study of block copolymer lithography using scft: new ...ghf/cfdc_2009/hur.pdfvarious types of...
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Study of Block Copolymer Lithography using SCFT:
New Patterns and Methodology
Su-Mi HurGlenn Fredrickson
Complex Fluids Design Consortium Annual Meeting
Monday, February 2, 2009
Materials Research LaboratoryUniversity of California, Santa Barbara
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Outline
Motivation & Block Copolymer Lithography
Numerical Method
AB + B’C (+ Confinement)
AB+ A + Confinement
Mixed Polymer Brushes + Confinement
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Lithography
Optical printing of complex circuit diagrams into pattern on the wafer (through mask onto photo-resist)
Complicated, expensive, and critical process of modern integrated circuit (IC) manufacturing
Scaling is limited by wavelength of light ( > 22nm)
Equipment cost exponentially increases as reducing the dimension. Aurangzeb Khan , Lecture note of VLSI Desing system
New families of imaging materials
and novel approaches
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Block Copolymer Lithography
Promising high resolution lithographic tool
Microscopic phase separation in the scale of
Various types of geometries in block copolymer thin film
R. Segalman, Matl. Sci. & Eng. 2005, 48, 191-226.
parallel cylinder perpendicular cylinder sphere
parallel lamellar perpendicular lamellar
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Control of Microdomain Ordering
High resolution - demand for smaller device structures
Placement accuracy
Reduction of defects density - yield loss
Throughput - manufacturing cost
Some applications require long-range perfect ordering.
Daniel J.C. Herr, Future Fab. Intl. Sec.5. 2005, Issue 18
Mechanical flow fieldElectrical fieldTemperature gradientChemically patterned substrateTopographically patterned substrate
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“Graphoepitaxy”:Topographically Patterned Substrate
Bottom-up self-assembly of block copolymers on 10 nm scales
Top-down conventional lithography in generating micron-scale wells
Lateral confinement can promote defect-free self-assembled block copolymer features.
J.Y.Cheng et al. Adv. Mater. 2006, 18, 2505-2521 R. A. Segalman and A. Hexemer and E. J. Kramer, Macromolecules. 2003, 36, 6831.
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Outline
Motivation & Block Copolymer Lithography
Numerical Method
AB + B’C (+ Confinement)
AB+ A + Confinement
Mixed Polymer Brushes + Confinement
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SCFT Algorithm
Start: Generate Random Initial
Field Configurations w(x,0)
Solve Modified Diffusion Equationfor chain propagator q (x, s ;[w])
Solve the Single Chain Partition Function Q
Calculate the densities
Update the field w(x,t)
Convergence Criterion is Satisfied?
ENDY
N
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How to Implement Confinement Wall
Predetermined
wall density function
four-fold modulated tanh function
Local incompressibility
Include contact interaction between the wall and A- and B- segments: possible to implement A- or B-wetting wall
Square mask and its cross section
0
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Alternative Approach to Square Confinement
Masking method:Periodic B.C with plane wave basisAdaptable to non-symmetric well geometriesSlow convergenceWasted computation in the masked area
Alternative approach using sine wave basis functionUse the actual cellDirichlet boundary condition at the edges
Sine wave basisSine FFT, rather than the complex FFTNo wasted computations in the masked areasFaster convergence in the field update scheme
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Overview
Block Copolymer Lithography
Numerical Method
AB + B’C (+ Confinement)
AB+ A + Confinement
Mixed polymer brushes + confinement
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AB + B’C
When do we observe square lattice? SCFT simulations of the system varying χBB’N , χACN and
χN( A/B(B’), C/B(B’))
CBA
Y. Mogi et al. Macromolecules, 1992, 25, 5408-5411
ABC triblock copolymer Binary blend of AB and B'C diblockcopolymers in which the B and B' blocks have attractive supramolecularinteractions
C. Tang et al. Science, 2008, 322, 429
CB’’
BA
Square array: canonical structure defined by Semiconductor Industry Association (SIA)
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Effect of repulsive interaction between A and C, χACN
A
HEX A and C are micible.
SQRA and C segregate into the core and shell of the cylinders in order to reduce A/C contacts.
DisorderedFree energy cost of A/C contacts are larger than for the A/B(B’) and C/B(B’).
