102  US 8,691,490 B2  101  The adding amount of the surfactant in the resist compo› sition of the present invention is 2 or less parts by mass, or  preferably 1 or less parts by mass, and when blended, prefer› ably 0.01 or more part by mass, relative to 100 parts by mass  of the base resin in the resist composition.  In the resist composition of the present invention, a surfac› tant having a function to reduce water penetration and leach› ing by orientating on the resist surface after spin coating may  be added in the case of the immersion exposure using water,  especially when a resist top coat is not used. This surfactant is  preferably a polymer-type surfactant having a property to be  dissolved in an alkaline developer but not in water, and in  particular the one giving a high water-repellent property with  an improved sliding property.  The adding amount of the polymer-type surfactant is 0.001  to 20 parts by mass, or preferably 0.01 to 10 parts by mass,  relative to 100 parts by mass of the base resin of the resist  composition. These are elaborated in Japanese Patent Laid› Open (kokai) No. 2007-297590.  When the polymer of the present invention is used for a  chemically amplified negative resist composition, it is neces› sary that the composition has a repeating unit having a sub› stituent crosslinkable by an acid crosslinker. More specific  examples of the repeating unit include a repeating unit  derived from acrylic acid, methacrylic acid, hydroxystyrene  (position of substitution is arbitrary), and hydroxyvinylnaph› thalene (position of substitution is arbitrary) and the like,  though it is not limited to them.  In addition, an alkaline-soluble resin other than the above  polymers may be added.  Examples of the resin include poly(p-hydroxystyrene),  poly(m-hydroxystyrene ), poly( 4-hydroxy-2-methylstyrene ),  poly( 4-hydroxy-3-methylstyrene ),  poly( a-methyl-p-hy› droxystyrene ), partially hydrogenated (p-hydroxystyrene)  copolymer, (p-hydroxystyrene-a-methyl-p-hydroxystyrene)  copolymer, (p-hydroxystyrene-a-methylstyrene) copolymer,  (p-hydroxystyrene-styrene) copolymer, (p-hydroxystyrene› m-hydroxystyrene) copolymer, (p-hydroxystyrene-styrene)  copolymer,  (p-hydroxystyrene-acrylic  acid)  copolymer,  (p-hydroxystyrene-methacrylic  acid)  copolymer,  (p-hy› droxystyrene-methyl acrylate) copolymer, (p-hydroxysty› rene-acrylic acid-methyl methacrylate) copolymer, (p-hy› droxystyrene-methyl  acrylate)  copolymer,  (p-hydroxystyrene-methacry lie acid-methy 1 methacry late)  copolymer, polymethacrylic acid, polyacylic acid, (acrylic  acid-methyl acrylate) copolymer, (methacrylic acid-methyl  methacrylate) copolymer, (acrylic acid-maleimide) copoly› mer, (methacrylic acid-maleimide) copolymer, (p-hydroxy› styrene-acrylic acid-maleimide) copolymer, (p-hydroxysty› rene-methacrylic acid-maleimide) copolymer, etc., but are  not limited to them.  The blending ratio of the polymer of the present invention  to the other alkaline-soluble resin is preferably in the range of  mass ratio of 100:0 to 10:90, in particular 100:0 to 20:80. The  blending ratio of the polymer of the present invention is  preferably in this range, because suitable performance as the  resist composition can be obtained efficiently. By appropri› ately changing the blending ratio, performance of the resist  composition can be controlled.  Here, not only one kind but also two or more kinds of the  alkaline-soluble resin can be added. Performance of the resist  composition can be controlled by using plural kinds of poly› mers.  Examples of a crosslinker of the component (F) that  crosslinks by an acid, that is, an acid crosslinker that forms a  crosslinking structure by action of an acid, include a com› pound having two or more groups selected from hydroxym- ethyl, alkoxymethyl, epoxy and vinyl ether groups in the  molecule. A substituted glycouril derivative, a urea deriva› tive, hexa(methoxymethyl) melamine and the like can be  suitably used as the acid crosslinker of the chemically ampli- fled negative resist composition of the present invention.  