| 1. |
- Haitjema, Jarich, et al.
(author)
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Soft X-ray absorption and fragmentation of tin-oxo cage photoresists
- 2024
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In: Physical Chemistry Chemical Physics. - 1463-9076. ; 26:7, s. 5986-5998
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Journal article (peer-reviewed)abstract
- “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.
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| 2. |
- Zhang, Yu, et al.
(author)
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Extreme ultraviolet photoemission of a tin-based photoresist
- 2021
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In: Applied Physics Letters. - : American Institute of Physics (AIP). - 0003-6951 .- 1077-3118. ; 118:17
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Journal article (peer-reviewed)abstract
- Tin is a suitable element for inclusion in extreme ultraviolet photoresists because of its relatively high-absorption cross section at 92eV. The electrons emitted after photon absorption are expected to generate secondary electrons in the solid film. In this way, several pathways lead to reactive species that cause a solubility switch. Here, we report the photoelectron spectra of tin oxo cage photoresists over the photon energy range 60-150eV, and the relative yields of photoelectrons from the valence band of the resist, from the Sn 4d orbitals, and of inelastically scattered electrons. The experimental excitation spectra differ considerably from those predicted by commonly used database cross section values, and from the combined computed subshell spectra: the maximum efficiency of ionization of Sn 4d both in the photoresists and in Sn metal occurs near the industrially relevant EUV wavelength of 13.5nm.
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| 3. |
- Zhang, Yu, et al.
(author)
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Photochemical conversion of tin-oxo cage compounds studied using hard x-ray photoelectron spectroscopy
- 2017
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In: Journal of Micro/Nanolithography. - 1932-5150 .- 1932-5134. ; 16:2
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Journal article (peer-reviewed)abstract
- Molecular inorganic materials are currently considered photoresists for extreme ultraviolet lithography (EUVL). Their high EUV absorption cross section and small building block size potentially allow high sensitivity and resolution as well as low line-edge roughness. The photochemical reaction mechanisms that allow these kinds of materials to function as photoresists, however, are still poorly understood. We discuss photochemical reactions upon deep UV (DUV) irradiation of a model negative-tone EUV photoresist material, namely the well-defined molecular tin-oxo cage compound [(SnBu)12O14(OH)6](OH)2, which is spin-coated to thin layers of 20 nm. The core electronic structures (Sn 3d, O 1s, and C 1s) of unexposed and DUV exposed films were then investigated using synchrotron radiation-based hard x-ray photoelectron spectroscopy. Different chemical oxidation states and concentrations of atoms and atom types in the unexposed and exposed films were found. We observed that the exposure in a nitrogen atmosphere prevented the oxidation but still led to carbon loss, albeit with a smaller conversion. Finally, a mechanistic hypothesis for the basic DUV photoreactions in molecular tin-oxo cages is proposed.
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| 4. |
- Zhang, Yu, et al.
(author)
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Photochemical conversion of tin-oxo cage compounds studied using hard x-ray photoelectron spectroscopy
- 2017
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In: ADVANCES IN PATTERNING MATERIALS AND PROCESSES XXXIV. - : SPIE. - 9781510607446 - 9781510607439
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Conference paper (peer-reviewed)abstract
- Several metal-containing molecular inorganic materials are currently considered as photoresists for extreme ultraviolet lithography (EUVL). This is primarily due to their high EUV absorption cross section and small building block size, properties which potentially allow both high sensitivity and resolution as well as low line-edge roughness. The photochemical reaction mechanisms that allow these kinds of materials to function as photoresists, however, are still poorly understood. As a step in this direction, we here discuss photochemical reactions upon deep UV (DUV) irradiation of a model negative-tone EUV photoresist material, namely the well-defined molecular tin-oxo cage compound [(SnR)12O14(OH)6]X2 (R = organic group; X = anion) which is spin coated to thin layers of 20 nm. The core electronic structure (Sn 3d, O 1s and C 1s) of fresh and DUV exposed films were then investigated using synchrotron radiationbased hard X-ray photoelectron spectroscopy (HAXPES). This method provides information about the structure and chemical state of the respective atoms in the material. We performed a comparative HAXPES study of the composition of the tin-oxo cage compound [(SnR)12O14(OH)6](OH)2, either fresh directly after spin-coated vs. DUV-exposed materials under either ambient condition or under a dry N2 atmosphere. Different chemical oxidation states and concentrations of atoms and atom types in the fresh and exposed films were found. We further found that the chemistry resulting from exposure in air and N2 is strikingly different, clearly illustrating the influence of film-gas interactions on the (photo)chemical processes that eventually determine the photoresist. Finally, a mechanistic hypothesis for the basic DUV photoreactions in molecular tin-oxo cages is proposed.
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