Polystyrene Brush Evolution by Grafting to Reaction on Deglazed and Not-Deglazed Silicon Substrates.

Two model substrates for the grafting to reaction are considered: not-deglazed silicon, whose surface is coated by a thin oxide layer with reactive silanol groups on its surface; and deglazed silicon, where the oxide layer is removed by treatment with hydrofluoric acid. The reactive polymers are hydroxy-terminated polystyrenes with molecular weights ranging from 3.9 to 13.9 kg mol⁻1. The grafting to reaction is carried out at different temperatures and for different periods of time on the two different substrates. The thickness and the thermal stability of the resulting brushes are evaluated. Furthermore, the grafting of a highly dispersed system is simulated by blending two polymers with different molecular weights. Although the brush thickness growth is found to be faster on deglazed silicon, the preferential grafting of short chains occurs with equal chain selection propensity on both substrates.

Quantification of molecular weight discrimination in grafting to reactions from ultrathin polymer films by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

In the present study, a reliable and robust method was developed to quantify the molecular weight discrimination that can occur in grafting to reactions via indirect MALDI-TOF quantification of the molecular weights of grafted chains by comparing the characteristics of the polymeric material before the grafting reaction with those of the unreacted material recovered after grafting. Two polystyrene samples with different molecular weights and narrow molecular weight distributions were employed to prepare model blends that were grafted to silicon wafers and an analytical method was developed and validated to assess and quantify the modification of the molecular weight distribution that takes place during the grafting to process. Particular attention was paid to the standardization of the sample treatment and to find the best data collection and calibration methodologies in order to have statistically significant data even in the presence of a very scarce amount of the sample. Furthermore, to evaluate the accuracy of the analytical procedure, the lack of suitable standard and certified materials required a further experiment to be carried out by comparing the new optimized MALDI-TOF method and direct measurements using TGA-GC-MS on a model blend containing deuterated and hydrogenated polystyrene samples with appropriate molecular weights and distributions. The optimized method was applied on samples obtained by a thermally induced grafting to reaction from ultrathin polymer films and, for the first time, to our knowledge, an enrichment effect occurring in the ultrathin grafted layer obtained from a melt was evidenced.

Engineering of the spin on dopant process on silicon on insulator substrate.

We report on a systematic analysis of phosphorus diffusion in silicon on insulator thin film via spin-on-dopant process (SOD). This method is used to provide an impurity source for semiconductor junction fabrication. The dopant is first spread into the substrate via SOD and then diffused by a rapid thermal annealing process. The dopant concentration and electron mobility were characterized at room and low temperature by four-probe and Hall bar electrical measurements. Time-of-flight-secondary ion mass spectroscopy was performed to estimate the diffusion profile of phosphorus for different annealing treatments. We find that a high phosphorous concentration (greater than 1020 atoms cm-3) with a limited diffusion of other chemical species and allowing to tune the electrical properties via annealing at high temperature for short time. The ease of implementation of the process, the low cost of the technique, the possibility to dope selectively and the uniform doping manufactured with statistical process control show that the methodology applied is very promising as an alternative to the conventional doping methods for the implementation of optoelectronic devices.

Thermodynamics and ordering kinetics in asymmetric PS-b-PMMA block copolymer thin films.

The ordering kinetics of standing cylinder-forming polystyrene-block-poly(methyl methacrylate) block copolymers (molecular weight: 39 kg mol-1) close to the order-disorder transition is experimentally investigated following the temporal evolution of the correlation length at different annealing temperatures. The growth exponent of the grain-coarsening process is determined to be 1/2, signature of a curvature-driven ordering mechanism. The measured activation enthalpy and the resulting Meyer-Neldel temperature for this specific copolymer along with the data already known for PS-b-PMMA block copolymers in strong segregation limit allow investigation of the interplay between the ordering kinetics and the thermodynamic driving force during the grain coarsening. These findings unveil various phenomena concomitantly occurring during the thermally activated ordering kinetics at segmental, single chain, and collective levels.

Nanoscale control of Si nanoparticles within a 2D hexagonal array embedded in SiO2 thin films.

