An investigation into the conversion of In2O3 into InN nanowires
© Papageorgiou et al; licensee Springer. 2011
Received: 9 December 2010
Accepted: 7 April 2011
Published: 7 April 2011
Straight In2O3 nanowires (NWs) with diameters of 50 nm and lengths ≥2 μm have been grown on Si(001) via the wet oxidation of In at 850°C using Au as a catalyst. These exhibited clear peaks in the X-ray diffraction corresponding to the body centred cubic crystal structure of In2O3 while the photoluminescence (PL) spectrum at 300 K consisted of two broad peaks, centred around 400 and 550 nm. The post-growth nitridation of In2O3 NWs was systematically investigated by varying the nitridation temperature between 500 and 900°C, flow of NH3 and nitridation times between 1 and 6 h. The NWs are eliminated above 600°C while long nitridation times at 500 and 600°C did not result into the efficient conversion of In2O3 to InN. We find that the nitridation of In2O3 is effective by using NH3 and H2 or a two-step temperature nitridation process using just NH3 and slower ramp rates. We discuss the nitridation mechanism and its effect on the PL.
Group III-Nitride (III-N) semiconductors have been investigated extensively over the past decades due to their applications as electronic and optoelectronic devices. In addition, they are promising for the realization of high efficiency, multi-junction solar cells since their band-gaps vary from 0.7 eV in InN through to 3.4 eV in GaN up to 6.2 eV in AlN; thereby, allowing the band gaps of the ternaries In x Ga1-x N and Al x Ga1-x N to be tailored in between by varying x. Nanowires solar cells (NWSCs) are also receiving increasing attention but so far they have been fabricated from Si and metal-oxide (MO) NWs. Nitride NWs such as InN , GaN  and AlN  are, therefore, promising for the realization of full-spectrum third generation NWSCs. However, their growth and properties must be understood beforehand in order to make nanoscale devices. So far we have grown InN  and GaN NWs  using the direct reaction of In or Ga with NH3, while more recently we showed that Ga2O3 NWs may be converted to GaN by post-growth nitridation using NH3 and H2. Here, we have undertaken a systematic investigation into the conversion of In2O3 to InN NWs, which has not been carried out previously by others, thereby complementing our earlier work on the conversion of Ga2O3 to GaN NWs.
Therefore, we have grown straight In2O3 NWs with diameters of 50 nm and a high yield and uniformity. We find that the post-growth nitridation of In2O3 NWs using NH3 leads to the elimination of the NWs above 600°C. The In2O3 NWs are preserved for temperatures less than 700°C but are not converted into InN even after long nitridation times of 6 h. However, the nitridation process was enhanced significantly via the use of H2 or by employing a two-step temperature nitridation process, which also lead to a suppression of the photoluminescence (PL) peak at 550 nm similar to the nitridation of Ga2O3 NWs .
Initially In2O3 NWs were grown using an atmospheric pressure chemical vapour deposition (APCVD) reactor described elsewhere . For the growth of In2O3 NWs, 0.2 g of fine In powder (Aldrich, Cyprus, Mesh 100, 99.99%) was weighed and loaded in a quartz boat, while square pieces of n + Si(001) ≈ 7 mm × 7 mm, coated with ≈1.0 nm of Au, were loaded at various distances from the In. The Au layer was deposited via sputtering using Ar under a pressure of ≈10-2 mBar. The boat was positioned directly above the thermocouple used to measure the heater temperature at the centre of the 1" quartz tube (QT). Another quartz boat with ≈5 ml of de-ionised (DI) H2O was positioned at the inlet of the tube. After loading the boats at room temperature (RT), Ar (99.999%) was introduced at a flow rate of 500 standard cubic centimetres per minute (sccm) for 10 min. Following this, the temperature was ramped to 850°C under a flow of 50 sccm Ar using a ramp rate of 30°C/min. Upon reaching the growth temperature (T G), the flow of Ar was maintained at 50 sccm for 30 min in order to grow the In2O3 NWs after which the reactor was allowed to cool down in a flow of 50 sccm of Ar for at least 30 min. The sample was always removed only when the temperature was lower than 100°C.
