Direct 3D Lithography of Reversible Photochromic Patterns with Tunable Luminescence in Amorphous Transparent Media

The integration of reversible photochromism and multicolor luminescence modulation in transparent glass offers significant potential for high-capacity, nonvolatile 3D optical storage. However, achieving effective multicolor luminescence modulation and 3D patterning remains a challenge. This study introduces a Mn²⁺/Sb⁵⁺ charge compensation mechanism to induce purple photochromism in gallium silicate glass via the Mn²⁺ → Mn³⁺ transition under 532 nm laser irradiation. The effect is fully reversible, with efficient thermal erasure. By codoping Tb³⁺ and Mn²⁺, wavelength-independent red and green luminescence modulation enables multidimensional optical encoding. Arbitrary 3D photochromic patterns are directly inscribed using a 532 nm laser and decoded via tunable luminescence. This multimodal system advances 4D optical storage by combining 3D spatial dimensions with tunable luminescence intensity multiplexing. Mn²⁺/Tb³⁺ doped gallium silicate glass represents a breakthrough for 3D information display, data encryption, and insights into photochromic mechanisms in transition-metal-doped photonic systems.