Directed Self- Assembly of Block Copolymers; an Alternative Tool for Sub- 20 nm Lithography Parvaneh Mokarian
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1 Directed Self- Assembly of Block Copolymers; an Alternative Tool for Sub- 20 nm Lithography Parvaneh Mokarian Department of Chemistry, University College Cork (UCC) and Tyndall National Institute, Cork, Ireland & Centre for Research on Adaptive Nanostructures and Nanodevices (CRANN), Trinity College Dublin Intel ERIC Conference, Croke Park, Dublin, 3-4 th Oct 2012
2 Overview What is a polymer? N: the degree of polymerisation (The number of monomers in a polymer ) Styrene monomer Polystyrene
3 Block Copolymers Covalent bond A n B n AB : Flory- Huggins interaction parameters The higher the The higher the chance of phase separation as cast polymer film after annealing A n B n
4 Thermodynamics of phase separation Two parameters control the phase behaviour of diblock copolymers: The volume fraction of A block : f A Combined interaction parameter: AB.N G mix /kt = (ln (f A ))/N A + (ln (f B ))/N B + AB f A f B AB 1 T Entropic terms Enthalpic term For phase separation: AB N 10.5
5 Thermodynamics of phase separation Block Copolymer s Phase Diagram
6 Applications Silica nanocone arrays with gold functionalized tip using BCPs as a nanolithography template Lindarti Purwaningsi, Beilstein J Nanotechnol. 2011; 2:
7 Applications 25 nm Magnetic Nanodot Arrays using BCP as nanolithography template A. Baruth et al, ACS Appl. Mater. Interfaces, 2011, 3 (9), pp Block copolymer thin film membrane for selective species transport for energy application Osoji lab,
8 Applications Controlled drug delivery Lo, K. et al, Acs Nano 2009, 3 (9),
9 In our lab Using BCPs as template to make sub 10 nm nanowires for transistors!! Creating nano patterns for other applications!
10 Hexagonal Phase PS-b-PEO Poly (Styrene-b- ethylene oxide) M w :42K-11.5K PS: amorphous, T g = 103 o C, ƒ PS = 0.8 PEO: crystalline, T g = -61 o C PS PEO N 40 (at 50 o C)
11 Creating line and dot pattern in PS-b-PEO Flipping of Morphology 10 min 20 min 40 min 60 min 75 min 90 min 105 min 120 min Mokarian-Tabari, P.; Morris, M. A. et al, Acs Nano 2011, 5 (6),
12 The Thermodynamics of the Swelling Swelling in polymers: mass uptake + chain stretching dc dt M ( t) d dx c0 dc D( ) dt Dt Fick s second low Case I diffusion Glassy polymer Case II diffusion ᵠ ᵠc Osmotic pressure Chains immobilised The front plasticised glassy d dt Elongational viscosity
13 Nano dots/pillars made by PS-b-PEO PEO block has been partially removed PS-b-PEO PS-b-PEO after wet etch in HI Protective cap 50 nm Si nano pillars EM cross section after pattern transfer Enhancing the etch contrast by iron oxide inclusion Patent: M.A. Morris, T. Ghoshal, D. Borah & P. Mokarian-Tabari T. Ghoshal, M.A. Morris et al, Adv. Mater. 2012, 24 (18),
14 Micro/Nano Patterns in Nature Combination of texture and material properties Superhydrophobic/superhydrophilic Anti reflective surfaces Self cleaning Water harvesting surfaces Park K., Barbastathis G., Acs Nano 2012, 6 (5),
15 Nano features Functionalised nano pillars Nano patterns + chemical functionalization Superhydrophobic property Wenzel state Cassie- Baxter state
16 Nanowire Challenges Smaller feature size,. N, chance of phase separation (investing in new polymer system with higher such as PS-PDMS, PS-PLA and PS- PEO) Etch contrast Defect free pattern (<0.01 cm -2 ) Directed self assembly (DSA) Confinement (trench substrate) Chemistry (surface functionalisation, selective side wall chemistry)
17 Directed Self Assembly Graphoepitaxy: Confinement effect PS-b-PEO Penalty associated with chain stretching
18 Directed Self Assembly Sparse Chemical pre-patterns 10 nm Nano-post for DSA Square arrays P. Nealey C.A. ROSS C.J. Hawker
19 Why Lamellar systems? Dot pattern Line pattern Etching issues!! Neutralised layer (brush chemistry) Parallel alignment (Due to the affinity of one of the blocks to the substrate/air interface)
20 ITRS Lithography
21 Microwave annealing Frequency: 2.4 GHz Power output 300 ±10% watts Using microwave for BCP self assembly: Zhang, X.J., et al.,. Acs Nano, , & Zhang, X.J., et al, Macromolecules 2011, 44,
22 Microwave annealing (Lamellar PS-b-PEO) T = 58 o C, 300 watts, solvents: toluene + water Si substrate water after 15 s!! after 30 s toluene Half pitch: 17 nm after 60 s after 120 s
23 Microwave annealing (Lamellar PS-b-PLA) Poly (styrene-b-lactic acid) Mn: (21k-19.5k), PDI:1.06 =0.22 PLA water soluble Good etch contrast Phase separated PS-b-PLA after solvent annealing in microwave for a few seconds! Excellent coverage (almost 100%) Unpublished data
24 Etch Contrast (Lamellar PS-b-PLA) Reactive Ion Etch Before etch Unpublished data After 15 s etch
25 Pattern Transfer (PS-b-PLA) 16 nm Si nanowires Pattern transfer in ICP/RIE, SF 6 /CHF 3 SEM cross section Unpublished data
26 He ion microscope SEM (poor contrast) PS-b-PMMA prior to etching A. Bell, CRANN He ion (excellent contrast)
27 Summary Thermodynamics of phase separation in BCPs (f A, AB N ) Dot and line pattern in cylinder forming PS-b-PEO Functionalised nano pillars with superhydrophobic properties Microwave annealing (process time is reduced to minutes) Perpendicular alignment in Lamellar PS-b-PEO without any brush or surface functionalisation PS-b-PLA system (sub 20 nm nanowires)
28 Acknowledgement Prof. M.A. Morris Cian Cummins, Timothy Collins, Sozaraj Rasappa, Ramsankar Senthamaraikannan, Dr. Benjamin O Driscoll, Vladimir Djara, Dr. Tandra Ghoshal, Dr. Dipu Borah, Dr. Alan Bell, Atul Chaudhari, Prof J. Holmes Intel Advanced Laboratory (IAL) and staff: Matt Shaw, Peter Gleeson, Christopher Murray and Jennifer McKenna AML (Advanced Microscopy Laboratory), CRANN, Trinity College Dublin CRANN/ CSET / SFI (Science Foundation Ireland) for funding Staff of the mechanical and electrical workshop, training fab and clean room and microscopy in Tyndall [email protected]
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