A surface treatment composition and methods for improving adhesion of an organic layer on a titanium-containing hardmask includes forming a self-assembled monolayer on a surface of the titanium-containing hardmask prior to depositing the organic layer. The self-assembled monolayer is formed from a blend of alkyl phosphonic acids of formula (I): X(CH.sub.2).sub.nPOOH.sub.2 (I), wherein n is 6 to 16 and X is either CH.sub.3 or COOH, wherein a ratio of the methyl terminated (CH.sub.3) alkyl phosphonic acid to the carboxyl terminated (COOH) alkyl phosphonic acid ranges from 25:75 to 75:25.

Techniques herein include methods of forming conformal films on substrates including semiconductor wafers. Conventional film forming techniques can be slow and expensive. Methods herein include depositing a self-assembled monolayer (SAM) film over the substrate. The SAM film can include an acid generator configured to generate acid in response to a predetermined stimulus. A polymer film is deposited over the SAM film. The polymer film is soluble to a predetermined developer and configured to change solubility in response to exposure to the acid. The acid generator is stimulated and generates acid. The acid is diffused into the polymer film. The polymer film is developed with the predetermined developer to remove portions of the polymer film that are not protected from the predetermined developer. These process steps can be repeated a desired number of times to grow an aggregate film layer by layer.

Materials and methods to immobilize photoacid generators on semiconducting substrates are provided. PAG-containing monomers are copolymerized with monomers to allow the polymer to bind to a surface, and optionally copolymerized with monomers to enhance solubility to generate PAG-containing polymers. The PAG-containing monomers can be coated onto a surface, where the immobilized PAGs can then be used to pattern materials coated on top of the immobilized PAGs, allowing direct patterning without the use of a photoresist, thereby reducing process steps and cost. The disclosed materials and processes can be used to produce conformal coatings of controlled thicknesses.

The present application provides a block copolymer and uses thereof. The block copolymer of the present application exhibits an excellent self-assembling property or phase separation property, can be provided with a variety of required functions without constraint and, especially, etching selectivity can be secured, making the block copolymer effectively applicable to such uses as pattern formation.

A surface treatment composition and methods for improving adhesion of an organic layer on a titanium-containing hardmask includes forming a self-assembled monolayer on a surface of the titanium-containing hardmask prior to depositing the organic layer. The self-assembled monolayer is formed from a blend of alkyl phosphonic acids of formula (I): X(CH.sub.2).sub.nPOOH.sub.2 (I), wherein n is 6 to 16 and X is either CH.sub.3 or COOH, wherein a ratio of the methyl terminated (CH.sub.3) alkyl phosphonic acid to the carboxyl terminated (COOH) alkyl phosphonic acid ranges from 25:75 to 75:25.

A method of processing a substrate includes: providing structures on a surface of a substrate; depositing a self-assembled monolayer (SAM) over the structures and the substrate, the SAM being reactive to a predetermined wavelength of radiation; determining a first pattern of radiation exposure, the first pattern of radiation exposure having a spatially variable radiation intensity across the surface of the substrate and the structures; exposing the SAM to radiation according to the first pattern of radiation exposure, the SAM being configured to react with the radiation; developing the SAM with a predetermined removal fluid to remove portions of the SAM that are not protected from the predetermined fluid; and depositing a spacer material on the substrate and the structures, the spacer material being deposited at varying thicknesses based on an amount of the SAM remaining on the surface of the substrate and the structures.

Methods for processing a substrate are provided. The method includes receiving a substrate. The substrate has a front side surface, a backside surface, and a side edge surface. The method also includes forming a first material in a first annular region of the front side surface, resulting in the first annular being coated with the first material. The first annular region is immediately adjacent to a perimeter of the substrate. The first annular region has a first outer perimeter proximate to the perimeter of the substrate and a first inner perimeter away from the perimeter of the substrate. The method also includes forming a second material in an interior region of the front side surface, the second material coating the front side surface without adhering to the annular region.

A method for improving EUV lithographic patterning of SnO.sub.2 layers is provided. One method embodiment includes introducing a hydrophobic surface treatment compound into a processing chamber for modifying a surface of an SnO.sub.2 layer. The modification increases the hydrophobicity of the SnO.sub.2 layer. The method also provides for depositing a photoresist layer on the surface of the SnO.sub.2 layer via spin coating. The modification of the surface of the SnO.sub.2 layer enhances adhesion of contact between the photoresist and the SnO.sub.2 layer during and after spin coating.

A method for manufacturing a graphitic sheet is used to obtain the graphitic sheet with similar characteristics to graphene. The method includes forming an ocatadecyltrichlorosilane (OTS) layer on a substrate to obtain a composite. The composite is annealed at 250-400 C. for 30-90 minutes, forming the graphitic sheet on the substrate via self-assembly of ocatadecyltrichlorosilane (OTS) in the OTS layer. The annealed composite is immersed in water, followed by being sonicated for 2 minutes with a frequency of 40 kHz and a power output of 200 W, to separate the graphitic sheet from the substrate.

A patterning method is described that utilizes self-assembled monolayers (SAMs) formed with hydroxamic acid compounds and area selective atomic layer deposition (ALD). In the examples, regions of the SAM exposed to extreme ultraviolet radiation (EUV) become resistant to ALD deposition. Subsequent treatment of the exposed SAM to an ALD process results in selective growth of an ALD film on the non-exposed regions of the SAM, leaving the exposed regions substantially free of ALD material.