Gallium nitride (GaN) nanostructures were successfully synthesized by the nitridation of the electrochemically deposited gallium oxide (Ga2O3) through the utilization of a so-called ammoniating process. Ga2O3 nanostructures were firstly deposited on Si substrate by a simple two-terminal electrochemical technique at a constant current density of 0.15 A/cm(2) using a mixture of Ga2O3, HCl, NH4OH and H2O for 2 h. Then, the deposited Ga2O3 sample was ammoniated in a horizontal quartz tube single zone furnace at various ammoniating times and temperatures. The complete nitridation of Ga2O3 nanostructures at temperatures of 850°C and below was not observed even the ammoniating time was kept up to 45 min. After the ammoniating process at temperature of 900°C for 15 min, several prominent diffraction peaks correspond to hexagonal GaN (h-GaN) planes were detected, while no diffraction peak of Ga2O3 structure was detected, suggesting a complete transformation of Ga2O3 to GaN. Thus, temperature seems to be a key parameter in a nitridation process where the deoxidization rate of Ga2O3 to generate gaseous Ga2O increase with temperature. The growth mechanism for the transformation of Ga2O3 to GaN was proposed and discussed. It was found that a complete transformation can not be realized without a complete deoxidization of Ga2O3. A significant change of morphological structures takes place after a complete transformation of Ga2O3 to GaN where the original nanorod structures of Ga2O3 diminish, and a new nanowire-like GaN structures appear. These results show that the presented method seems to be promising in producing high-quality h-GaN nanostructures on Si.
A seed/catalyst-free growth of ZnO on graphene by thermal evaporation of Zn in the presence of O2 gas was further studied. The effects of substrate positions and graphene thicknesses on the morphological, structural, and optical properties were found to be very pronounced. By setting the substrate to be inclined at 90°, the growth of ZnO nanostructures, namely, nanoclusters and nanorods, on single-layer (SL) graphene was successfully realized at temperatures of 600°C and 800°C, respectively. For the growth on multilayer (ML) graphene at 600°C with an inclination angle of 90°, the grown structures show extremely thick and continuous cluster structures as compared to the growth with substrate's inclination angle of 45°. Moreover, the base of nanorod structures grown at 800°C with an inclination angle of 90° also become thicker as compared to 45°, even though their densities and aspect ratios were almost unchanged. Photoluminescence (PL) spectra of the grown ZnO structures were composed of the UV emission (378-386 nm) and the visible emission (517-550 nm), and the intensity ratio of the former emission (I UV) to the latter emission (I VIS) changed, depending on the temperature. The structures grown at a low temperature of 600°C show the highest value of I UV/I VIS of 16.2, which is almost two times higher than the structures grown on SL graphene, indicating fewer structural defects. The possible growth mechanism was proposed and described which considered both the nucleation and oxidation processes. From the results obtained, it can be concluded that temperature below 800°C, substrate position inclined at 90° towards the gas flow, and ML graphene seems to be preferable parameters for the growth of ZnO structures by thermal evaporation because these factors can be used to overcome the problem of graphene's oxidation that takes place during the growth.
We report the seed/catalyst-free vertical growth of high-density electrodeposited ZnO nanostructures on a single-layer graphene. The absence of hexamethylenetetramine (HMTA) and heat has resulted in the formation of nanoflake-like ZnO structure. The results show that HMTA and heat are needed to promote the formation of hexagonal ZnO nanostructures. The applied current density plays important role in inducing the growth of ZnO on graphene as well as in controlling the shape, size, and density of ZnO nanostructures. High density of vertically aligned ZnO nanorods comparable to other methods was obtained. The quality of the ZnO nanostructures also depended strongly on the applied current density. The growth mechanism was proposed. According to the growth timing chart, the growth seems to involve two stages which are the formation of ZnO nucleation and the enhancement of the vertical growth of nanorods. ZnO/graphene hybrid structure provides several potential applications in electronics and optoelectronics such as photovoltaic devices, sensing devices, optical devices, and photodetectors.
We report a synthesis of β-Ga2O3 nanostructures on Si substrate by electrochemical deposition using a mixture of Ga2O3, HCl, NH4OH, and H2O. The presence of Ga3+ ions contributed to the deposition of Ga2O3 nanostructures on the Si surface with the assistance of applied potentials. The morphologies of the grown structures strongly depended on the molarity of Ga2O3 and pH level of electrolyte. β-Ga2O3 nanodot-like structures were grown on Si substrate at a condition with low molarity of Ga2O3. However, Ga2O3 nanodot structures covered with nanorods on top of their surfaces were obtained at higher molarity, and the densities of nanorods seem to increase with the decrease of pH level. High concentration of Ga3+ and OH- ions may promote the reaction of each other to produce Ga2O3 nanorods in the electrolyte. Such similar nature of Ga2O3 nanorods was also obtained by using hydrothermal process. The grown structures seem to be interesting for application in electronic and optoelectronic devices as well as to be used as a seed structure for subsequent chemical synthesis of GaN by thermal transformation method.
