US 9,829,796 B2  276  275  TABLE I-continued  Example  0.05  SG-1  28.0  32  4.6  8.9  19.2  A  1-34  Example  0.05  SG-3  27.5  31  4.4  8.0  19.6  A  1-35  Comparative  0.05  SG-3  32.0  42  6.4  12.2  15.1  C  Example  1-1  Comparative  0.05  TM-1  38.0  48  7.9  16.7  13.0  A  Example  1-2  Comparative  0.05  SG-3  36.0  46  7.3  15.1  14.0  C  Example  1-3  Comparative  0.05  SG-3  37.0  48  8.4  16.0  12.5  C  Example  1-4  Comparative  0.05  SG-3  37.0  48  7.8  16.5  12.9  C  Example  1-5  The concentration of each component represents a concentration(% by mass) based on the total solid content of the composition.  For example, whereas, in JP2012-242556A, a resolution  of a 75 nm half-pitch was evaluated using an ArF light  source, and, in JP2013-11866A, a resolution of a 90 nm  half-pitch was evaluated using the same ArF light source, as  can be seen from the above table, Examples 1-1 to 1-35 of  the present invention can satisfy high sensitivity, high LWR  performance, film loss reduction performance, high EL, and,  high dry etching resistance at a high resolution of 38 nm or  less at the same time to a very high level.  In more detail, it was found that, first, in contrast to  Comparative Example 1-1 in which a comparative resin  (CP-1) which did not have a repeating unit containing a  cross-linking group was used, Example 1-14 in which the  resin (P-14) of the present invention having the same  components except for a repeating unit containing a cross› linking group had all of high resolution, high sensitivity,  high LWR performance, film loss reduction performance,  high EL, and high  dry  etching resistance.  It  is thought that  this is because, at the exposed portion, an acid group such as  a carboxylic group or a phenolic hydroxyl group is gener› ated by a deprotection reaction of the acid-decomposable  group in the resin, and a crosslinking reaction can also be  caused by a cross-linking group in the resin, and due to this,  the exposed portion can be further insolubilized and cured  for forming a film.  It  is thought that further insolubilization  of the exposed portion by the crosslinking reaction is  effective for resolution enhancement by film loss reduction  or contrast improvement, LWR performance improvement,  and sensitivity enhancement, and curing for forming a film  of the exposed portion by the crosslinking reaction is  effective for EL improvement by acid diffusion suppression,  resolution enhancement by falling prevention, and dry etch› ing resistance improvement.  Furthermore, it was found that, in Comparative Example  1-2 in which the same compositions as that in Example 1-22  was alkali-developed, the performance thereof was inferior,  and thus, it is important for expression of the effects to  combine development using an organic-based developer.  Next, it was found that, in contrast to Comparative  Example 1-3 in which the resin (CP-2) which did not have  the repeating unit represented by General Formula (I) such  as a hydroxystyrene repeating unit was used, Example 1-14  in which the components were the same as those in Com› parative Example 1-3, and the resin (P-14) having a hydrox- ystyrene repeating unit was used had all of high resolution,  high sensitivity, high LWR performance, film loss reduction  performance, high EL, and high dry etching resistance.  It  is  thought that this is because, based on the fact that the  phenolic hydroxyl group in the hydroxystyrene repeating  unit is prone to undergo a crosslinking reaction, the effects  of insolubilization and curing for forming a film are  increased, and secondary electrons are greatly generated  from the phenol structure by exposure, and as a result, acid  is greatly generated, and a deprotection reaction of an  acid-decomposable group in the resin quickly and greatly  proceeds, and thus, these contribute to further enhancement  of sensitivity, LWR performance, and resolution.  This is thought to be due to the same reason that Com› parative Examples 1-4 and 1-5 in which the resin (CP-3)  described in JP2012-242556A and the  resin (CP-4)  described in JP2013-11866A were used are inferior to  Examples of the present invention including Example 1-14.  From comparison of Example 1-7 or 1-8 with other  Comparative Examples, it was also found that the effects are  more significant with a hydroxystyrene structure rather than  with a hydroxyphenyl methacrylate structure or a hydroxy› phenylmethacryl amide structure among the same phenol  structures, and this is preferable.  Furthermore, it was also found that a resin having the  acid-decomposable group (for example, Examples 1-19 to  1-27, 1-31 to 1-33, and 1-35) represented by General For› mula (IV) or the acid-decomposable group (for example,  Examples 1-11 to 1-13, 1-16, 1-28, and 1-29) represented by  General Formula (III-1) was excellent in terms of all of  resolution, sensitivity, film loss reduction performance, and  LWR performance, compared to a resin having no acid› decomposable group represented by General Formula (IV)  or (III-1), for example, as Examples 1-6 to 1-10.  It  is thought  that this is because the deprotection activation energy of the  acid-decomposable group is low, and thus, carboxylic acid  can be easily generated with a small amount of an acid.  It  was found that, as the group containing a cross-linking  group ofB$_{8 }$ in General Formula (V), a phenol structure or a  urea structure having a hydroxymethyl group or an  alkoxymethyl group compared to a group having an oxirane  ring or an oxetane ring is excellent. Furthermore, it was  found that the phenol structure having a hydroxymethyl  group or an alkoxymethyl group was more excellent com› pared to the urea structure having a hydroxymethyl group or  an alkoxymethyl group, by comparing Example 1-11 in  which the resin (P-11) was used and Example 1-12 in which  the resin (P-12) was used, and Example 1-22 in which the 