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Laser initiation has attracted increasing interest owing to its extraordinary safety and high reliability. However, traditional metal complex‐based laser‐ignitable primary explosives are limited by high input laser energy and low detonation ability. In this study, an efficient laser‐ignitable primary explosive‐based copper azide is prepared by constructing core‐shell hetero‐framework Cu‐MOF@COF as the precursor. The pyrolysis of Cu‐MOF@COF hybrid material affords copper azide (CA) nanoparticle confined in a porous carbon shell, referred to CA@C Shell. The evenly coated porous carbon shell functions as light‐to‐heat conversion layer efficiently promoting the laser initiation process of inside CA. Consequently, CA@C Shell can be initiated at lower laser energy thresholds (0.80 mJ at 1064 nm). This value is significantly lower than typical laser ignitable metal complex tetraamine‐cis‐bis(5‐nitro‐2H‐tetrazolato‐N2)cobalt(III)perchlorate (726 mJ at 808 nm). Moreover, the CA@C Shell successfully detonates the secondary explosives CL‐20 by laser energy when it is assembled in a micro‐detonator system. This study offers a unique method for constructing high performance laser‐ignitable primary explosives for micro‐detonator applications.
A copper azide‐based laser ignitable primary explosive with a low laser energy threshold and high detonation power is realized by constructing a core‐shell hetero‐framework as a precursor. The resultant CA@C Shell is capable of detonating secondary explosive CL‐20 at low laser energy when assembled in micro‐electro‐mechanical systems.