In this work, we investigate the ability to control Si nanoparticles (NPs) spatially arranged in a hexagonal network of 20 nm wide nanovolumes at controlled depth within SiO2 thin films. To achieve this goal an unconventional lithographic technique was implemented based on a bottom-up approach, that is fully compatible with the existing semiconductor technology. The method combines ultra-low energy ion beam synthesis with nanostructured block-copolymer thin films that are self-assembled on the SiO2 substrates to form a nanoporous template with hexagonally packed pores. A systematic analytical investigation using time of flight-secondary ion mass spectroscopy and low-loss energy filtered transmission electron microscopy demonstrates that by adjusting few fabrication parameters, it is possible to narrow the size distribution of the NPs and to control the number of NPs per nanovolume. Experimental results are critically discussed on the basis of literature data, providing a description of the mechanism involved in the formation of Si NPs.

Synthesis and characterization of P δ-layer in SiO2 by monolayer doping.

Achieving the required control of dopant distribution and selectivity for nanostructured semiconducting building block is a key issue for a large variety of applications. A promising strategy is monolayer doping (MLD), which consists in the creation of a well-ordered monolayer of dopant-containing molecules bonded to the surface of the substrate. In this work, we synthesize a P δ-layer embedded in a SiO2 matrix by MLD. Using a multi-technique approach based on time of flight secondary ion mass spectrometry (ToF-SIMS) and Rutherford backscattering spectrometry (RBS) analyses, we characterize the tuning of P dose as a function of the processing time and temperature. We found the proper conditions for a full grafting of the molecules, reaching a maximal dose of 8.3 × 10(14) atoms/cm(2). Moreover, using 1D rate equation model, we model P diffusion in SiO2 after annealing and we extract a P diffusivity in SiO2 of 1.5 × 10(17) cm(2) s(-1).

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.

Fabrication of periodic arrays of metallic nanoparticles by block copolymer templates on HfO2 substrates.

Block copolymer-based templates can be exploited for the fabrication of ordered arrays of metal nanoparticles (NPs) with a diameter down to a few nanometers. In order to develop this technique on metal oxide substrates, we studied the self-assembly of polymeric templates directly on the HfO2 surface. Using a random copolymer neutralization layer, we obtained an effective HfO2 surface neutralization, while the effects of surface cleaning and annealing temperature were carefully examined. Varying the block copolymer molecular weight, we produced regular nanoporous templates with feature size variable between 10 and 30 nm and a density up to 1.5 × 10¹¹ cm⁻². With the adoption of a pattern transfer process, we produced ordered arrays of Pt and Pt/Ti NPs with diameters of 12, 21 and 29 nm and a constant size dispersion (σ) of 2.5 nm. For the smallest template adopted, the NP diameter is significantly lower than the original template dimension. In this specific configuration, the granularity of the deposited film probably influences the pattern transfer process and very small NPs of 12 nm were achieved without a significant broadening of the size distribution.

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.

Thermally induced self-assembly of cylindrical nanodomains in low molecular weight PS-b-PMMA thin films.

The phase behaviour in thin films of an asymmetric polystyrene-b-polymethylmethacrylate (PS-b-PMMA) block copolymer with a molecular weight of 39 kg mol(-1) was assessed at a wide range of temperatures and times. Cylindrical PMMA structures featuring a diameter close to 10 nm and perpendicularly oriented with respect to the substrate were obtained at 180 °C in relatively short annealing times (t ≤ 30 min) by means of a simple thermal treatment performed in a standard rapid thermal processing machine.

Sequential Infiltration Synthesis of Al2O3 in PMMA Thin Films: Temperature Investigation by Operando Spectroscopic Ellipsometry.

Sequential infiltration synthesis (SIS) is a scalable and valuable technique for the synthesis of organic-inorganic materials with several potential applications at the industrial level. Despite the increasing interest for this technique, a clear picture of the fundamental physicochemical phenomena governing the SIS process is still missing. In this work, infiltration of Al2O3 into thin poly(methyl methacrylate) (PMMA) films using trimethyl aluminum (TMA) and H2O as precursors is investigated by operando dynamic spectroscopic ellipsometry (SE) analysis. The TMA diffusion coefficient values at temperatures ranging from 70 to 100 °C are determined, and the activation energy for the TMA diffusion process in PMMA is found to be Ea = 2.51 ± 0.03 eV. Additionally, systematic data about reactivity of TMA molecules with the PMMA matrix as a function of temperature are obtained. These results provide important information, paving the way to the development of a comprehensive theory for the modeling of the SIS process.

Fabrication of nitrogen-hyperdoped silicon by high-pressure gas immersion excimer laser doping.

