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Soft X-ray absorpti...
Soft X-ray absorption and fragmentation of tin-oxo cage photoresists
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- Haitjema, Jarich (author)
- Advanced Research Center for Nanolithography (ARCNL)
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Castellanos, Sonia (author)
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Lugier, Olivier (author)
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Bespalov, Ivan (author)
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- Lindblad, Rebecka (author)
- Lund University,Lunds universitet,Synkrotronljusfysik,Fysiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Synchrotron Radiation Research,Department of Physics,Departments at LTH,Faculty of Engineering, LTH,Helmholtz Association of German Research Centers
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- Timm, Martin (author)
- Helmholtz Association of German Research Centers
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- Bülow, Christine (author)
- Albert-Ludwigs University Freiburg,Helmholtz Association of German Research Centers
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- Zamudio-Bayer, Vicente (author)
- Helmholtz Association of German Research Centers
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- Lau, J. Tobias (author)
- Helmholtz Association of German Research Centers,Albert-Ludwigs University Freiburg
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- von Issendorff, Bernd (author)
- Albert-Ludwigs University Freiburg
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- Hoekstra, Ronnie (author)
- University of Groningen
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- Witte, Katharina (author)
- Paul Scherrer Institute
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- Watts, Benjamin (author)
- Paul Scherrer Institute
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- Schlathölter, Thomas (author)
- University of Groningen
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- Brouwer, Albert M. (author)
- University of Amsterdam
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(creator_code:org_t)
- 2024
- 2024
- English 13 s.
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In: Physical Chemistry Chemical Physics. - 1463-9076. ; 26:7, s. 5986-5998
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Abstract
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- “Tin-oxo cage” organometallic compounds are considered as photoresists for extreme ultraviolet (EUV) photolithography. To gain insight into their electronic structure and reactivity to ionizing radiation, we trapped bare gas-phase n-butyltin-oxo cage dications [(BuSn)12O14(OH)6]2+ in an ion trap and investigated their fragmentation upon soft X-ray photoabsorption by means of mass spectrometry. In complementary experiments, the tin-oxo cages with hydroxide and trifluoroacetate counter-anions were cast in thin films and studied using X-ray transmission spectroscopy. Quantum-chemical calculations were used to interpret the observed spectra. At the carbon K-edge, a distinct pre-edge absorption band can be attributed to transitions in which electrons are promoted from C1s orbitals to the lowest unoccupied molecular orbitals, which are delocalized orbitals with strong antibonding (Sn-C ?*) character. At higher energies, the most prominent resonant transitions involve C-C and C-H ?* valence states and Rydberg (3s and 3p) states. In the solid state, the onset of continuum ionization is shifted by ?5 eV to lower energy with respect to the gas phase, due to the electrostatic effect of the counterions. The O K-edge also shows a pre-edge absorption, but it is devoid of any specific features, because there are many transitions from the different O1s orbitals to a large number of vacant orbitals. In the gas phase, formation of the parent [(BuSn)12O14(OH)6]3+ radical ion is not observed at the C K-edge nor at the O K-edge, because the loss of a butyl group from this species is very efficient. We do observe a number of triply charged photofragment ions, some of which have lost up to 5 butyl groups. Structures of these species are proposed based on quantum-chemical calculations, and pathways of formation are discussed. Our results provide insight into the electronic structure of alkyltin-oxo cages, which is a prerequisite for understanding their response to EUV photons and their performance as EUV photoresists.
Subject headings
- NATURVETENSKAP -- Fysik -- Atom- och molekylfysik och optik (hsv//swe)
- NATURAL SCIENCES -- Physical Sciences -- Atom and Molecular Physics and Optics (hsv//eng)
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- ref (subject category)
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- By the author/editor
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Haitjema, Jarich
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Castellanos, Son ...
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Lugier, Olivier
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Bespalov, Ivan
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Lindblad, Rebeck ...
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Timm, Martin
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Bülow, Christine
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Zamudio-Bayer, V ...
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Lau, J. Tobias
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von Issendorff, ...
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Hoekstra, Ronnie
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Witte, Katharina
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Watts, Benjamin
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Schlathölter, Th ...
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Brouwer, Albert ...
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- NATURAL SCIENCES
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NATURAL SCIENCES
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and Atom and Molecul ...
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Physical Chemist ...
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Lund University