Electron spin resonance (ESR) spectroscopy of 2,2′,7,7′-tetrakis-(N,N-di-p-methoxyphenylamine)9,9′-spirobifluorene (spiro-OMeTAD) thin films and perovskite (CH3NH3PbI3)/spiro-OMeTAD layered films are reported. Clear ESR signals (g = 2.0030) were observed by adding a dopant lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) to the spiro-OMeTAD thin films, which directly showed the spin (hole) formation in spiro-OMeTAD by the Li-TFSI doping. The number of spins in the spiro-OMeTAD thin film has increased by more than two orders of magnitude by the Li-TFSI doping under dark conditions, which demonstrates from a microscopic viewpoint that Li-TFSI has high doping effects for the spiro-OMeTAD thin films. Under simulated solar irradiation, the spin density in the spiro-OMeTAD thin films and the perovskite/spiro-OMeTAD layered films largely increased by the Li-TFST doping due to the formation of long-lived holes in spiro-OMeTAD. The transient responses of the number of photogenerated spins, Nspin, of the layered films upon the light irradiation showed the increase and the decrease in the Nspin due to the hole transfer and recombination at the perovskite/spiro-OMeTAD interface. The states of long-lived holes in the spiro-OMeTAD layers were analyzed using the simulation of the ESR spectra, which reveals the mobile photogenerated holes with a lifetime >10 μs.

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