In the realization of further miniaturization at scales of 10nm and below in semiconductor devices, it is essential to get the new resist design such as hybrid inorganic-organic resist materials for ionizing radiation to clarify the effect of metal resist structure on resist performances. In this study, some hybrid inorganic-organic resist materials known as metal-oxo clusters were synthesized and their lithographic characteristics were investigated to clarify the difference in sensitivity and resolution among Ti-based, Zr-based and Hf-based oxo clusters by using EUV and EB exposure. Our results indicated that the sensitivity in Hf-based oxo clusters was higher than those of Ti-based and Zr-based oxo clusters in both EB and EUV exposure. Also, we clarified that it is very important for the new resist design such as hybrid inorganic-organic resist to increase photo-absorption cross section and density of elements. In particular, the size and homogeneity of particle and film quality is very important for resist performance of hybrid inorganic-organic resist materials. In addition, it is clarified that etch durability increased by annealing metal oxo clusters.
For the advancement of lithography, the resist materials and processes are the most critical issue in the microfabrication of semiconductors. Especially in the sub-20nm half pitch resolution region, the development process of resist materials is of particular importance from the viewpoint of reducing the line width roughness (LWR) and stochastic defects. In this study, a quartz crystal microbalance (QCM) method was used to investigate the dissolution dynamics of poly(4-hydroxystyrene-co-methacrylic acid) (PHSMA) films in tetraalkylammonium hydroxide aqueous solutions. The PHSMA film showed a characteristic dissolution kinetics in tetraalkylammonium hydroxide aqueous solutions, which was not observed for poly(4-hydroxystyrene) film.
To investigate the development kinetics, this study categorized the dissolution dynamics in tetraalkylammonium hydroxide (TAAH) aqueous solutions into six classes based on frequency and impedance variations during the development process using quartz crystal microbalance (QCM) measurements. These classifications were examined against various material attributes via decision trees and support vector machine (SVM) models. The feature values included in this analysis comprised the length of alkyl chains, molecular weight, solute concentration, viscosity of developers, protection ratios, molar masses, contact angles, and surface free energy of polymer. Accuracy for the test dataset was approximately 0.80 and 0.75 for the decision trees and SVM, respectively, when validated.
For the advancement of lithography, the resist materials and processes are the most critical issue in the microfabrication of semiconductors. Especially in the sub-20 nm half pitch resolution region, the development process of resist materials is of particular importance from the viewpoint of reducing the line width roughness (LWR) and stochastic defects. In this study, a quartz crystal microbalance (QCM) method was used to investigate the dissolution dynamics of poly(4-hydroxystyrene) (PHS) films containing triphenylphosnium-nonaflate (TPS-nf) in tetraalkylammonium hydroxide aqueous solutions. The comparison of dissolution dynamics in five different developer solutions with different alkyl chain lengths was done.
Recently chemically amplified resists are approaching their performance limits due to the fixed development process. In this study, the dissolution, swelling, and impedance change of resist polymers were measured by a development analyzer with a quartz crystal microbalance method. The resist polymer was poly(4-hydroxystyrene) (PHS), the hydroxyl groups of which were partially protected with t-butoxycarbonyl groups. The alkyl chain lengths of tetraalkylammonium hydroxide were varying from methyl to pentyl groups. When the alkyl chain length of TAAH increased from two to three, the dissolution mode markedly changed.
The dissolution (including the formation of transient swelling layer) of a resist polymer is key to the realization of ultrafine patterning. However, the details of the dissolution of resist polymers remain unclarified. In this study, the swelling and dissolution kinetics of poly(4-hydroxystyrene) (PHS) film in pure water and alkaline aqueous solution were investigated. PHS is a typical backbone polymer (a dissolution agent) of chemically amplified resists. By changing the length of alkyl chains of amines, the swelling and dissolution kinetics of PHS were observed. Their dependences on the film thickness of PHS and the concentration of amines were discussed.
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