Monica Ceresoli

Ordering dynamics in symmetric PS-b-PMMA diblock copolymer thin films during rapid thermal processing

The pattern coarsening dynamics in symmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymer thin films under conventional thermal treatments is extremely slow, resulting in limited correlation length values even after prolonged annealing at relatively high temperatures. This study describes the kinetics of symmetric block copolymer microphase separation when subjected to a thermal treatment based on the use of a Rapid Thermal Processing (RTP) system. The proposed methodology allows self-organization of symmetric PS-b-PMMA thin films in few seconds, taking advantage of the amount of solvent naturally trapped within the film during the spinning process. Distinct and self-registered morphologies, coexisting along the sample thickness, are obtained in symmetric PS-b-PMMA samples, with periodic lamellae laying over a hexagonal pattern of PMMA cylinders embedded in the PS matrix and perpendicularly oriented with respect to the substrate. The ordering dynamics and morphological evolution of the coexisting dual structures are delineated and the intimate mechanism of the self-assembly and coarsening processes is discussed and elucidated.

Flash grafting of functional random copolymers for surface neutralization

Tailoring surface energies is the key factor to control the orientation of nanoscopic structures in thin block copolymer (BCP) films. In the general frame of the “grafting to” approach, this paper reports on the use of Rapid Thermal Processing (RTP) technology to perform flash grafting reactions of a hydroxyl terminated poly(styrene-r-methylmethacrylate) random copolymer to the activated silicon wafer surface. The perpendicular orientation of the cylindrical morphology of an asymmetric PS-b-PMMA block copolymer is achieved when the thickness of the random copolymer layer is higher than 6.0 nm. The grafting time to achieve this thickness reduces from about 750 s, when the RTP grafting process is performed at 230 °C, to 15 s at 310 °C. For a symmetric PS-b-PMMA block copolymer, the perpendicularly oriented lamellar morphology is obtained when the random layer thickness is higher than 3.5 nm, that is after 60 s RTP grafting time at 250 °C. In addition, TGA-GC-MS analysis indicates that a chain structural reorganization, which occurs during the RTP treatment at high temperature, affords a more stable film structure without changing its surface characteristics. In conclusion, the RTP technology allows the “grafting to” approach to be successfully integrated into the next generation lithographic processes and affords the unprecedented opportunity to study the grafting of macromolecules on time scales and in temperature ranges that have never been explored before, shedding new light on the early stages and on the dynamics of these processes.

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.

Evolution of lateral ordering in symmetric block copolymer thin films upon rapid thermal processing

This work reports experimental findings about the evolution of lateral ordering of lamellar microdomains in symmetric PS-b-PMMA thin films on featureless substrates. Phase separation and microdomain evolution are explored in a rather wide range of temperatures (190-340 °C) using a rapid thermal processing (RTP) system. The maximum processing temperature that enables the ordering of block copolymers without introducing any significant degradation of macromolecules is identified. The reported results clearly indicate that the range of accessible temperatures in the processing of these self-assembling materials is mainly limited by the thermal instability of the grafted random copolymer layer, which starts to degrade at T > 300 °C, inducing detachment of the block copolymer thin film. For T ⩽ 290 °C, clear dependence of correlation length (ξ) values on temperature is observed. The highest level of lateral order achievable in the current system in a quasi-equilibrium condition was obtained at the upper processing temperature limit after an annealing time as short as 60 s.

Scaling of correlation length in lamellae forming PS-b-PMMA thin films upon high temperature rapid thermal treatments

Perpendicularly oriented lamellar forming block copolymers are promising candidates for the fabrication of high aspect ratio nanostructures either by means of direct pattern transfer to the underlying substrate or by sequential infiltration processes. In this work, highly ordered lamellar grains (ξ > 500 nm) were produced by thermally treating the samples at high temperature (Ttarget > 250 °C) in a Rapid Thermal Processing (RTP) machine. The variation of the lateral order of the nanostructures during the annealing process was investigated in detail, by decoupling the effect of the transients and of the isothermal step of the thermal treatment. Moreover, the self-assembly process was studied as a function of the annealing time and temperature in order to identify the processing parameters that maximize the lateral order avoiding, and at the same time, any degradation of the macromolecules. From this study the activation energy (Ea ∼ 55 kJ mol−1) of the lamellar grain coarsening process on featureless substrates was determined. The specific process conditions that promote the self-assembly of lamellar thin films reaching a level of lateral order that is suitable for nanostructure fabrication were established.

Enhanced Lateral Ordering in Cylinder Forming PS-b-PMMA Block Copolymers Exploiting the Entrapped Solvent.

The self-assembly of block copolymer (BCP) thin films produces dense and ordered nanostructures. Their exploitation as templates for nanolithography requires the capability to control the lateral order of the nanodomains. Among a multiplicity of polymers, the widely studied all-organic polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP can easily form nanodomains perpendicularly oriented with respect to the substrate, since the weakly unbalanced surface interactions are effectively neutralized by grafting to the substrate an appropriate poly(styrene-random-methyl methacrylate) P(S-r-MMA) random copolymer (RCP). This benefit along with the selective etching of the PMMA component and the chemical similarity with the standard photoresist materials deserved for PS-b-PMMA the role of BCP of choice for the technological implementation in nanolithography. This work demonstrates that the synergic effect of thermal annealing with the initial solvent naturally trapped in the basic RCP + BCP system after the deposition process can be exploited to enhance the lateral order. The solvent content embedded in the total RCP + BCP system can be tuned by changing the molecular weight and thus the thickness of the grafted RCP brush layer, without introducing external reservoirs or dedicated setup and/or systems. The appropriate supply of solvent supports a grain coarsening kinetics following a power law with a 1/3 growth exponent for standing hexagonally ordered cylinders.

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

AbstractIn 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. Graphical abstractA 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

Neutral wetting brush layers for block copolymer thin films using homopolymer blends

Binary homopolymer blends of two hydroxyl-terminated polystyrene (PS-OH) and polymethylmethacrylate (PMMA-OH) homopolymers (Mn ~ 16000 g mol−1) were grafted on SiO2 substrates by high-temperature (T > 150 °C), short-time (t < 600 s) thermal treatments. The resulting brush layer was tested to screen preferential interactions of the SiO2 substrate with the different symmetric and asymmetric PS-b-PMMA block copolymers deposited on top of the grafted molecules. By properly adjusting the blend composition and the processing parameters, an efficient surface neutralization path was identified, enabling the formation, in the block copolymer film, of homogeneous textures of lamellae or cylinders perpendicularly oriented with respect to the substrate. A critical interplay between the phase segregation of the homopolymer blends and their grafting process on the SiO2 was observed. In fact, the polar SiO2 is preferential for the PMMA-rich phase that forms a homogeneous layer on the substrate, while the PS-rich phase i...

Detection and Prevention of Palladium Contamination in Silicon Devices

In this work we report the results of a set of experiments carried out to assess the ability of recombination lifetime measurements for the detection of palladium contamination in silicon. Palladium is found to be a very effective recombination center, so recombination lifetime measurements are a very sensitive method to detect palladium in silicon. The surface segregation of palladium was monitored by the reduction of its recombination activity in the silicon volume. The palladium segregation at the wafer surface was checked by selective etching, and by Transmission Electron Microscopy (TEM) and Energy Dispersive X-ray (EDX) analysis.After validating recombination lifetime measurements for palladium detection, we use these measurements to define suitable approaches to the prevention of palladium contamination of silicon devices. The efficiency of a diffusion barrier layer (silicon nitride) and of decontamination by wet cleaning are tested.