US 9,703,193 B2  192  191  TABLE 5  Acid  Resist  Resin  generator  Quencher  Surfactant  Solvent 1  Solvent 2  composition  (pbw)  (pbw)  (pbw)  (pbw)  (pbw)  (pbw)  Comparative  1-1  R-15  P-1  PAG-A  Q-1  SF-1  PGMEA  GBL  Example  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-2  R-16  P-1  PAG-B  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-3  R-17  P-1  PAG-D  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-4  R-18  P-1  PAG-E  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-5  R-19  P-1  PAG-F  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-6  R-20  P-1  PAG-G  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-7  R-21  P-1  PAG-H  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-8  R-22  P-1  PAG-1  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-9  R-23  P-1  PAG-J  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  1-10  R-24  P-1  PAG-K  Q-1  SF-1  PGMEA  GBL  (80)  (7)  (1.5)  (3.0)  (1,536)  (384)  Evaluation of Depth-of-Focus (DOF) Margin  The results are shown in Table 6.  The hole size printed at the optimum dose was measured  is under TD-SEM (S-9380 by Hitachi Hitechnologies, Ltd.).  The margin ofDOF capable of forming a resist pattern with  a size of 40–5 nm was determined. A larger value indicates  a smaller change of pattern size per DOF change and hence,  better DOF margin.  On a silicon wafer, 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 (Shin-Etsu  Chemical Co., Ltd.) having a silicon content of 43 wt% was  deposited thereon to a thickness of35 nm. On this substrate  for trilayer process, each of the resist compositions (Inven- tive R-1 to R-14 or Comparative R-15 to R-24) was spin  coated and baked on a hot plate at 100°  C. for 60 seconds to  form a resist film of 100 nm thick.  Using an ArF excimer laser immersion lithography step- per (NSR-610C by Nikon Corp., NA 1.30,  a  0.98/0.78,  dipole opening 20 deg., azimuthally polarized illumination,  dipole illumination, 6% halftone phase shift mask), the resist  film was exposed through a first mask having X-axis direc- tion lines with a pitch of 80 nm and a width of 40 nm and  then through a second mask having Y-axis direction lines  with a pitch of 80 nm and a width of 40 nm. After exposure,  the resist film was baked (PEB) at the temperature shown in  Table 6 for 60 seconds and developed. Specifically, butyl  acetate was injected from a development nozzle for 3  seconds while the wafer was spun at 30 rpm, which was  followed by stationary puddle development for 27 seconds.  Evaluation of Sensitivity  The resist pattern thus formed was observed under an  electron microscope. The optimum dose (Eop) is a dose  (mJ/cm 2 )  which provides a hole pattern having a diameter of  40 nm at a pitch of 80 nm.  4) ArF Lithography Patterning Test #1: Evaluation  of Hole Pattern  Examples 2-1 to 2-14 and Comparative Examples  2-1 to 2-10  MEF~(pattern space width)/(mask line width)-b  wherein b is a constant. A value closer to unity (1) indicates  better performance.  Evaluation of Mask Error Factor (MEF)  A pattern was formed by exposure in the optimum dose  ( determined in the sensitivity evaluation) through a mask  with the pitch fixed and the line width varied. MEP was  calculated from variations of the mask line width and the  pattern space width according to the following equation:  It is evident from Table 6 that when the inventive resist  composition is processed by lithography and organic solvent  development, a hole pattern with improved sensitivity, MEF  and DOF is formed.  TABLE 6  Resist  PEB temp.  Eop  DOF  composition  (" c.)  (mJ/cm 2 )  MEF  (nm)  Example  2-1  R-1  85  37  2.45  100  2-2  R-2  85  33  2.88  120  2-3  R-3  85  37  2.90  90  2-4  R-4  85  31  2.67  105  2-5  R-5  85  30  2.70  100  2-6  R-6  90  39  2.66  95  2-7  R-7  90  30  3.01  105  2-8  R-8  90  29  3.15  100  2-9  R-9  85  35  3.15  100  2-10  R-10  90  32  3.10  105  2-11  R-11  85  33  2.90  125  2-12  R-12  90  37  2.92  100  2-13  R-13  85  31  2.54  105  2-14  R-14  85  37  3.19  100  Comparative  2-1  R-15  85  47  3.89  85  Example  2-2  R-16  85  51  3.75  90  2-3  R-17  85  25  3.90  80  2-4  R-18  85  44  4.12  85  2-5  R-19  85  27  3.85  90  2-6  R-20  85  50  3.57  80  2-7  R-21  85  51  4.44  75  2-8  R-22  85  25  4.12  70  2-9  R-23  85  55  4.56  75  2-10  R-24  85  48  4.98  80 