We report the growth of gallium-based compounds, i.e., gallium oxynitride (GaON) and gallium oxide (Ga2O3) on multilayer graphene (MLG) on insulator using a mixture of ammonium nitrate (NH4NO3) and gallium nitrate (Ga(NO3)3) by electrochemical deposition (ECD) method at room temperature (RT) for the first time. The controlling parameters of current density and electrolyte molarity were found to greatly influence the properties of the grown structures. The thicknesses of the deposited structures increase with the current density since it increases the chemical reaction rates. The layers grown at low molarities of both solutions basically show grain-like layer with cracking structures and dominated by both Ga2O3 and GaON. Such cracking structures seem to diminish with the increases of molarities of one of the solutions. It is speculated that the increase of current density and ions in the solutions helps to promote the growth at the area with uneven thicknesses of graphene. When the molarity of Ga(NO3)3 is increased while keeping the molarity of NH4NO3 at the lowest value of 2.5 M, the grown structures are basically dominated by the Ga2O3 structure. On the other hand, when the molarity of NH4NO3 is increased while keeping the molarity of Ga(NO3)3 at the lowest value of 0.8 M, the GaON structure seems to dominate where their cubic and hexagonal arrangements are coexisting. It was found that when the molarities of Ga(NO3)3 are at the high level of 7.5 M, the grown structures tend to be dominated by Ga2O3 even though the molarity of NH4NO3 is made equal or higher than the molarity of Ga(NO3)3. When the grown structure is dominated by the Ga2O3 structure, the deposition process became slow or unstable, resulting to the formation of thin layer. When the molarity of Ga(NO3)3 is increased to 15 M, the nanocluster-like structures were formed instead of continuous thin film structure. This study seems to successfully provide the conditions in growing either GaON-dominated or Ga2O3-dominated structure by a simple and low-cost ECD. The next possible routes to convert the grown GaON-dominated structure to either single-crystalline GaN or Ga2O3 as well as Ga2O3-dominated structure to single-crystalline Ga2O3 structure have been discussed.
A seedless growth of zinc oxide (ZnO) structures on multilayer (ML) graphene by electrochemical deposition without any pre-deposited ZnO seed layer or metal catalyst was studied. A high density of a mixture of vertically aligned/non-aligned ZnO rods and flower-shaped structures was obtained. ML graphene seems to generate the formation of flower-shaped structures due to the stacking boundaries. The nucleation of ZnO seems to be promoted at the stacking edges of ML graphene with the increase of applied current density, resulting in the formation of flower-shaped structures. The diameters of the rods/flower-shaped structures also increase with the applied current density. ZnO rods/flower-shaped structures with high aspect ratio over 5.0 and good crystallinity were obtained at the applied current densities of -0.5 and -1.0 mA/cm(2). The growth mechanism was proposed. The growth involves the formation of ZnO nucleation below 80°C and the enhancement of the growth of vertically non-aligned rods and flower-shaped structures at 80°C. Such ZnO/graphene hybrid structure provides several potential applications in sensing devices.
We report the seed/catalyst-free growth of ZnO on multilayer graphene by thermal evaporation of Zn in the presence of O2 gas. The effects of substrate temperatures were studied. The changes of morphologies were very significant where the grown ZnO structures show three different structures, i.e., nanoclusters, nanorods, and thin films at 600°C, 800°C, and 1,000°C, respectively. High-density vertically aligned ZnO nanorods comparable to other methods were obtained. A growth mechanism was proposed based on the obtained results. The ZnO/graphene hybrid structure provides several potential applications in electronics and optoelectronics.
Hydrothermal zinc oxide (ZnO) thick films were successfully grown on the chemical vapor deposition (CVD)-grown thick ZnO seed layers on a-plane sapphire substrates using the aqueous solution of zinc nitrate dehydrate (Zn(NO3)2). The use of the CVD ZnO seed layers with the flat surfaces seems to be a key technique for obtaining thick films instead of vertically aligned nanostructures as reported in many literatures. All the hydrothermal ZnO layers showed the large grains with hexagonal end facets and were highly oriented towards the c-axis direction. Photoluminescence (PL) spectra of the hydrothermal layers were composed of the ultraviolet (UV) emission (370 to 380 nm) and the visible emission (481 to 491 nm), and the intensity ratio of the former emission (I UV) to the latter emission (I VIS) changed, depending on both the molarity of the solution and temperature. It is surprising that all the Hall mobilities for the hydrothermal ZnO layers were significantly larger than those for their corresponding CVD seed films. It was also found that, for the hydrothermal films grown at 70°C to 90°C, the molarity dependences of I UV/I VIS resembled those of mobilities, implying that the mobility in the film is affected by the structural defects. The highest mobility of 166 cm(2)/Vs was achieved on the hydrothermal film with the carrier concentration of 1.65 × 10(17) cm(-3) grown from the aqueous solution of 40 mM at 70°C.