Chinese Journal of Electronics Vol.18, No.4, Oct.

2009

Synthesis and IR Vibrational Spectrum on GaN Nanocrystalline Prepared by Sol-gel Method

LI Enling1, MA Deming1, WANG Xuewen2 , QI Wei1 and ZHU Hong1
(1.Science School, Xian University of Technology, Xian 710048, China) (2.Electronic Information Science and Engineering School, Northwestern University, Xian 710068, China)
Abstract High quality GaN nanocrystalline has been prepared by sol-gel method. The results of X-ray diraction (XRD), Selected-area electron diraction (SAED) and High-resolution transmission electron microscopy (HRTEM) measurement indicate that as-prepared sample is single crystalline GaN with wurtzite structure. Transmission electron microscopy (TEM) displays that the diameters of the grains of GaN nanocrystalline change from 30nm to 100nm. X-ray photoelectron spectroscopy (XPS) conrms the formation of the bond between Ga and N in the sample, and IR spectrum measurement showed E1 (TO) vibrational modes at 570cm1. Vibrational frequency of GaN small clusters has been calculated using Density functional theory (DFT). Using the result, IR spectrum of the sample has been analyzed further. Key words GaN, Nanocrystalline, Sol-gel, Density functional theory (DFT).

method. The crude materials are Ga2 O3 powder, the mixture of concentrated HCl and HNO3, citric acid, acetone, ammonium hydroxide, ethylenediamine and 99.99% free ammonia. Structure, composition and vibrational spectrum of the GaN nanocrystalline have been analyzed respectively in XRD, TEM, XPS and IR spectrum. Vibrational frequency of GaN small clusters has been calculated using Density functional theory (DFT), IR spectrum of the sample has been analyzed further.

II. Experimental
Firstly, about 7.25g Ga2 O3 has been dissolved in the mixture of concentrated HCl and HNO3, and the solution has been neutralized to pH 7.58.0 by adding ammonium hydroxide. Then an overdose Citric acid (CA) has been added in the solution. The solution has been stirred with a magnetic stirrer at 350K temperature for 2.5 hours to obtain white shiny crystals which are Ga-citrate-amine crystals ((NH4)3[Ga(C6 H5O7 )2]4H2 O). The crystals have been ltered, then washed with acetone, and heated for drying at 400K temperature in a vacuum desiccator. Having been entirely grounded with a full ball-milling process, then the dried crystalline has been dissolved into ethylenediamine at room temperature, and stirred with the magnetic stirrer for 2 hours to ensure complete mixing. The uniformly transparent and lightyellow sol thus formed and is rather stable. It took several days to be gelated in the desiccator at room temperature. Subsequently, the gel has been dried in the desiccator at 423K for 4 hours, and calcined at 673K for 1 hour in a mue furnace, then has been entirely grounded with a ball mill, and treated for 3 hours after free ammonia in an atmosphere furnace with a quartz tube. In the ammoniating period, the gas ow of free ammonia is 300 ml/h, the temperature has been up to 950K at 10K/min heating-up rate.

I. Introduction
Gallium nitride (GaN) is a promising optoelectronic material because of the excellent property and direct wide band gap (Eg = 3.45 eV at room temperature), so the electronic and optoelectronic devices made of GaN and related materials have been developed in recent years, for example hightemperature and high-power transistors, blue and ultraviolet (UV) Light emitting diodes (LEDs), and so on[13] . Owing to the great prospects of GaN nanomaterials in devices applications and the low-cost nanotechnology, GaN nanomaterials have attracted extensive interests in the related study[47]. Since direct application of the complex materials of high molecular quantum dots and vapor synthesis of excellent onedimensional and bulk GaN materials are needed, it is the key to synthesize well-crystallized GaN nanomaterials with even grain diameter. GaN nanocrystalline has been synthesized with Ga2 O3 by Di Lello and his co-workers, as well as Cho and his co-workers[7,8], and has composed with GaAs by Isherwood and his co-workers[9] , with GaP by Gao et al.[10]. In this paper, GaN nanocrystalline with good quality has been prepared by a simple and cost-eective sol-gel
Manuscript

III. Results and Discussion

Fig.1 shows XRD pattern of the samples. All the dirac-

Received June 2008; Accepted Mar. 2009. This work is supported by Xian Science and Technology Fund (No.Y07064), Xian Applied Materials Innovation Fund Application (No.XA-AM-200812), Doctor Startup Fund of Xian University of Technology (No.108-210904).

