Felipe Kessler

Radiation-Sensitive Novel Polymeric Resist Materials: Iterative Synthesis and Their EUV Fragmentation Studies

Polymerization of (4-(methacryloyloxy)phenyl)dimethylsulfoniumtriflate (MAPDST), as a key monomer containing the radiation sensitive sulfonium functionality, with various other monomers such as methyl methacrylate (MMA), 4-carboxy styrene (STYCOOH), N-vinyl carbazole (NVK) in different molar ratios via free-radical polymerization method is described. This methodology led to the development of a small chemical library of six different radiation sensitive polymers for lithography applications. Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy identified the reaction products as MAPDST homopolymer and MAPDST-MMA, MAPDST-STYCOOH, MAPDST-NVK copolymers. Molecular weights were obtained from gel permeation chromatography and the decomposition temperature (Td) values were determined using thermogravimetric analysis (TGA). The effect of extreme ultraviolet (EUV) irradiation on a thin poly(MAPDST) film was investigated using monochromatic synchrotron excitation. These new polymeric materials were also exposed to electron-beam lithography (EBL) and extreme ultraviolet lithography (EUVL) to achieve 20-nm line patterns.

Performance evaluation of nonchemically amplified negative tone photoresists for e-beam and EUV lithography

Abstract. Although extreme ultraviolet (EUV) lithography is being considered as one of the most promising next-generation lithography techniques for patterning sub-20 nm features, the development of suitable EUV resists remains one of the main challenges confronting the semiconductor industry. The goal is to achieve sub-20 nm line patterns having low line edge roughness (LER) of <1.8  nm and a sensitivity of 5 to 20  mJ/cm2. The present work demonstrates the lithographic performance of two nonchemically amplified (n-CARs) negative photoresists, MAPDST homopolymer and MAPDST-MMA copolymer, prepared from suitable monomers containing the radiation sensitive sulfonium functionality. Investigations into the effect of several process parameters are reported. These include spinning conditions to obtain film thicknesses <50  nm, baking regimes, exposure conditions, and the resulting surface topographies. The effect of these protocols on sensitivity, contrast, and resolution has been assessed for the optimization of 20 nm features and the corresponding LER/line width roughness. These n-CARs have also been found to possess high etch resistance. The etch durability of MAPDST homopolymer and MAPDST-MMA copolymer (under SF6 plasma chemistry) with respect to the silicon substrate are 7.2∶1 and 8.3∶1, respectively. This methodical investigation will provide guidance in designing new resist materials with improved efficiency for EUVL through polymer microstructure engineering.

Selective surface functionalization of polystyrene by inner-shell monochromatic irradiation and oxygen exposure

The surfaces of polystyrene (PS) thin films were selectively functionalized by a combination of monochromatic synchrotron radiation with oxygen exposure. By selecting specific K-shell excitation energies, it was shown that highly efficient surface functionalization can be obtained. After the treatments, several oxygen functionalities were detected by XPS and NEXAFS spectroscopy. The functionalization strongly depended on the excitation energy. C 1s → σ*C–C transitions produced an extremely efficient oxidation of the uppermost monolayer of the PS films. The COO and CO elemental contributions in the C 1s envelope at the PS surface was higher than 70%. On the contrary, other excitation energies did not introduce COO functionalities efficiently. The obtained results were explained by taking into account the known Auger stimulated desorption mechanism. The present research will open new ways to functionalize a polymer surface by a combination of monochromatic inner-shell excitation together with exposure to a reactive gas atmosphere.

Biodegradation improvement of poly(3-hydroxy-butyrate) films by entomopathogenic fungi and UV-assisted surface functionalization