SQRCylinders composedsolely of either the Aor C component.
Increasing repulsive interaction between the minor blocks A and C, χACN
5 10 15 20 25 30 35 40
A+C
Fixing χBB’N = -7.468 , χN = 18.875, fB/B’ = 0.7 CB’’
BA
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Phase Diagram of AB+B’CIncreasing repulsive interaction between the minor blocks A and C, χACN
Increasing repulsive
interaction between other
blocks,χN
5 10 15 20 25 30 35 40
12
16
18.875
20
25
30
40
50
Representative density profiles of A and C
Fixing χBB’N = -7.468
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AB+B’C in a square well
Square lateral confinement controls and improves defect-free tetragonal orderingχBB’N = -3.468, χACN = 55.5 χN = 13.875 (A/B(B’) and C/B(B’))C attractive and A repulsive square wall Side length, L = 84Rg ~ 1 μm
Evolution of A segment concentration
CB’’
BAL
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Overview
Block Copolymer Lithography
Numerical Method
AB + B’C (+ Confinement)
AB+ A + Confinement
Mixed Polymer Brushes + Confinement
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AB + Square well
fA = 0.7A-attractive square wellL = 14 Rg
χN = 13.75 15.75 17 17Tetragonal ordering is induced by the square lateral confinement during annealing stage.
Lattice subsequently twists into hexagonal ordering in order to reduce the stress in the interstitial sites.
Representative density profiles of A segment
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AB + A + Square well
Total A-segment density profiles
A homopolymersegment concentration
fA = 0.7L = 23 RgB wetting wallα =1.75 (NAh/N)VAh = 0.23
Lα = NAh/NNAh/
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Phase Diagrams
fA = 0.7, A attractive wall conditionfixed α = 2.1 (NAh/N)
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Robustness on Line Edge Roughness
Perturbation on the wall
Tetragonal OrderingDefective
2
Present system Reference system(Tetragonal Ordering)
A. Onikoyi , E. J. Kramer (2008)
Order parameter
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Robustness on Line Edge Roughness
∆ = 0 0.5 1 (Rg)
Perturbation on the wall Tetragonal OrderingDefective
L =16 (Rg)
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AB + A + 60° Bends
AB + neutral wall
fA = 0.5, L = 18 Rg
AB + A-attractive wall
+ A (α = 0.5 (NAh/N), V_Ah=0.2)
M. P.Stoykovich et al. Materials today. 2006, 9(9), 20
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Overview
Block Copolymer Lithography
Numerical Method
AB + B’C (+ Confinement)
AB+ A + Confinement
Mixed Polymer Brushes + Confinement
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Mixed Polymer Brushes
Collaboration with Sandia National Lab.Predict phase-separated morphologies and mechanisms Understand how the system parameters affect the feasibility of targeted pattern.
Project Proposal of Sandia National Lab.
~ μm ~ nm
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Laterally Confined Polymer Brush
Simulation domain: mixed polymer brushes region only
Prefixed narrow pure polymer brush wall in lateral direction
Virtual wall in z-direction, including substrate and surface interaction
Sine basis simulation
Delta function initial condition of propagator at the grafting point at z= dz one step analytic extension
Non-uniform grafting density over the substrate due to lateral wall
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Surface Interaction
Increasing surface attraction, χw(top)N
Doubling grafting density
fA = 0.5χABN = 12 0
12
16
20
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Lateral Confinement
fA = 0.5χABN = 12
Turn on the B-attractive wall on the side, χWN = -12
Turn on the B-attractive wall on the side
Increase NB(=1.5 NA)
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Ripple Phase in 3D
Usov et al, Macromolecules, 2007
Laterally confined by pure brush region
30 Rg
3Rg
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Evolution of Long-ranged Defect-free Structure
Pattern size
~ 56 Rg3Rg
Evolution and self-healing of long-ranged ordering
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Conclusions
Phase diagram of AB+B’C helps us understand to important parameters in designing systems which will produce a square lattice.
Confinement helps AB+B’C in generating and controlling square ordering.
AB + A + confinement can generate square lattice and non-regular structures.
Mixed brushes phase separation can be controlled using a new graphoepitaxy-type technique.