The demands for high resolution and issues of line edge roughness require a reconsideration of current resist design strategies. In particular, EUV lithography will provide an opportunity to examine new resist concepts including new elemental compositions and low molar mass resists or molecular resists. In the former case, resist compositions incorporating elements such as silicon and boron have been explored for EUV resists and will be described. In an example of the latter case, molecular glass resists have been designed using synthetic architectures in globular and core-arm forms ranging from one to multiple arms. Moreover, our studies include a series of ring and irregularly shaped small molecules modified to give imaging performance. These materials have been explored to improve line edge roughness (LER) compared to common polymer resists. Several examples of polymeric and molecular glass resists will be described. Several compositions showed high glass transition temperatures (T<sub>g</sub>) of ~ 120°C and possessed no crystallinity as seen from XRD studies. Negative-tone molecular glass resists with a T-shaped phenolic core structure, 4-[4-[1,1-Bis(4-hydroxyphenyl)ethyl]]-α,α-dimethylbenzylphenol, have demonstrated feature sizes as small as 50mn. Similarly, negative-tone images made using spiro-based compounds showed feature size as small as 60nm in lines/space patterns using e-beam lithography. Most recently we have demonstrated that fully and partially <i>tert</i>-butoxycarbonyl (<i>t</i>-Boc) protected calixresorcinarene derivatives can be successfully studied as a positive-tone resist using EUV and E-beam lithography. Resolution as low as 35nm was obtained by EUV exposure.
The uniqueness in extreme ultraviolet (EUV) Lithography is encouraging the development of new polymer platform as a resist material. The absorbance characteristic of materials at the EUV region demands the use of polymers containing highly transparent silicon atoms. Also very low level of outgassing is required due to the vacuum environment during exposure and the extremely high cost of the EUV tools. To fulfill those requirements, two types of silicon backbone polymers were studied; chemically amplifiable polysilanes and polysilsesquiazanes. In the former case, the direct incorporation of acid sensitive groups into the polymer backbone allows for a solubility switch upon exposure. In the later system, this nitrogen-containing silicon polymer can be cleaved upon exposure to induce a solubility switch. These polymers possess many essential properties including low absorbance, low outgassing, and high sensitivity. Polymers having different substituents and branching ratios were synthesized. The properties of the polymers will be discussed relating to their lithographic performances.
To fulfill industry requirements for EUV resists, the development of entirely new polymer platforms is needed. In order to address transparency issues, we have been studying low absorbance materials, specifically silicon based resist platforms. In this approach, we have synthesized and studied resist materials based on polysilanes, polycarbosilane, and polysilsesquiazanes. Poly(methylphenylsilane) was chemically modified to incorporate polar groups to enhance solubility in polar solvents and developer solution. Copolymerization of the modified polysilane with an acid sensitive monomer has been used to produce chemically amplified copolymers. Preliminary studies have shown promising behavior. Polysilsesquiazanes-based resist were synthesized and tested using a 248 nm stepper. They showed excellent lithographic performance but some issues, including long term stability, are presently unknown. Our strategy to produce silicon-based resist together with outgassing and lithography issues will be discussed.
Performance requirements for EUV resists may require the development of entirely new polymer platforms. In the first approach, we have synthesized norbornene-based copolymers using ring-opening metathesis polymerization (ROMP). Silicon containing norbornenes were synthesized and copolymerized with a series of monomers having acid sensitive and polar groups, including nitrile, carboxylic acid, hydroxyl, and anhydride functions to achieve random copolymers with suitable properties to be applied as resist materials. Using well-characterized metal alkylidene complexes, we could prepared polymers having controlled molecular weights and low polydispersities. From initial exposure studies using an EUV interferometer, we were able to pattern 150 nm pitchs without additional optimization. In the second approach, polysilane has been copolymerized with acid sensitive monomers (acrylate and styrene derivatives) to produced chemically amplified polysilane-copolymers.