Patterning of organometallic radiation sensitive compositions is facilitated using a gaseous form of a contrast enhancing agent, which can include a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof, in which the mixture can be of the same class or different class of compounds. Contact with the contrast enhancing reactive compound is provided after irradiation of the organometallic composition to form a latent image. The contrast enhancing agent can be delivered before or after physical pattern development, and processing with the contrast enhancing agent can involve removal in a thermal process of some or substantially all of the non-irradiated organometallic composition. The contrast enhancing agent can be used in a dry thermal development step. If the contrast enhancing agent is used after a distinct development step, use of the contrast enhancing agent can involve improvement of the pattern quality. Apparatuses for performing processing with contrast enhancing agents are described.

Patterning of organometallic radiation sensitive compositions is facilitated using a gaseous form of a contrast enhancing agent, which can include a carboxylic acid, an amide, a sulfonic acid, an alcohol, a diol, a silyl halide, a germanium halide, a tin halide, an amine, a thiol, or a mixture thereof, in which the mixture can be of the same class or different class of compounds. Contact with the contrast enhancing reactive compound is provided after irradiation of the organometallic composition to form a latent image. The contrast enhancing agent can be delivered before or after physical pattern development, and processing with the contrast enhancing agent can involve removal in a thermal process of some or substantially all of the non-irradiated organometallic composition. The contrast enhancing agent can be used in a dry thermal development step. If the contrast enhancing agent is used after a distinct development step, use of the contrast enhancing agent can involve improvement of the pattern quality. Apparatuses for performing processing with contrast enhancing agents are described.

A patterning method includes forming a multilayer photoresist stack on a substrate. The multilayer photoresist stack includes a first layer of a wet photoresist, deposited by spin-on deposition, over a second layer of a dry photoresist, deposited by vapor deposition. The multilayer photoresist stack is exposed to a first pattern of actinic radiation including relative, spatially-varying doses of actinic radiation and including high-dose regions, mid-dose regions and low-dose regions. The multilayer photoresist stack and the first pattern of actinic radiation are configured such that after the exposing the multilayer photoresist stack to the first pattern of actinic radiation, in the high-dose regions, developability of both the first layer and the second layer is changed; in the mid-dose regions, developability of the first layer is changed while developability of the second layer is unchanged; in the low-dose regions, developability of both the first layer and the second layer is unchanged.

Various embodiments described herein relate to methods, apparatus, and systems for treating metal-containing photoresist to modify material properties of the photoresist. For instance, the techniques herein may involve providing a substrate in a process chamber, where the substrate includes a photoresist layer over a substrate layer, and where the photoresist includes metal, and treating the photoresist to modify material properties of the photoresist such that etch selectivity in a subsequent post-exposure dry development process is increased. In various embodiments, the treatment may involve exposing the substrate to elevated temperatures and/or to a remote plasma. One or more process conditions such as temperature, pressure, ambient gas chemistry, gas flow/ratio, and moisture may be controlled during treatment to tune the material properties as desired.

A metal-containing photoresist film may be deposited on a semiconductor substrate using a dry deposition technique. Unintended metal-containing photoresist material may form on internal surfaces of a process chamber during deposition, bevel and backside cleaning, baking, development, or etch operations. An in situ dry chamber clean may be performed to remove the unintended metal-containing photoresist material by exposure to an etch gas. The dry chamber clean may be performed at elevated temperatures without striking a plasma. In some embodiments, the dry chamber clean may include pumping/purging and conditioning operations.

A composition for flattening uneven substrates. The composition for flattening uneven substrates, which is applied on an organic pattern, includes a solvent and a polysiloxane including a hydrolysis condensate of a hydrolyzable silane, wherein the polysiloxane includes silanol groups in a proportion of 20 mol % or less with respect to Si atoms, and the weight-average molecular weight of the polysiloxane is 1,000-50,000.

A composition for flattening uneven substrates. The composition for flattening uneven substrates, which is applied on an organic pattern, includes a solvent and a polysiloxane including a hydrolysis condensate of a hydrolyzable silane, wherein the polysiloxane includes silanol groups in a proportion of 20 mol % or less with respect to Si atoms, and the weight-average molecular weight of the polysiloxane is 1,000-50,000.

A method of microfabrication includes depositing a photoresist film on a working surface of a semiconductor wafer, the photoresist film being sensitive to extreme ultraviolet radiation; exposing the photoresist film to a pattern of extreme ultraviolet radiation; performing a hybrid develop of the photoresist film. The hybrid develop includes executing a first development process to remove a first portion of the photoresist film; stopping the development of the photoresist film after the first development process, the photo resist film including a structure having a first critical dimension larger than a target critical dimension after the stopping; and after stopping the development, executing a second development process to remove a second portion of the photoresist film and shrinking the critical dimension of the structure from the first critical dimension to a second critical dimension that is less than the first critical dimension.

A method of microfabrication includes depositing a photoresist film on a working surface of a semiconductor wafer, the photoresist film being sensitive to extreme ultraviolet radiation; exposing the photoresist film to a pattern of extreme ultraviolet radiation; performing a hybrid develop of the photoresist film. The hybrid develop includes executing a first development process to remove a first portion of the photoresist film; stopping the development of the photoresist film after the first development process, the photo resist film including a structure having a first critical dimension larger than a target critical dimension after the stopping; and after stopping the development, executing a second development process to remove a second portion of the photoresist film and shrinking the critical dimension of the structure from the first critical dimension to a second critical dimension that is less than the first critical dimension.

A method for forming a nanopore device includes providing a sapphire substrate and forming oxide layers on the front and back sides of the sapphire substrate. The oxide layer on the back is patterned to form an etch mask. The method also includes performing a crystalline orientation dependent wet anisotropic etch on the backside of the sapphire substrate using the etch mask to form a cavity having sloped sides to expose a portion of the first oxide layer. A silicon nitride membrane layer is formed on the oxide layer on the front side of the sapphire substrate. Next, the exposed portion of the oxide layer in the cavity is removed to cause the exposed portion of the silicon nitride membrane layer to be suspended over the cavity in the sapphire substrate. Subsequently, an opening is formed in the suspended portion of the silicon nitride membrane layer to form the nanopore.