US20120196094A1 - Hybrid-guided block copolymer assembly - Google Patents

Hybrid-guided block copolymer assembly Download PDF

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Publication number
US20120196094A1
US20120196094A1 US13/018,416 US201113018416A US2012196094A1 US 20120196094 A1 US20120196094 A1 US 20120196094A1 US 201113018416 A US201113018416 A US 201113018416A US 2012196094 A1 US2012196094 A1 US 2012196094A1
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Prior art keywords
bcp
block
resist
polystyrene
template
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Abandoned
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US13/018,416
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English (en)
Inventor
Yuan Xu
Kim Lee
Wei Hu
Koichi Wago
David Shiao-Min Kuo
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Seagate Technology LLC
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Seagate Technology LLC
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Priority to US13/018,416 priority Critical patent/US20120196094A1/en
Assigned to SEAGATE TECHNOLOGY LLC reassignment SEAGATE TECHNOLOGY LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HU, WEI, KUO, DAVID SHIAO-MIN, LEE, KIM, WAGO, KOICHI, XU, YUAN
Assigned to SEAGATE TECHNOLOGY LLC reassignment SEAGATE TECHNOLOGY LLC CORRECTIVE ASSIGNMENT TO CORRECT THE ADDITION OF SIXTH INVENTOR, SUNDEEP CHAUHAN PREVIOUSLY RECORDED ON REEL 026058 FRAME 0566. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT OF ASSIGNOR'S INTEREST. Assignors: CHAUHAN, SUNDEEP, HU, WEI, KUO, DAVID SHIAO-MIN, LEE, KIM, WAGO, KOICHI, XU, YUAN
Priority to PCT/US2012/021781 priority patent/WO2012106121A2/en
Priority to JP2013552018A priority patent/JP5990539B2/ja
Publication of US20120196094A1 publication Critical patent/US20120196094A1/en
Priority to US13/798,087 priority patent/US9079216B2/en
Priority to US14/728,908 priority patent/US9928867B2/en
Priority to US14/830,534 priority patent/US9460747B2/en
Abandoned legal-status Critical Current

