XUV Induced Bleaching of a Tin Oxo Cage Photoresist Studied by High Harmonic Absorption Spectroscopy

Sadegh, Najmeh; Geest, Maarten van der; Haitjema, Jarich; Campi, Filippo; Castellanos, Sonia; Kraus, Peter M.; Brouwer, Albert M.

doi:10.2494/photopolymer.33.145

Cited by 9 publications

(10 citation statements)

References 34 publications

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“…At higher photon energies, the ''atomic approximation'' becomes increasingly accurate, 49 and a recent study shows that the data from the CXRO database correspond fairly well with the absorption spectrum of a thin film of tin-oxo cages between 25 eV and 40 eV. 50 An alternative explanation could be that smaller fragments are formed at higher photon energies, which are not detected within the m/z range of the present experiment.…”

Section: Vuv Irradiation Of Tin-oxo Cage Ionssupporting

confidence: 68%

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

Haitjema

Giuliani

et al. 2021

Phys. Chem. Chem. Phys.

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Section: Vuv Irradiation Of Tin-oxo Cage Ionssupporting

confidence: 68%

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

Haitjema

Giuliani

et al. 2021

Phys. Chem. Chem. Phys.

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“…Figure shows the bleachable and nonbleachable fractions of the absorption as the red and gray areas, respectively. Plots of the absorption coefficient α and Dill parameters obtained using eqs and are shown as a function of energy in Figure S5 (Supporting Information). A normalD normali normall normall = ( A 0 o b s − A ∞ o b s ) / z B normalD normali normall normall = A ∞ normalo normalb normals / z The values of A Dill are slightly higher than those reported for TinOH for the energy range of 25–40 eV, due to higher numbers of oxygen and carbon in TinOAc than in TinOH …”

Section: Resultsmentioning

confidence: 92%

“…The values of A Dill are slightly higher than those reported for TinOH for the energy range of 25−40 eV, due to higher numbers of oxygen and carbon in TinOAc than in TinOH. 39 Quantum Yield. Knowing the absorbance and the dose impinging on the sample in each time interval during the exposure, we can calculate the number of photons absorbed in each time interval.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…The chemical structure of the compound investigated in the present study, named TinOAc, is shown in Chart . In a preliminary study on the related TinOH, we measured the absorption spectrum and photobleaching in a smaller energy range (25–40 eV) . In the present work, we give a full account of our experiments with an improved setup, covering a larger energy range and a quantitative evaluation that allows us to estimate the quantum yield of tin–carbon bond breaking.…”

Section: Introductionmentioning

confidence: 99%

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XUV Absorption Spectroscopy and Photoconversion of a Tin-Oxo Cage Photoresist

Sadegh,

Evrard,

Kraus

et al. 2024

J. Phys. Chem. C

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Extreme ultraviolet lithography has recently been introduced in high-volume production of integrated circuits for manufacturing the smallest features in high-end computer chips. Hybrid organic/inorganic materials are considered as the next generation of photoresists for this technology, but detailed knowledge about the response of such materials to the ionizing radiation used (13.5 nm, 92 eV) is still scarce. In the present work, we use broadband high-harmonic radiation in the energy range 22−70 eV for absorption spectroscopy and photobleaching (that is, the decrease of absorbance) of thin films of an n-butyltin oxocage, a representative of the class of metal-based EUV photoresist. The shape of the absorption spectrum in the range 22−92 eV matches well with the spectrum predicted using tabulated atomic cross sections. The photobleaching results are consistent with loss of the butyl side groups due to the breaking of Sn−C bonds following photoionization. Bleaching is strongest in the low-energy range (<40 eV), where the absorption is largely due to the carbon atoms in the organic groups. At higher energies (42−70 eV), absorption is dominated by the tin atoms, and since these remain in the film after photoconversion, the absorption change in this region is smaller. It is estimated that after prolonged irradiation (up to ∼3 J cm −2 in the range 22−40 eV) about 70% of the hydrocarbon groups are removed from the film. The rate of bleaching is high at the beginning of exposure, but it rapidly decreases with increasing conversion. We rationalize this using density functional theory calculations: the first Sn−C bonds are efficiently cleaved (quantum yield Φ ≈ 0.9), because the highest occupied molecular orbitals (HOMOs) (from which an electron is removed after photoionization) are located on Sn−C sigma bonds. In the photoproducts, the HOMO is localized on tin atoms that have lost their hydrocarbon group (formally reduced to the Sn(II) oxidation state), and holes formed on those tin atoms lead to less efficient cleavage reactions. Our results reveal the primary reaction steps following excitation with ionizing radiation of tin-oxo cages. Our methodology represents a systematic approach of studying and quantitatively assessing the performance of new photoresists and as such enables the development of future EUV photoresists.

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“…16 The study of XUV-induced dynamics and XUV-initiated chemical reactions is therefore gaining interest. [17][18][19] Most of the HHG studies mentioned above, however, excited dynamics at longer wavelengths and then probed the dynamics in the XUV.…”

Section: Introductionmentioning

confidence: 99%

Extreme Ultraviolet-Excited Time-Resolved Luminescence Spectroscopy Using an Ultrafast Table-Top High-Harmonic Generation Source

van der Geest,

Sadegh,

Meerwijk

et al. 2021

Preprint

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We present a table-top extreme ultraviolet (XUV) beamline for measuring time-and frequencyresolved XUV excited optical luminescence (XEOL) with additional femtosecond-resolution XUV transient absorption spectroscopy functionality. XUV pulses are generated via high-harmonic generation using a near-infrared pulse in a noble gas medium, and focused to excite luminescence from a solid sample. The luminescence is collimated and guided into a streak camera, where its spectral components are temporally resolved with picosecond temporal resolution. We time-resolve XUV excited luminescence and compare the results to luminescence decays excited at longer wavelengths for three different materials : (i) sodium salicylate, an often used XUV scintillator, (ii) fluorescent labeling molecule 4-carbazole benzoic acid (CB), and (iii) a zirconium metal oxo-cluster labeled with CB, which is a photoresist candidate for extreme-ultraviolet lithography. Our results establish time-resolved XEOL as a new technique to measure transient XUV-driven phenomena in solid-state samples, and identify decay mechanisms of molecules following XUV and soft-X-ray excitation.

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XUV Induced Bleaching of a Tin Oxo Cage Photoresist Studied by High Harmonic Absorption Spectroscopy

Cited by 9 publications

References 34 publications

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

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

XUV Absorption Spectroscopy and Photoconversion of a Tin-Oxo Cage Photoresist

Extreme Ultraviolet-Excited Time-Resolved Luminescence Spectroscopy Using an Ultrafast Table-Top High-Harmonic Generation Source

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