Resist-Free Directed Self-Assembly Chemo-Epitaxy Approach for Line/Space Patterning.

This work reports a novel, simple, and resist-free chemo-epitaxy process permitting the directed self-assembly (DSA) of lamella polystyrene-block-polymethylmethacrylate (PS-b-PMMA) block copolymers (BCPs) on a 300 mm wafer. 193i lithography is used to manufacture topographical guiding silicon oxide line/space patterns. The critical dimension (CD) of the silicon oxide line obtained can be easily trimmed by means of wet or dry etching: it allows a good control of the CD that permits finely tuning the guideline and the background dimensions. The chemical pattern that permits the DSA of the BCP is formed by a polystyrene (PS) guide and brush layers obtained with the grafting of the neutral layer polystyrene-random-polymethylmethacrylate (PS-r-PMMA). Moreover, data regarding the line edge roughness (LER) and line width roughness (LWR) are discussed with reference to the literature and to the stringent requirements of semiconductor technology.

Hierarchical Order in Dewetted Block Copolymer Thin Films on Chemically Patterned Surfaces.

We investigated the dewetting process on flat and chemically patterned surfaces of ultrathin films (thickness between 2 and 15 nm) of a cylinder forming polystyrene- block-poly(methyl methacrylate) (PS- b-PMMA) spin coated on poly(styrene- r-methyl methacrylate) random copolymers (RCPs). When the PS- b-PMMA film dewets on a 2 nm-thick RCP layer, the ordering of the hexagonally packed PMMA cylinders in the dewetted structures extends over distances far exceeding the correlation length obtained in continuous block copolymer (BCP) films. As a result, micrometer-sized circular droplets featuring defectless single grains of self-assembled PS- b-PMMA with PMMA cylinders perpendicularly oriented with respect to the substrate are generated and randomly distributed on the substrate. Additionally, alignment of the droplets along micrometric lines was achieved by performing the dewetting process on large-scale chemically patterned stripes of 2 nm thick RCP films by laser lithography. By properly adjusting the periodicity of the chemical pattern, it was possible to tune and select the geometrical characteristics of the dewetted droplets in terms of maximum thickness, contact angle and diameter while maintaining the defectless single grain perpendicular cylinder morphology of the circular droplets.

GISAXS Analysis of the In-Depth Morphology of Thick PS-b-PMMA Films.

The morphological evolution of cylinder-forming poly(styrene)-b-poly(methyl methacrylate) block copolymer (BCP) thick films treated at high temperatures in the rapid thermal processing (RTP) machine was monitored by means of in-depth grazing-incidence small-angle X-ray scattering (GISAXS). The use of this nondisruptive technique allowed one to reveal the formation of buried layers composed of both parallel- and perpendicular-oriented cylinders as a function of the film thickness (24 ≤ h ≤ 840 nm) and annealing time (0 ≤ t ≤ 900 s). Three distinct behaviors were observed depending on the film thickness. Up to h ≤ 160 nm, a homogeneous film consisting of perpendicular-oriented cylinders is observed. When h is between 160 and 700 nm, a decoupling process between both the air-BCP and substrate-BCP interfaces takes place, leading to the formation of mixed orientations (parallel and perpendicular) of the cylinders. Finally, for h > 700 nm, the two interfaces are completely decoupled, and the formation of a superficial layer of about 50 nm composed of perpendicular cylinders is observed. Furthermore, the through-film morphology affects the nanodomain long-range order, which substantially decreases in correspondence with the beginning of the decoupling process. When the thick samples are exposed to longer thermal treatments, an increase in the long-range order of the nanodomains occurs, without any sensible variation of the thickness of the superficial layer.

Effect of Entrapped Solvent on the Evolution of Lateral Order in Self-Assembled P(S-r-MMA)/PS-b-PMMA Systems with Different Thicknesses.

Block copolymers (BCPs) are emerging as a cost-effective nanofabrication tool to complement conventional optical lithography because they self-assemble in highly ordered polymeric templates with well-defined sub-20-nm periodic features. In this context, cylinder-forming polystyrene-block-poly(methyl methacrylate) BCPs are revealed as an interesting material of choice because the orientation of the nanostructures with respect to the underlying substrate can be effectively controlled by a poly(styrene-random-methyl methacrylate) random copolymer (RCP) brush layer grafted to the substrate prior to BCP deposition. In this work, we investigate the self-assembly process and lateral order evolution in RCP + BCP systems consisting of cylinder-forming PS-b-PMMA (67 kg mol-1, PS fraction of ∼70%) films with thicknesses of 30, 70, 100, and 130 nm deposited on RCP brush layers having thicknesses ranging from 2 to 20 nm. The self-assembly process is promoted by a rapid thermal processing machine operating at 250 °C for 300 s. The level of lateral order is determined by measuring the correlation length (ξ) in the self-assembled BCP films. Moreover, the amount of solvent (Φ) retained in the RCP + BCP systems is measured as a function of the thicknesses of the RCP and BCP layers, respectively. In the 30-nm-thick BCP films, an increase in Φ as a function of the thickness of the RCP brush layer significantly affects the self-assembly kinetics and the final extent of the lateral order in the BCP films. Conversely, no significant variations of ξ are observed in the 70-, 100-, and 130-nm-thick BCP films with increasing Φ.