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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/74—Record carriers characterised by the form, e.g. sheet shaped to wrap around a drum
    • G11B5/743—Patterned record carriers, wherein the magnetic recording layer is patterned into magnetic isolated data islands, e.g. discrete tracks
    • G11B5/746—Bit Patterned record carriers, wherein each magnetic isolated data island corresponds to a bit
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers
    • G11B5/855—Coating only part of a support with a magnetic layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • This disclosure relates generally to the use of block copolymers for high density patterning.
  • Bit pattern media has been extensively explored by the magnetic recording industry as one of several key solutions to expand perpendicular magnetic recording (PMR) technology in high density disk drives (HDDs).
  • a typical BPM media consists of two repeating zones—a data zone and a servo zone.
  • Data zones consist of homogenous dots to store data bits.
  • Servo zones consist of dots with various patterns to describe a location and address of information in the data zone. In the servo zone, dots need be arranged into various pattern and spacings to encode information such as head position, timing, and tracking following information for a respective data zone.
  • BPM The storage capacity of BPM is dependent upon the density of the magnetic islands, or “bits” on the media substrate surface.
  • Current processes for achieving high density patterned media include imprint mold fabrication, nano-imprinting and pattern transfer into magnetic dots, and the like.
  • Self-assembling block copolymer (BCP) enables high-density lithographic bit patterning capability and is a promising material for BPM template fabrication.
  • Directed self-assembly combines ‘top-down’ lithography (pre-registered pattern) and ‘bottom-up’ self-assembling materials like block copolymers. Directed self-assembly may generate ultra-high density homogenous patterns.
  • a method for nan-opatterning includes imprinting features in a resist on a substrate with an imprint mold to form one or more topographic surface patterns on the resulting imprinted resist.
  • a a block copolymer (“BCP”) material is deposited on the resulting imprinted resist, wherein a molecular dimension L 0 of the BCP material correlates by an integer multiple to a spacing dimension of the one or more topographic surface patterns on the resulting imprinted resist.
  • the deposited BCP is annealed and at least a portion of the annealed BCP is removed, forming a template having discrete domains.
  • FIG. 1A is an SEM image showing data zones and servo zones in bit patterned media in accordance with an embodiment.
  • FIG. 1B is an SEM image showing high resolution segments of the bit patterned media of FIG. 1A .
  • FIG. 2 is a scanning electron microscope (“SEM”) image of patterned media pre-patterned using e-beam lithography followed by a BCP patterning process, according to an embodiment.
  • SEM scanning electron microscope
  • FIGS. 3A-3F illustrates a hybrid pre-pattern structure for self-guided assembly of servo zone and data zone structures, according to an embodiment.
  • FIGS. 4A-4F illustrate another example for integrated template fabrication using hybrid guiding pre-pattern for BCP self-assembly with cylindrical block copolymer of servo zone and data zone structures, according to an embodiment.
  • a high density disk drive (HDD) 100 is a medium that has different regions besides the regions used for storing data (data zones 110 ).
  • a bit pattern media HDD 100 includes the data zone 110 which consists of homogeneous dots to store data bits.
  • the HDD 110 may typically have a servo zone 120 used to describe the location and address information in the data zone 110 .
  • Various shapes and spacings may be formed in the servo zone 120 to encode information such as head position, timing, and track-following information for a respective data zone.
  • FIG. 2 is a scanning electron microscope (“SEM”) image of bit patterned media (BPM) pre-patterned using e-beam lithography followed by a BCP patterning process.
  • SEM scanning electron microscope
  • FIG. 2 illustrates, the long-range lateral ordering of the bits are compromised by contaminants left behind by the e-beam lithography.
  • the chemicals used in the e-beam lithography wet stripping process are typically hazardous to human health and are environmentally unsound.
  • the method of applying hybrid guiding pre-patterning for BCP self-assembly disclosed here may provide both BCP long-range order for formation of the data zone 110 by utilizing pre-register dots to guide formation of data zone dots and simultaneous shape manipulation for formation of the servo zone 120 by utilizing ridge-groove guiding to form patterns of servo zone dots.
  • block copolymer self-assembly in the data zone 110 is guided with pre-patterned dots created with a template.
  • the pre-patterned dots may create chemical/topographical contrast to anchor self-assembly location of polymer blocks and achieve the long range ordering for block copolymer assembly in the data zone.
  • a method of self-assembling density multiplied block copolymers (BCP) structures in the data zone 110 includes coating a substrate with an imprint resist.
  • a composition of the BCP is chosen to have a selected molecular weight and natural lattice constant L 0 , wherein the BCP composition includes a first polymer block (A) and a second polymer block (B).
  • the imprint resist is cured, and additional process may be performed to prepare the substrate and imprint resist for coating with the BCP.
