Organic polar solvent (1-butanol) versus aqueous base (tetramethylammonium hydroxide, (TMAH)) development quality are distinguished by neutral versus charged polymer (polyelectrolyte) dissolution behavior of photoresist bilayers on silicon substrates comprising poly(4-hydroxystyrene) and poly(4-tert-butoxycarbonyloxystyrene), PHOSt and PBOCSt, respectively. This model line-edge was broadened by photoacid catalyzed deprotection to a final interfacial width of 35.7 Å and subjected to different developers. 1-butanol develops with an increased penetration depth than aqueous base development consistent with an increased solubility of the protected containing component in the organic solvent. This enhanced dissolution with the polar solvent results in an increased surface roughness of 73 Å, whereas the development with TMAH at concentrations between (0.1 to 1.1) M1 leads to surface roughness between (4.5 to 14.4) Å, as measured by atomic force microscopy. These measurements suggest that the elimination of resist swelling, in the presence of a protection gradient, is a viable strategy to reduce roughness and control critical dimensions. The influence of added salt to developer solutions was also examined by developing the model bilayer. A decrease in surface roughness from (10 to 6.5) Å was observed between (0 to 0.70) M KCl in 0.26 M TMAH.
The performance of chemically amplified photoresists, including next generation thin film 157 nm fluorinated copolymers and blends, is affected by such phenomena as polymer/substrate and polymer/air interfacial (surface energy) effects, blend miscibility, small molecule diffusion in thin films, permeability of airborne contaminants, and interactions with products from the deprotection reaction. Using near edge x-ray absorption fine structure (NEXAFS) spectroscopy, it is possible to simultaneously probe the surface and bulk chemistry of chemically amplified photoresists to determine possible causes of pattern degradation, including post exposure delay induced material failure, blend component and small molecule diffusion/segregation to the photoresist surface, and interactions between components of the photoresist formulation and developer. The surface and bulk chemistry of model photoresists were analyzed in the NEXAFS vacuum chamber, equipped with in situ processing capabilities for exposure, controlled dosing of a model contaminant gas (NMP or water vapor), and heating, to quantify component segregation and identify surface phenomena that may be responsible for pattern degradation. For model 157 nm blend films, it was found that there is segregation of one component to the surface of the photoresist film, in excess of the composition of that component in the blend. For polymer blends the more hydrophobic or lower surface tension species will typically wet the film surface when heated in air. Segregation of photo-acid generator has also been demonstrated and the effect of reducing film thickness investigated. As photoresist film thickness continually decreases and the photoresists become increasingly sensitive to environmental contaminants, the interfacial and surface regions dominate the behavior of the material and it is crucial to understand both their physical and chemical nature.
With the increasing drive towards smaller feature sizes in integrated circuits and the consequent use of shorter exposure wavelengths, the imaging resist layer and underlying bottom anti-reflective coating (BARC) layer are becoming thinner. At this scale, the performance of chemically amplified resists can be adversely affected by the BARC-resist interfacial interactions. These interactions can cause distortion of resist profiles and lead to footing, undercut, or pattern collapse. BARC components can immensely influence the deprotection and dissolution properties of the resist. A thorough understanding of the physico-chemical interactions at these interfaces is essential to design and develop new material platforms with minimal adverse interactions and maximum compatibility between BARC and resist. Results are reported from studies of (A) surface versus bulk chemistry of BARC materials as a function of cure temperature, (B) the dependence of the thickness and composition of the residual layer (resist material remaining on the surface of the BARC after development) on BARC components, as determined by formulating the BARC or resist with an excess of various BARC components, and (C) the dependence of the residual layer thickness on crosslink density, exposure does, and resist bake temperature. The BARC thin films and the interphase between BARC and resist were characterized with near edge x-ray absorption fine structure (NEXAFS) spectroscopy. Surface chemical properties of BARC films were derived from contact angle measurements of various liquids on these thin films. Preliminary results from these studies indicate that some BARC components may migrate to the BARC-resist interphase and act as dissolution inhibitors. Similarly, small molecule additives in the resist may migrate into the BARC layer, causing chemical modifications.
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