High-Resolution Lithographic Patterning with Organotin Films: Role of CO2 in Differential Dissolution Rates.

Details of the chemistry enabling the patterning of organotin photoresists to single-digit-nm resolution continue to engage study. In this report, we examine the contributions of atmospheric gases to the differential dissolution rates of an n-butyltin oxide hydroxide photoresist. Cryo scanning tunneling electron microscopy (cryo-STEM) produces a micrograph of the latent image of an irradiated resist film, readily distinguishing exposed and unexposed regions. Temperature-programmed desorption mass spectrometry (TPD-MS) and cryo electron energy loss spectroscopy (cryo-EELS) show that irradiated films are depleted in carbon through desorption of butane and butene. Upon aging in air, irradiated films absorb H2O, as previously established. TPD-MS also reveals a previously unrecognized absorption of CO2, which correlates to a heightened dissolution contrast. This absorption may play an active role in determining intrinsic patterning performance and its variability based on changes in atmospheric-gas composition.

Hydrolysis and Condensation of n-BuSnCl3: Enabling Deposition of Smooth Metal Oxide Photoresist Thin Films.

Herein, we report hydrolysis and condensation chemistries of C4H9SnCl3 to molecular clusters and gel films. Precursor speciation plays a key role in film formation and quality toward realization of atomically smooth surfaces. Density functional theory investigations of C4H9SnCl3 and its reactions show that hydrolysis of the dimer (C4H9Sn)2(OH)2Cl4(H2O)2 has a high energetic penalty in the gas phase and when using a polarizable continuum solvation model based on density. These computations support our observed stability of the dimeric cluster in air, in various solvents, and through initial film deposition. It hydrolyzes and condenses to the [(C4H9Sn)12O14(OH)6]2+ dodecamer on-chip after a post film-deposition bake at 80 °C. Consequently, film surface smoothness is uniquely retained through on-wafer condensation.

Demonstration of Fowler-Nordheim Tunneling in Simple Solution-Processed Thin Films.

The production of high-quality thin-film insulators is essential to develop advanced technologies based on electron tunneling. Current insulator deposition methods, however, suffer from a variety of limitations, including constrained substrate sizes, limited materials options, and complexity of patterning. Here, we report the deposition of large-area Al2O3 films by a solution process and its integration in metal-insulator-metal devices that exhibit I- V signatures of Fowler-Nordheim electron tunneling. A unique, high-purity precursor based on an aqueous solution of the nanocluster flat-Al13 transforms to thin Al2O3 insulators free of the electron traps and emission states that commonly inhibit tunneling in other films. Tunneling is further confirmed by the temperature independence of device current.

Alkyltin Keggin Clusters Templated by Sodium.

Dodecameric (Sn12 ) and hexameric topologies dominate monoalkyltin-oxo cluster chemistry. Their condensation, triggered by radiation exposure, recently produced unprecedented patterning performance in EUV lithography. A new cluster topology was crystallized from industrial n-BuSnOOH, and additional characterization techniques indicate other clusters are present. Single-crystal X-ray analysis reveals a ß-Keggin cluster, which is known but less common than other Keggin isomers in polyoxometalate and polyoxocation chemistry. The structure is formulated [NaO4 (BuSn)12 (OH)3 (O)9 (OCH3 )12 (Sn(H2 O)2 )] (ß-NaSn13 ). SAXS, NMR, and ESI MS differentiate ß-NaSn13 , Sn12 , and other clusters present in crude "n-BuSnOOH" and highlight the role of Na as a template for alkyltin Keggin clusters. Unlike other alkyltin clusters that are cationic, ß-NaSn13 is neutral. Consequently, it stands as a unique model system, absent of counterions, to study the transformation of clusters to films and nanopatterns.