This paper discusses the continued evolution of Polymer-bound PAG [PBP] resists for sub-20nm lithography. Utilizing EUV wavelength, there has been enough progress in resolution and sensitivity to justify the use of these materials. PBP resists have shown that the principal demerit of acid diffusion can be overcome through attachment of the PAG anion to the lithographic polymer. Since the introduction of this chemically amplified resist approach, we have seen steady improvement in resolution, sensitivity, and LWR. Using a 0.30NA EUV tool with dipole, we can achieve 22nm hp resolution, with 12mJ dose, and 4.2nm LWR. Through rational PAG cation design, we have substantially reduced to a factor of 1/10th the PBP resist response to Out-of-Band Radiation compared to a TPS-based PBP. In this way, the resist can act as in situ spectral filter for unwanted longer wavelength exposure.

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The cyclic carbophosphazene N3P2CCI5 undergoes thermal ring-opening polymerization at 120 °C to yield the poly(chlorocarbophosphazene) [NsP2CCl6]" as a hydrolytically sensitive elastomer. This polymer was allowed to react with a variety of aryloxide nucleophiles to afford a range of hydrolytically stable poly[(aryloxy)carbophosphazenes] [N3P2C(OAr)6]"• These macromolecules were characterized by 31P, lH, and 13C NMR spectroscopy, IR spectroscopy, elemental analysis, differential scanning calorimetry, gel permeation chromatography and, in one case, light scattering. Analogous, small-molecule model reactions, in which the cyclocarbophosphazene N3P2CCI6 was allowed to react with the same aryloxide nucleophiles to yield the cyclic species N3P2C(OAr)s, are also described. The glass transition temperatures of the poly-[ (aryloxy)carbophosphazenes] are 16-42 °C higher than those of their classical polyphosphazene analogues [NP(OAr)2]". Possible reasons for the lower skeletal flexibility of poly(carbophosphazenes) compared to classical polyphosphazenes are discussed.

Resolution, line edge roughness, sensitivity and low outgassing are the key focus points for extreme ultraviolet (EUV) resist materials. Sensitivity has become increasingly important so as to address throughput concerns in device manufacturing and compensate for the low power of EUV sources. Recent studies have shown that increasing the polymer linear absorption absorption coefficient in EUV resists translates to higher acid generation efficiency and good pattern formation. In this study, novel high absorbing polymer platforms are evaluated. The contributing effect of the novel absorbing chromophore to the resultant chemically amplified photoresist is evaluated and comparedwith a standard methacrylate PAG Bound Polymer (PBP) platform. We report that by increasing EUV absorption, we cleanly resolved 17 nm 1:1 line space can be achieved at a sensitivity of 14.5 mJ/cm 2 , which is consistent with dose requirements dictated by the ITRS roadmap. We also probe the effect of fluorinated small molecule additives on acid yield generation (Dil C) at EUV of a PBP platform.

The cyclic carbophosphazene N3P2CCls reacts with sodium methoxide, sodium trifluoroethoxide, and sodium phenoxide to yield the corresponding pentaalkoxy-and pentakis(ary1oxy)cyclocarbophosphazenes. By contrast, N3PzCCls does not react with the main group and transition metal nucleophiles lithium diphenylphosphide and lithium pentacarbonylmanganate and reacts incompletely with sodium dicarbonyl(q~-2,4-~yclopentadicn-1 -yl)ferrate. The title compound undergoes thermal ring-opening polymerization when heated to 120 "C. This polymerization was monitored by 3lP NMR spectroscopy. Aspects of the mechanism of polymerization are discussed. Crystal structures of N3P2CCls and N3P2C(OPh)5 were obtained by X-ray diffraction. The crystals of N3PzCCls are orthorhombic, of space group Pbca, with a = 7.7880 A, b = 29.3560 A, c = 16.7990 A, j3 = 90.00°, V = 3840 A' , and Z = 16, whereas crystals of N3P2C(OC6H5)5 are triclinic, of space group P i , with a = 10.249(2) A, b = 12.290(4) A, c = 14.437(2) A, CY = 84.65(2)", 0 = 85.57(1)", y = 70.82(2)", V = 1708.08 A3, and Z = 2.