Fabrication and properties of ZnO/GaN heterostructure nanocolumnar thin film on Si (111) substrate
© Wei et al.; licensee Springer. 2013
Received: 29 December 2012
Accepted: 11 February 2013
Published: 28 February 2013
Zinc oxide thin films have been obtained on bare and GaN buffer layer decorated Si (111) substrates by pulsed laser deposition (PLD), respectively. GaN buffer layer was achieved by a two-step method. The structure, surface morphology, composition, and optical properties of these thin films were investigated by X-ray diffraction, field emission scanning electron microscopy, infrared absorption spectra, and photoluminiscence (PL) spectra, respectively. Scanning electron microscopy images indicate that the flower-like grains were presented on the surface of ZnO thin films grown on GaN/Si (111) substrate, while the ZnO thin films grown on Si (111) substrate show the morphology of inclination column. PL spectrum reveals that the ultraviolet emission efficiency of ZnO thin film on GaN buffer layer is high, and the defect emission of ZnO thin film derived from Zni and Vo is low. The results demonstrate that the existence of GaN buffer layer can greatly improve the ZnO thin film on the Si (111) substrate by PLD techniques.
ZnO is attractive for its various applications in electrical and optical devices by employing excitonic effects since it possesses promising wide and direct bandgap (3.37 eV at room temperature) and much larger exciton binding energy (60 meV) [1, 2]. There has been considerable research interest in ZnO due to many potential applications in short wavelength for optoelectronic devices operating in the blue and ultraviolet (UV) region such as light-emitting diodes (LED) and gas-sensing applications . It is found that a proper substrate is crucial to achieve a high-quality ZnO thin film and nanostructure . Many substrates such as silicon, sapphire, quartz, etc. have been used to fabricate ZnO films [5–7]. Among these, Si is the most popular substrate due to its low cost, high crystalline perfection, and high productivity in large-area wafer. However, the large mismatch of lattice constants and thermal expansion coefficients between ZnO and Si will deteriorate the optical property of the ZnO films on Si substrates [8, 9]. The employment of buffer layers such as GaN , MgO , and SiC  becomes a positive way to solve this problem. GaN is a perfect candidate because it has similar crystal structure as ZnO, and the lattice mismatch is 1.8 % on the c-plane; furthermore, the thermal expansion coefficients of ZnO are close to those of GaN. Recently, ZnO films have been grown on GaN template using molecular beam epitaxy, metal-organic chemical vapor deposition, magnetron sputtering, pulsed laser deposition (PLD), etc. [13–15]. Jang et al. [16, 17] grew different ZnO nanostructures on GaN epitaxial layers via a hydrothermal method generating a variety of structures including rod-, sea urchin-, and flower-like structures. Studies on the growth of GaN-based and ZnMgO/MgO heterostructure materials have proved that column crystal growth is an effective way to relax part of the stress and improve the quality of the epitaxial layers [18–20]. That is, the formation of nanocolumnar microstructure allows the combination of materials with large lattice mismatch without generating dislocations, bringing on some novel low-dimensional physical phenomena.
In this paper, we obtained the novel ZnO/GaN heterostructure by growing GaN nanocolumns on Si substrate with PLD method, and then the annealing process was used to improve the crystallinity, respectively. The structure, surface morphology, composition, and optical properties of ZnO/GaN/Si thin films were investigated by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), infrared (IR) absorption spectra, and photoluminescence (PL) spectra.
Samples and measurements
First, GaN thin films were grown on Si (111) substrate by PLD at the growth temperature of 800°C using a GaN ceramic target. The film deposition was carried out in a stainless steel vacuum chamber evacuated by a turbomolecular pump to a base pressure of 5.6 × 10−5 Pa. A pulsed Nd:YAG laser with a wavelength of 1,064 nm (repetition 10 Hz, duration 10 ns) was focused by a lens on the ZnO target at an angle of incidence of 45°. During the deposition, the laser incident energy was maintained at 300 mJ/pulse. The size of the ablation spot is about 0.5 mm in diameter. A series of Si (111) substrate was placed at 40 mm from the target surface. For the ZnO target ablation and even thin film fabrication, GaN target and substrate rotated reversely with a frequency of 7 rpm. GaN films were deposited in the nitrogen background of 1.3 Pa, and depositing time was 15 min. The thickness of GaN thin films measured is about 50 nm. Second, the samples were placed on a quartz carrier and annealed in a high-temperature tube quartz furnace. After the furnace reached the equilibrium temperature of 1,000°C the carrier with the GaN samples was placed in a constant temperature region of the furnace. Flowing N2 was introduced into the tube for 5 min at a flow rate of 100 ml/min to flush out the residual air. Then, we terminated N2 flow and introduced NH3 into the tube at a flow rate of 800 ml/min for 20 min. Finally, the NH3 was flushed out by N2 introduced into the tube for another 5 min before the carrier was removed from the furnace. Third, ZnO thin films were fabricated on GaN (111) template by PLD at a growth temperature of 400°C in O2 ambience with a pressure of 1.3 Pa using a ZnO ceramic target. The laser incident energy was maintained at 200 mJ/pulse, and depositing time was 60 min. The thickness of ZnO thin films is about 600 nm, which was measured by the weight technique. The structural properties of thin films were studied by Rigaku D/max-rB XRD (Tokyo, Japan) spectroscopy with Cu Kα line radiation at 0.15418 nm. The surface morphology and the microstructure were studied using FESEM (QUANTA 250, FEI Co., Hillsboro, OR, USA). The IR spectra were acquired using a BRUKER TENSOR27 spectrophotometer (Bruker Optik Gmbh, Ettlingen, Germany; wavenumber range 400 to 4,000 cm−1, optical resolution 4 cm−1, transmission mode). The optical properties of ZnO thin films were characterized by photoluminescence spectra with the excitation wavelength of 320 nm pumped by Xe lamp.
