Inpria Corporation

Stephen T Meyers

Kai Jiang

Jeremy T Anderson

Brian J Cardineau

Douglas A Keszler

Alan J Telecky

Joseph Burton Edson

Andrew Grenville

Benjamin L Clark

Michael K Kocsis

William Earley

Lauren B McQuade

Dominick Smiddy

Margaret Wilson-Moses

Mollie Waller

Jason K Stowers

Peter De Schepper

Michael Greer

Amrit K Narasimhan

Sonia Castellanos Ortega

Kirsten Louthan

Organometallic radiation resist compositions are described based on tin ions with alkyl ligands. Some of the compositions have branched alkyl ligands to provide for improved patterning contrast while maintaining a high degree of solution stability. Blends of compounds with distinct alkyl ligands can provide further improvement in the patterning. High resolution patterning with a half-pitch of no more than 25 nm can be achieved with a line width roughness of no more than about 4.5 nm. Synthesis techniques have been developed that allow for the formation of alkyl tin oxide hydroxide compositions with very low metal contamination.

Organometallic solution based high resolution patterning compositions and corresponding methods

Organometallic precursors are described for the formation of high resolution lithography patterning coatings based on metal oxide hydroxide chemistry. The precursor compositions generally comprise ligands readily hydrolysable by water vapor or other OH source composition under modest conditions. The organometallic precursors generally comprise a radiation sensitive organo ligand to tin that can result in a coating that can be effective for high resolution patterning at relatively low radiation doses and is particularly useful for EUV patterning. The precursors compositions are readily processable under commercially suitable conditions. Solution phase processing with in situ hydrolysis or vapor based deposition can be used to form the coatings.

Organotin oxide hydroxide patterning compositions, precursors, and patterning

Developer compositions are described based on blends of solvents, in which the developers are particularly effective for EUV patterning using organometallic based patterning compositions. Methods for use of these developing compositions are described. The blends of solvents can be selected based on Hansen solubility parameters. Generally, one solvent has low polarity as express by the sum of δP+δH, and a second solvent component of the developer has a higher value of δP+δH. Corresponding solvent compositions are described.

Organometallic photoresist developer compositions and processing methods

Organometallic solutions have been found to provide high resolution radiation based patterning using thin coatings. The patterning can involve irradiation of the coated surface with a selected pattern and developing the pattern with a developing agent to form the developed image. The patternable coatings may be susceptible to positive-tone patterning or negative-tone patterning based on the use of an organic developing agent or an aqueous acid or base developing agent. The radiation sensitive coatings can comprise a metal oxo/hydroxo network with organic ligands. A precursor solution can comprise an organic liquid and metal polynuclear oxo-hydroxo cations with organic ligands having metal carbon bonds and/or metal carboxylate bonds.

Organometallic solution based high resolution patterning compositions

Organotin clusters are described with the formula RSn(OCR')(OH)(μ-O) with 0≤x<2; R=branched or cycloalkyl with 1 to 31 carbon atoms; R′═H or alkyl with 1 to 20 carbon atoms. Three carboxylato ligands are bridging, and two OH ligands are bridging. The remaining two carboxylato ligands are in non-bridging configurations, and the non-bridging carboxylato ligands are exchangeable in solution. Solutions of these clusters are suitable for forming radiation sensitive coatings that can be used to pattern nanometer scale structures. The radiation sensitive coatings are particularly suitable for EUV patterning.

Organotin clusters, solutions of organotin clusters, and application to high resolution patterning

Precursor solutions for radiation patternable coatings are formed with an organic solvent and monoalkyl tin trialkoxides in which the water content of the solvent is adjusted to be within 10 percent of a selected value. Generally, the water content of the solvent is adjusted through water addition, although water removal can also be used. In some embodiments, the adjusted water content of the solvent can be from about 250 ppm by weight to about 10,000 ppm by weight. With the appropriate selection of ligands, the adjusted precursor solutions can be stable for at least about 42 days, and in some cases at least 8 months.

Stable solutions of monoalkyl tin alkoxides and their hydrolysis and condensation products

Patterning compositions are described based on organo tin dodecamers with hydrocarbyl ligands, oxo ligands, hydroxo ligands and carboxylato ligands. Alternative dodecamer embodiments have organo tin ligands in place of hydrocarbyl ligands. The organo tin ligands can be incorporated into the dodecamers from a monomer with the structure (RCC)SnQ, where R is a hydrocarbyl group and Q is a alkyl tin moiety with a carbon bonded to the Sn atom of the monomer and with a Sn bonded as a replacement of a quaternary carbon atom with bonds to 4 carbon atoms. Some or all of the carboxylato and hydroxyl ligands can be replaced with fluoride ions. Good EUV patterning results are obtained with the dodecamer based patterning compositions.

Tin dodecamers and radiation patternable coatings with strong EUV absorption

The processing of radiation patternable organometallic coatings is shown to be improved through the appropriate selection of post processing conditions between coating and development of the pattern. In particular, a coated wafer can be subjected to process delays to allow aging of the coating at various process points, in particular following irradiation. Process delays can be combined and interspersed with heating steps. The atmosphere above the coated wafer at various process steps can be adjusted to obtain desired improvements in the development of the pattern. Reactive gases can be beneficial with respect to improvement of coating properties.

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Corvallis, OR, United States of America

Stephen T Meyers