Reactive Ion Etching of Cylindrical Polyferrocenylsilane Block Copolymer Micelles: Fabrication of Ceramic Nanolines on Semiconducting Substrates

Abstract

The diblock copolymers, poly(isoprene‐block‐ferrocenyldimethylsilane) (PI‐b‐PFDMS) and poly(ferrocenyldimethylsilane‐block‐dimethylsiloxane) (PFDMS‐b‐PDMS), form cylindrical micelles with an organometallic polyferrocenylsilane core in a solvent of hexanes. These cylindrical micelles were deposited onto a Si substrate from solution by either spin or dip coating, and upon reactive ion etching, continuous ceramic nanolines with lengths of micrometers and widths as small as 8 nm were created. The nanolines were characterized by scanning force microscopy (SFM) and transmission electron microscopy (TEM), and were shown to contain Fe, Si, and O from X‐ray photoelectron spectroscopy (XPS) studies. The widths of the nanolines could be varied from ca. 8 to 30 nm, depending on the composition of the corona (PI or PDMS). The oriented deposition of these cylindrical micelles can be achieved along pre‐patterned grooves on a resist film using capillary forces. Following treatment with hydrogen or oxygen plasma, oriented ceramic nanolines can be fabricated. The approach reported here represents a relatively simple method to create ceramic nanolines with large aspect ratio on semiconducting substrates.

Anionic Ring‐Opening Polymerization of a Germanium‐Bridged [1]Ferrocenophane: Synthesis and Morphology of Well‐Defined Polyferrocenylgermane Homopolymers and Block Copolymers

“…graphy due to the etch resistance of the PFS block. [10,17,[44][45][46] To investigate whether PFG block copolymers can also function as nanolithographic templates, thin films of 6 and 7 were prepared by spin-coating onto silicon wafers and subsequently exposed to an Ar plasma. AFM height images of the etched films ( Figure 7) showed that after exposure to the plasma, the organic phase (PI) has been almost exclusively removed.…”

“…[17] Moreover, shell-cross-linked cylindrical PI-b-PFS block copolymer micelles can act as hosts for onedimensional arrays of metal and semiconductor metal generating peapod-type nanostructures by in situ redox reactions between the PFS core and metal ions. [18] Recently, it has been discovered that short cylindrical micelles generated by ultrasonication can undergo crystallizationdriven living polymerization to form block co-micelles upon addition of further block copolymer.…”

Synthesis and Patterning of Prussian Blue Nanostructures on Silicon Wafer via Galvanic Displacement Reaction

“…In recent years, nanoscale metallic features directly interfacing to semiconductors is a new area of nanoscience and nanotechnology. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] However, reports on synthesis of materials other than metals are scarce. [18][19][20] Prussian Blue (PB), formula Fe III4 (Fe II (CN) 6 ) 3 , and its related metal hexacyanates have aroused intensive interest because of their potential application as molecule-based magnets, [21,22] electrochromic materials, [23,24] and potential cation sensors.…”

Metallopolymers: New Multifunctional Materials

“…One potential application of these well-defined aggregates may be as etch resists for semiconducting substrates, such as GaAs or Si, and they offer potential access to magnetic or semiconducting nanoscopic patterns on various substrates. [132] Möller, Winnik, and Manners and co-workers have studied cylindrical micelles derived from the self-assembly of PFS-b-poly(dimethylsiloxane) (PFS-b-PDMS, 28b, R=R′ = Me) in the PDMS-selective solvent hexanes which possess an organometallic PFS core and a PDMS corona. Dip-or spin-coating of the micelles is possible and they can be positioned on the surface of a GaAs resist by capillary forces along grooves, which were previously formed from electron beam etching of the surface.…”