Publication date: 11th March 2026
The highest expectations for future photovoltaics are undoubtedly associated with halide perovskites. This is because halide perovskite solar cells are made of abundant and low-cost materials, yet they show high solar conversion efficiencies.
Large-scale applications such as photovoltaics require scalable and well-controllable deposition methods for halide perovskite thin films. The currently used methods are simple and low-cost but are difficult to scale up for industrial mass production. Atomic layer deposition (ALD) is well known for its unique controllability and excellent scalability and can therefore become a key method in halide perovskite photovoltaics. Indeed, ALD is being widely studied for deposition of charge transfer and protective layers for halide perovskite solar cells.
In contrast, reports on ALD of halide perovskite thin films are limited to those published by our team. Our main contributions are ALD-based processes for CsPbI3 [1] and CsSnI3 [2]. Our approach to deposit halide perovskites relies on combining ALD processes of the binary iodides CsI [1], PbI2 [3], and SnI2 [2]. CH3NH3PbI3 can be prepared too, by exposing ALD-PbI2 to CH3NH3I vapor [3], but an actual ALD process for this essential compound has been missing until now.
In this work we report the world’s first ALD processes for CH3NH3I and CH3NH3PbI3. The ALD process of CH3NH3I is a key advancement since it enables, for the first time, ALD deposition of CH3NH3PbI3. This opens up new possibilities for compositional tuning of halide perovskites with ALD.
The CH3NH3I films were deposited at 20 – 80 °C using methylamine and anhydrous HI gas generated on site with a self-designed setup. Crystalline CH3NH3I films were formed at all deposition temperatures. The films consisted of grains that were tens of nanometers in size and agglomerated into larger clusters.
The CH3NH3PbI3 thin films were deposited by a two-step approach: first, a PbI2 film was deposited at 65 °C, followed by deposition of CH3NH3I on top of the PbI2 without breaking the vacuum. The PbI2 films were deposited using lead(II)bis[bis(trimethylsilyl)amide] (Pb(btsa)2) and anhydrous HI gas. The PbI2 film reacts with the CH3NH3I being deposited on it, forming CH3NH3PbI3. A sufficient number of CH3NH3I cycles results in full conversion of PbI2 to CH3NH3PbI3. The conversion of PbI2 to CH3NH3PbI3 causes the film grains to grow and merge to form a continuous network. Lowering the conversion temperature results in films with larger grains and fewer pinholes.
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