Near edge x-ray absorption fine structure measurements of surface segregation in 157 nm photoresist blends

Jablonski, Erin L.; Prabhu, Vivek M.; Sambasivan, Sharadha; Lin, Eric K.; Fischer, Daniel A.; Goldfarb, Darı́o L.; Angelopoulos, Marie; Itô, Hiroshi

doi:10.1116/1.1624256

Cited by 11 publications

(13 citation statements)

References 5 publications

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“…This length scale corresponds to 1 to 2 molecular layers of the polyfluorene backbone; [25,26] surface counterion accumulation within this region would therefore still permit ion pairing. We note that strong surface segregation typically occurs in blends of nonionic polymers and aromatic small molecules, especially in photoresist/photoacid generator (PAG) blends; [27] the PAG triphenylsulfonium perfluoro-1-butanesufonate chemically resembles our PF-X counterions. Similar forces -hydrophobicity and surface tension -operating at both interfaces and balanced by electrostatic pairing are likely responsible for the result observed here.…”

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confidence: 99%

Structural Characterization of Conjugated Polyelectrolyte Electron Transport Layers by NEXAFS Spectroscopy

et al. 2008

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confidence: 99%

Structural Characterization of Conjugated Polyelectrolyte Electron Transport Layers by NEXAFS Spectroscopy

et al. 2008

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“…This is in contrast to the known examples of PAG surface segregation and inhomogeneous distribution that have been previously reported in the literature for blended-PAG materials. 9,19 Since the PAG is bound and dispersed into the polymer chain, its ability to undergo any significant micro-phase separation or segregation is virtually eliminated. The distribution of PAG in the polymer-bound PAG and blended PAG resist films used in this work were probed to confirm this advantage.…”

Section: Resultsmentioning

confidence: 99%

“…Such blended-PAG CAR materials are known to have a number of potential problems, including low PAG solubility and thus low maximum PAG loadings, PAG aggregation and segregation that lead to non-uniform resist film composition, and photoacid diffusion that can lead to blurring of images and loss of critical dimension control. [9][10][11][12] These problems ultimately create a tradeoff between achieving the desired characteristics of high resolution, high sensitivity, and low line edge roughness through formulation changes to blended-PAG CAR systems (see Figure 1) and expose the main challenge for resist materials design for the next generation lithography. [13][14][15] Methods for designing resist materials that can achieve all three characteristics (i.e.…”

Section: Introductionmentioning

confidence: 99%

Photosensitivity and line-edge roughness of novel polymer-bound PAG photoresists

et al. 2007

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Substantially improved photoresist material designs, which can provide higher photosensitivity and precise critical dimension and edge roughness control, will be required to enable the application of next generation lithography technology to the production of future sub-65 nm node IC device generations. The development and characterization of novel material platforms that solve the aforementioned basic problems with chemically amplified resists (CARs) is essential and is already one of the major subjects of modern lithography research. In that regard, we have pursued development of a variety of 193 nm and EUV CARs that contain photoacid generator (PAG) units covalently bonded directly to the resin polymer backbone. However, the detailed structure-property relationships that result from this direct attachment of the PAG functional group to the polymer have previously not yet been rigorously characterized. In this work, the lithographic properties of a polymer-bound PAG CAR (GBLMA-co-EAMA-co-F4-MBS.TPS) and its blended-PAG analog resist (GBLMA-co-EAMA blend F4-IBBS.TPS) were studied and compared. The direct incorporation of PAG functionality into the resist polymer, where the resulting photoacid remains bound to the polymer, showed improved photosensitivity, resolution, and lower LER as compared with the analogous blended-PAG resist. The improved resolution and LER were expected due to the restricted photoacid diffusion and uniform PAG distribution provided by direct incorporation of the PAG into the polymer backbone to make a single-component resist material. The ability to load higher levels of PAG into the resist provided by this PAG incorporation into the polymer, as compared to the low PAG concentrations attainable by traditional blending approaches, overcomes the sensitivity loss that should result from reduction in photoacid diffusivity and concomitant smaller acid-catalytic chain lengths. In fact, the polymer-bound PAG resist achieves a faster photospeed than the blended-PAG analog material under DUV radiation in the case of the materials reported here while still providing all of the aforementioned improvements such as the improved line edge roughness.

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“…These results are presumably due to the segregation of the copolymer Resin 1 to the air interface. Among Resins (3)(4)(5), Resin 5 that contains the most hydrophobic Monomer C, has been shown to have a higher water contact angles (static and receding angle) than Resin 3 and 4. It is expected that hydrophobicity of polymers correlates with the contact angles.…”

Section: Water Contact Angle Measurement Of Blend Filmsmentioning

confidence: 98%

“…Work by the Jablonski group demonstrated that polymer blend constituents having different hydrophobicity or surface tension, the more hydrophobic or lower surface tension species would typically wet the blend film surface when heated in air. 4 Work by the Irie group at TOK demonstrated that fluorine localized at the film surface for the blended polymer, in contrast to the uniform distribution for the fluorine-incorporated polymer. 5 The addition of the fluorine material is advantageous for altering the surface of the resist films.…”

Section: Introductionmentioning

confidence: 94%

Tailoring surface properties of ArF resists thin films with functionally graded materials (FGM)

Takemoto

Ando²,

Edamatsu³

et al. 2007

SPIE Proceedings

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Our recent research effort has been focused on new top coating-free 193nm immersion resists with regard to leaching of the resist components and lithographic performance. We have examined methacrylate-based resins that control the surface properties of ArF resists thin films by surface segregation behavior. For a better understanding of the surface properties of thin films, we prepared the six resins (Resin 1-6) that have three types fluorine containing monomers, a new monomer (Monomer A), Monomer B and Monomer C, respectively. We blended the base polymer (Resin 0) with Resin (1-6), respectively. We evaluated contact angles, surface properties and lithographic performances of the polymer blend resists. The static and receding contact angles of the resist that contains Resin (1-6) are greater than that of the base polymer (Resin 0) resist. The chemical composition of the surface of blend polymers was investigated with X-ray photoelectron spectroscopy (XPS). It was shown that there was significant segregation of the fluorine containing resins to the surface of the blend films. We analyzed Quantitative Structure-Property Relationships (QSPR) between the surface properties and the chemical composition of the surface of polymer blend resists. The addition of 10 wt% of the polymer (Resin 1-6) to the base polymer (Resin 0) did not influence the lithographic performance. Consequently, the surface properties of resist thin films can be tailored by the appropriate choice of fluorine containing polymer blends.

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Near edge x-ray absorption fine structure measurements of surface segregation in 157 nm photoresist blends

Cited by 11 publications

References 5 publications

Structural Characterization of Conjugated Polyelectrolyte Electron Transport Layers by NEXAFS Spectroscopy

Structural Characterization of Conjugated Polyelectrolyte Electron Transport Layers by NEXAFS Spectroscopy

Photosensitivity and line-edge roughness of novel polymer-bound PAG photoresists

Tailoring surface properties of ArF resists thin films with functionally graded materials (FGM)

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