A semi-quantitative tribo-electric series for polymeric materials: the influence of chemical structure and properties

A positive resist composition comprising: at least one compound selected from a compound capable of generating an acid represented by the formula (I) as defined herein upon irradiation with actinic rays or radiation and a compound capable of generating an acid represented by the following formula (II) upon irradiation with actinic rays or radiation; and a compound capable of generating an acid represented by the formula (III) as defined herein upon irradiation with actinic rays or radiation.

Positive resist composition and pattern-forming method using the same

A long debate on the charge identity and the associated mechanisms occurring in contact-electrification (CE) (or triboelectrification) has persisted for many decades, while a conclusive model has not yet been reached for explaining this phenomenon known for more than 2600 years! Here, a new method is reported to quantitatively investigate real-time charge transfer in CE via triboelectric nanogenerator as a function of temperature, which reveals that electron transfer is the dominant process for CE between two inorganic solids. A study on the surface charge density evolution with time at various high temperatures is consistent with the electron thermionic emission theory for triboelectric pairs composed of Ti-SiO2 and Ti-Al2 O3 . Moreover, it is found that a potential barrier exists at the surface that prevents the charges generated by CE from flowing back to the solid where they are escaping from the surface after the contacting. This pinpoints the main reason why the charges generated in CE are readily retained by the material as electrostatic charges for hours at room temperature. Furthermore, an electron-cloud-potential-well model is proposed based on the electron-emission-dominatedcharge-transfer mechanism, which can be generally applied to explain all types of CE in conventional materials.

On the Electron-Transfer Mechanism in the Contact-Electrification Effect.

A polymer obtained through copolymerization of a monomer having a hexafluoroalcohol pendant whose hydroxyl moiety has been protected and a monomer having an acid labile group is useful as an additive to a photoresist composition for immersion lithography. When processed by immersion lithography, the resist composition exhibits good water repellency and water slip and produces few development defects.

Polymer, resist composition and patterning process

The identity of charges generated by contact electrification on dielectrics has remained unknown for centuries and the precise determination of the charge density is also a long-standing challenge. Here, electrostatic charges on Teflon (polytetrafluoroethylene) produced by rubbing with Lucite (polymethylmethacrylate) were directly identified as electrons rather than ions by electrochemical (redox) experiments with charged Teflon used as a single electrode in solution causing various chemical reactions: pH increases; hydrogen formation; metal deposition; Fe(CN)(6)(3-) reduction; and chemiluminescence in the system of Teflon(-)/Ru(bpy)(3)(2+)/S(2)O(8)(2-) (analogous to electrogenerated chemiluminescence). Moreover, copper deposition could be amplified by depositing Pd first in a predetermined pattern, followed by electroless deposition to produce Cu lines. This process could be potentially important for microelectronic and other applications because Teflon has desirable properties including a low dielectric constant and good thermal stability. Charge density was determined using Faraday's law and the significance of electron transfer processes on charged polymers and potentially other insulators have been demonstrated.

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Electrostatic electrochemistry at insulators.

Fluorocarbinol- and/or fluoroacid-functionalized silsesquioxane polymers and copolymers are provided. The polymers are substantially transparent to ultraviolet radiation (UV), i.e., radiation of a wavelength less than 365 nm and are also substantially transparent to deep ultraviolet radiation (DUV), i.e., radiation of a wavelength less than 250 nm, including 157 nm, 193 nm and 248 nm radiation, and are thus useful in single and bilayer, positive and negative, lithographic photoresist compositions, providing improved sensitivity and resolution. A process for using the composition to generate resist images on a substrate is also provided, i.e., in the manufacture of integrated circuits or the like.

Substantially transparent aqueous base soluble polymer system for use in 157 nm resist applications

Importance of dissociated ions in contact charging

Bilayer thin film imaging is one approach to extend 248 nm optical lithography to 150 nm regime and beyond. In this paper, we report our progress in the development of a positive-tone bilayer resist system consisting of a thin silicon containing imaging layer over a recently developed crosslinked polymeric underlayer. The chemically amplified imaging layer resist is based on a novel dual-functional silicon containing monomer, tris(trimethylsilyl)silylethyl methacrylate, which in addition to providing etch resistance, also functions as the acid sensitive functionality. The stabilization of (beta) -silyl carboncation by silicon allows this moiety to serve as an acid sensitive protecting group. Thus high silicon content and high resist contrast are achieved simultaneously. Lithographic evaluation of the bilayer resist with a 0.63 NA and a 0.68 NA 248 nm exposure tool has demonstrated resolution down to 125 nm equal line/space features with a dose latitude of 16 percent and depth of focus (DOF) of 0.6 um. The dose latitude and DOF for 150 nm equal line/space features are 22 percent and 1.2 um, respectively. Finally, residue-free, ultra-high aspect ratio resist features have been obtained by O 2 or O 2 /SO 2 reactive ion etching using a high-density plasma etch system. The resist design, deprotection chemistry, lithographic and etch characteristics of the top layer, as well as the design of the new underlay, will be discussed.

High-resolution 248-nm bilayer resist

This new photoresist system extends the capability of the ESCAP platform previously discussed. (1) This resist material features a modified ESCAP type 4-hydroxystyrene-t-butyl acrylate polymer system which is capable of annealing due to the increased stability of the t-butyl ester blocking group. The resist based on this polymer system exhibits excellent delay stability and enhanced etch resistance versus previous DUV resists, APEX and UV2HS. Improved stabilization of chemically amplified photoresist images can be achieved through reduction of film volume by film densification. When the host polymer provides good thermal stability the soft bake conditions can be above or near the Tg (glass transition) temperature of the polymer. The concept of annealing (film densification) can significantly improve the environmental stability of the photoresist system. Improvements in the photoacid generator, processing conditions and overall formulation coupled with high NA (numerical aperture) exposure systems, affords linear lithography down to 0.15 micrometer for isolated lines with excellent post exposure delay stability. In this paper, we discuss the UV4 and UV5 photoresist systems based on the ESCAP materials platform. The resist based on this polymer system exhibits excellent delay stability and enhanced etch resistance versus APEX-E and UV2HS. Due to lower acrylate content, the R max for this system can be tuned for feature-type optimization. We demonstrate sub-0.25 micrometer process window for isolated lines using these resists on a conventional exposure tool with chrome on glass masks. We also discuss current use for various device levels including gate structures for advanced microprocessor designs. Additional data will be provided on advanced DRAM applications for 0.25 micrometer and sub-0.25 micrometer programs.

New ESCAP-type resist with enhanced etch resistance and its application to future DRAM and logic devices

193nm lithography will be the future technology for sub- 150nm resolution. As the dimensions get smaller, resist thickness is also needed to be reduced for better resolution and wider process window. Single layer 193nm resist, with thickness of less than 500nm, may not be able to satisfy some of the substrate etch requirement. With bilayer resist scheme, the thin resist offers the advantages of high resolution and good process window. The thick underlayer provides the etch resistance required for substrate etching. IBM has developed a silane substituted alternating copolymer based 193nm bilayer resist system and demonstrates sub-120nm resolution using Nikon 0.6NA stepper with Chrome on Glass (COG) mask. Lithographic performance and formulation optimizations of this 193nm bilayer resist as well as underlayer evaluation and some etch study will be discussed.

Debra Fenzel-Alexander

Papers

Substantially transparent aqueous base soluble polymer system for use in 157 nm resist applications

Importance of dissociated ions in contact charging

High-resolution 248-nm bilayer resist

New ESCAP-type resist with enhanced etch resistance and its application to future DRAM and logic devices

IBM 193-nm bilayer resist: materials, lithographic performance, and optimization