Dolores C. Miller

Direct observation of amorphous to crystalline phase transitions in nanoparticle arrays of phase change materials

We have used time-resolved x-ray diffraction to study the amorphous-crystalline phase transition in 20–80nm particles of the phase change materials Ge2Sb2Te5, nitrogen-doped Ge2Sb2Te5, Ge15Sb85, Sb2Te, and Sb2Te doped with Ag and In. We find that all samples undergo the phase transition with crystallization temperatures close to those of similarly prepared blanket films of the same materials with the exception of Sb2Te that shows the transition at a temperature that is about 40°C higher than that of blanket films. Some of the nanoparticles show a difference in crystallographic texture compared to thick films. Large area arrays of these nanoparticles were fabricated using electron-beam lithography, keeping the sample temperatures well below the crystallization temperatures so as to produce particles that were entirely in the amorphous phase. The observation that particles with diameters as small as 20nm can still undergo this phase transition indicates that phase change solid-state memory technology should...

Novel thin film composite membrane containing ionizable hydrophobes: pH-dependent reverse osmosis behavior and improved chlorine resistance

New polyamide thin film composite membranes were prepared by interfacial polymerization of hexafluoroalcohol (HFA)-containing aromatic diamine and trimesoyl chloride (TMC) on a porous polysulfone support. The surface properties of the resulting membranes were characterized by water contact angle, XPS, and SEM. Additionally, the desalination separation performance was evaluated by the cross-flow filtration of 2000 ppm NaCl solution. Water contact angle and XPS analyses indicated that the HFA-containing polyamide membrane is relatively hydrophobic at neutral conditions but becomes hydrophilic at basic conditions due to ionization of the HFA groups, so we refer to this group as an “ionizable hydrophobe” or “i-phobe”. The membrane showed strongly pH-dependent reverse osmosis behavior with enhanced performance (high water flux and high salt rejection) at high pH (ca. 10). Both the electron withdrawing nature and the steric bulkiness of the HFA functionality are also advantageous in protecting the polyamide membrane from chlorine attack. Based upon NMR studies of model polymers (linear polyamides with and without the HFA functionality) and the membrane performance measured before and after chlorine exposure, the HFA-containing polyamide has improved chlorine stability compared to the reference polyamide made from m-phenylenediamine and TMC.

Antiadhesion considerations for UV nanoimprint lithography

Low surface energy fluorosilane layers are widely used as release coatings for quartz templates in UV nanoimprint lithography, yet they are generally found to degrade with use. It is found that these layers are chemically attacked when used with UV cured methacrylate and vinyl ether resists, as found previously for acrylate resists, leading to the conclusion that low reactivity and not low surface energy is of importance for effective release layers. It is shown that an ion-beam deposited diamondlike carbon release coating is a useful alternative, having both stability in a reactive environment and lower adhesion despite its higher surface energy.

Polymer design for 157-nm chemically amplified resists

Based on UV measurements at 157nm of in-house fluoropolymers we have selected (alpha) -trifluoromethylacrylate and norbornene bearing a pendant hexafluoroisopropanol group as our building blocks for 157nm resist polymers. Polymers consisting of these repeat units have an optical density/micrometers of 3 or below at 157nm. We have found that the (alpha) -trifluoromethylacrylate derivatives conveniently undergo radical copolymerization with norornenes, which has provided a breakthrough in preparation of our 157nm resist polymers. This approach offers flexibility and versatility because an acidic moiety or acid-labile group can be placed in either acrylate or norbornene repeat unit. Other platforms of interest include all acrylic, all-norbornene, and acrylic-styrenic polymers.

Liquid immersion lithography: evaluation of resist issues

We address in this report a set of key questions tied to the implementation of liquid immersion lithography, from the perspective of the resist materials. We discuss the broad question of whether chemically amplified resists are capable of achieving the spatial resolution that ultimately will be required for the most advanced immersion scenario. Initial studies undertaken using model 193 nm resist materials provide some insight into how an aqueous liquid immersion process can affect the resist material.

Nuclear magnetic resonance quantum computing using liquid crystal solvents

Liquid crystals offer several advantages as solvents for molecules used for nuclear magnetic resonance quantum computing (NMRQC). The dipolar coupling between nuclear spins manifest in the NMR spectra of molecules oriented by a liquid crystal permits a significant increase in clock frequency, while short spin-lattice relaxation times permit fast recycling of algorithms, and save time in calibration and signal-enhancement experiments. Furthermore, the use of liquid crystal solvents offers scalability in the form of an expanded library of spin-bearing molecules suitable for NMRQC. These ideas are demonstrated with the successful execution of a two-qubit Grover search using a molecule (13C 1HCl3) oriented in a liquid crystal and a clock speed eight times greater than in an isotropic solvent. Perhaps more importantly, five times as many logic operations can be executed within the coherence time using the liquid crystal solvent.

