Controlled Surface Polarity and Crystallinity of Gallium Nitride on Si (111) Using Atomic Layer Deposition for Selective Wet-Etch and STEM Analysis

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Gallium nitride (GaN) has gained interest as photoelectronic materials and a buffer layer for other III-V deposition with applications in power electronics operated at high voltage and high temperature. The crystallinity and polarity of III-V semiconductors have a key role for the passivation layers on microLED, the formation of 2D electron gasses in high electron mobility transistors, and for templating growth of piezoelectric materials. The atomic layer annealing (ALA) was reported to improve the crystallinity of the III-V compounds (aluminum nitride) at low temperatures as compared to the conventional thermal ALD. In ALA, a pulse of ion bombardment is added to each ALD cycle to ensure polycrystalline film formation at low temperature. Polycrystalline GaN has been deposited by ALA at low temperatures even on amorphous substrates, but the polarity was not reported. The selective wet-etch process has several advantages for the III-V semiconductor device integration since the conventional plasma ion etching process is expensive, complicated, and leads to the surface damage by reactive plasma ion. The GaN surface polarity (N-polar or metal-polar) on sapphire was selectively etched by aqueous KOH solution. However, electrochemical etching study on the polarity of GaN ALD films has not yet been studied as types of ALD process. Figure 1a and 1b show the process parameter switching diagram for the GaN thermal ALD and GaN ALA processes, respectively. The chemical compositions of ALA and ALD GaN on Si were estimated by in-situ AES as shown in Figure 1c. Lower O content (below 3.3 at. %) and higher N/Ga atomic ratio were observed in the ALA GaN on Si (111) as compared to the thermal ALD GaN film (4.6 at. %). Figure 1d shows that the intensity of GaN (002) XRD pattern in thermal ALD GaN on Si was greatly improved in the GaN stacks (GaN thermal ALD/ALA/Si) with an ALA GaN buffer layer. The electrochemical behavior of the GaN ALD films was studied to elucidate the impact of surface polarity on selective KOH wet-etch. The linear sweep voltammograms of GaN thermal ALD and GaN ALA films in 1 M KOH solution were shown in Figure 1e. The applied potential was swept from zero (vs. Normal Hydrogen Electrode) to positive 3.7 V. The peak of current density at ~1.7 V was observed in the voltammogram of the GaN ALA film (N-polar), suggesting the occurrence of etching reaction by the dissolution and formation via the equations in Figure 1f. On the other hand, the absence of current density peak in the GaN thermal ALD film (Ga-polar) could suggest the unfavorable etching reaction as compared to the GaN ALA film. Figure 2a and 2b shows the HAADF-STEM images of ALD GaN on Si demonstrate highly ordered 3 nm x 5 nm ALD GaN layers with bright and dark regions. The circles of bright regions and the center of dark regions represent Ga atoms and tunnel points (empty element), respectively. The GaN polarity could be determined by drawing triangles connecting adjacent three tunnel points without the interruption of Ga. Using this method, upward triangles were obtained in the HAADF-STEM image (Figure 2a), suggesting the formation of N-polar GaN layers during the ALA GaN process on Si. Conversely, downward triangles from the STEM image of thermal ALD GaN /ALA GaN /Si (Figure 2b) suggested Ga-polar GaN during GaN thermal ALD process. The inset figures show the top-view SEM image of selectively wet-etched (30 min, 20 wt.% KOH (aq)) GaN films. The etched surface on the ALA GaN layers (inset of Figure 2a) indicated N-polar GaN surface. The inset SEM image in Figure 2b shows a nearly unchanged GaN surface in thermal ALD GaN /ALA GaN / Si is consistent with the Ga-polar GaN surface. These observations are in good agreement with the HAADF-STEM images.The data is consistent with being able to control the polarity of GaN by switching between thermal ALD and ALA. The ion bombardment in ALA promotes N-polar GaN while thermal ALD promotes metal polar GaN. This allows the facile formation of both electron and hole gas layers between ALA and ALD GaN. Figure 1