Examples  of the  crosslinker  include  N,N,N’,N’-tet› ramethoxymethyl urea, hexamethoxymethyl melamine, tet› rahydroxymethyl-substituted glycolurils, tetraalkoxymethyl› substituted  glycolurils  such  as  tetramethoxymethyl  glycoluril, substituted or unsubstituted bis-hydroxymethyl  phenols, and a condensate of a phenolic compound such as  bisphenol A and epichlorohydrin and the like. Particularly  preferable crosslinkers include 1,3,5,7-tetraalkoxymethyl  glycoluril such as 1,3,5,7-tetramethoxymethyl glycoluril,  1,3 ,5, 7 -tetrahydroxymethy 1  glycoluril,  2, 6-dihydroxym› ethy l-p-cresol, 2,6-dihydroxymethyl phenol, 2,2’,6,6’-tetran› dyroxymethyl-bisphenol A, 1,4-bis[2-(2-hydroxypropyl)]› benzene,  N,N,N’,N’-tetramethoxymethyl  urea,  hexamethoxymethyl melamine, etc.  The adding amount of the acid crosslinker of the compo- nent (F) in the resist composition of the present invention is  arbitrary, but preferable is 1 to 20 parts by mass or especially  5 to 15 parts by mass, relative to 100 parts by mass of the base  resin in the resist composition. These crosslinkers may be  used solely or in a combination of two or more kinds.  In addition to the above components, other components  such as a dissolution inhibitor, an acidic compound, a stabi› lizer, and pigments may also be added in the resist composi› tion of the present invention as the arbitrary components as  appropriate. Here, each adding amount of these arbitrary  components is usual in the range not impairing the effects of  the present invention.  Patterning by using the resist composition of the present  invention may be carried out with a heretofore known lithog- raphy technology. One example is shown below, but the pat› terning process of the present invention is not limited to this.  For example, coating is done on a substrate for integrated  circuit manufacturing (Si, SiO$_{2}$ ,  SiN, SiON, TiN, WSi,  BPSG, SOG, an organic anti-reflection film, and the like) or  on a substrate for mask circuit manufacturing (Cr, CrO,  CrON, MoSi, and the like) by a technique such as spin› coating to make the film thickness of0.05 to 2.0 pm, and then  a pre-bake is done on a hot plate at 60 to 150°  C. for 1 to 20  minutes, or preferably at 80 to 140°  C. for 1 to 10 minutes.  After that, a high energy beam such as a deep-ultraviolet  beam, an excimer laser, and an X-ray, or an electron beam is  irradiated onto a mask that covers the resist film to form an  intended pattern. Alternatively, an electron beam is directly  irradiated for drawing without via the mask for patterning.  The exposure dose is 1 to 200 mJ/cm 2 ,  or preferably about 10  mJ/cm$^{2 }$to about 100 mJ/cm$^{2 }$in the case of the light exposure,  and is about 0.1 µC/cm 2  to about 20 µC/cm 2 ,  or preferably  about 3 µC/cm $^{2 }$to about 10 µC/cm $^{2 }$in the case of the electron  beam exposure. Exposure is done by a usual exposure  method, and as appropriate, an immersion method in which  the space between a mask and a resist film is immersed with  a liquid can also be used. In that case, a top coat not soluble in  water can also be used.After that, a post-exposure bake (PEB)  is done on a hot plate at 60 to 150°  C. for 1 to 20 minutes, or  preferably at 80 to 140°  C. for 1 to 10 minutes. Further,  development is done by using a developer of an alkaline  aqueous solution such as tetramethyl animonium hydroxide  (TMAH) with a concentration of 0.1 to 3% by mass, or  preferably 2 to 3% by mass, for0.1 to 3 minutes, or preferably  0.5 to 2 minutes by a usual method such as a dip method, a  puddle method, and a spray method to form an intended  pattern on the substrate. Meanwhile, the resist composition of 