Photothermal AFM-IR Depth Sensitivity: An Original Pathway to Tomographic Reconstruction

Photothermal atomic force microscopy-infrared (AFM-IR) enables label-free chemical imaging and spectroscopy with nanometer-scale spatial resolution through the integration of atomic force microscopy (AFM) and infrared radiation. The capability for subsurface and three-dimensional (3D) tomographic material analysis remains, however, largely unexplored. Here, we establish a simple and robust empirical relationship between the probing depth and laser repetition rate for three important modes of AFM-IR operation: resonance-enhanced, tapping, and surface-sensitive AFM-IR. Using this empirical relationship, we demonstrate, based on the example of resonance-enhanced operation, how photothermal AFM-IR of thin surface/subsurface layers of polystyrene domains in the poly(methyl methacrylate) matrix can result in 3D representations revealing the size and thickness of small polystyrene domains in the poly(methyl methacrylate) matrix with nanometer-scale resolution. Experimental findings are confirmed by analytical models.