The use of CH
4 as an energy source is increasing every day. To increase the efficiency of CH
4 combustion and ensure that the equipment meets ecological requirements, it is necessary to measure the CH
4 concentration in the exhaust gases of combustion systems. To this end, sensors are required that can withstand extreme operating conditions, including temperatures of at least 600 °C, as well as high pressure and gas flow rate. ZnGa
2O
4, being an ultra-wide bandgap semiconductor with high chemical and thermal stability, is a promising material for such sensors. The synthesis and investigation of the structural and CH
4 sensing properties of ceramic pellets made from pure and Er-doped ZnGa
2O
4 were conducted. Doping with Er leads to the formation of a secondary Er
3Ga
5O
12 phase and an increase in the active surface area. This structural change significantly enhanced the CH
4 response, demonstrating an 11.1-fold improvement at a concentration of 10
4 ppm. At the optimal response temperature of 650 °C, the Er-doped ZnGa
2O
4 exhibited responses of 2.91 a.u. and 20.74 a.u. to 100 ppm and 10
4 ppm of CH
4, respectively. The Er-doped material is notable for its broad dynamic range for CH
4 concentrations (from 100 to 20,000 ppm), low sensitivity to humidity variations within the 30–70% relative humidity range, and robust stability under cyclic gas exposure. In addition to CH
4, the sensitivity of Er-doped ZnGa
2O
4 to other gases at a temperature of 650 °C was investigated. The samples showed strong responses to C
2H
4, C
3H
8, C
4H
10, NO
2, and H
2, which, at gas concentrations of 100 ppm, were higher than the response to CH
4 by a factor of 2.41, 2.75, 3.09, 1.16, and 1.64, respectively. The study proposes a plausible mechanism explaining the sensing effect of Er-doped ZnGa
2O
4 and discusses its potential for developing high-temperature CH
4 sensors for applications such as combustion monitoring systems and determining the ideal fuel/air mixture.
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