High-chi block copolymers for directed self-assembly

Patent metadata

Field	Value
Publication number	US-2018163003-A1
Application number	US-201715841472-A
Country	US
Kind code	A1
Filing date	Dec 14, 2017
Priority date	Dec 14, 2016
Publication date	Jun 14, 2018
Grant date	—

Abstract

The present invention is broadly concerned with novel directed self-assembly compositions, processes utilizing those compositions, and the resulting structures that are formed. The composition comprises a block copolymer of polystyrene and a polymethylmethacrylate block with polylactic acid side chains (“PS-b-P(MMA-LA)”). The block copolymer is capable of crosslinking and micro-phase separating into lines and spaces measuring about 10-nm or smaller with sub-20 nm L 0 capability. Additionally, PS-b-P(MMA-LA) can be thermally annealed without a top-coat for simpler processing than the prior art. The polylactic acid side chains also increase the etch rate of the poly(methylmethacrylate) block when exposed to oxygen plasma, as well as lower the T g .

First claim

We claim:

1 . A method of forming a microelectronic structure, said method comprising:
providing a stack comprising:
a substrate having a surface; and
one or more optional intermediate layers on said substrate surface;
applying a composition to said intermediate layers, if present, or to said substrate surface, if no intermediate layers are present, said composition comprising a block copolymer comprising a first block and a second block, said first block being a copolymer that includes recurring monomers comprising lactic acid moieties; and causing said composition to self-assemble into a self-assembled layer, wherein said self-assembled layer comprises a first self-assembled region and a second self-assembled region different from said first self-assembled region.

2 . The method of claim 1 , wherein said lactic acid moieties are present as side chains on said recurring monomers.

3 . The method of claim 2 , wherein said recurring monomers are selected from the group consisting of 2-hydroxyethyl methacrylate monomers, 3-hydroxypropyl methacrylate, and mixtures thereof, and said lactic acid moieties are side chains on said recurring monomers.

4 . The method of claim 1 , wherein said first block further comprises recurring monomers of methyl methacrylate.

5 . The method of claim 1 , wherein said second block comprises recurring monomers selected from the group consisting of styrene, other styrene-containing monomers, alkyl vinylbenzyl ethers, vinylbenzyl ethers, vinylbiphenyl, vinylbenzocyclobutene, vinylnaphthalene, vinylphenanthrene, vinylanthracene, vinylanisole, vinylpyridine, vinylnaphthalate, and mixtures thereof.

6 . The method of claim 1 , said first block being a random copolymer.

7 . The method of claim 1 , wherein said first block comprises less than about 5% by weight methyl methacrylate side chains, based upon the total weight of the first block taken as 100% by weight.

8 . The method of claim 1 , wherein said causing comprises heating said composition to at least about the glass transition temperature of said block copolymer, said self-assembling occurring during said heating.

9 . The method of claim 1 , wherein said stack comprises an intermediate layer selected from the group consisting of bottom anti-reflective coatings, neutral brush layers, hardmask neutral layers, hardmasks, spin-on carbon layers, etch block layers, and imaging layers.

10 . The method of claim 1 , wherein said substrate is a semiconductor substrate.

11 . The method of claim 1 , further comprising removing said second self-assembled region to yield a pattern in said self-assembled layer.

12 . The method of claim 1 , wherein an intermediate layer is present, said intermediate layer comprising a pre-pattern comprising a plurality of raised features, said raised features being spaced apart and each being defined by respective sidewalls and a top surface, wherein said self-assembling composition is applied directly on top of said intermediate layer in spaces between said raised features.

13 . The method of claim 12 , wherein said plurality of raised features are formed by:
applying a photosensitive composition to form an imaging layer on any other intermediate layer, if present, or on said substrate surface, if no other intermediate layers are present; and patterning said imaging layer to yield said pre-pattern, before applying said composition to said imaging layer.

14 . The method of claim 1 , wherein at least one intermediate layer is present, said intermediate layer being selected from the group consisting of hardmask layers and neutral layers, and wherein said intermediate layer comprises a surface having surface-modified regions and non-modified regions, said first and second self-assembled regions being adjacent said non-modified regions.

15 . The method of claim 14 , wherein, before applying said composition to said intermediate layer, said surface-modified regions and non-modified regions are formed by:
forming an imaging layer on said intermediate layer; and patterning said imaging layer to yield a pre-pattern, wherein said patterning comprises selectively removing portions of said imaging layer to uncover portions of said intermediate layer; contacting said uncovered portions of intermediate layer with a developer or solvent to yield said surface-modified regions; and removing remaining portions of said imaging layer from said intermediate layer to yield said non-modified regions.

16 . The method of claim 14 , wherein, before applying said composition to said intermediate layer, said surface-modified regions and non-modified regions are formed by selectively exposing said intermediate layer to radiation.

17 . The method of claim 1 , wherein said causing is carried out after said applying, without applying a further layer being formed on, or a second composition being applied to, said composition.

18 . A composition comprising a block copolymer dissolved or dispersed in a solvent system, said block copolymer comprising:
a first block comprising a copolymer that includes recurring monomers comprising lactic acid moieties; and a second block comprising a polymer that includes recurring monomers selected from the group consisting of styrene, other styrene-containing monomers, alkyl vinylbenzyl ethers, vinylbenzyl ethers, vinylbiphenyl, vinylbenzocyclobutene, vinylnaphthalene, vinylphenanthrene, vinylanthracene, vinylanisole, vinylpyridine, vinylnaphthalate, and mixtures thereof.

19 . The composition of claim 18 , wherein said lactic acid moieties are present as side chains on said recurring monomers.

20 . The composition of claim 19 , wherein said recurring monomers are selected from the group consisting of 2-hydroxyethyl methacrylate monomers, 3-hydroxypropyl methacrylate, and mixtures thereof, and said lactic acid moieties are side chains on said recurring monomers.

21 . The composition of claim 18 , wherein said first block further comprises recurring monomers of methyl methacrylate.

22 . The composition of claim 21 , wherein said second block is polystyrene.

23 . The composition of claim 18 , said first block being a random copolymer.

24 . The composition of claim 18 , wherein said first block comprises less than about 5% by weight methyl methacrylate side chains, based upon the total weight of the first block taken as 100% by weight.

25 . A microelectronic structure comprising:
a substrate having a surface; one or more optional intermediate layers on said substrate surface; and a layer of a self-assembling composition formed on said one or more optional intermediate layers, if present, or on said substrate surface, if no intermediate layers are present, said self-assembling composition comprising a block copolymer comprising a first block and a second block, said first block being a copolymer that includes recurring monomers comprising lactic acid moieties.

26 . The structure of claim 25 , wherein said lactic acid moieties are present as side chains on said recurring monomers.

27 . The structure of claim 26 , wherein said recurring monomers are selected from the group consisting of 2-hydroxyethyl methacrylate monomers, 3-hydroxypropyl methacrylate, and mixtures thereof, and said lactic acid moieties are side chains on said recurring monomers.

28 . The structure of claim 25 , wherein said first blo

Assignees

• Brewer Science Inc

Inventors

• Sweat Daniel
• Xu Kui

Classifications

• H10P76/20 Primary

  of masks comprising organic materials · CPC title

• C08F2438/03

  Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] · CPC title

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08L87/00

  Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• C08G63/08

  Lactones or lactides · CPC title