Microstructure and properties of ultrathin amorphous silicon nitride protective coating

The effect of N content on the structure and properties of rf reactively sputtered amorphous silicon nitride (a-SiNx) has been studied by Rutherford backscattering spectrometry, x-ray reflectivity, ellipsometry, and nano-indentation. The N content in the film increased with the N2 concentration in the sputtering gas until the Si3N4 stoichiometry was reached. The hardness of a-SiNx increased with density, which in turn increased with the N content. The maximum hardness of 25 GPa and density of 3.2 g/cm3 were attained at the stoichiometric Si3N4 composition. With the application of a protective overcoat for magnetic disks in mind, thin a-SiNx films were deposited on CoPtCr media to examine their coverage, pinhole density, and wear resistance. According to x-ray photoelectron spectroscopy, the minimum thickness of a-SiNx required to protect the CoPtCr alloy from oxidation was 10 A, which was 10 A thinner than that of the reference amorphous nitrogenated carbon (a-CNx). A statistic model showed this lower thi...

Aliphatic platforms for the design of 157-nm chemically amplified resists

Our primary platform for 157 nm positive resists is built on a copolymer of t-butyl 2-trifluoromethylacrylate (TBTFMA) and norbornene bearing hexafluoroisopropanol (NBHFA) as an acid group, which is prepared by radical copolymerization. The radical copolymerization of 2-trifluoromethylacrylic monomers with norbornene derivatives has been found through reactivity ratio determination and in situ 1H NMR analysis of kinetics to deviate from the terminal model but to follow the penultimate model. These copolymers typically contain >50 mol% TBTFMA, are lipophilic, and fail to provide good imaging due to poor wettability. Blending a homopolymer of NBHFA (optical density (OD)=1.7/micrometers at 157 nm) into the copolymers (OD=2.5-2.7/micrometers ) increases the hydrophilicity and reduces OD to 2.2-2.0/micrometers , providing high resolution images. Another platform we have identified is a copolymer of TBTFMA with vinyl ethers, which can be prepared by using a common radical initiator. Some of the vinyl ether copolymers are also homogeneously miscible with the NBHFA homopolymer and thus their OD and aqueous base development can be improved by blending.

Investigation of the radical copolymerization and terpolymerization of maleic anhydride and norbornenes by an in situ 1H NMR analysis of kinetics and by the mercury method: Evidence for the lack of charge‐transfer‐complex propagation

The radical copolymerization of electron-deficient maleic anhydride (MA) and electron-rich norbornene (NB) derivatives with 2,2′-azobis(isobutyronitrile) (AIBN) in dioxane-d8 has been monitored in situ by 1H NMR spectroscopy with free induction decays recorded every 30 min at 60, 70, or 84 °C. The ratios of the monomer pairs were varied in some cases. The NB derivatives employed in this study included bicyclo[2.2.1]hept-2-ene (NB), t-butyl 5-norbornene-2-carboxylate, methyl 5-norbornene-2-methyl-2-carboxylate, and ethyl tetracyclo[4.4.0.12,5.17,10]dodec-3-ene-8-carboxylate. Decomposition of AIBN, consumption of the monomers, feed ratios, endo/exo ratios, copolymer compositions, and copolymer yields were studied as a function of polymerization time. Furthermore, a homopolymerizable third monomer (t-butyl methacrylate, methacrylic acid, t-butyl acrylate, or acrylic acid) was added to the NB/MA 1/1 system, revealing that the methacrylic monomer polymerizes rapidly in the early stage and that the ratio of MA to NB in the terpolymer strongly deviates from 1/1. In contrast, however, the acrylic monomers are more uniformly incorporated into the polymer. Nevertheless, these studies indicate that MA and NB do not always behave as a pair in radical polymerization and disproves the commonly believed charge-transfer mechanism. Electron-deficient fumaronitrile was also included in the kinetics study. To further understand the copolymerization mechanism, MA and NB were competitively reacted with a cyclohexyl radical generated by the treatment of cyclohexylmercuric chloride with sodium borohydride (mercury method). A gas chromatographic analysis of the reaction mixtures has revealed that a cyclohexyl radical reacts with MA almost exclusively in competition and that the cyclohexyl adduct of MA essentially accounts for all the products in a mass balance experiment, eliminating a possibility of the formation of an adduct involving the MA–NB charge-transfer complex. Thus, the participation of a charge-transfer complex in the copolymerization of MA and NB cannot be important.

Fluoro-alcohol materials with tailored interfacial properties for immersion lithography

Immersion lithography has placed a number of additional performance criteria on already stressed resist materials. Much work over the past few years has shown that controlling the water-resist interface is critical to enabling high scan rates (i.e. throughput) while minimizing film pulling and PAG extraction (i.e. defectivity). Protective topcoat polymers were developed to control the aforementioned interfacial properties and emerged as key enablers of 193 nm immersion lithography. Achieving the delicate balance between the low surface energies required for high water contact angles (generally achieved via the incorporation of fluorinated groups) and the base solubility required for topcoat removal is challenging. More recently, additional strategies using fluoropolymer materials to control the water-resist interface have been developed to afford topcoat-free resist systems. In our explorations of fluoroalcohol-based topcoat materials, we have discovered a number of structure-property relationships of which advantage can be taken to tailor the interfacial properties of these fluorinated materials. This paper will address the effect of structure on immersion specific properties such as water contact angle, aqueous base contact angle, and dissolution rate.