UV and VUV-induced fragmentation of tin-oxo cage ions

Haitjema, Jarich; Wu, Lianjia; Giuliani, Alexandre; Nahon, Laurent; Castellanos, Sonia; Brouwer, Albert M.

doi:10.1039/d1cp03148a

Cited by 17 publications

(43 citation statements)

References 48 publications

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“…As EUV was operated in a high vacuum system, the amount of water on the lm is very limited. With EUV excitation, clusters 1 and 2 undergo photolytic ionization to form species A and A ′ to release an electron, 33,34 This proposed mechanism well explains our XPS study at J = 30-60 mJ cm −2 that oxygen content is increased with the elimination of carboxylate, Sn-butyl and chloro ligands for tin cluster 1, further forming new Sn-O bonds. In the case of photoresist 2, molecular aggregation relies on radical polymerization of its vinyltin moiety; this process is clearly indicated by refractive FTIR and HRXPS analysis.…”

Section: Resultssupporting

confidence: 73%

“…Photolytic cleavage of a Sn–Bu bond is well established on 12-tin oxide clusters. 33,34 These refractive FTIR spectra show complete decomposition of tin ligands with no polymerization of the 2-methyl-3-butenoate ligands for photoresist 1 .…”

Section: Resultsmentioning

confidence: 98%

“…As EUV was operated in a high vacuum system, the amount of water on the film is very limited. With EUV excitation, clusters 1 and 2 undergo photolytic ionization to form species A and A′ to release an electron, 33,34 further yielding two cations B and C together with CO 2 and Cl and R radicals. Cluster 1 releases an additional n -butyl radical with a facile Sn–butyl bond cleavage.…”

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Novel hexameric tin carboxylate clusters as efficient negative-tone EUV photoresists: high resolution with well-defined patterns under low energy doses

Liu

Lin

et al. 2023

Nanoscale Adv.

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Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

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Novel hexameric tin carboxylate clusters as efficient negative-tone EUV photoresists: high resolution with well-defined patterns under low energy doses

Liu

Lin

et al. 2023

Nanoscale Adv.

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“…The tin oxo cages presented in this work are positively charged clusters of twelve tin atoms bridged by oxygen and have one butyl group attached to each tin atom forming a layer at the surface of the inorganic core enhancing its solubility (see figure 1). The tin-carbon bonds can be cleaved upon EUV exposure 6,7 . Models suggest 8 that this dissociation is generating active sites on the tin atoms that lead to the cross-linking between neighbouring clusters, rendering the material insoluble.…”

Section: Introductionmentioning

confidence: 99%

Influence of the anion in tin-based EUV photoresists properties

Evrard

Sadegh

Hsu

et al. 2023

Advances in Patterning Materials and Processes XL

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In this work we assess the effect of the change of counter-anions on the photolithography properties of butyl-Sn12 oxo hydroxo cages. The hydroxide anions were exchanged with tetrakis(pentafluorophenyl)borate (B(PFP)4)- and (phenyl) trifluoroborate (BF3Ph)- anions which exhibit a photoabsorption cross section at 92 eV that is similar to that of the butyl-Sn12 oxo hydroxo cages. The degradation of the EUV photoresist was monitored via in-situ EUV exposure followed by X-ray photoelectron spectroscopy (XPS) at the BEAR beamline (Elettra, Italy) at the C1s-edge. Both systems exhibit similar carbon losses of around 25% for 100 mJ/cm2 dose. The Sn12 cluster with acetate anions, as a reference compound, exhibit a loss of C1s XPS signal from the butyl chains of around 23% for the same 100 mJ/cm2 EUV exposure dose indicating a larger degradation of the Sn12 cluster for the latter. We also evaluated the patterning performance of the Sn12(B(PFP)4) resist via interference lithography at the XIL-II beamline (PSI, Switzerland) and found the positive tone character of the resist and its ability to write lines with 50 nm half pitch resolution for doses of 30 mJ/cm2. In contrast, Sn12(BF3Ph) acts as a sensitive negative tone resist, with doses of 12.5 mJ/cm2 sufficient to write 50 nm half pitch lines.

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“…During the past few decades, the semiconductor world has witnessed the astonishing evolution of electronic chips with the shrinking of the node size at a faster rate than expected. Among several technological aspects responsible for such amazing developments, the remarkable progress in the area of lithography where resist technology plays an important role has been a critical factor. − Coping with the fast-changing semiconductor nodes has been a grand challenge for resist developers.…”

Section: Introductionmentioning

confidence: 99%

Macrocycle Network-Aided Nanopatterning of Inorganic Resists on Silicon

Nandi

Khillare

Moinuddin

et al. 2022

ACS Appl. Nano Mater.

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Inorganic resists have emerged as promising candidates in semiconductor industries to realize sub-10 nm node technology. However, controlling vertical shrinkage of resist films during the pattern development process, particularly for ultralow thin film applications, is among the highly pressing limitations of inorganic resists along with pattern roughness and poor resist shelf-life characteristics. Tin-based clusters and small molecules have been recently introduced as resist materials. They possess a high absorption coefficient and fast solubility transitions under irradiation exposure. As we investigated, n-butylstannoic acid (BTA) showed ∼38% vertical shrinkage when its film was exposed with deep ultraviolet photons (DUV, ∼254 nm) and could pattern features of ∼120 nm. We hypothesized and experimentally validated an approach that provided control on shrinkage issues, along with improving its patterning potential to sub-15 nm regime. In our approach, BTA was embedded into a polyhydroxy organic host matrix composed of noria (water-wheel-like macrocycle) derivatives. The rigid molecular cage structure and photo-inert nature of noria (N-Me) were utilized as the host matrix that apprehended the inorganic resist material within its intermolecular space. Ultrathin films (∼20 nm) were coated on silicon, and various nanofeatures including 10 nm lines, meshlike grids with 10 nm width, complex patterns, and so forth were patterned using electron beam and helium ion beam lithography. Most importantly, we were able to drastically reduce the vertical shrinkage to ∼13% with respect to initial thickness, which substantiates the potential of our hypothesis. We also noticed good shelf-life (6 months), good etch resistance, and low line edge roughness (LER)/line width roughness (LWR) for the developed resist composition.

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UV and VUV-induced fragmentation of tin-oxo cage ions

Abstract: Photoresist materials are being optimized for the recently introduced Extreme Ultraviolet (EUV) photolithographic technology. Organometallic compounds are potential candidates for replacing the ubiquitous polymer-based chemically amplified resists. Tin (Sn) has...

Cited by 17 publications

References 48 publications

Novel hexameric tin carboxylate clusters as efficient negative-tone EUV photoresists: high resolution with well-defined patterns under low energy doses

Novel hexameric tin carboxylate clusters as efficient negative-tone EUV photoresists: high resolution with well-defined patterns under low energy doses

Influence of the anion in tin-based EUV photoresists properties

Macrocycle Network-Aided Nanopatterning of Inorganic Resists on Silicon

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