The present disclosure is directed to organotin cluster compounds having formula (I) and their use as photoresists in extreme ultraviolet lithography processes. ##STR00001##

The present disclosure is directed to organotin cluster compounds having formula (I) and their use as photoresists in extreme ultraviolet lithography processes. ##STR00001##

Methods for making thin-films on semiconductor substrates, may be patterned using EUV, include: depositing the organometallic polymer-like material onto the surface of the semiconductor substrate, exposing the surface to EUV to form a pattern, and developing the pattern for later transfer to underlying layers. The depositing operations may be performed by chemical vapor deposition (CVD), atomic layer deposition (ALD), and ALD with a CVD component, such as a discontinuous, ALD-like process in which metal precursors and counter-reactants are separated in either time or space.

Methods for making thin-films on semiconductor substrates, may be patterned using EUV, include: depositing the organometallic polymer-like material onto the surface of the semiconductor substrate, exposing the surface to EUV to form a pattern, and developing the pattern for later transfer to underlying layers. The depositing operations may be performed by chemical vapor deposition (CVD), atomic layer deposition (ALD), and ALD with a CVD component, such as a discontinuous, ALD-like process in which metal precursors and counter-reactants are separated in either time or space.

A method for producing flexographic printing plates, using as starting material a photopolymerizable flexographic printing element which at least comprises, arranged one atop another, a dimensionally stable support, and at least one photopolymerizable, relief-forming layer, at least comprising an elastomeric binding, an ethylenically unsaturated compound, and a photoinitiator, a digitally imagable layer, and the method comprises at least the following steps (a) producing a mask by imaging the digitally imagable layer, (b) exposing the photopolymerizable, relief-forming layer through the mask with actinic light, and photopolymerizing the image regions of the layer, and (c) developing the photopolymerized layer by washing out the unphotopolymerized regions of the relief-forming layer with an organic solvent, or by thermal development, characterized in that step (b) comprises two or more exposure cycles (b 1) to (b n) with actinic light with an intensity of 100 to 5000 mW/cm.sup.2 from a plurality of UV-LEDs, the energy input into the photopolymerizable, relief-forming layer per exposure cycle being 0.1 to 5 J/cm.sup.2.

A method for producing flexographic printing plates, using as starting material a photopolymerizable flexographic printing element which at least comprises, arranged one atop another, a dimensionally stable support, and at least one photopolymerizable, relief-forming layer, at least comprising an elastomeric binding, an ethylenically unsaturated compound, and a photoinitiator, a digitally imagable layer, and the method comprises at least the following steps (a) producing a mask by imaging the digitally imagable layer, (b) exposing the photopolymerizable, relief-forming layer through the mask with actinic light, and photopolymerizing the image regions of the layer, and (c) developing the photopolymerized layer by washing out the unphotopolymerized regions of the relief-forming layer with an organic solvent, or by thermal development, characterized in that step (b) comprises two or more exposure cycles (b 1) to (b n) with actinic light with an intensity of 100 to 5000 mW/cm.sup.2 from a plurality of UV-LEDs, the energy input into the photopolymerizable, relief-forming layer per exposure cycle being 0.1 to 5 J/cm.sup.2.

Vacuum-integrated photoresist-less methods and apparatuses for forming metal hardmasks can provide sub-30 nm patterning resolution. A metal-containing (e.g., metal salt or organometallic compound) film that is sensitive to a patterning agent is deposited on a semiconductor substrate. The metal-containing film is then patterned directly (i.e., without the use of a photoresist) by exposure to the patterning agent in a vacuum ambient to form the metal mask. For example, the metal-containing film is photosensitive and the patterning is conducted using sub-30 nm wavelength optical lithography, such as EUV lithography.

Method of forming pattern in photoresist layer includes forming photoresist layer over substrate, selectively exposing photoresist layer to actinic radiation forming latent pattern. Latent pattern is developed by applying developer to form pattern. Photoresist layer includes photoresist composition including polymer: ##STR00001##
A.sub.1, A.sub.2, L are direct bond, C4-C30 aromatic, C4-C30 alkyl, C4-C30 cycloalkyl, C4-C30 hydroxylalkyl, C4-C30 alkoxy, C4-C30 alkoxyl alkyl, C4-C30 acetyl, C4-C30 acetylalkyl, C4-C30 alkyl carboxyl, C4-C30 cycloalkyl carboxyl, C4-C30 hydrocarbon ring, C4-C30 heterocyclic, —COO—, A1 and A2 are not both direct bonds, and are unsubstituted or substituted with a halogen, carbonyl, or hydroxyl; A.sub.3 is C6-C14 aromatic, wherein A.sub.3 is unsubstituted or substituted with halogen, carbonyl, or hydroxyl; R.sub.1 is acid labile group; Ra, Rb are H or C1-C3 alkyl; R.sub.f is direct bond or C1-C5 fluorocarbon; PAG is photoacid generator; 0≤x/(x+y+z)≤1, 0≤y/(x+y+z)≤1, and 0≤z/(x+y+z)≤1.

Method of forming pattern in photoresist layer includes forming photoresist layer over substrate, selectively exposing photoresist layer to actinic radiation forming latent pattern. Latent pattern is developed by applying developer to form pattern. Photoresist layer includes photoresist composition including polymer: ##STR00001##
A.sub.1, A.sub.2, L are direct bond, C4-C30 aromatic, C4-C30 alkyl, C4-C30 cycloalkyl, C4-C30 hydroxylalkyl, C4-C30 alkoxy, C4-C30 alkoxyl alkyl, C4-C30 acetyl, C4-C30 acetylalkyl, C4-C30 alkyl carboxyl, C4-C30 cycloalkyl carboxyl, C4-C30 hydrocarbon ring, C4-C30 heterocyclic, —COO—, A1 and A2 are not both direct bonds, and are unsubstituted or substituted with a halogen, carbonyl, or hydroxyl; A.sub.3 is C6-C14 aromatic, wherein A.sub.3 is unsubstituted or substituted with halogen, carbonyl, or hydroxyl; R.sub.1 is acid labile group; Ra, Rb are H or C1-C3 alkyl; R.sub.f is direct bond or C1-C5 fluorocarbon; PAG is photoacid generator; 0≤x/(x+y+z)≤1, 0≤y/(x+y+z)≤1, and 0≤z/(x+y+z)≤1.

A radiation sensitive composition including a siloxane polymer exhibiting phenoplast crosslinking reactivity as a base resin, which is excellent in resolution and can be used as a radiation sensitive composition capable of allowing a pattern having a desired-shape to be formed with sufficient precision. A radiation sensitive composition including as a silane, a hydrolyzable silane, a hydrolysis product thereof, or a hydrolysis-condensation product thereof; and a photoacid generator, in which the hydrolyzable silane includes hydrolyzable silanes of Formula (1)
R.sup.1.sub.aR.sup.2.sub.bSi(R.sup.3).sub.4-(a+b)  Formula (1)
wherein R.sup.1 is an organic group of Formula (1-2) ##STR00001##
and is bonded to a silicon atom through a Si—C bond or a Si—O bond, and R.sup.3 is a hydrolyzable group; and Formula (2)
R.sup.7.sub.cR.sup.8.sub.dSi(R.sup.9).sub.4-(c+d)  Formula (2)
wherein R.sup.7 is an organic group of Formula (2-1) ##STR00002##
and is bonded to a silicon atom through a Si—C bond or a Si—O bond, and R.sup.9 is a hydrolyzable group.