Inpria Corporation

Gas releasing compositions that can facilitate improved patterning of organometallic resists are described. The gas releasing compositions can release water, carbon dioxide, or alcohols in response to radiation or heating. A film-forming composition is composed of a flowable blend of a reactive gas releasing moiety, a matrix forming species, an organic solvent, and an optional activating agent. An underlayer composition is composed of a blend of a reactive gas releasing moiety, a polymer matrix and an optional activating additive. Multilayer structures are described based on organometallic radiation sensitive patterning compositions, such as alkyl tin oxo-hydroxo compositions, which are placed over a gas releasing underlayer formed on a substrate, such as a semiconductor wafer. Methods for patterning multilayer structures are also described.

The purification of monoalkyl tin trialkoxides and monoalkyl tin triamides are described using fractional distillation and/or ultrafiltration. The purified compositions are useful as radiation sensitive patterning compositions or precursors thereof. The fractional distillation process has been found to be effective for the removal of metal impurities down to very low levels. The ultrafiltration processes have been found to be effective at removal of fine particulates. Commercially practical processing techniques are described.

In the context of forming radiation patternable structures especially for EUV patterning, wafer structures are described comprising a substrate having a smooth top surface and a radiation sensitive organometallic coating having an average thickness of no more than 100 nm and no more than about 1 defect per square centimeter with a defect size of greater than 48 nm, evaluated with a 3 mm edge exclusion. Corresponding methods for forming a low defect coating comprise spin coating a purified radiation sensitive organometallic resist solution onto a wafer using a spin coater system comprising a delivery line and a delivery nozzle connected to the delivery line to form a coated wafer, and drying the coated wafer to form a radiation sensitive organometallic coating having no more than about 1 defect per square centimeter with a defect size of greater than 48 nm, evaluated with a 3 mm edge exclusion. Methods are provided for improved filtering for particle removal from radiation patternable organometallic resist compositions.

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) 3 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.

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.

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.

As described herein, photosensitive composition comprises RSnL 3 , where R is a hydrocarbyl ligand with 1-20 carbon atoms and one or more silicon and/or germanium heteroatoms and L is an acetylide ligand (—C≡CA, where A is a silyl group with 0 to 6 carbon atoms or an organo group with 1 to 10 carbon atoms). Methods are described wherein photosensitive compositions are synthesized by reacting RX, where X is a halide, and MSnL 3 , where M is an alkali metal, alkali earth metal or a pseudo-alkali earth metal, L is an acetylide or a dialkylamide. The radiation sensitive compositions are effective for radiation based patterning, such as with EUV light.

The purification of monoalkyl tin trialkoxides and monoalkyl tin triamides are described using fractional distillation and/or ultrafiltration. The purified compositions are useful as radiation sensitive patterning compositions or precursors thereof. The fractional distillation process has been found to be effective for the removal of metal impurities down to very low levels. The ultrafiltration processes have been found to be effective at removal of fine particulates. Commercially practical processing techniques are described.

Stabilized precursor solutions can be used to form radiation inorganic coating materials. The precursor solutions generally comprise metal suboxide cations, peroxide-based ligands and polyatomic anions. Design of the precursor solutions can be performed to achieve a high level of stability of the precursor solutions. The resulting coating materials can be designed for patterning with a selected radiation, such as ultraviolet light, x-ray radiation or electron beam radiation. The radiation patterned coating material can have a high contrast with respect to material properties, such that development of a latent image can be successful to form lines with very low line-width roughness and adjacent structures with a very small pitch.

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.