Focused electron beam induced deposition (FEBID) is a single-step, direct-write nanofabrication technique capable of writing three-dimensional metal-containing nanoscale structures on surfaces using electron-induced reactions of organometallic precursors. Currently FEBID is, however, limited in resolution due to deposition outside the area of the primary electron beam and in metal purity due to incomplete precursor decomposition. Both limitations are likely in part caused by reactions of precursor molecules with low-energy (<100 eV) secondary electrons generated by interactions of the primary beam with the substrate. These low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface studies on adsorbed precursor molecules can provide information on surface speciation and identify species desorbing from a substrate during electron irradiation under conditions more representative of FEBID. Comparing gas phase and surface science studies allows for insight into the primary deposition mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in FEBID, specifically, dissociative electron attachment, dissociative ionization, neutral dissociation, and dipolar dissociation, emphasizing the different nature and energy dependence of each process. We then explore the value of studying these processes through comparative gas phase and surface studies for four commonly-used FEBID precursors: MeCpPtMe₃, Pt(PF₃)₄, Co(CO)₃NO, and W(CO)₆. Through these case studies, it is evident that this combination of studies can provide valuable insight into potential mechanisms governing deposit formation in FEBID. Although further experiments and new approaches are needed, these studies are an important stepping-stone toward better understanding the fundamental physics behind the deposition process and establishing design criteria for optimized FEBID precursors.

Using a crossed electron/molecule beam technique the dissociative electron attachment (DEA) to gas phase L-valine, (CH3)2CHCH(NH2)COOH, is studied by means of mass spectrometric detection of the product anions. Additionally, ab initio calculations of the structures and energies of the anions and neutral fragments have been carried out at G2MP2 and B3LYP levels. Valine and the previously studied aliphatic amino acids glycine and alanine exhibit several common features due to the fact that at low electron energies the formation of the precursor ion can be characterized by occupation of the π* orbital of the carboxyl group. The dominant negative ion (M–H)− (m∕Z=116) is observed at electron energies of 1.12eV. This ion is the dominant reaction product at electron energies below 5eV. Additional fragment ions with m∕Z=100, 72, 56, 45, 26, and 17 are observed both through the low lying π* and through higher lying resonances at about 5.5 and 8.0–9.0eV, which are characterized as core excited resonances. According to the threshold energies calculated here, rearrangements play a significant role in the formation of DEA fragments observed from valine at subexcitation energies.

Relative cross sections for dissociative electron attachment (DEA) and dissociative ionization (DI) of the FEBID precursor, trimethyl (methylcyclopentadienyl) platinum(IV), MeCpPtMe₃, are presented. The most pronounced DEA process is the loss of one methyl radical, while the loss of two or three methyl groups along with hydrogen is the main pathway in DI. Further fragments are formed in DEA and through DI by more complex rearrangement reactions but complete dissociation to bare Pt⁻ in DEA or Pt⁺ in DI is minor. The transient negative ion (TNI) formation in DEA is discussed and fragmentation mechanisms are proposed for individual processes. From the thermodynamics of the DEA processes we derive a lower limit for the electron affinity of the MeCpPtMe₂ radical (1.7 eV). Appearance energies (AE) of MeCpPtMe₃ ⁺ (7.7 eV) and Pt⁺ (18.6 eV) formation through electron impact ionisation (EI) and through DI, respectively, are determined. Finally, the current DEA and DI results are compared and brought into context with earlier surface science studies on electron-induced decomposition of adsorbed MeCpPtMe₃ as well as gas phase and surface science studies on the FEBID precursors [Co(CO)₃NO] and [Pt(PF₃)₄]. These comparisons strongly indicate that DEA is an important process in the electron-induced decomposition of these molecules in FEBID.