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Photon upconversion, particularly via triplet–triplet annihilation (TTA), could prove beneficial in expanding the efficiencies and overall impacts of optoelectronic devices across a multitude of technologies. The recent development of bulk metal halide perovskites as triplet sensitizers is one potential step toward the industrialization of upconversion-enabled devices. Here, we investigate the impact of varying additions of bromide into a lead iodide perovskite thin film on the TTA upconversion process in the annihilator molecule rubrene. We find an interplay between the bromide content and the overall device efficiency. In particular, a higher bromide content results in higher internal upconversion efficiencies enabled by more efficient charge extraction at the interface likely due to a more favorable band alignment. However, the external upconversion efficiency decreases as the absorption cross section in the near infrared is reduced. The highest upconversion performance is found in our study for a bromide content of 5%. This result can be traced back to a high absorption cross section in the near infrared and higher photoluminescence quantum yield in comparison to the iodide-only perovskite and an increased driving force for charge transfer.

Photon upconversion via triplet–triplet annihilation could allow for the existing efficiency limit of single junction solar cells to be surpassed. Indeed, efficient upconversion at subsolar fluences has been realized in bulk perovskite-sensitized systems. Many questions have remained unanswered, in particular, regarding their behavior under photovoltaic operating conditions. Here, we investigate the impact of repeated and continuous illumination on bilayer perovskite/rubrene upconversion devices. We find that variations of the underlying perovskite carrier recombination dynamics greatly impact the upconversion process. Trap filling and triplet sensitization are in direct competition: more saturated trap states in the perovskite and, thus, longer underlying perovskite photoluminescence lifetimes allow for an increased number of carriers to diffuse to the perovskite/rubrene interface and undergo charge extraction to the triplet state of rubrene. As a result, the upconversion efficiency is greatly influenced by the underlying trap density: the upconverted photoluminescence intensity increases by two orders of magnitude under continuous illumination for 4 h. This shows that the upconversion efficiency is difficult to define for this system. Importantly, these results indicate that perovskite-sensitized upconversion devices exhibit peak performance under continuous illumination, which is a requirement for their successful integration into photovoltaics to help overcome the Shockley–Queisser limit in single junction solar cells.