We propose a new time ($t$)-resolved method of both vertical- and horizontal-temperature gradients in an orthogonal configuration $\left[t\text{−}\mathrm{resolved}T\right(t\left)\text{−}\mathrm{HVOT}\right]$ to provide real interpretations of the enhancement in the thermoelectric Seebeck effect (SE) observed during the structural phase transition. We apply our new method to superionic-state semiconductors of $p$-type $\mathrm{C}{\mathrm{u}}_2\mathrm{Se}$ and $n$-type $\mathrm{A}{\mathrm{g}}_2\mathrm{S}$. The experimental data differentiate the two types of enhancements during the phase transition: a colossal SE ($S_{\mathrm{colossal}}$), exhibiting an enormous value of 5 to 10 mV/K, and a slight enhancement in SE ($S_{\mathrm{structure}}$), approximately 1.5 to 2.0 times larger than those in the absence of the phase transition. We provide critical insights that the enhancement in $S_{\mathrm{colossal}}$ arising during the structural phase transition is not an intrinsic phenomenon. In addition, $S_{\mathrm{structure}}$ also requires more careful discussion, based on the principle of the Seebeck phenomenon.

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• Electrical properties
• Structural phase transition
• Thermodynamics
• Thermoelectric effects
• Thermoelectrics
• Transport phenomena