In recent years, research on hyperdoped semiconductors has accelerated, displaying dopant concentrations far exceeding solubility limits to surpass the limitations of conventionally doped materials. Nitrogen defects in silicon have been extensively investigated for their unique characteristics compared to other pnictogen dopants. However, previous practical investigations have encountered challenges in achieving high nitrogen defect concentrations due to the low solubility and diffusivity of nitrogen in silicon, and the necessary non-equilibrium techniques, such as ion implantation, resulting in crystal damage and amorphisation. In this study, we present a single-step technique called high-pressure gas immersion excimer laser doping (HP-GIELD) to manufacture nitrogen-hyperdoped silicon. Our approach offers ultrafast processing, scalability, high control, and reproducibility. Employing HP-GIELD, we achieved nitrogen concentrations exceeding 6 at% (3.01 × 1021 at/cm3) in intrinsic silicon. Notably, nitrogen concentration remained above the liquid solubility limit to ~1 µm in depth. HP-GIELD's high-pressure environment effectively suppressed physical surface damage and the generation of silicon dangling bonds, while the well-known effects of pulsed laser annealing (PLA) preserved crystallinity. Additionally, we conducted a theoretical analysis of light-matter interactions and thermal effects governing nitrogen diffusion during HP-GIELD, which provided insights into the doping mechanism. Leveraging excimer lasers, our method is well-suited for integration into high-volume semiconductor manufacturing, particularly front-end-of-line processes.

Plasma-Assisted Atomic Layer Deposition of IrO2 for Neuroelectronics.

In vitro and in vivo stimulation and recording of neuron action potential is currently achieved with microelectrode arrays, either in planar or 3D geometries, adopting different materials and strategies. IrO2 is a conductive oxide known for its excellent biocompatibility, good adhesion on different substrates, and charge injection capabilities higher than noble metals. Atomic layer deposition (ALD) allows excellent conformal growth, which can be exploited on 3D nanoelectrode arrays. In this work, we disclose the growth of nanocrystalline rutile IrO2 at T = 150 °C adopting a new plasma-assisted ALD (PA-ALD) process. The morphological, structural, physical, chemical, and electrochemical properties of the IrO2 thin films are reported. To the best of our knowledge, the electrochemical characterization of the electrode/electrolyte interface in terms of charge injection capacity, charge storage capacity, and double-layer capacitance for IrO2 grown by PA-ALD was not reported yet. IrO2 grown on PtSi reveals a double-layer capacitance (Cdl) above 300 µF∙cm-2, and a charge injection capacity of 0.22 ± 0.01 mC∙cm-2 for an electrode of 1.0 cm2, confirming IrO2 grown by PA-ALD as an excellent material for neuroelectronic applications.

Periodic Arrays of Dopants in Silicon by Ultralow Energy Implantation of Phosphorus Ions through a Block Copolymer Thin Film.

In this work, block copolymer lithography and ultralow energy ion implantation are combined to obtain nanovolumes with high concentrations of phosphorus atoms periodically disposed over a macroscopic area in a p-type silicon substrate. The high dose of implanted dopants grants a local amorphization of the silicon substrate. In this condition, phosphorus is activated by solid phase epitaxial regrowth (SPER) of the implanted region with a relatively low temperature thermal treatment preventing diffusion of phosphorus atoms and preserving their spatial localization. Surface morphology of the sample (AFM, SEM), crystallinity of the silicon substrate (UV Raman), and position of the phosphorus atoms (STEM- EDX, ToF-SIMS) are monitored during the process. Electrostatic potential (KPFM) and the conductivity (C-AFM) maps of the sample surface upon dopant activation are compatible with simulated I-V characteristics, suggesting the presence of an array of not ideal but working p-n nanojunctions. The proposed approach paves the way for further investigations on the possibility to modulate the dopant distribution within a silicon substrate at the nanoscale by changing the characteristic dimension of the self-assembled BCP film.

Improving HfO2-Based Resistive Switching Devices by Inserting a TaOx Thin Film via Engineered In Situ Oxidation.

Resistive switching (RS) devices with binary and analogue operation are expected to play a key role in the hardware implementation of artificial neural networks. However, state of the art RS devices based on binary oxides (e.g., HfO2) still do not exhibit enough competitive performance. In particular, variability and yield still need to be improved to fit industrial requirements. In this study, we fabricate RS devices based on a TaOx/HfO2 bilayer stack, using a novel methodology that consists of the in situ oxidation of a Ta film inside the atomic layer deposition (ALD) chamber in which the HfO2 film is deposited. By means of X-ray reflectivity (XRR) and time-of-flight secondary ion mass spectrometry (ToF-SIMS), we realized that the TaOx film shows a substoichiometric structure, and that the TaOx/HfO2 bilayer stack holds a well-layered structure. An exhaustive electrical characterization of the TaOx/HfO2-based RS devices shows improved switching performance compared to the single-layer HfO2 counterparts. The main advantages are higher forming yield, self-compliant switching, lower switching variability, enhanced reliability, and better synaptic plasticity.