Micrometer-Scale Ordering of Silicon-Containing Block Copolymer Thin Films via High-Temperature Thermal Treatments.

Block copolymer (BCP) self-assembly is expected to complement conventional optical lithography for the fabrication of next-generation microelectronic devices. In this regard, silicon-containing BCPs with a high Flory-Huggins interaction parameter (χ) are extremely appealing because they form high-resolution nanostructures with characteristic dimensions below 10 nm. However, due to their slow self-assembly kinetics and low thermal stability, these silicon-containing high-χ BCPs are usually processed by solvent vapor annealing or in solvent-rich ambient at a low annealing temperature, significantly increasing the complexity of the facilities and of the procedures. In this work, the self-assembly of cylinder-forming polystyrene-block-poly(dimethylsiloxane-random-vinylmethylsiloxane) (PS-b-P(DMS-r-VMS)) BCP on flat substrates is promoted by means of a simple thermal treatment at high temperatures. Homogeneous PS-b-P(DMS-r-VMS) thin films covering the entire sample surface are obtained without any evidence of dewetting phenomena. The BCP arranges in a single layer of cylindrical P(DMS-r-VMS) nanostructures parallel-oriented with respect to the substrate. By properly adjusting the surface functionalization, the heating rate, the annealing temperature, and the processing time, one can obtain correlation length values larger than 1 µm in a time scale fully compatible with the stringent requirements of the microelectronic industry.

Composition of ultrathin binary polymer brushes by thermogravimetry-gas chromatography-mass spectrometry.

In the present paper, a reliable and rugged thermogravimetry-gas chromatography-mass spectrometry (TGA-GC-MS) method was developed to determine the composition of ultrathin films consisting of binary blends of functional polystyrene (PS) and polymethylmethacrylate (PMMA) grafted to a silicon wafer. A general methodology will be given to address the composition determination problem for binary or even multicomponent polymer brush systems using the PS/PMMA-based samples as a paradigmatic example. In this respect, several distinct tailor-made materials were developed to ensure reliable calibration and validation stages. The analytical method was tested on unknown samples to follow the composition evolution in PS/PMMA brushes during the grafting reaction. A preferential grafting of the PMMA was revealed in full agreement with its preferential interaction with the SiO2 polar surface.

Thickness and Microdomain Orientation of Asymmetric PS-b-PMMA Block Copolymer Films Inside Periodic Gratings.

The ordering process of asymmetric PS-b-PMMA block copolymers (BCPs) is investigated on flat SiO2 surfaces and on topographically patterned substrates. The topographic patterns consist of periodic gratings of 10 trenches defined by conventional top-down approaches and subsequently neutralized using a P(S-r-MMA) random copolymer (RCP). When the ordering process is accomplished on a flat surface at a temperature ranging between 180 and 230 °C, cylindrical microdomains perpendicularly oriented with respect to the substrate are observed irrespective of annealing temperature. In contrast, when the ordering process occurs on topographically patterned substrates, different phenomena have to be considered. The simultaneous effect of the flow around the gratings and the BCP flux from the zone located between adjacent trenches (mesa) into the inner part of the trenches results in significant thickness variations of the confined BCP film. Therefore, the amount of BCP inside the trenches depends on the width of the mesa region, which acts as a BCP reservoir. Moreover, within each trench group, the BCP thickness progressively decreases from the external to the central trenches composing the periodic grating. The thickness variation of the BCP film within the trenches strongly affects the ordering process, ultimately leading to different orientations of the microdomains within the trenches. In particular, when the annealing temperature is 190 °C a precise confinement of the BCP within the trenches featuring a perpendicular cylinder morphology is observed. At higher temperatures, mixed or parallel orientations of the microdomains are obtained depending on the width of the trenches in the periodic grating.

Ultrathin random copolymer-grafted layers for block copolymer self-assembly.

