Characterizing the Three-Dimensional Structure of Block Copolymers via Sequential Infiltration Synthesis and Scanning Transmission Electron Tomography

被引:104
作者
Segal-Peretz, Tamar [1 ,2 ]
Winterstein, Jonathan [5 ]
Doxastakis, Manolis [1 ,2 ]
Ramirez-Hernandez, Abelardo [1 ,2 ]
Biswas, Mahua [3 ]
Ren, Jiaxing [1 ]
Suh, Hyo Seon [1 ,2 ]
Darling, Seth B. [1 ,4 ]
Liddle, J. Alexander [5 ]
Elam, Jeffrey W. [3 ]
de Pablo, Juan J. [1 ,2 ]
Zaluzec, Nestor J. [4 ]
Nealey, Paul F. [1 ,2 ]
机构
[1] Univ Chicago, Inst Mol Engn, Chicago, IL 60637 USA
[2] Argonne Natl Lab, Div Mat Sci, Argonne, IL 60439 USA
[3] Argonne Natl Lab, Div Energy Syst, Argonne, IL 60439 USA
[4] Argonne Natl Lab, Ctr Nanoscale Mat, Argonne, IL 60439 USA
[5] NIST, Ctr Nanoscale Sci & Technol, Gaithersburg, MD 20899 USA
关键词
block copolymers; self-assembly; TEM; STEM; tomography; SIS; THIN-FILMS; DIRECT VISUALIZATION; WETTING BEHAVIOR; RADIATION-DAMAGE; STEM TOMOGRAPHY; MORPHOLOGY; LAYER; ANGLE; ORIENTATION; TRANSITIONS;
D O I
10.1021/acsnano.5b01013
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Understanding and controlling the three-dimensional structure of block copolymer (BCP) thin films is critical for utilizing these materials for sub-20 nm nanopatterning in semiconductor devices, as well as in membranes and solar cell applications. Combining an atomic layer deposition (ALD)-based technique for enhancing the contrast of BCPs in transmission electron microscopy (TEM) together with scanning TEM (STEM) tomography reveals and characterizes the three-dimensional structures of poly(styrene-block-methyl methacrylate) (PS-b-PMMA) thin films with great clarity. Sequential infiltration synthesis (SIS), a block-selective technique for growing inorganic materials in BCPs films in an ALD tool and an emerging technique for enhancing the etch contrast of BCPs, was harnessed to significantly enhance the high-angle scattering from the polar domains of BCP films in the TEM. The power of combining SIS and STEM tomography for three-dimensional (3D) characterization of BCP films was demonstrated with the following cases: self-assembled cylindrical, lamellar, and spherical PS-b-PMMA thin films. In all cases, STEM tomography has revealed 3D structures that were hidden underneath the surface, including (1) the 3D structure of defects in cylindrical and lamellar phases, (2) the nonperpendicular 3D surface of grain boundaries in the cylindrical phase, and (3) the 3D arrangement of spheres in body-centered-cubic (BCC) and hexagonal-closed-pack (HCP) morphologies in the spherical phase. The 3D data of the spherical morphologies was compared to coarse-grained simulations and assisted in validating the simulations' parameters. STEM tomography of SIS-treated BCP films enables the characterization of the exact structure used for pattern transfer and can lead to a better understating of the physics that is utilized in BCP lithography.
引用
收藏
页码:5333 / 5347
页数:15
相关论文
共 59 条
  • [1] Phase behavior in thin films of cylinder-forming diblock copolymer: Deformation and division of heptacoordinated microdomains
    Aissou, Karim
    Baron, Thierry
    Kogelschatz, Martin
    Pascale, Alina
    [J]. MACROMOLECULES, 2007, 40 (14) : 5054 - 5059
  • [2] [Anonymous], 2008, Springer Ser. Opt. Sci.
  • [3] [Anonymous], 2004, CHEM MATER, V16, P639
  • [4] STEM tomography for thick biological specimens
    Aoyama, Kazuhiro
    Takagi, Tomoko
    Hirase, Ai
    Miyazawa, Atsuo
    [J]. ULTRAMICROSCOPY, 2008, 109 (01) : 70 - 80
  • [5] SMALL-ANGLE NEUTRON-SCATTERING DETERMINATION OF MACRO-LATTICE STRUCTURE IN A POLYSTYRENE POLYBUTADIENE DIBLOCK CO-POLYMER
    BATES, FS
    COHEN, RE
    BERNEY, CV
    [J]. MACROMOLECULES, 1982, 15 (02) : 589 - 592
  • [6] Biswas M., 2015, J PHYS CHEM IN PRESS
  • [7] Impact of Out-of-Plane Translational Order in Block Copolymer Lithography
    Bosworth, Joan K.
    Dobisz, Elizabeth A.
    Hellwig, Olav
    Ruiz, Ricardo
    [J]. MACROMOLECULES, 2011, 44 (23) : 9196 - 9204
  • [8] Morphology of multi-component polymer systems:: single chain in mean field simulation studies
    Daoulas, Kostas Ch.
    Mueller, Marcus
    de Pablo, Juan J.
    Nealey, Paul F.
    Smith, Grant D.
    [J]. SOFT MATTER, 2006, 2 (07) : 573 - 583
  • [9] Directing the self-assembly of block copolymers
    Darling, S. B.
    [J]. PROGRESS IN POLYMER SCIENCE, 2007, 32 (10) : 1152 - 1204
  • [10] Monte Carlo simulations of a coarse grain model for block copolymers and nanocomposites
    Detcheverry, Francois A.
    Kang, Huiman
    Daoulas, Kostas Ch.
    Mueller, Marcus
    Nealey, Paul F.
    de Pablo, Juan J.
    [J]. MACROMOLECULES, 2008, 41 (13) : 4989 - 5001