammonium sulfonate groups and vicinal diol functionalities. The salt provides the means of rendering the polymer water soluble. The diol undergoes an acid catalyzed pinacol rearrangement that results in a polarity switch within the exposed polymer film, i.e. a solubility differential. The styrene backbone was chosen to provide dry etch resistance. Positive tone imaging requires two solubility switches. The two solubility switches are based on the reaction between acidic hydroxyl groups in a matrix polymer and vinyl ethers that are introduced as a pendant group of the polymer or as a monomeric cross-linker, i.e. a bisvinyl ether. During the post application bake, the vinyl ether reacts with an acidic hydroxyl group in a thermally activated switch, forming a crosslinked, water insoluble network through acetal linkages. These acid labile crosslink sites are then cleaved by a photochemical switch through the generation of acid, thereby rendering the exposed areas water developable.

Using alicyclic polymers in top surface imaging systems to reduce line-edge roughness

Top surface imaging (TSI) systems based on vapor phase silylation have been investigated for use at a variety of wavelengths. This approach to generating high aspect ratio, high resolution images held great promise particularly for 193 nm and EUV lithography applications. Several 193 nm TSI systems have been described that produce very high resolution (low k factor) images with wide process latitude. However, because of the line edge roughness associated with the final images, TSI systems have fallen from favor. In fact, top surface imaging and line edge roughness have become synonymous in the minds of most. Most of the 193 nm TSI systems are based on poly(p-hydroxystyrene) resins. These polymers have an unfortunate combination of properties that limit their utility in this application. These limiting properties include (1) High optical density (2) Poor silylation contrast (3) Low glass transition temperature of the silylated material. These shortcomings are related to inherent polymer characteristics and are responsible for the pronounced line edge roughness in the poly(p-hydroxystyrene) systems. We have synthesized certain alicyclic polymers that have higher transparency and higher glass transition temperatures. Using these polymers, we have demonstrated the ability to print high resolution features with very smooth sidewalls. This paper will describe the synthesis and characterization of the polymers and their application to top surface imaging at 193 nm. Additionally, it will describe the analysis that was used to tailor the processing and the polymers physical properties to achieve optimum imaging.

Design and study of water-soluble positive- and negative-tone imaging materials

The interest in imaging materials with improved environmental characteristics has led us to consider imaging formulations coated from and developed in aqueous media, thus avoiding the need for both organic solvents and basic aqueous developer solutions. We have previously reported on the design of several negative-tone resists operating via radiation-induced crosslinking, and while the performance of these negative-tone systems met our basic goals, the resolution that could be achieved was limited due to swelling occurring during development. We now report on various other designs based on polyoxazoline, poly(vinyl alcohol), and methacrylate resins that circumvent this problem with approaches towards both negative- and positive- tone systems.