Photobase Generator Enabled Pitch Division: A Progress Report

Pitch division lithography (PDL) with a photobase generator (PBG) allows printing of grating images with twice the pitch of a mask. The proof-of-concept has been published in the previous paper[1, 2] and demonstrated by others[1]. Forty five nm half-pitch (HP) patterns were produced using a 90nm HP mask, but the image had line edge roughness (LER) that does not meet requirements. Efforts have been made to understand and improve the LER in this process. Challenges were summarized toward low LER and good performing pitch division. Simulations and analysis showed the necessity for an optical image that is uniform in the z direction in order for pitch division to be successful. Two-stage PBGs were designed for enhancement of resist chemical contrast. New pitch division resists with polymer-bound PAGs and PBGs, and various PBGs were tested. This paper focuses on analysis of the LER problems and efforts to improve patterning performance in pitch division lithography.Chemical Engineerin

Fluorinated Polymethacrylates as Highly Sensitive Non-chemically Amplified E-beam Resists

In an effort to improve upon the sensitivity of commercial non-chemically amplified e-beam resists, four polyacrylates functionalized with alpha-CF3 and/or CH2CF3 alkoxy substituents were studied. The alpha-CF3 substituent is known to increase backbone-scission efficiency while simultaneously eliminating acidic out-gassing and cross-linking known to occur in alpha-halogen substituted polyacrylates. Contrast curves for the polymeric alpha-CF3 acrylates, generated through e-beam exposure, showed the resists required an order of magnitude less dose than the current industry-standards, PMMA and ZEP. The fundamental sensitivity of these materials to backbone scissioning was determined via Co-60 gamma-ray irradiation. The chain scissioning, G(s), and cross-linking, G(x), values calculated from the resulting change in molecular weight demonstrated that all fluorinated resists possess higher G(s) values than either PMMA or ZEP and have no detectable G(x) values. Utilizing e-beam and EUV interference lithographies, the photospeed of PMTFMA was found to be 2.8x and 4.0x faster, respectively, than PMMA.Chemistr

Photochemical generation of a primary vinyl cation from (E)-bromostyrene: Mechanisms of formation and reaction

The photochemistry of (E)-bromostyrene was investigated to determine the nature of the product-forming intermediates and to clarify the mechanism of formation of vinylic cations and vinylic radicals. Both a cation- and a radical-derived product are formed, and the ionic origin of the former product is demonstrated by significant scrambling of the label, starting from specifically deuterated (E)-bromostyrene. MO calculations show that the isolated incipient primary vinyl cation is not a metastable species, but that specific interaction with a counterion in combination with a polar environment makes it metastable. The effects of variation of the wavelength of irradiation, solvent polarity, temperature, and isotopic substitution all agree with a mechanism of direct heterolytic C-Br bond cleavage producing an ion pair followed by formation of a radical pair via electron transfer. The vinylic cation is proposed to stem directly from the indirectly populated lowest excited singlet state of bromostyrene with an energy of activation of 6.7 kcal/mol. Branching between proton loss and electron transfer in the resulting ion pair determines the ratio of cation- to radical-derived product. The E/Z-isomerization occurs in a separate process and does not involve C-Br bond cleavag

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2D and 3D photoresist line roughness characterization

International audienc