A method of forming a photolithographic pattern by negative tone development, comprising: (a) providing a substrate comprising one or more layers to be patterned over a surface of the substrate; (b) applying a layer of a photoresist composition over the one or more layers to be patterned; (c) patternwise exposing the photoresist composition layer to actinic radiation; (d) heating the exposed photoresist composition layer in a post-exposure bake process; and (e) applying an organic developer to the photoresist composition layer, wherein unexposed portions of the photoresist layer are removed by the organic developer, leaving a photoresist pattern over the one or more layers to be patterned; wherein the photoresist composition comprises: a first matrix polymer which is acid sensitive comprising an acid-cleavable group; a second additive polymer formed from a monomer having the following general formula: wherein: P is a polymerizable functional group having the following general structure: wherein R 2 is chosen from hydrogen and substituted and unsubstituted C 1 to C3 alkyl; and X is oxygen or is represented by the formula NR 3, wherein R 3 is chosen from hydrogen and substituted and unsubstituted C1 to C10 linear, branched and cyclic hydrocarbons; Z is a spacer unit chosen from optionally substituted linear or branched aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from -O-, -S-, -COO- and -CONR 1 -, wherein R 1 is chosen from hydrogen and substituted and unsubstituted C 1 to C10 linear, branched and cyclic hydrocarbons; m is an integer from 0 to 5; and R is represented by the formula C n H 2n+1, wherein n is an integer from 1 to 20; wherein the second polymer is acid insensitive and free of fluorine and silicon, wherein the second polymer has a surface energy lower than a surface energy of the first polymer and wherein the second polymer migrates to the upper surface of the resist coating layer to form a surface layer substantially made up of the additive polymer; a photoacid generator; and a solvent. (a) providing a substrate comprising one or more layers to be patterned over a surface of the substrate; (b) applying a layer of a photoresist composition over the one or more layers to be patterned; (c) patternwise exposing the photoresist composition layer to actinic radiation; (d) heating the exposed photoresist composition layer in a post-exposure bake process; and (e) applying an organic developer to the photoresist composition layer, wherein unexposed portions of the photoresist layer are removed by the organic developer, leaving a photoresist pattern over the one or more layers to be patterned; wherein the photoresist composition comprises: a first matrix polymer which is acid sensitive comprising an acid-cleavable group; a second additive polymer formed from a monomer having the following general formula: wherein: P is a polymerizable functional group having the following general structure: wherein R 2 is chosen from hydrogen and substituted and unsubstituted C 1 to C3 alkyl; and X is oxygen or is represented by the formula NR 3, wherein R 3 is chosen from hydrogen and substituted and unsubstituted C1 to C10 linear, branched and cyclic hydrocarbons; Z is a spacer unit chosen from optionally substituted linear or branched aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from -O-, -S-, -COO- and -CONR 1 -, wherein R 1 is chosen from hydrogen and substituted and unsubstituted C 1 to C10 linear, branched and cyclic hydrocarbons; m is an integer from 0 to 5; and R is represented by the formula C n H 2n+1, wherein n is an integer from 1 to 20; wherein the second polymer is acid insensitive and free of fluorine and silicon, wherein the second polymer has a surface energy lower than a surface energy of the first polymer and wherein the second polymer migrates to the upper surface of the resist coating layer to form a surface layer substantially made up of the additive polymer; a photoacid generator; and a solvent. a first matrix polymer which is acid sensitive comprising an acid-cleavable group; a second additive polymer formed from a monomer having the following general formula: wherein: P is a polymerizable functional group having the following general structure: wherein R 2 is chosen from hydrogen and substituted and unsubstituted C 1 to C3 alkyl; and X is oxygen or is represented by the formula NR 3, wherein R 3 is chosen from hydrogen and substituted and unsubstituted C1 to C10 linear, branched and cyclic hydrocarbons; Z is a spacer unit chosen from optionally substituted linear or branched aliphatic and aromatic hydrocarbons, and combinations thereof, optionally with one or more linking moiety chosen from -O-, -S-, -COO- and -CONR 1 -, wherein R 1 is chosen from hydrogen and substituted and unsubstituted C 1 to C10 linear, branched and cyclic hydrocarbons; m is an integer from 0 to 5; and R is represented by the formula C n H 2n+1, wherein n is an integer from 1 to 20; wherein the second polymer is acid insensitive and free of fluorine and silicon, wherein the second polymer has a surface energy lower than a surface energy of the first polymer and wherein the second polymer migrates to the upper surface of the resist coating layer to form a surface layer substantially made up of the additive polymer; a photoacid generator; and a solvent.