Summary of post-growth nitridation conditions for the conversion of In2O3 NWs to InN.
(I) T N (°C)
500°C, 3 h
500°C, 6 h
600°C, 1 h
600°C, 2 h
600°C, 3 h
The morphology of the as grown In2O3 NWs and those treated with NH3 were examined with a TESCAN scanning electron microscope (SEM), while their crystal structure and phase purity were investigated using a SHIMADZU, X-ray diffraction (XRD-6000), with Cu-Ka source, by performing a scan of θ - 2θ in the range between 10° and 80°. Finally, PL measurements were carried using above bandgap (approx. 3.75 eV ) excitation at 267 nm. The pulse excitation was the second harmonic of a beam from an optical parametric amplifier pumped with a mode-locked TiSapphire laser. The pulses were 100 fs FWHM at a repetition rate of 250 kHz. The energy per pulse incident on the samples was 40 pJ over a spot of 2 mm in diameter.
Results and discussion
Next, we will describe the conversion of In2O3 NWs into InN and in particular consider the nitridation of In2O3 NWs at different temperatures. To begin with In2O3 NWs were subjected to 250 sccm of NH3 for 1 h at various temperatures between 500 and 900°C as listed in Table 1.
The XRD spectra of the In2O3 NWs treated at different temperatures is shown in Figure 2. As can be seen most of the oxide peaks disappear at temperatures >600°C. However, a new peak appears, which corresponds to the (101) crystallographic direction of InN . Furthermore, SEM images reveal that the In2O3 NWs have been eliminated above 600°C, but a thin layer of InN remains on the Si(001). Evidently, the nitridation of the In2O3 NWs is destructive above 600°C due to the fast decomposition of In2O3 to In2O, which is a gas. We should also point out that in addition to the temperature we also varied the nitridation time. In particular, we carried out nitridations of In2O3 NWs at 500 and 600°C under a flow of 125 sccm NH3 for different times as described in Table 1.
In addition, the two-step process lead to the effective conversion of In2O3 NWs to InN using just NH3. In this case, the temperature was ramped at 10°C/min up to 500°C and held constant over a period of 1 h, after which the temperature was ramped again slowly to 700°C in order to promote the nitridation. Recall that the In2O3 NWs were eliminated during a single-step nitridation process at 700°C using a fast ramp rate of 30°C/min. However, it should be noted that the NWs treated by this two-step temperature nitridation process were bent probably due to the fact that the crystal structure changes from bcc to the hexagonal wurtzite structure, and there is a non-uniform strain distribution between the core and shell. The effect of the post-growth nitridations on the PL of the In2O3 NWs is shown in Figure 3.
In the case of the nitridation using just NH3 for 3 h at 500°C, one may observe that there is no substantial change in the shape of the PL of the In2O3 NWs except from the fact that the PL intensity has been reduced. However, the nitridation of the In2O3 NWs using NH3 and H2 leads to a clear suppression of the peak at 550 nm, which is attributed to oxygen consistent with previous investigations on Ga2O3. The peak around 400 nm maybe attributed to In vacancies , but not O2 as commonly suggested [11–13]. However, further work is required to clarify the origin of the PL peak around 400 nm.
Straight In2O3 NWs with diameters of 50 nm, lengths ≥2 μm and a bcc crystal structure have been grown on Au/Si(001) via the wet oxidation of In at 850°C. These exhibited two broad peaks in the PL, centred around 400 and 550 nm. The post-growth nitridation of In2O3 NWs was found to be effective by using NH3 and H2 at 500 and 600°C or a two-step temperature, nitridation process at 500 and 700°C. This lead to a suppression of the PL peak around 550 nm related to O2 consistent with previous investigations on Ga2O3. In contrast, single-step temperature, nitridations using just NH3, carried out with fast ramp rates above 600°C lead to the complete elimination of the In2O3 NWs, while they were not effective at 500 and 600°C.
atmospheric pressure chemical vapour deposition
body centred cubic
nanowires solar cells
scanning electron microscope
This work was supported by the Research Promotion Foundation of Cyprus under grant BE0308/03.
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