  • the BCP is annealed to laterally segregate the BCP into self-assembled structures of the first polymer block A surrounded by the second polymer block B, the structures having a lateral spatial pitch of L 0 .
  • the linear density of block A structures e.g., pillars, spheres, and the like, depending on the choice of polymers
  • hcp hexagonal close-packed
  • annealing may be a thermal, chemical (including solvent), irradiative process, or the like.
  • BCP self-assembly is mainly guided by pre-defined line patterns provided by the template.
  • the BCP assembles in grooves between the line ridges.
  • self-assembly of BDP may be confined to servo zone formation.
  • BCPs bit pattern media
  • An imprint technique may be used to guide the growth of BCP structures.
  • embodiments of this disclosure may avoid the pattern defects and chemo-toxicity associated with e-beam lithography techniques.
  • BCPs may be used, such as a cylindrical, lamellar or spherical BCP.
  • the BCP may have organic components, inorganic components, or a combination of organic and inorganic components.
  • BCP selection may be based upon the size, molecular weight, or other features of the BCP constituent units that are described further below. While specific BCPs are selected for the particular application, the process disclosed herein is a generalized process. Other variations are discussed further below and are illustrated in the figures.
  • the BCP is comprised of at least two constituent units, structural units or “blocks”, herein termed “block A” and “block B”, or “A block” and “B block”.
  • block A and block B may be organic or inorganic, or block A may be organic, and block B inorganic, or block A may be inorganic and block B organic.
  • block A or block B comprises an organic polystyrene-block-polymethylmethacrylate (PS-b-PMMA), polystyrene-block-poly2-vinylpyridine, polystyrene-block-poly4-vinylpyridine, polystyrene-block-polyethyleneoxide, polystyrene-block-polyisoprene or polystyrene-block-butadiene.
  • block A or block B comprises an inorganic polystyrene-block-polydimethylsiloxane (PS-b-PDMS or, more compactly, PS-PDMS) or polystyrene-block-polyferrocenylsilane.
  • FIGS. 3A-3F illustrates an example of a method 300 for integrated data zone 110 and servo zone 120 template fabrication, using PS-PDMS as a typical spherical BCP.
  • a method 300 of self-assembling density multiplied block copolymers (BCP) structures in the data zone 110 and the servo zone 120 includes coating a substrate 315 with an imprint resist.
  • a low resolution template produces pillars 310 in the data zone 110 of a first height and spacing, and lines 320 of a second height in the servo zone 120 . For reasons discussed below, the second height of the lines 320 is greater than the first height of the pillars 310 .
  • a composition of the BCP is chosen to have a selected molecular weight and natural lattice constant L 0 , wherein the BCP composition includes a first polymer block (A) and a second polymer block (B).
  • the imprint resist is cured, and additional process steps may be performed to prepare the substrate and imprint resist for coating with the BCP.
  • the BCP is annealed to laterally segregate the BCP into self-assembled structures of the first polymer block A surrounded by the second polymer block B, the structures having a lateral spatial pitch of L 0 .
  • the linear density of block A structures e.g., pillars, spheres, and the like, depending on the choice of polymers
  • the areal density is n 2 times that of the template.
  • BCP self-assembly is mainly guided by pre-defined lines 320 provided by the template.
  • the BCP is not able to self-segregate during annealing in the space over the lines 320 , but only assembles in grooves between the lines 320 .
  • self-assembly of BDP will be confined to desired servo zone 120 formation.
  • FIG. 3A shows a cross-section
  • FIG. 3B shows a plan view of an example structure of a hybrid self-assembly guiding pre-pattern
  • pre-register pillars 310 are formed in resist at a spacing L s patterned for BCP guided self-assembly in an hcp array with the lattice constant L 0 , determined by the choice of polymers A and B, on a substrate 315 .
  • the BCP is annealed to induce lateral segregation of the A and B block polymers.
  • n 2, but L s may be chosen for n having another integer value.
  • the height of the ridge lines 330 and the thickness of the BCP coating over the lines 320 may be chosen to be too thin to permit formation of block A polymer on top of the lines 320 .
  • FIG. 3D illustrates the result removal of selective etch removal of the exposed B polymer block and imprint resist after annealing.
  • the selective etch may be an O 2 reactive ion etch, for example, which does not substantially remove the A polymer block, which acts as an etch mask.
  • formation of pillars comprising spherical block PDMS atop a columns of PS masked by the PDMS during the etch removal process resulting in long-range ordered pillar features 350 with high placement accuracy may be achieved in the data zone 110 .
  • block copolymer on top of the ridge lines 320 may not self-assemble well due to copolymer thinness. Grooves force BCP to align to them and confine BCP into designed servo formation.
  • substrate 315 may he quartz, or a material suitable for etching in a process that does not also substantially etch the A and B polymers and resist.
  • the substrate may be etched to produce a template 316 from the substrate, as shown in FIG. 3E , after removal of the A and B polymers and resist.
  • a plan view of the template 316 is shown in FIG. 3F , where the dots represent the pillars remaining after the substrate 316 has been etched and all polymers and resist removed.
