Activation and control of organolanthanide synthesis by supersonic molecular beams: Erbium-porphyrin test case

Hybrid Er-Tetraphenylporphyrin (Er-TPP) thin films have been synthesized on a ${\text{SiO}}_2/\text{Si}\left(100\right)$ substrate in a co-deposition approach that combines an ${\text{H}}_2\text{TPP}$ seeded supersonic molecular beam and an effusive molecular beam of the metal. As confirmed by detailed surface electron spectroscopies, our experiments in ultrahigh vacuum demonstrate the ability to produce and control the chemical reactivity between the two species on the surface of the growing film. This is achieved by fully exploiting the unique features of the supersonic molecular-beam deposition approach in a co-deposition scheme that we show to be ideally suited to induce and control chemical reactivity. We believe that the ability to synthesize organolanthanides films, showing a thickness that is suitable for applications in optoelectronics, could pave the way to a class of devices based on active materials chemically engineered via this solid-state/vapor phase approach in vacuum.

Figure 1

Tetraphenylporphyrin ${\text{H}}_2\text{TPP}$ molecule (planar representation). The different carbon and nitrogen atomic species are shown.

Figure 2

(a) UPS (HeI 21.2 eV photon source) valence-band spectra from the ${\text{H}}_2\text{TPP}$ film and from the Er-TPP film. (b) A detailed view of the HOMO region is also shown.

Figure 3

(Color) $\text{N}1s$ core levels (background subtracted) from the ${\text{H}}_2\text{TPP}$ film and from the Er-TPP film (empty circles). The peak deconvoluted components ${\text{N}}_{\text{A}}$, ${\text{N}}_{\text{B}}$, and ${\text{N}}_{\text{S}}$ are shown (see text for details). The fit curve is the sum of the several components.

Figure 4

(Color) $\text{C}1s$ core levels (background subtracted) from the ${\text{H}}_2\text{TPP}$ film and from the Er-TPP film (empty circles). The peak deconvoluted components ${\text{C}}_{\text{A}}$, ${\text{C}}_{\text{B}}$, ${\text{C}}_{\text{C}}$, and ${\text{C}}_{\text{S}}$ are shown (see text for details). The fit curve is the sum of the several components.