102  US 9,665,002 B2  101  TABLE 4-continued  Acid diffusion  Resin  PAG  control agent  Surfactant  Solvent 1  Solvent 2  Resist  (pbw)  (pbw)  (pbw)  (pbw)  (pbw)  (pbw)  1-12  R-12  P-12  PAG-X  Q-1  SF-1  PGMEA  GBL  (80)  (7.6)  (2.5)  (3.0)  (1,728)  (192)  1-13  R-13  P-1  PAG-X  Q-1  SF-1  PGMEA  GBL  (80)  (13.3)  (2.5)  (3.0)  (1,728)  (192)  1-14  R-14  P-2  PAG-Y  Q-1  SF-1  PGMEA  GBL  80  (13.3)  (2.5)  (3.0)  (1,728)  (192)  Comparative  1-1  R-15  P-1  PAG-X  Q-2  SF-1  PGMEA  GBL  Example  (80)  (7.6)  (1.7)  (3.0)  (1,728)  (192)  1-2  R-16  P-1  PAG-X  Q-3  SF-1  PGMEA  GBL  (80)  (7.6)  (3.8)  (3.0)  (1,728)  (192)  1-3  R-17  P-1  PAG-X  Q-4  SF-1  PGMEA  GBL  (80)  (7.6)  (3.4)  (3.0)  (1.728)  (192)  1-4  R-18  P-1  PAG-X  Q-5  SF-1  PGMEA  GBL  (80)  (7.6)  (3.0)  (3.0)  (1,728)  (192)  1-5  R-19  P-1  PAG-X  Q-6  SF-1  PGMEA  GBL  (80)  (7.6)  (4.1)  (3.0)  (1,728)  (192)  1-6  R-20  P-1  PAG-X  Q-7  SF-1  PGMEA  GBL  (80)  (7.6)  (5.1)  (3.0)  (1,728)  (192)  1-7  R-21  P-1  PAG-Y  Q-2  SF-1  PGMEA  GBL  (80)  (13.3)  (1.7)  (3.0)  (1,728)  (192)  Col- lapse  Re- Eop  LWR  DOF  limit  sist  (mJ/cm 2 )  (nm)  MEF  (nm)  (nm)  Example  2-1  R-1  31  2.6  2.4  75  30  2-2  R-2  32  2.8  2.5  75  28  2-3  R-3  34  2.8  2.5  75  27  2-4  R-4  33  2.5  2.4  70  29  2-5  R-5  32  2.6  2.3  70  30  2-6  R-6  36  2.7  2.3  75  27  2-7  R-7  30  2.9  2.3  70  26  2-8  R-8  31  2.7  2.3  70  27  2-9  R-9  33  2.8  2.1  75  27  2-10  R-10  31  2.8  2.2  70  28  2-11  R-11  33  2.7  2.2  70  29  2-12  R-12  34  2.8  2.7  70  29  2-13  R-13  31  2.5  2.4  65  30  2-14  R-14  32  2.6  2.4  70  27  Comparative  2-1  R-15  38  3.5  4.0  40  39  Example  2-2  R-16  31  3.1  4.3  35  35  2-3  R-17  35  3.3  4.1  45  35  2-4  R-18  34  3.4  3.9  45  38  2-5  R-19  33  3.2  4.3  35  35  2-6  R-20  32  3.3  4.2  35  36  2-7  R-21  40  3.3  3.9  40  38  TABLE 5  Examples 2-1 to 2-14 and Comparative Examples  2-1 to 2-7  Examples 3-1 to 3-14 and Comparative Examples  3-1 to 3-7  On a silicon substrate, an antireflective coating solution  (ARC-29A, Nissan Chemical Industries, Ltd.) was coated  and baked at 200°  C. for 60 seconds to form an ARC of 100  nm thick. Each of the resist solutions shown in Table 4 was  spin coated on the silicon substrate and baked on a hot plate  at 100°  C. for 60 seconds, forming a resist film of 90 nm  thick on the ARC. The wafer was exposed on an ArF  excimer laser immersion lithography scanner (NSR-S610C  by Nikon Corp., NA 1.30, dipole illumination, Cr mask),  baked (PEB) at 80°  C. for 60 seconds, and developed in a  2.38 wt% tetramethylammonium hydroxide (TMAH) aque- ous solution for 60 seconds, forming a pattern.  Resist evaluation was made on a 40-nm 1:1 line-and- space pattern. On observation under an electron microscope,  the optimum exposure dose (Eop) was defined as an expo- sure dose (mJ/cm 2 )  which provided a line width of 40 nm.  The width of lines of a 40-nm 1: 1 line-and-space pattern  was measured under SEM to determine a line width varia- tion (30 points measured,  3a  value computed), which was  reported as line width roughness (LWR). A smaller value of  LWR indicates a line pattern with a less fluctuation and of  better profile. In this test, the sample is rated good when  LWR is equal to or less than 3.0 nm and poor when LWR is  equal to or more than 3 .1 nm.  An LIS pattern was formed by exposure in the optimum  dose (determined in the sensitivity evaluation) through the  mask with the pitch fixed and the line width varied. MEF  was calculated from variations of the mask line width and  the pattern space width according to the following equation:  wherein b is a constant. A value closer to unity (1) indicates  better performance.  Further, for a trench pattern printed at the optimum  exposure dose, the dependency of trench size on focus was  examined. A range (nm) of focus capable of resolution was  determined and reported as DOF.  The collapse limit was a minimum width (nm) of lines  which could be resolved without collapse when the line  On a substrate, a spin-on carbon film ODL-50 (Shin-Etsu  Chemical Co., Ltd.) having a carbon content of 80 wt% was  deposited to a thickness of 200 nm and a silicon-containing  spin-on hard mask SHB-A940 having a silicon content of 43  wt% was deposited thereon to a thickness of35 nm. On this  As seen from the results of Table 5, the resist composi- tions within the scope of the invention offer advantages  including improved LWR, MEF, DOF, and collapse limit,  and are suited as resist material for ArF immersion lithog- raphy.  width was reduced by increasing the exposure dose. A  smaller value indicates better collapse resistance.  The results of evaluation are shown in Table 5.  MEF~(pattern space widtb)/(mask line widtb)-b  Resist Test 2 (ArF Lithography)  Resist Test 1 (ArF Lithography) 