Alicyclic Polymers for 193 nm Resist Applications:  Synthesis and Characterization

Okoroanyanwu, Uzodinma; Shimokawa, Tsutomu; Byers, and Jeffrey; Willson, C. Grant

doi:10.1021/cm9705045

Cited by 65 publications

(48 citation statements)

References 59 publications

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“…The reduced residual catalyst aggregated and precipitated out. [14] Polynorbornene (PNB)-dialkyl esters, prepared in this manner, are readily soluble in common organic solvents such as THF, chloroform, and dichloromethane. In comparison, unsubstituted PNBs can be dissolved only in chlorobenzene or decaline (M < 8 Â 10 4 in chloroform).…”

Section: Resultsmentioning

confidence: 99%

“…The polymer was filtered and dried under vacuum at 60 8C. In order to remove catalysts, the polymer was dissolved in tetrahydrofuran (THF) and then the solution was stirred under a H 2 balloon for 4 h following the method described by Okoroanyanwu et al [14] The dark solution was left to yield aggregated catalyst residue, which was filtered through Celite. Drying under vacuum at 60 8C yielded the polymer product.…”

Section: Cis-norbornene-exo-23-dicarboxylic Acid Diethyl Estermentioning

confidence: 99%

See 1 more Smart Citation

Vinyl‐Type Polymerization of Norbornene Dicarboxylic Acid Dialkyl Esters

Shin

Jang

Yoon

et al. 2004

Macromol. Rapid Commun.

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Summary: Poly(cis‐norbornene‐exo‐2,3‐dicarboxylic acid dialkyl esters) (alkyl = Me, Et, Pr, Bu, Pen, and Hex) are synthesized as a vinyl‐type with a palladium(II) catalyst in high yield from easily prepared, pure exo‐monomers. The polymers show good solubility in common organic solvents and excellent thermal stability up to 330 °C. The polymers with alkyl groups larger than methyl exhibit a two‐step thermal degradation profile of an initial thermal degradation of side‐chains starting at 350 °C, followed by thermal degradation of the norbornene backbone starting at ca. 430 °C. The glass transition temperature decreases and the mechanical flexibility increases as the alkyl length of the side‐chain increases.Normalized loss shear modulus (G″) versus temperature for polynorbornene dicarboxylic acid dialkyl esters.imageNormalized loss shear modulus (G″) versus temperature for polynorbornene dicarboxylic acid dialkyl esters.

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Section: Resultsmentioning

confidence: 99%

Section: Cis-norbornene-exo-23-dicarboxylic Acid Diethyl Estermentioning

confidence: 99%

Vinyl‐Type Polymerization of Norbornene Dicarboxylic Acid Dialkyl Esters

Shin

Jang

Yoon

et al. 2004

Macromol. Rapid Commun.

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“…22 For photopatterning, the polymer must initially be insoluble in aqueous base. A formulation with higher NBHFA with respect to NBTBE will not be inhibited because the hexafluoroalcohol, NBHFA, has an acidic proton that can dissolve in aqueous base.…”

Section: Resultsmentioning

confidence: 99%

Chemically Amplified, Positive Tone, Polynorbornene Dielectric for Microelectronics Packaging

Mueller

Schwartz

Sutlief

et al. 2014

ECS J. Solid State Sci. Technol.

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A low permittivity, positive tone, polynorbornene dielectric has been developed that exhibits excellent lithographic and electrical properties. The polymer resin is a random copolymer of a norbornene hexafluoroalcohol (NBHFA) and a norbornene tert-butyl ester (NBTBE). High optical sensitivity and contrast were achieved using a chemically amplified solubility switching mechanism through the acid-catalyzed deprotection of the tert-butyl ester functionality. After developing in aqueous base, the film was thermally cured through a Fischer esterification reaction, resulting in a cross-linked permanent dielectric. The effect of the photoacid generator (PAG) concentration on the lithographic patterning and curing reactions was studied. Higher PAG loading was favorable for both sensitivity and dielectric constant. The sensitivity of a formulation was measured as low as 8.09 mJ/cm 2 . The molar ratio of the two monomers composing the polymer was varied. A higher NBHFA content was favorable because it resulted in a lower modulus, lower shrinkage, and lower dielectric constant and loss. A formulation with 70 mol% of the NBHFA had a modulus of 2.60 GPa, a 12.2% volume decrease during cure, and a dielectric constant of 2.23. The direction-dependent coefficient of thermal expansion was measured, and it was found that the anisotropy of the PNB films decreased with higher NBTBE content. Permanent dielectric materials are used in microelectronic devices and packages to separate and insulate components and interconnect. Low dielectric constant (low-k) insulators are desirable for on-chip, chip-to-chip, chip-to-package, and on-package wiring to avoid electrical delay and lower the energy consumed in the signal interconnect. [1][2][3] Polymers are widely used for these purposes because they offer a low-stress, easily processed alternative to inorganic dielectrics. [2][3][4][5] In addition, photosensitive dielectrics are desirable because they can be directly patterned by photolithographic means. Lithographically printed dielectrics do not require the use of photoresist or additional pattern transfer steps, which can be costly and expose the device to aggressive wet or dry etch process steps.Positive tone dielectrics are especially attractive because they result in sloped sidewalls that are generally favored for void-free electroplating of copper. Positive tone materials also exhibit better process yield because exposures through dark-field masks are less susceptible to particle defects. The ability to develop the latent image in an aqueous base developer mitigates the need for environmentally unfriendly organic solvent developers. High sensitivity is very important since it directly leads to higher throughput and tool utilization since less optical energy is required for the solubility switching reaction. The sensitivity of the photopatternable material is coupled to the quantum efficiency of the photoactive compound. Poor quantum efficiency often requires a high loading of the photoactive compounds to effect the inhibition or solu...

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“…Several polymers based on norbornene and norbornene derivatives were synthesized via these routes and were evaluated as potential resist materials. [34][35][36][37] The most promising of these polymers, shown in Fig. 7, was an alternating copolymer of tertbutyl norbornene-5-carboxylate (BNC) and maleic anhydride (MA) prepared by free radical polymerization.…”

Section: Photoresists For Arf Lithographymentioning

confidence: 99%