Elucidating the patterning mechanism of zirconium-based hybrid photoresists

Kosma, Vasiliki; Kasahara, Kazuki; Xu, Hong; Odent, Jérémy; Ober, Christopher K.; Giannelis, Emmanuel P.

doi:10.1117/1.jmm.16.4.041007

Cited by 27 publications

(21 citation statements)

References 37 publications

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“…7. A partial decarboxylation was observed, in line with previously reported studies, 10 whereas a rise in the concentration of Zr-OH species was observed. It should be noted that the cluster may hydrate after exposure due to adsorption of moisture from the air, since these are ex situ experiments.…”

Section: Origin Of the Solubility Switchsupporting

confidence: 92%

“…It had been previously observed that upon redissolution of the film made of the commercial ZrMc material, the individual molecular cluster could not be recovered as such. 10 Furthermore, Matson et al 26,27 found that the chemical stability of Hf-based oxoclusters with methacrylate ligands upon different postapplication baking conditions had an important effect in the solubility of the thin films prepared with this material. In this work, this material is evidenced to lose the extra carboxylic acid molecules upon deposition.…”

Section: Lithographic Performancementioning

confidence: 99%

“…Recently, Mattson et al proposed that rearrangements of the carboxylate ligands in Hf-based clusters as well as condensation reactions between the inorganic cores lead to solubility changes of the deposited materials compared to the bulk powder. 10,26,27 Yet, it should be noted that XPS probes the surface of the film and the ligand loss might be less in the bulk of the layer.…”

Section: Origin Of the Solubility Switchmentioning

confidence: 99%

“…1,3 It is generally accepted that the metallic atoms absorb a large fraction of the EUV light 7,8 while reactions of the organic parts are responsible for the solubility switching properties. [9][10][11][12] A particular mechanism that illustrates this distinction of the roles of organic and inorganic components in hybrid photoresists was proposed for the well-known Inpria type of nonchemically amplified resists, where the insolubility of the exposed areas arise from ligand cleavage and inorganic core aggregation. 13 In addition, the inorganic components in the photoresist provide the final patterns with good mechanical and chemical stability.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic insights in Zr- and Hf-based molecular hybrid EUV photoresists

Baljozović

Portale

et al. 2019

J. Micro/Nanolith. MEMS MOEMS

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Background: Inorganic resists show promising performances in extreme ultraviolet (EUV) lithography. Yet, there is a need for understanding the exact chemical mechanisms induced by EUV light on these materials. Aim: To gain knowledge on the EUV chemistry of inorganic resists, we investigate hybrid inorganic-organic molecular compounds, metal oxoclusters (MOCs). Their molecular nature allows for the monitoring of specific structural changes by means of spectroscopy and thus for the elucidation of the mechanisms behind pattern formation. Approach: We compare the sensitivity of MOCs based on Zr and Hf, and methacrylate ligands as EUV resists. The chemical and structural changes causing the solubility switch were investigated by ex situ x-ray spectroscopy, infrared spectroscopy, ultraviolet-visible spectroscopy, and grazing incidence x-ray scattering. Results: Higher sensitivity was detected for the Hf-based material, in line with its higher absorptivity. A small fraction of the carboxylate ligands is lost at doses that yield solubility contrast, whereas aggregation of the inorganic clusters was not observed. Conclusions: These results provide evidence that, although the mechanism of solubility switch in these materials starts with decarboxylation reactions, it mainly proceeds through cross linking of the organic shells instead of aggregation of the inorganic clusters.

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Section: Origin Of the Solubility Switchsupporting

confidence: 92%

Section: Lithographic Performancementioning

confidence: 99%

Section: Origin Of the Solubility Switchmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Mechanistic insights in Zr- and Hf-based molecular hybrid EUV photoresists

Baljozović

Portale

et al. 2019

J. Micro/Nanolith. MEMS MOEMS

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“…Recently, the focus of our group has changed from the development of new resist platforms to the investigation of EUV photomechanisms. A number of papers have been published that explore the photomechanism through instrumentation such as XPS, FTIR, TGA, electrospray ionization mass spectrometry and modelling [16][17][18][19][20]. Our recent work has focused on investigating the photomechanism of our antimony-carboxylate platform, by studying the volatile photoproducts following exposure to EUV (Fig.…”

Section: Introductionmentioning

confidence: 99%

Isotopic Labeling Studies of EUV Photoresists Containing Antimony

Murphy

Sitterly

Grzeskowiak

et al. 2018

J. Photopol. Sci. Technol.

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We have investigated the mechanism of photodecomposition of antimony carboxylate complexes of the type Ph 3 Sb(O 2 CR′) 2 by means of EUV outgassing in combination with isotopic labeling. When exposed to EUV light, these compounds decompose to form CO 2 , benzene and phenol. The source of hydrogen needed to create phenol can be traced to hydrogens originating in the original organometallic complex. However, it is much more difficult to trace the origin of the hydrogen needed to convert the phenyl groups to benzene (Ph-H). We propose that the primary source of hydrogen to create benzene is external to the film. Additionally, we have prepared isotopically-labeled versions of Ph3Sb(O2CCH(CH3)2)2 in which the hydrogens in the isobutyrate ligand were replaced with 0, 1, 6 and 7 deuteriums, to provide information about the relative reactivity of these protons during EUV exposure as analyzed by mass spectrometry. High reaction selectivity was identified within the carboxylate dictated by hydrogen location relative to the carbonyl for both benzene and phenol generation. Lastly, the results of these studies were used to propose a series of reaction pathways to generate the aforementioned reaction byproducts.

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Creating the Future with Silicon

Jung

2023

Adv Materials Technologies

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The rise of AI technology, the expansion of smart and connected devices, and the COVID‐19 global pandemic have driven a change in the nature of social interactions from face‐to‐face to contact‐free/remote, which has tremendously increased the demand for various semiconductor devices. However, scaling and performance improvement of semiconductor devices are becoming more difficult every year, and extensive studies have been conducted to overcome these technological roadblocks. This paper reviews the present state of semiconductor development and discusses several approaches to overcome these scaling and performance limitations. Additionally, the importance of collaboration and the related ecosystem is emphasized to strengthen the cooperation among semiconductor stakeholders and support further semiconductor development.

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Elucidating the patterning mechanism of zirconium-based hybrid photoresists

Cited by 27 publications

References 37 publications

Mechanistic insights in Zr- and Hf-based molecular hybrid EUV photoresists

Mechanistic insights in Zr- and Hf-based molecular hybrid EUV photoresists

Isotopic Labeling Studies of EUV Photoresists Containing Antimony

Creating the Future with Silicon

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