International Business Machines Corporation

San Diego State University Research Foundation

Az Electronic Materials (luxembourg) S.a.r.l.

Melia Tjio

Joy Cheng

Daniel Sanders

Ankit Vora

Anindarupa Chunder

Michael A Guillorn

Chi-Chun Liu

Hsinyu Tsai

Markus Brink

Gurpreet Singh

Alexander M Friz

Robert Dennis Miller

Matthew Earl Colburn

Victor Yee-Way Lee

Guanyang Lin

Joseph Sly

Margareta Paunescu

Durairaj Baskaran

Orest Polishchuk

Gregory S Doerk

Eri Hirahara

The present invention relates to a novel block copolymer of structure 1, wherein, A- is a block polymer chain, B is a block polymer chain,wherein, A- and B- are chemically different, covalently connected polymer chains, which are phase separable and the moiety X(Y(Z))is a junction group, which comprises a surface active pendant moiety Y(Z)wherein:

Block copolymers with surface-active junction groups, compositions and processes thereof

Hybrid pre-patterns were prepared for directed self-assembly of a given block copolymer capable of forming a lamellar domain pattern. The hybrid pre-patterns have top surfaces comprising independent elevated surfaces interspersed with adjacent recessed surfaces. The elevated surfaces are neutral wetting to the domains formed by self-assembly. Material below the elevated surfaces has greater etch-resistance than material below the recessed surfaces in a given etch process. Following other dimensional constraints of the hybrid pre-pattern described herein, a layer of the given block copolymer was formed on the hybrid pre-pattern. Self-assembly of the layer produced a lamellar domain pattern comprising self-aligned, unidirectional, perpendicularly oriented lamellae over the elevated surfaces, and parallel and/or perpendicularly oriented lamellae over recessed surfaces. The domain patterns displayed long range order along the major axis of the pre-pattern. The lamellar domain patterns are useful in forming transfer patterns comprising two-dimensional customized features.

Hybrid topographical and chemical pre-patterns for directed self-assembly of block copolymers

Guiding pattern portions are formed on a surface of a lithographic material stack that is disposed on a surface of a semiconductor substrate. A copolymer layer is then formed between each neighboring pair of guiding pattern portions and thereafter a directed self-assembly process is performed that causes phase separation of the various polymeric domains of the copolymer layer. Each guiding pattern portion is selectively removed, followed by the removal of each first phase separated polymeric domain. Each second phase separated polymeric domain remains and is used as an etch mask in forming semiconductor fins in an upper semiconductor material portion of the semiconductor substrate.

Graphoepitaxy directed self-assembly process for semiconductor fin formation

A film layer comprising a high-chi (&#x3c7;) block copolymer for self-assembly and a hexafluoroalcohol-containing surface active polymer (SAP) was prepared on a substrate surface that was neutral wetting to the domains of the self-assembled block copolymer. The block copolymer comprises at least one polycarbonate block and at least one other block (e.g., a substituted or unsubstituted styrene-based block). The film layer, whose top surface has contact with an atmosphere, self-assembles to form a lamellar or cylindrical domain pattern having perpendicular orientation with respect to the underlying surface. Other morphologies (e.g., islands and holes of height 1.0Lo) were obtained with films lacking the SAP. The SAP is preferentially miscible with, and lowers the surface energy of, the domain comprising the polycarbonate block.

Fluoro-alcohol additives for orientation control of block copolymers

Block polymers are formed by ring opening polymerization (ROP) of a cyclic carbonate monomer using a polymeric initiator for the ROP that comprises repeating functionalized ethylene units. The block polymers are free of, or substantially free of, any polymer having a chemical structure that does not comprise the polymer backbone of the polymeric initiator. The block polymers are capable of directed self-assembly.

Methods of forming block polymers for directed self-assembly

An orientation control layer (OCL) for self-assembly of block copolymers comprises a random copolymer comprising a first repeat unit having an ethylenic backbone functional group and a side chain aromatic ring, a second repeat unit comprising an ethylenic backbone functional group and a side chain polycarbonate, and a third repeat unit comprising an ethylenic backbone functional group and a side chain ester or amide bearing an active group capable of forming a covalent bond with a substrate surface (e.g., a silicon wafer). The OCLs are neutral wetting to block copolymers having a high Flory-Huggins interaction parameter chi (&#x3c7;) ('high-chi' block copolymers) such as a block copolymer comprising a polystyrene block and a polycarbonate block. The neutral OCL wetting properties allow for formation of lamellar domain patterns of the self-assembled high-chi block copolymers to be oriented perpendicular to the OCL surface.

Orientation control materials for block copolymers used in directed self-assembly applications

A film layer comprising a high-chi (&#x3c7;) block copolymer for self-assembly and a surface active polymer (SAP) was prepared on a substrate surface that was neutral wetting to the domains of the self-assembled block copolymer. The block copolymer comprises at least one polycarbonate block and at least one other block (e.g., a styrene-based block). The SAP comprises a hydrophobic fluorinated first repeat unit and a non-fluorinated second repeat unit bearing at least one pendent OH group present as an alcohol or acid (e.g., carboxylic acid). The film layer, whose top surface has contact with an atmosphere, self-assembles to form a lamellar or cylindrical domain pattern having perpendicular orientation with respect to the underlying surface. Other morphologies (e.g., islands and holes of height 1.0Lo) were obtained with films lacking the SAP. The SAP is preferentially miscible with, and lowers the surface energy of, the domain comprising the polycarbonate block.

Additives for orientation control of block copolymers

Methods are disclosed for reducing the number of defects in a directed self-assembled structure formed on a guiding pre-pattern (e.g., a chemical pre-pattern) on a substrate. A first layer comprising a first self-assembly material is applied onto the guiding pre-pattern, with the first self-assembly material forming domains whose alignment and orientation are directed by the guiding pre-pattern; as a result, a first self-assembled structure is formed. The first self-assembled structure is washed away, and a second layer comprising a second self-assembly material is then applied. The second self-assembly material forms a second self-assembled structure having fewer defects than the first self-assembled structure.

Methods of reducing defects in directed self-assembled structures

A nanoshell is disclosed, comprising a star polymer occlusion complex comprising i) an amphiphilic unimolecular star polymer having a crosslinked core covalently linked to 6 or more independent polymer arms, and ii) a cargo material occluded in the star polymer; and a shell comprising an inorganic material in contact with a peripheral surface of the star polymer occlusion complex.

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San Jose, CA, United States of America

Melia Tjio