Femtosecond to nanosecond excited state dynamics of vapor deposited copper phthalocyanine thin films

Vapor deposited thin films of copper phthalocyanine (CuPc) were investigated using transient absorption spectroscopy. Exciton-exciton annihilation dominated the kinetics at high exciton densities. When annihilation was minimized, the observed lifetime was measured to be 8.6 ± 0.6 ns, which is over an order of magnitude longer than previous reports. In comparison with metal free phthalocyanine (H₂Pc), the data show evidence that the presence of copper induces an ultrafast relaxation process taking place on the ca. 500 fs timescale. By comparison to recent time-resolved photoemission studies, this is assigned as ultrafast intersystem crossing. As the intersystem crossing occurs ca. 10⁴ times faster than lifetime decay, it is likely that triplets are the dominant excitons in vapor deposited CuPc films. The exciton lifetime of CuPc thin films is ca. 35 times longer than H₂Pc thin films, while the diffusion lengths reported in the literature are typically quite similar for the two materials. These findings suggest that despite appearing to be similar materials at first glance, CuPc and H₂Pc may transport energy in dramatically different ways. This has important implications on the design and mechanistic understanding of devices where phthalocyanines are used as an excitonic material.