Al2O3 Dot and Antidot Array Synthesis in Hexagonally Packed Poly(styrene-block-methyl methacrylate) Nanometer-Thick Films for Nanostructure Fabrication.

Nanostructured organic templates originating from self-assembled block copolymers (BCPs) can be converted into inorganic nanostructures by sequential infiltration synthesis (SIS). This capability is particularly relevant within the framework of advanced lithographic applications because of the exploitation of the BCP-based nanostructures as hard masks. In this work, Al2O3 dot and antidot arrays were synthesized by sequential infiltration of trimethylaluminum and water precursors into perpendicularly oriented cylinder-forming poly(styrene-block-methyl methacrylate) (PS-b-PMMA) BCP thin films. The mechanism governing the effective incorporation of Al2O3 into the PMMA component of the BCP thin films was investigated evaluating the evolution of the lateral and vertical dimensions of Al2O3 dot and antidot arrays as a function of the SIS cycle number. The not-reactive PS component and the PS/PMMA interface in self-assembled PS-b-PMMA thin films result in additional paths for diffusion and supplementary surfaces for sorption of precursor molecules, respectively. Thus, the mass uptake of Al2O3 into the PMMA block of self-assembled PS-b-PMMA thin films is higher than that in pure PMMA thin films.

Sequential Infiltration Synthesis of Al2O3 in Biodegradable Polybutylene Succinate: Characterization of the Infiltration Mechanism.

The introduction of inorganic materials into biopolymers has been envisioned as a viable option to modify the optical and structural properties of these polymers and promote their exploitation in different application fields. In this work, the growth of Al2O3 in freestanding ∼30-µm-thick poly(butylene succinate) (PBS) films by sequential infiltration (SIS) at 70 °C via trimethylaluminum (TMA) and H2O precursors was investigated for the first time. The incorporation of Al2O3 into the PBS matrix was clearly demonstrated by XPS analysis and SEM-EDX cross-sectional images showing a homogeneous Al2O3 distribution inside the PBS films. Raman measurements on infiltrated freestanding PBS show a reduction of the signal related to the ester carbonyl group as compared to pristine freestanding PBS films. Accordingly, FTIR and NMR characterization highlighted that the ester group is involved in polymer-precursor interaction, leading to the formation of an aliphatic group and the concomitant rupture of the main polymeric chain. Al2O3 mass uptake as a function of the number of SIS cycles was studied by infiltration in thin PBS films spin-coated on Si substrates ranging from 30 to 70 nm. Mass uptake in the PBS films was found to be much higher than in standard poly(methyl methacrylate) (PMMA) films, under the same process conditions. Considering that the density of reactive sites in the two polymers is roughly the same, the observed difference in Al2O3 mass uptake is explained based on the different free volume of these polymers and the specific reaction mechanism proposed for PBS. These results assessed the possibility to use SIS as a tool for the growth of metal oxides into biopolymers, paving the way to the synthesis of organic-inorganic hybrid materials with tailored characteristics.

Phosphorus doping of ultra-small silicon nanocrystals.

P-doped Si nanocrystals (radius

Effect of Trapped Solvent on the Interface between PS-b-PMMA Thin Films and P(S-r-MMA) Brush Layers.

The orientation of block copolymer (BCP) features in thin films can be obtained by spin-coating a BCP solution on a substrate surface functionalized by a polymer brush layer of the appropriate random copolymer (RCP). Although this approach is well established, little work reporting the amount and distribution of residual solvent in the polymer film after the spin-coating process is available. Moreover, no information can be found on the effect of trapped solvent on the interface between the BCP film and RCP brush. In this work, systems consisting of poly(styrene)-b-poly(methyl methacrylate) thin films deposited on poly(styrene-r-methyl methacrylate) brush layers are investigated by combining neutron reflectivity (NR) experiments with simulation techniques. An increase in the amount of trapped solvent is observed by NR as the BCP film thickness increases accompanied by a significant decrease of the interpenetration length between the BCP and RCP, thus suggesting that the interpenetration between grafted chains and block copolymer chains is hampered by the solvent. Hybrid particle-field molecular dynamics simulations of the analyzed system confirm the experimental observations and demonstrate a clear correlation between the interpenetration length and the amount of trapped solvent.