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The precipitation of iron carbides is a crucial factor that determines the properties of tempered martensite. However, the effect of alloying elements on the carbon concentration of ε carbide has not yet been clarified. In this work, we studied the effect of alloying elements on the carbon concentration of ε carbide using first-principles calculations and a three-dimensional atom probe. The first-principles calculations showed that ε carbide with a lower carbon concentration tends to form by the inclusion of Si. The carbon concentration in ε carbide measured by the three-dimensional atom probe was consistent with the first-principles calculations.