The rapidly developing fields of atomically dispersed catalysis as well as optoelectronic, photonic, and quantum information devices enabled by active dopants overlap in their need for advanced materials synthesis and microstructure control. Precise control of the engineered microstructure and electronic state distribution, in the length scale across angstroms to micrometers, is vital for device performance. Such a feat is challenging due to the tendency of dopants to diffuse and form clusters during deposition. Atomic layer deposition (ALD) through its layer-by-layer, surface-reaction-dominated growth mechanism can overcome such challenges and fabricate materials with the requisite microstructure. Methods by which ALD has chemical control over the deposited film include tuning the substrate surface chemistry (i.e., the introduction of chemically distinct anchoring sites) and tuning the precursor chemistry (i.e., modification of steric hindrance). In addition, the crystalline structure and oxidation state of ALD-grown materials can be fine-tuned by introducing annealing steps during the ALD growth. Combining these chemical modifications with engineering techniques, such as programmable supercycles, enables the fabrication of ternary and other complex materials with angstrom scale precision.