Ligand‐Induced Digital Programmable Photochromic CdS Materials Toward Dual‐Mode Light‐Printing and Information Encryption

Abstract The explosive growth of information and its widespread availability underscores the need for robust encryption and anticounterfeiting measures. In this study, CdS quantum dots are engineered (QDs) to manifest multiple visual responses to a single trigger through strategic ligand design. The surface engineering method allows QDs to transition from yellow to black upon photoexcitation‐induced electron transfer from Cd(II) to Cd(0). Surface ligands desorption under hole injection, leading to an increase in QDs size and resulting in a redshift in photoluminescence. This photoexcitation‐induced redox reaction reveals unprecedented photochromism and photoluminescence phenomena, establishing a foundation for advanced information protection measures. Utilizing these QDs, excellent writing performance under UV irradiation is achieved in solid‐state substrates, while a dual‐mode encryption system is realized in gel matrices, opening up new avenues for information encryption as well as cumulative and interactive information protection. Furthermore, the redox reaction of CdS QDs is employed as ink for 3D printing, enabling for the creation of digitally programmable materials with distinct temporally evolving appearances by controlling the oxygen content in the ink to regulate the rate of photochromism. This advancement also sheds light on the progress in 3D printing technology.