Results and discussion
Structural property of ZnO/GaN thin films
XRD peaks of ZnO films grown on GaN/Si substrate show merely (002) orientation, and an obvious promotion of crystalline quality of ZnO thin film grown on GaN/Si substrate can be obtained. Moreover, the (002) positions of ZnO and GaN show that the ZnO has very similar c-axis lattice parameter with GaN. The XRD pattern indicates that the growth direction of ZnO/GaN/Si is , and the orientation relationship with GaN epilayer is ZnO//GaN. This implies that ZnO (002) plane is synthesized parallel to the basal plane of the GaN epitaxial layer substrate.
Figure 2a,b,c shows the SEM photographs of ZnO/Si films, GaN/Si films, and ZnO/GaN/Si films. Large and uneven grains are distributed on the ZnO surface for the thin film grown on Si (111) substrate as shown in Figure 2a. In Figure 2b, the incline columnar GaN structure annealed on the Si (111) substrate is presented. Besides, the obvious increase of crystalline grain with the hexagonal ZnO wurtzite structure is observed in Figure 2c; the incline columnar growth on the Si (111) substrate is transformed into a nanoflower grain on GaN/Si (111) template as shown in Figure 2c. Figure 2c illustrates that the surface property of ZnO/GaN/Si thin film is improved, and the thin film becomes more even than ZnO/Si film. It demonstrates that the quality of ZnO thin film was improved due to epitaxial growth of crystalline grain by GaN epitaxial layer. The reason is that the GaN buffer layer, especially nanocolumn, plays an important role for the epitaxial growth of ZnO thin films. As shown in Figure 2c, a lot of grains with hexagonal ZnO wurtzite structure can be observed. It is beneficial for growing high-quality epitaxial ZnO thin films on a GaN template. Figure 2d shows the cross-sectional images of the ZnO nanostructure on GaN/Si (111) substrates. The nanoflower ZnO nanostructure with the size of about 1 μm on the surface of thin film can be observed.
Compared with the growth of the most heterostructure with compact structure, the ZnO/GaN heterostructure interface in this study is loose, that is, the growth of ZnO nanostructure on GaN thin film with a column crystal. Also, the PL spectra of the ZnO grown on the GaN shows that the UV emission based on column crystal growth of ZnO has a higher emission efficiency and power than that grown with the conventional method.
From the EDX spectrum of ZnO nanostructure in Figure 2e derived from Figure 2c, the existence of the Zn and O peaks represented the elementary characterization of ZnO nanostructure. After the quasi-quantitative determination of the EDS spectrum, the weight percentages of O and Zn (K) were 38.23 and 11.98, respectively, and the atomic percentages of O and Zn (K) were 63.34 and 4.86, respectively. It is demonstrated that the purity of the fabrication is excellent without other residues (except C and Ga derived from the substrate and GaN buffer layer). It is also supposed that the ratio of Zn/O is more than 1 compared with that of the perfect chemical stoichiometry of ZnO. It reveals that there exists some O vacancy in the ZnO thin film.
IR absorption spectra of ZnO thin film
As shown in Figure 4 (a), the UV emission located at 367 nm is increased, and the visible emission at 456 nm is decreased. The increase of UV emission and the decrease of the defect emission indicate that the structure of ZnO/GaN/Si thin film becomes more perfect. The UV peak appears as a redshift from 367 to 373 nm. The relaxation of interface strain is the main reason because of the formation of ZnO/GaN/Si heterostructure. The PL spectra of ZnO thin film fabricated on two different substrates show that the PL property of thin film fabricated using GaN buffer layer is more superior to that of ZnO/Si film. The ratio of visible emission of ZnO thin film fabricated on Si substrate is high, indicating that more defects exists in ZnO thin film. This is consistent with the analysis of two XRD spectra of ZnO thin films above.
ZnO thin films have been fabricated on GaN/Si and Si (111) substrates at the deposited temperature of 400°C, respectively. The structural and optical properties of ZnO thin films fabricated on different substrates are investigated systematically by XRD, FESEM, FTIR, and PL spectra. The FESEM results show that the ZnO/GaN/Si film is two-dimensionally grown with flower-like structure, while the ZnO/Si film is the (002) orientation grown with an incline columnar structure. The GaN buffer layer plays an important role for the transformation of the growth mode of ZnO thin films from one-dimensional to two-dimensional. The high UV emission of ZnO/GaN/Si films and the less defect emission with Zni and Vo reveal that the film possesses high quality by introducing a GaN buffer layer on the Si (111) substrate. In conclusion, it is favorable to fabricate high emission efficiency ZnO thin film on GaN/Si substrate rather than Si (111) substrate. The study provides an opportunity for constructing the nanopillar array ZnO/GaN heterostructure and deep UV emission LED devices.
The authors are grateful for the financial support by the Shandong Provincial Natural Science Foundation (Y2008A21, ZR2009FZ006, ZR2010EL017), the Encouragement Foundation for Excellent Middle-aged and Young Scientist of Shandong Province (grant no. BS2012CL005), the Doctor Foundation of University of Jinan (XBS0833), the Shandong Provincial Science and Technology Project (2009GG20003028), and the Research Foundation of the University of Jinan (grant no. XKY1127).
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