International Business Machines Corporation

Globalfoundries Inc.

Jsr Corporation

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

Joy Cheng

Daniel Sanders

Ho-Cheol Kim

Charles Thomas Rettner

Michael A Guillorn

Chi-Chun Liu

Hsinyu Tsai

Ankit Vora

Melia Tjio

Kafai Lai

Ratnam Sooriyakumaran

Linda Karin Sundberg

Jed Walter Pitera

Anindarupa Chunder

Matthew Earl Colburn

Wai-Kin Li

Young-Hye Na

William Dinan Hinsberg

Gregory S Doerk

Robert Dennis Miller

Markus Brink

Hiroshi Ito

Steven J Holmes

Hoa D Truong

Da Yang

Mark Whitney Hart

Hayato Namai

Gurpreet Singh

Alexander M Friz

James L Hedrick

Wu-Song S Huang

Dario Leonardo Goldfarb

Gregory Michael Wallraff

Stefan Harrer

Teddie Peregrino Magbitang

David Robert Medeiros

Kuang-Jung Chen

Alshakim Nelson

Daniel Joseph Coady

Guanyang Lin

Kristin Schmidt

Blake W Davis

Hareem Tariq Maune

Noel Arellano

Margareta Paunescu

Durairaj Baskaran

Jassem Ahmed Abdallah

Orest Polishchuk

Atsuko Ito, Legal Representative

Dirk Pfeifer

Libor Vylicky

Eri Hirahara

Daniel Paul Sanders

Wai-Kim c/o Ibm United Kingdom Limited Li

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

The disclosure provides methods for directed self-assembly (DSA) of a block co-polymer (BCP). In one embodiment, a method includes: forming an oxide spacer along each of a first sidewall and a second sidewall of a cavity in a semiconductor substrate; forming a neutral layer between the oxide spacers and along a bottom of the cavity; and removing the oxide spacers to expose the first and second sidewalls and a portion of the bottom of the cavity adjacent the first and second sidewalls.

Directed self-assembly

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

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

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 1.0 Lo) 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

A chemical pattern layer including an orientation control material and a prepattern material is formed over a substrate. The chemical pattern layer includes alignment-conferring features and additional masking features. A self-assembling material is applied and self-aligned over the chemical pattern layer. The polymeric block components align to the alignment-conferring features, while the alignment is not altered by the additional masking features. A first polymeric block component is removed selective to a second polymeric block component by an etch to form second polymeric block component portions having a pattern. A composite pattern of the pattern of an etch-resistant material within the chemical pattern layer and the pattern of the second polymeric block component portions can be transferred into underlying material layers employing at least another etch.

Pattern decomposition method for wiring patterns with chemoepitaxy based directed self assembly

After forming spacers over a hard mask layer using a sidewall image transfer process, a neutral material layer is formed on the portions of the hard mask layer that are not covered by the spacers. The spacers and the neutral material layer guide the self-assembly of a block copolymer material. The microphase separation of the block copolymer material provides a lamella structure of alternating domains of the block copolymer material.

Pattern decomposition for directed self assembly patterns templated by sidewall image transfer

Block copolymers (BCPs) for self-assembly applications comprise a linear fluorinated linking group L' joining a pair of adjacent blocks. A film layer comprising a BCP, which is disposed on an underlayer and in contact with an atmosphere, is capable of forming a perpendicularly oriented domain pattern when the underlayer is preferentially wetted by one domain of an otherwise identical self-assembled BCP in which all fluorines of L&#x2032; are replaced by hydrogen. The BCP can be a low-chi or high-chi BCP. In a preferred embodiment, the BCP comprises a styrene-based first block, and a second block comprises a carbonate and/or ester repeat unit formed by ring opening polymerization of a cyclic carbonate and/or cyclic ester monomer. The linking group L&#x2032; has a lower surface energy than each of the polymer blocks.

Block copolymers for directed self-assembly applications

After forming a material stack including, from bottom to top, a dielectric material layer, a transfer layer, a hard mask layer and a neutral layer over a substrate, the neutral layer and the hard mask layer is patterned to create trenches therein that correspond to areas where unnecessary lines generated by a self-assembly of a self-assembling material subsequently formed and/or unnecessary portions of such lines are present. The self-assembling material is applied over the top surfaces of the patterned neutral layer and the transfer layer to form a self-aligned lamellar structure including alternating first and second domains. The second domains are removed selective to the first domains to provide a directed self-assembly (DSA) pattern of the first domains. Portions of the first domains not intersecting the trenches can be transferred into the patterned hard mask layer, resulting in a composite pattern of a pattern of trenches and the DSA pattern.

Chemoepitaxy-based directed self assembly process with tone inversion for unidirectional wiring

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.

A patterned photoresist is provided atop a substrate. A hardening agent is applied to the patterned photoresist to provide a polymeric coated patterned photoresist. The polymeric coated patterned photoresist is baked to provide a hardened photoresist, and subsequent the baking step, the polymeric coating is removed from the hardened photoresist by rinsing. The hardened photoresist can be removed anytime during the patterning of the substrate by an aqueous resist developer.

Method to harden photoresist for directed self-assembly processes

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San Jose, CA, United States of America

Joy Cheng