The angular distribution of intact organic molecules desorbed by energetic C60 primary ions was probed both experimentally and with molecular dynamics computer simulations. For benzo[a]pyrene, the angular distribution of intact molecules is observed to peak at off-normal angles. Molecular dynamics computer simulations on a similar system show the mechanism of desorption involves fast deposition of energy followed by fluid-flow and effusive-type emission of intact molecules. The off-normal peak in the angular distribution is shown to arise from emission of intact molecules from the rim of a crater formed during the cluster impact. This signature is unique for molecules because fragmentation processes remove molecules that would otherwise eject at directions near-normal to the surface.

Molecular depth profiles of an organic thin film of guanine vapor deposited onto a Ag substrate are obtained using a 40 keV C 60 cluster ion beam in conjunction with time-of-flight secondary ion mass spectrometric (ToF-SIMS) detection. Strong-field, femtosecond photoionization of intact guanine molecules is used to probe the neutral component of the profile for direct comparison with the secondary ion component. The ability to simultaneously acquire secondary ions and photoionized neutral molecules reveals new fundamental information about the factors that influence the properties of the depth profile. Results show that there is an increased ionization probability for protonated molecular ions within the first 10 nm due to the generation of free protons within the sample. Moreover, there is a 50% increase in fragment ion signal relative to steady state values 25 nm before reaching the guanine/Ag interface as a result of interfacial chemical damage accumulation. An altered layer thickness of 20 nm is observed as a consequence of ion beam induced chemical mixing. In general, we show that the neutral component of a molecular depth profile using the strong-field photoionization technique can be used to elucidate the effects of variations in ionization probability on the yield of molecular ions as well as to aid in obtaining accurate information about depth dependent chemical composition that cannot be extracted from TOF-SIMS data alone.

Molecular depth profiles of model organic thin films were performed using a 40 keV C60+ cluster ion source in concert with TOF-SIMS. Strong-field photoionization of intact neutral molecules sputtered by 40 keV C60+ primary ions was used to analyze changes in the chemical environment of the guanine thin films as a function of ion fluence. Direct comparison of the secondary ion and neutral components of the molecular depth profiles yields valuable information about chemical damage accumulation as well as changes in the molecular ionization probability. An analytical protocol based on the erosion dynamics model is developed and evaluated using guanine and trehalose molecular secondary ion signals with and without comparable laser photoionization data.

The quality of molecular depth profiles created by erosion of organic materials by cluster ion beams exhibits a strong dependence upon temperature. To elucidate the fundamental nature of this dependence, we employ the Irganox 3114/1010 organic delta layer reference material as a model system. This delta-layer system is interrogated using a 40 keV C60+ primary ion beam. Parameters associated with the depth profile such as depth resolution, uniformity of sputtering yield and topography are evaluated between 90 K and 300 K using a unique wedge-crater beveling strategy that allows these parameters to be determined as a function of erosion depth from atomic force microscope measurements. The results show that the erosion rate calibration performed using the known Δ-layer depth in connection with the fluence needed to reach the peak of the corresponding SIMS signal response is misleading. Moreover, we show that the degradation of depth resolution is linked to a decrease of the average erosion rate and the buildup of surface topography in a thermally activated manner. This underlying process starts to influence the depth profile above a threshold temperature between 210 and 250 K for the system studied here. Below that threshold, the process is inhibited and steady-state conditions are reached with constant erosion rate, depth resolution and molecular secondary ion signals from both the matrix and the Δ-layers. In particular, the results indicate that further reduction of the temperature below 90 K does not lead to further improvement of the depth profile. Above the threshold, the process becomes stronger at higher temperature, leading to an immediate decrease of the molecular secondary ion signals. This signal decay is most pronounced for the highest m/z ions but is less for the smaller m/z ions, indicating a shift toward small fragments by accumulation of chemical damage. The erosion rate decay and surface roughness buildup, on the other hand, exhibit a rather sudden delayed onset after erosion of about 150 nm, indicating that a certain damage level must be reached in order to influence the erosion dynamics. Only after that onset does the depth resolution become compromised, indicating that the temperature reduction does not significantly influence parameters like ion-beam mixing or the altered-layer thickness. In general, the wedge-crater beveling protocol is shown to provide a powerful basis for increased understanding of the fundamental factors that affect the important parameters associated with molecular depth profiling.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy (AFM) are employed to characterize a wedge-shaped crater eroded by a 40 keV C60+ cluster ion beam on an organic thin film of 402 nm of barium arachidate (AA) multilayers prepared by the Langmuir-Blodgett (LB) technique. Sample cooling to 90 K was used to help reduce chemical damage, improve depth resolution and maintain constant erosion rate during depth profiling. The film was characterized at 90 K, 135 K, 165 K, 205 K, 265 K and 300 K. It is shown that sample cooling to 205 K or lower helps to inhibit erosion rate decay, whereas at 300 K and 265 K the erosion rate continues to drop after 250 nm of erosion, reaching about half of the initial value after removal of the entire film. Depth profiles are acquired from the SIMS images of the eroded wedge crater. The results suggest that sample cooling only slightly improves the altered layer thickness, but eliminates the decrease in erosion rate observed above 265 K.