Controlling a state of material between its crystalline and glassy phase has fostered many real-world applications. Nevertheless, design rules for crystallization and vitrification kinetics still lack predictive power. Here, we identify stoichiometry trends for these processes in phase change materials, i.e. along the GeTe-GeSe, GeTe-SnTe, and GeTe-Sb2Te3 pseudo-binary lines employing a pump-probe laser setup and calorimetry. We discover a clear stoichiometry dependence of crystallization speed along a line connecting regions characterized by two fundamental bonding types, metallic and covalent bonding. Increasing covalency slows down crystallization by six orders of magnitude and promotes vitrification. The stoichiometry dependence is correlated with material properties, such as the optical properties of the crystalline phase and a bond indicator, the number of electrons shared between adjacent atoms. A quantum-chemical map explains these trends and provides a blueprint to design crystallization kinetics.

To design advanced functional materials, different concepts are currently pursued, including machine learning and high-throughput calculations. Here, a different approach is presented, which uses the innate structure of the multidimensional property space. Clustering algorithms confirm the intricate structure of property space and relate the different property classes to different chemical bonding mechanisms. For the inorganic compounds studied here, four different property classes are identified and related to ionic, metallic, covalent, and recently identified metavalent bonding. These different bonding mechanisms can be quantified by two quantum chemical bonding descriptors, the number of electrons transferred and the number of electrons shared between adjacent atoms. Hence, we can link these bonding descriptors to the corresponding property portfolio, turning bonding descriptors into property predictors. The close relationship between material properties and quantum chemical bonding descriptors can be used for an inverse material design, identifying particularly promising materials based on a set of target functionalities.

Chalcogenides possess interesting optical properties, which are attractive for a variety of applications such as data storage, neuromorphic computing, and photonic switches. Lately a group of covalently bonded chalcogenides including Sb2Se3 and Sb2S3 has moved into the focus of interest for such photonic applications, where high optical contrast as well as reliable and fast switching is of crucial importance. Here, these properties of Sb2Se3 are examined and compared with typical phase change materials such as GeSb2Te4 and Ge2Sb2Te5. Sb2Se3 is favorable for many photonic applications due to its larger band gap, yet, the maximum optical contrast achievable is smaller than for GeTe and Ge2Sb2Te5. Furthermore, crystallization needs significantly longer and exhibits a distinctively wider stochastic distribution of reflectances after crystallization, which provides challenges for the usage in photonic applications. At the same time, the glassy/amorphous state of Sb2Se3 is more stable. These differences can be attributed to differences in bonding of the crystalline state, which is more covalent for Sb2Se3. A quantum‐chemical map can help to understand and explain these trends and facilitates the design of tailored materials for photonic applications.