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tion peaks are completely consistent with the standard card of GaN, and the peaks can be indexed to a hexagonal wurtzite GaN with lattice constants of a = 0.3186nm and c = 0.5178nm. There is no diraction peaks from other impurities in any of our samples, which indicates that the sample is of high purity, and the sharp diraction peaks also reveal that the sample is highly crystallized.

Fig. 1. XRD pattern of the GaN nanocrystalline

The TEM images of the samples are given in Fig.2. In Fig.2(a), the diameters of the grains of the powder change from 30nm to 100nm. A High resolution TEM (HRTEM) lattice image and the corresponding Selected area electron diraction (SAED) of an individual grain are shown in Fig.2(b). The regular and order diraction spots correspond with the different planes of hexagonal wurtzite GaN, which explains that the sample is single crystal and is in accordance with the preceded XRD result. The spacing between adjacent fringes is about 0.246 nm which is similar to the spacing of 0.243 nm between two (101) lattice planes, which further indicates that the growth direction of the GaN nanograin is perpendicular to the (101) plane.

cm1 is close to Ga-N stretch vibrational frequency of GaN. Vibrational frequencies of Gan N (n = 2 8) and Gan N2 (n = 3 7), GaNm (m = 2 7) and Ga2 Nm (m = 3 6), Gan Nn (n = 2 6) clusters have been calculated using Density functional theory (DFT), B3LYP/631G level in Gaussian03. The frequencies of single Ga-Ga bond, Ga-N bond and N-N bond are 200.0 cm1 (from Ga2 cluster), 761.5 cm1 (from GaN cluster) and 2457.6 cm1 (from N2 cluster) respectively. The rst three intensity vibrational frequencies of the clusters are showed in Table 1 and Table 2 (intensity I1 > I2 > I3). The geometric structure of ground state and lower state of the clusters are showed in Refs.[1214]. The vibrational frequencies of the Ga reached clusters in Table 1 are close to the peaks of the phonon vibration modes of the wurtzite structure GaN. The most intensively vibrational frequencies of N reached clusters in Table 2 are all near to 2200 cm1 , some of the vibrational frequencies of Gan Nn (n = 2 6) clusters are also close to 2200 cm1. Then 2200 cm1 is an intensive vibrational frequency of N-N bond stretch in N reached GaN. In addition, some of the vibrational frequencies in Table 2 are close to 1300 cm1, this is a weak vibrational frequency of N-N bond stretch in GaN. The peak at 1384 cm1 in Fig.3 is close to this frequency. The peak at 1630 cm1 in Fig.3 is a multiple or sum frequency of other vibrational frequencies. The full scanning spectrum of XPS has been showed in Fig.4(a). In the XPS spectrum, the main elements contained in GaN nanocrystalline are Ga, N, C and O. The corresponding photoelectron emission peaks are of Ga3d (19.6eV), Ga3p

Fig. 2. (a) Typical TEM image of the GaN nanocrystalline; (b) HRTEM lattice image of an individual grain of the GaN nanocrystalline, inset is the SAED pattern

Fig. 3. IR spectrum of GaN nanocrystalline

Fig.3 shows IR spectrum of GaN nanocrystalline. The peak at 570cm1 is E1 (TO) vibrational modes[11] , and the peak has shift to high energy because of the small size eects, surface and interface eects or stress and strain of GaN nanocrystalline. The peak at 996
Fig. 4. XPS spectra of the GaN nanocrystalline