US 9,557,643 B2  283  284  -continued  (PA-16)  (PA-17)  (PA-18)  (1) Preparation of Coating Solution of Actinic Ray-Sensitive  or Radiation-Sensitive Resin Composition, and Coating  The coating solution composition according to the for› mulation shown in the Table below was microfiltered  through a membrane filter having a pore size of 0.1 µm  to  obtain an actinic ray-sensitive or radiation-sensitive resin  composition (resist composition) solution.  This actinic ray-sensitive or radiation-sensitive resin com› position solution was coated on a 6-inch Si wafer previously  subjected to a hexamethyldisilazane (HMDS) treatment, by  using a spin coater, Mark 8, manufactured by Tokyo Elec› tron Ltd. and dried on a hot plate at 100°  C. for 60 seconds  to obtain a resist film having a thickness of 50 nm.  (2) EB Exposure and Development  The resist film-coated wafer obtained in (1) above was  patternwise irradiated by using an electron beam lithography  apparatus (HL 7 50, manufactured by Hitachi, Ltd., acceler- ating voltage: 50 keV). At this time, the lithography was  performed to form a 1:1 line-and-space pattern. After the  electron beam lithography, the wafer was heated on a hot  plate at 110° C. for 60 seconds, then developed for 30  seconds by puddling the organic developer shown in the  Table below, rinsed by using the rinsing solution shown in  the Table below, rotated at a rotational speed of 4,000 rpm  for 30 seconds and heated at 90°  C. for 60 seconds to obtain  a resist pattern composed of a 1:1 line-and-space pattern  having a line width of 50 nm.  Preparation of an actinic ray-sensitive or radiation-sensi› tive resin composition and pattern formation were per› formed in the same manner as in Example 1 except for  changing the formulation as shown in the Table below,  performing the development with an aqueous alkali solution  (TMAH, an aqueous 2.38 mass  % tetramethylannnonium  hydroxide solution) in pace of the organic developer, and  using water as the rinsing solution.  (3) Evaluation of Resist Pattern  The obtained resist pattern was evaluated for sensitivity,  resolution and LWR by means of a scanning electron micro› scope (S-9220, manufacture by Hitachi Ltd.) by the follow› ing methods. The results obtained are shown in the Tables  below.  (3-1) Sensitivity  The irradiation energy below which the 1:1 line-and› space pattern having a line width of 50 nm cannot be  resolved was taken as the sensitivity (Eop). A smaller value  indicates higher performance.  (3-2) Resolution  The minimum line width below which the line-and-space  (1: 1) pattern at the Eop above cannot be separated was taken  as the resolution. A smaller value indicates higher perfor- mance.  (3-3) Line Width Roughness (LWR)  With respect to the line width roughness, at arbitrary 50  points in the longitudinal 0.5  µm region of the line-and› space space pattern having a line width of 50 nm (in  Comparative Examples 5 and 6, the 1: 1 line-and-space  pattern having a line width of 100 nm), the line width at the  Eop above was measured and after determining the standard  deviation thereof,  3a  was computed. A smaller value indi› cates higher performance.  Examples 1 to 28 and Comparative Examples 1 to  4  Electron Beam (EB) Exposure  Comparative Examples 5 and 6 (Electron Beam  (EB) Exposure)  OH  O  0  ~#  ,.,..s  0  OH  O  0  ~~#  ,.,..s  0  ~\#°  ,.,..s  0  #  TABLE 3  EB  ex osure  Acid  Acid-Increasing Solvent  Generator Agent  (mass ratio)  Basic  Resin (A)  (B)  (compound  (C))  (40 g)  Compound  Example 1  Al-1-1  z45  PA-17  S-1/S-2  D-3  (0.794 g)  (0.160 g)  (0.035 g)  (80/20)  (6 mg)  Example 2  Al-1-2  z45  PA-13  S-1/S-2  D-3  (0.652 g)  (0.250 g)  (0.087 g)  (80/20)  (6 mg)  Example 3  Al-2  zll 7  PA-18  S-1  D-1  (0.733 g)  (0.210 g)  (0.052 g)  (5 mg)  Example 4  Al-3  z119  PA-2  S-1/S-2  D-1  (0.856 g)  (0.100 g)  (0.031 g)  (40/60)  (8 mg)  Example 5  Al-4  z120  PA-7  S-1  D-4  (0.813 g)  (0.150 g)  (0.027 g)  (5 mg)  Example 6  Al-5  z114  PA-5  S-1/S-2  D-3  (0.728 g)  (0.210 g)  (0.053 g)  (80/20)  (4 mg)  Surfactant Developer  Rinsing Sensitivity Resolution LWR  (5 mg)  (mass ratio)  Solution (µC/cm 2 )  (nm)  (nm)  W-1  S-5  S-8  11.3  32 .. 0  3.6  W-1  S-5  S-8  11.0  31.5  3.5  None  S-5  S-8  11.4  32.0  3.7  W-2  S-5  S-10  12.5  32.0  3.9  W-3  S-5  S-12  12.5  33.0  4.1  W-1  S-5  S-8  11.8  32.0  3.7 