3.2 Germanium Deposition
3.2.1 Germanium Thin Films
Films of Ge were electrodeposited from [GeI3]- onto TiN electrodes from [EMIM][BF- 4]/[EMIM][GeI3] and [NnBu4][BF4]/ [NnBu4][ GeI3] in supercritical CH2F2 (deposition by
Charlie Cummings at the University of Southampton). TiN was chosen as an electrode as, unlike gold, it does not form alloys with Ge.128-129 Deposition was undertaken for 4000 s at -
1.05 V versus Ag|LaF3 in scCH2F2 at 19.1 MPa and 358 K from a) 16 mM [EMIM][GeI3]
with 60 mM [EMIM][BF4] and b) 16 mm [NnBu4][ GeI3] with 60 mM [NnBu4][BF4].
A deposition rate of 3.22 C cm-2 h-1 and 4.32 C cm-2 h-1 was calculated through
integration of the current in the chronoamperograms, Figure 3.1 A, for the [NnBu
4]+ and
[EMIM]+ electrolytes respectively. Assuming 100% faradaic efficiency this corresponds to
a plating rate of 2.27 and 3.04 µm h-1 which is comparable to reported deposition rates for
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This may be explained by the experimental set up, in which an undivided cell is used during the electrodeposition process, therefore allowing mixing and reactions from the counter electrode and the working electrode.
Figure 3.1: A) Chronoamperogram recorded for Ge deposition from electrolyte i) [EMIM]+
and ii) [NnBu
4]+. B) SEM cross section of as-deposited Ge films from i) [EMIM]+ and ii)
[NnBu
4]+ systems. C) Low- and D) High – magnification SEM images of [EMIM]+ system
highlighting the low coverage and Ge grain size. E) Low- and F) High – magnification SEM images of [NnBu
4]+ system highlighting larger Ge grain size.
The as-deposited films were initially analysed with SEM followed by XRD and Raman then finally by TEM. Cross-sectional imaging of both samples reveals similar film
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thicknesses of 1 – 2 µm for both the [EMIM]+ and [NnBu
4]+ systems, Figures 3.1 B i and ii
respectively. The effect of the different cations can clearly be seen when examining the surface of the films. The [EMIM]+ system has considerably less coverage with regions of
bare TiN visible across the sample, Figure 3.1 C and D. This may be a result of delamination during depressurisation or poor surface adhesion. The Ge that is deposited forms in grains of 0.1 – 1 µm. The [NnBu
4]+ system has considerably better coverage with much larger grains
of 2 – 5 µm, Figure 3.1 E and F. Again delamination is observed but this cracking delamination is similar to that reported by Klavetter for Ge electrodeposition.132 EDX
analysis highlighted a number of impurities within the sample, including O, I and F. O is expected as Ge is known to readily oxidise in atmosphere. It is believed that the I and F arise from the depressurisation of the supercritical fluid, leaving precipitates on the electrode surface. It was found that washing the sample in dichloromethane decreased the concentration of contaminates.
Figure 3.2: XRD for as-deposited Ge film (blue) and the same film post annealing at 700 º C under argon (red). (Acquired by A. Hector, University of Southampton)
Grazing incidence XRD of the as-deposited films in Figure 3.2 show two broad features around 27º and 50º with sharp reflection arising from the substrate and electrolyte components. The broad features may be the result of amorphous Ge attributed to the 111, 220 and 311 Ge lattice spacings. As previously stated O is present in the sample suggesting
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that the crystalline peaks are being disrupted by amorphous GeO. To remove the oxide, the samples were thermally annealed under Argon at 700 º C, this resulted in crystalline Ge in close proximity to the position of the broad features, Figure 3.2.133
Further characterisation was undertaken using Raman spectroscopy, as it is sensitive to both amorphous and crystalline materials. The as-deposited films, Figure 3.3 A and B ii), show amorphous spectra characterised by a broad hump for both systems. The post annealed films, Figure 3.3 A and B i), show a clear peak attributed to crystalline germanium however the broadness of the peak suggests that there is still a considerable amorphous signature. We have deemed this material as protocrystalline in nature, containing quantities of both amorphous and crystalline Ge.
Figure 3.3: A) Raman spectrum for i) post annealing and ii) as deposited [EMIM]+ system.
B) Raman spectrum for i) post annealing and ii) as deposited [NnBu
4]+ system. (Acquired by
J. Spencer, University of Southampton)
In further efforts to understand the nature of the protocrystalline Ge films, a sample of the post annealed [EMIM]+ system was imaged inside the TEM. The sample was prepared
by scraping the surface onto a lacey carbon film to create electron transparent flakes for investigation. Selected area electron diffraction of the Ge flakes highlights the protocrystallinity suggested from the XRD and Raman spectra, Figure 3.4 B. Both diffuse rings, consistent with amorphous materials, and bright spots, representing the repeating
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crystalline lattice, are easily observed in the selected area electron diffraction pattern (SADP). The radial intensity distribution plot, Figure 3.4 C, conveys this diffraction result in which the broad humps arise from the amorphous material and sharp peaks from individual crystallites.
Figure 3.4: A) Dark field image of Ge flake highlighting Ge crystallites embedded within amorphous Ge. B) Selected area diffraction pattern from flake including the objective aperture used to generate the dark field image. C) Radial intensity distribution of selected area diffraction pattern indicating crystallites (sharp peaks) in an amorphous membrane (broad peaks).
Bright field images show the flakes to have uniform contrast however dark-field images, generate contrast from the diffracting crystalline Ge. The embedded crystallites have a range of diameters between 5 – 30 nm. They appear to be embedded within an amorphous Ge matrix, as shown in Figure 3.4 A. Quantification of the crystallites proved impossible due to the crystallites amorphising under the electron beam.
This is the first reported case of successful electrodeposition of Ge from a supercritical fluid, in which TEM characterisation allowed for the visualisation and confirmation of a system theorised from two different measurements. The Ge flakes were
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shown to be highly beam sensitive undergoing in situ amorphisation as a result of electron beam irradiation.