Ultraviolet (UV)-assisted surface modification in the presence of oxygen was used as initial step to achieve controlled degradation of poly(3-hydroxy-butyrate), PHB, films by entomopathogenic fungi. Treated surfaces were investigated by surface analysis techniques (water contact angle, Fourier Transformed Infrared Spectroscopy in Attenuated Total Reflectance mode, X-ray Photoelectron Spectroscopy, Near-edge X-ray Absorption Fine Structure, Gel Permeation Chromatography, Optical Microscopy, Scanning Electron Microscopy, and weight loss). After the UV-assisted treatments, new carbonyl groups in new chemical environments were detected by XPS and NEXAFS spectroscopy. The oxidizing atmosphere did not allow the formation of CC bonds, indicating that Norrish Type II mechanism is suppressed during or by the treatments. The higher hydrophilicity and concentration of oxygenated functional groups at the surface of the treated films possibly improved the biodegradation of the films. It was observed a clear increase in the growth of this fungus when oxygenated groups were grafted on the polymers surfaces. This simple methodology can be used to improve and control the degradation rate of PHB films in applications that require a controllable degradation rate.

Wettability and cell spreading enhancement in poly(sulfone) and polyurethane surfaces by UV-assisted treatment for tissue engineering purposes

The surface of Poly(sulfone) (PSU) and Polyurethane (PU) films were treated with ultraviolet (UV) light in the presence of oxygen to improve their wettability, adhesion and cell spreading properties. XPS and WCA results illustrated the effective conversion of the PSU and PU surfaces from hydrophobic to hydrophilic with grafting of new oxidized functional groups during the photochemical treatments. Treated films showed a larger number of adhered cells compared to the untreated films and that number of adhered cells was comparable to the number of adhered cells in the control group. The results showed that the cell response does not only depend on the hydrophilicity but on the chemical surface alterations which occur as a result of UV-assisted treatment in the presence of oxygen. Better cell adhesion, spreading and growing on the PSU and PU substrates modified by the present UV methodology confirmed the biocompatibility of the treated surfaces.

Optimization of processing parameters and metrology for novel NCA negative resists for NGL

It is expected that EUV resists must simultaneously pattern 20-nm half-pitch and below, with an LWR of <1.8 nm, and a sensitivity of 5–20 mJ/cm2. In order to make a resist perform optimally, new resist chemistry is required. One such approach being investigated by us is the development of polymeric non-CAR negative photo resists for sub 16 nm technology which is directly sensitive to radiation without utilizing the concept of chemical amplification (CARs). These resist designs are accomplished by homopolymers which are prepared from monomers containing sulfonium groups. We have achieved 20 nm patterns by e-beam lithography using this system. Here we will discuss in detail process parameters such as: spinning conditions for film thicknesses <50 nm and resulting surface topographies, baking regimes, exposure conditions and protocols on sensitivity, contrast, resolution and LER/LWR. Etch resistance data on these thin films will also be provided. Our results are aimed to provide a clear understanding of how these critical steps in the lithographic imaging process will affect extendibility of the non-CAR resist concept to sub 20 nanoscale features. Photodynamics and EUV exposure data will be covered.

UV-Surface Treatment of Fungal Resistant Polyether Polyurethane Film-Induced Growth of Entomopathogenic Fungi

Synthetic polymers are the cause of some major environmental impacts due to their low degradation rates. Polyurethanes (PU) are widely used synthetic polymers, and their growing use in industry has produced an increase in plastic waste. A commercial polyether-based thermoplastic PU with hydrolytic stability and fungus resistance was only attacked by an entomopathogenic fungus, Metarhiziumanisopliae, when the films were pre-treated with Ultraviolet (UV) irradiation in the presence of reactive atmospheres. Water contact angle, Fourier transform infrared spectroscopy in attenuated total reflection mode (FTIR-ATR), scanning electron microscopy (SEM), and profilometer measurements were mainly used for analysis. Permanent hydrophilic PU films were produced by the UV-assisted treatments. Pristine polyether PU films incubated for 10, 30, and 60 days did not show any indication of fungal growth. On the contrary, when using oxygen in the UV pre-treatment a layer of fungi spores covered the sample, indicating a great adherence of the microorganisms to the polymer. However, if acrylic acid vapors were used during the UV pre-treatment, a visible attack by the entomopathogenic fungi was observed. SEM and FTIR-ATR data showed clear evidence of fungal development: growth and ramifications of hyphae on the polymer surface with the increase in UV pre-treatment time and fungus incubation time. The results indicated that the simple UV surface activation process has proven to be a promising alternative for polyether PU waste management.