Flux and fluence effects on the vacuum-UV photodesorption and photoprocessing of CO2 ices.

CO2 is a major component of the icy mantles surrounding dust grains in planet and star formation regions. Understanding its photodesorption is crucial for explaining gas phase abundances in the coldest environments of the interstellar medium irradiated by vacuum-UV (VUV) photons. Photodesorption yields determined experimentally from CO2 samples grown at low temperatures (T = 15 K) have been found to be very sensitive to experimental methods and conditions. Several mechanisms have been suggested for explaining the desorption of CO2, O2 and CO from CO2 ices. In the present study, the cross-sections characterizing the dynamics of photodesorption as a function of photon fluence (determined from released molecules in the gas phase) and of ice composition modification (determined in situ in the solid phase) are compared for the first time for different photon flux conditions (from 7.3 × 1012 photon per s cm-2 to 2.2× 1014 photon per s cm-2) using monochromatic synchrotron radiation in the VUV range (on the DESIRS beamline at SOLEIL). This approach reveals that CO and O2 desorptions are decorrelated from that of CO2. CO and O2 photodesorption yields depend on photon flux conditions and can be linked to surface chemistry. In contrast, the photodesorption yield of CO2 is independent of the photon flux conditions and can be linked to bulk ice chemical modification, consistently with indirect desorption induced by an electronic transition (DIET) process.

Low-energy electron interaction with 2-(trifluoromethyl)acrylic acid, a potential component for EUVL resist material.

Motivated by the current introduction of extreme ultraviolet lithography (EUVL) into chip manufacturing processes, and thus the transition to electron-induced chemistry within the respective resist materials, we have studied low energy electron-induced fragmentation of 2-(trifluoromethyl)acrylic acid (TFMAA). This compound is chosen as a potential resist component, whereby fluorination enhances the EUV adsorption and may at the same time promote electron-induced dissociation. Dissociative ionization and dissociative electron attachment are studied, and to aid the interpretation of the observed fragmentation channels, the respective threshold values are calculated at the DFT and coupled cluster level of theory. Not surprisingly, we find significantly more extensive fragmentation in DI than in DEA and in fact, the only significant DEA fragmentation channel is the cleavage of HF from the parent molecule upon electron attachment. Rearrangement and new bond formation are substantial in DI and are, in fact, similar to DEA, mainly associated with HF formation. The observed fragmentation reactions are discussed in relation to the underlying reactions and potential implications for the suitability of TFMAA as a component of EUVL resist materials.

Cryogenic Chemistry and Quantitative Non-Thermal Desorption from Pure Methanol Ices: High-Energy Electron versus X-Ray Induced Processes.

X-Ray irradiation of interstellar ice analogues has recently been proven to induce desorption of molecules, thus being a potential source for the still-unexplained presence of gaseous organics in the coldest regions of the interstellar medium, especially in protoplanetary disks. The proposed desorption mechanism involves the Auger decay of excited molecules following soft X-ray absorption, known as X-ray induced electron-stimulated desorption (XESD). Aiming to quantify electron induced desorption in XESD, we irradiated pure methanol (CH3 OH) ices at 23 K with 505 eV electrons, to simulate the Auger electrons originating from the O 1s core absorption. Desorption yields of neutral fragments and the effective methanol depletion cross-section were quantitatively determined by mass spectrometry. We derived desorption yields in molecules per incident electron for CO, CO2 , CH3 OH, CH4 /O, H2 O, H2 CO, C2 H6 and other less abundant but more complex organic products. We obtained desorption yields remarkably similar to XESD values.