Past exam of the MPhil in micro- and nanotechnology enterprise course of the University of Cambridge / 2021 / Paper 1 / 8 / i

The main characteristic peaks identify nickel and phosphorus: the spectrum has a strong Ni $K\alpha$ peak near $7.48\mathrm{keV}$, the Ni $L$ region near $0.85\mathrm{keV}$ and P $K\alpha$ near $2.01\mathrm{keV}$. Weaker associated lines, including Ni $K\beta$ near $8.26\mathrm{keV}$, can accompany them. The continuous background is bremsstrahlung from decelerated electrons.

Small carbon and oxygen signals at low energy can arise from contamination, surface oxide or preparation materials; a copper contribution can arise from the adjacent substrate within the finite interaction volume. The Cu $L$ region lies close to Ni $L$, so overlap is particularly troublesome at low energy. A weak Cu $K\alpha$ contribution near $8.04\mathrm{keV}$ is better separated, though still close to Ni $K\beta$. At $30\mathrm{kV}$ the beam can excite these K lines.

Peak height is not an atomic fraction: ionization cross-sections, fluorescence yields, absorption, detector response, background and line overlap require correction. The large nickel peak therefore supports the nickel-rich assignment but does not directly give the nickel-to-phosphorus atomic ratio.

Use the supplied polynomial as an effective-atomic-number approximation for the alloys. Interpreting each quoted phosphorus number as an atomic fraction $x_P=N_P/(N_P+N_{\mathrm{Ni}})$,The gold reference yield is $\eta (79)=0.486996$. Substitution gives:

The ordering is gold brightest, then copper, NiP${}_z$, NiP${}_x$ and NiP${}_y$. The phosphorus-rich layer has the lowest effective atomic number.

There is a wording ambiguity in “atomic fraction of P relative to Ni.” If those numbers instead mean $r=N_P/N_{\mathrm{Ni}}$, first convert $x_P=r/(1+r)$, giving $\bar{Z}=(28+15r)/(1+r)$. The three alloy contrasts then become $0.4243$, $0.4361$, $0.4129$, respectively. The qualitative ordering is unchanged. Both calculations explicitly use $\eta (\bar{Z})$; this simple alloy approximation is not a full electron-transport simulation.

Atomic-number contrast can explain why the gold-rich regions are bright and why the phosphorus-rich NiP${}_y$ layer should be somewhat darker than the other nickel–phosphorus layers. However, the calculated alloy yields differ only modestly: the NiP${}_y$ and NiP${}_z$ yields differ by about $5.5\%$ relative to NiP${}_z$. Composition-only backscattering does not explain all of the strong local edge and defect contrast.

An Everhart–Thornley detector normally collects secondary electrons, not a pure backscattered-electron signal. Secondary-electron escape and collection depend strongly on local slope and edge geometry. Differential polishing, relief at interfaces, a crack or cavity, surface oxidation and local charging can therefore alter brightness without the corresponding change in bulk atomic number. backscattered electrons can also generate secondary electrons elsewhere. Crystallographic channeling and orientation can contribute additional contrast. The observed dark and bright areas should therefore be correlated with topography and composition rather than assigned a phase from intensity alone.