Hydroxyl-terminated P(S-r-MMA) random copolymers (RCPs) with molecular weights (Mn) from 1700 to 69000 and a styrene unit fraction of approximately 61% were grafted onto a silicon oxide surface and subsequently used to study the orientation of nanodomains with respect to the substrate, in cylinder-forming PS-b-PMMA block copolymer (BCP) thin films. When the thickness (H) of the grafted layer is greater than 5-6 nm, a perpendicular orientation is always observed because of the efficient decoupling of the BCP film from the polar SiO2 surface. Conversely, if H is less than 5 nm, the critical thickness of the grafted layer, which allows the neutralization of the substrate and promotion of the perpendicular orientation of the nanodomains in the BCP film, is found to depend on the Mn of the RCP. In particular, when Mn = 1700, a 2.0 nm thick grafted layer is sufficient to promote the perpendicular orientation of the PMMA cylinders in the PS-b-PMMA BCP film. A proximity shielding mechanism of the BCP molecules from the polar substrate surface, driven by chain stretching of the grafted RCP molecules, is proposed.

Thermal stability of functional P(S-r-MMA) random copolymers for nanolithographic applications.

Two strategies are envisioned to improve the thermal stability of the grafted layer and to allow the processing of the random copolymer/block copolymer (RCP/BCP) system at high temperature. From one side, a high-temperature thermal treatment of a commercial α-hydroxyl ω-2,2,6,6-tetramethylpiperidinyloxy functional RCP, namely, TR58, leads to the formation of a stabilized layer able to induce the perpendicular orientation of a symmetric BCP to temperatures higher than 310 °C. On the other side, an α-hydroxyl ω-Br functional RCP, namely, BrR58, with the same molar mass and composition of TR58, was prepared by activator regenerated by electron transfer atom transfer radical polymerization. The resulting brush layer can sustain the self-assembly of the symmetric BCP for processing temperatures as high as 330 °C. In both systems, the disruption of the BCP film, deposited on the grafted RCP layer, occurs because of the formation of bubbles, due to a low-temperature evolution of monomers from the RCP layer. The extent of the low-temperature monomer evolution is higher for TR58 than it is for BrR58 and starts at lower temperatures. For both copolymers, the thermal treatment offsets the low-temperature monomer evolution while still maintaining surface characteristics suitable to induce the perpendicular orientation of the BCPs, thus ultimately extending the range of processing temperatures of the BCP film and consequently speeding the self-organization process.

Characterization of ultra-thin polymeric films by Gas chromatography-Mass spectrometry hyphenated to thermogravimetry.

Polymeric materials are widely employed to build up tunable nanomasks for nano-patterning technologies. Ultrathin polymer layers are involved in this process. A Thermo Gravimetric Analysis-Mass Spectrometry (TGA-GC-MS) method was optimised, validated and successfully applied to investigate the thermal behavior of ultrathin poly(styrene-r-methylmethacrylate) random copolymer layers P(S-r-MMA) grafted to a silicon wafer surface. The interface between TGA and MS is highly versatile since many instrumental parameters (i.e. loop volumes, pulsed sampling frequencies, acquisition modalities, carrier gases, flow rates) can be easily tuned. Samples featuring substantial scale difference, i.e. bulk materials, thick films (few µm thickness), thin and ultrathin films (few nm thickness) can be analyzed without any instrumental modification or sample pretreatments. The TGA-GC-MS analysis was used to highlight subtle differences in samples featuring different thicknesses, in the 2-6 nm range, and subjected to various thermal treatments, thus indicating that this hyphenated technique could be successfully applied to the investigation of ultrathin polymer films.

Fine tuning of lithographic masks through thin films of PS-b-PMMA with different molar mass by rapid thermal processing.

The self-assembly of asymmetric polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA) block copolymer based nanoporous thin films over a broad range of molar mass (Mn) between 39 kg·mol(-1) and 205 kg·mol(-1) is obtained by means of a simple thermal treatment. In the case of standard thermal treatments, the self-assembly process of block copolymers is hindered at small Mn by thermodynamic limitations and by a large kinetic barrier at high Mn. We demonstrate that a fine tuning of the annealing parameters, performed by a Rapid Thermal Processing (RTP) machine, permits us to overcome those limitations. Cylindrical features are obtained by varying Mn and properly changing the corresponding annealing temperature, while keeping constant the annealing time (900 s), the film thickness (∼30 nm), and the PS fraction (∼0.7). The morphology, the characteristic dimensions (i.e., the pore diameter d and the pore-to-pore distance L0), and the order parameter (i.e., the lattice correlation length ξ) of the samples are analyzed by scanning electron microscopy and grazing-incidence small-angle X-ray scattering, obtaining values of d ranging between 12 and 30 nm and L0 ranging between 24 and 73 nm. The dependence of L0 as a 0.67 power law of the number of segments places these systems inside the strong segregation limit regime. The experimental results evidence the capability to tailor the self-assembly processes of block copolymers over a wide range of molecular weights by a simple thermal process, fully compatible with the stringent constraints of lithographic applications and industrial manufacturing.