  • the resulting template may be used to imprint a resist or other imprintable material a substrate on which, for example, magnetic, magneto-optical, optical, electronic or equivalent high density features may be formed.
  • FIGS. 4A-4F illustrates another example for integrated template fabrication using hybrid guiding pre-pattern for BCP self-assembly with cylindrical block copolymer, such as PS-PMMA.
  • FIG. 4A illustrate a side view of a substrate 415 having a resist imprinted with a low density template (not shown). The template may imprint features with different heights, as described below.
  • low-density pre-registered pillar dots 410 of resist of a first height are formed for guided BCP self-assembly.
  • BCP assembly will be confined by a combination of resist lines 420 and low density pre-registration resist pillar dots 425 .
  • Pre-registered pillar dots 410 , 425 and lines 420 may be either feature protruded (pillar-type) or feature recessed (hole-type). In the following drawing, pillars are applied to illustrate the example. The height of the pillar dots 410 and 425 are lower than the height of the lines 420 for the same reasons given above with respect to FIGS. 3A-3F .
  • additional descumming and cleaning steps such as reactive oxygen ion etching, oxygen plasma ashing, or the like, may be used.
  • FIG. 4C illustrate block copolymer self-assembly on the hybrid pre-pattern shown in FIGS. 4A and 4B .
  • the resist imprinted substrate 415 is then coated with BCP, such as PS-PMMA.
  • BCP laterally segregates into columns of PMMA polymer (block A) surrounded by PS (polystyrene), where the pillars 410 of resist anchor and enforce the long range order of the density multiplied columns.
  • block copolymer on top of lines 420 may not self-assemble due to a small thickness of BCP above the lines 420 imposed by the greater height of the lines 420 .
  • the grooves in the servo zone 120 between the lines 420 urge BCP lateral segregation to self-align and assemble to the PMMA block.
  • FIG. 4D removing the PMMA block (e.g., block A) by an appropriate etching or chemical process leaves high density holes 440 in PS (polystyrene) with long range ordering and high placement accuracy in the data zone 110 and high density holes 440 in PS (polystyrene) with long range ordering and high placement accuracy in the servo zone 120 due to the combination of the gap between lines 420 and pillar dots 425 .
  • FIG. 4E is a plan view of the pattern of FIG. 4D .
  • the PS and lines 420 (of resist) coating the substrate 415 may be thinned by an appropriate removal technique (e.g., dry etching) to expose the substrate 415 beneath the holes 440 .
  • the entire etched substrate 415 including the remaining resist and PS, may be coated with a masking layer, such as Cr, and the remaining resist and PS removed, leaving Cr dots where PMMA columns previously stood.
  • the substrate 415 may be an etch processible material like quartz, silicon, or the like, which can be etched with the Cr dots serving as a mask.
  • the etching then forms a high density template, as shown in FIG. 4F , of pillars on the substrate including both the data zone 110 and the servo zone 120 , which may be used for imprint production of high density BPM.
  • the processes illustrated in FIGS. 3-4 and described herein may form part of a BMP media fabrication process.
  • this disclosure may be applied to any fabrication process featuring large-area high-density nano-patterning with long-range lateral ordering, such as patterning magnetic film layers in storage media, semiconductor production, and the like.
  • the processes described herein may be used to fabricate a template for use as a mask, thereby facilitating the deposition of functional materials or other additive processes.
  • the processes described herein may be used to facilitate the etching of functional materials, to directly or indirectly form a pattern on storage media, or other subtractive processes. Other applications arc possible without departing from the scope of this disclosure.
  • “at least one of: a, b, or c” is intended to cover: a; b; c; a and b; a and c; b and c; and a, b and c.
  • All structural and functional equivalents to the elements of the various aspects described throughout this disclosure that are known or later come to be known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the claims.
  • nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. No claim element is to be construed under the provisions of 35 U.S.C. ⁇ 112, sixth paragraph, unless the element is expressly recited using the phrase “means for” or, in the case of a method claim, the element is recited using the phrase “step for.”

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  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
US13/018,416 2011-01-31 2011-01-31 Hybrid-guided block copolymer assembly Abandoned US20120196094A1 (en)

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Application Number Priority Date Filing Date Title
US13/018,416 US20120196094A1 (en) 2011-01-31 2011-01-31 Hybrid-guided block copolymer assembly
PCT/US2012/021781 WO2012106121A2 (en) 2011-01-31 2012-01-18 Forming a template with discrete domains
JP2013552018A JP5990539B2 (ja) 2011-01-31 2012-01-18 個別領域を有するテンプレートの形成
US13/798,087 US9079216B2 (en) 2011-01-31 2013-03-13 Methods of patterning with protective layers
US14/728,908 US9928867B2 (en) 2011-01-31 2015-06-02 Templates for patterned media
US14/830,534 US9460747B2 (en) 2011-01-31 2015-08-19 Hybrid-guided block copolymer assembly

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US14/830,534 Division US9460747B2 (en) 2011-01-31 2015-08-19 Hybrid-guided block copolymer assembly

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