Past exam of the chemistry A course of the University of Cambridge / 2021 / Paper 2 / A10 / b

Two derivatives of the free-electron dispersion giveThe band effective mass becomes the ordinary electron mass when no periodic-potential modification of the quadratic dispersion relation is present.

Differentiating the tight binding dispersion produced by the Hückel method givesHenceUnlike a free particle, the band effective mass depends on wavevector and can change sign. At an inflection point $\cos (ka)=0$, the inverse mass vanishes and the curvature-based mass diverges; a quadratic approximation then ceases to describe the dispersion locally. For the usual $\beta <0$ convention, the bottom at $k=0$ has positive mass and the top at $k=\pi /a$ has negative electron mass. The constant $\alpha$ has no effect on curvature.

In a weakly doped n-type semiconductor, the mobile electrons occupy states near the bottom of the conduction band. Their local band curvature is positive, so their band effective mass is positive and approximately constant sufficiently near that minimum. For the usual $\beta <0$ convention, expand about $k=0$:Stronger overlap gives larger $|\beta |$, greater curvature and a smaller mass within this model. Positive $\beta$ simply places the minimum at the zone boundary and again gives a positive edge mass. A negative electron mass near a band maximum instead motivates the positive-mass electron hole description; it is not the usual conduction-edge situation for an n-type semiconductor. No numerical comparison with $m_e$ follows without values of $a$ and $\beta$.