APPLIED PHYSICS LETTERS 90, 063110 2007

Generation of electricity in GaN nanorods induced by piezoelectric effect

W. S. Su and Y. F. Chena
Department of Physics, National Taiwan University, Taipei, Taiwan 10617, Republic of China

C. L. Hsiao and L. W. Tu
Department of Physics and Center for Nanoscience and Nanotechnology, National Sun Yat-Sen University, Kaohsiung, Taiwan 80424, Republic of China

Received 4 December 2006; accepted 10 January 2007; published online 8 February 2007 Conversion of mechanical energy into electric energy has been demonstrated in GaN nanorods. The measurement was achieved by deecting GaN nanorods with a conductive atomic force microscope PtIr tip in contact. The mechanism relies on the coupling between piezoelectric and semiconducting properties in GaN nanorod, which creates a strain eld and drives the charge ow across the nanorod. The result shown here opens up an opportunity for harvesting electricity from wasted mechanical energies in the ambient environment, which may lead to the realization of self-powered nanodevices. 2007 American Institute of Physics. DOI: 10.1063/1.2472539 For the investigation of nanoscale science and technology, it will be very attractive if one can develop a selfpowered nanodevice without depending on a battery. In this way, one may be able to create wireless devices with a portable integrated system. It will be even more alluring if the nanodevice can harvest electricity from the wasted energy in the ambient environment. Here we made an initial attempt to convert mechanical energy into electric energy in GaN nanorods. It is well known that nitride semiconductors have the wurtzite crystal structure, which has the two important characteristics, including the noncentral symmetry and polar surface. They lead to pronounced piezoelectric properties.1,2 We demonstrated that with the usage of a moving atomic force microscope AFM tip to deect GaN nanorod, it is possible to generate an output current. The underlying physics can be well understood in terms of the coupling between piezoelectricity and semiconducting property of GaN nanorod. Besides, we showed that the formation of the Schottky barrier at the interface between the AFM tip and GaN nanorod as well as the polarity of GaN nanorod can signicantly inuence the current output due to the bended nanorod. The samples studied here were grown on Si 111 wafers by plasma-assisted molecular beam epitaxy Veeco-Applied Epi 930 . The Ga source is 7N5 pure metal in a conventional effusion cell. 6N pure N2 is further puried through a nitrogen purier Aeronex and then fed into a plasma generator. The Si substrate was degreased and then lightly etched with diluted HF. A reconstructed 7 7 reection high-energy electron diffraction pattern was obtained for the Si substrate after thermal treatment at 800 C to ensure excellent surface condition. After low temperature buffer layer deposition at 500 600 C, high temperature GaN growth started at 720 C. Self-assembled vertical nanorods can be clearly seen in the eld emission scanning electron microscope SEM images, as shown in Fig. 1 a . Detailed studies with various growth parameters have been published elsewhere.3 The AFM system we used was a standalone SMENA apparatus NT-MDT in contact mode. The silicon tips of contact mode produced by NENOSENORS were coated by PtIr. The thickness of the PtIr coating is about 23 nm. The force cona

stant is about 2.8 N / m. The tip was scanned over the top of the GaN nanorod, and the height of the tip was adjusted according to the surface morphology and local contacting force. The thermal vibration of the nanorod at room temperature was negligible. For the electric contact at the bottom of the nanorod, Ohmic contacts were formed by depositing indium drops to the samples, and annealing the samples at 240 C for 10 min. No external voltage was applied in any stage of the experiment. Figure 1 b illustrates our experimental measurement for obtaining output current by deforming a piezoelectric nanorod with a conductive AFM tip. When the AFM tip was scanned over the aligned nanorod, both the topography feedback signal from the scanner and the corresponding current images were recorded simultaneously; a typical result is shown in Figs. 1 c and 1 d . In the image, sharp output current peaks were observed. These peaks are about several times the noise level with a magnitude of 0.03 nA. It is interesting that the location of the current peak can be corre-

Electronic mail: yfchen@phys.ntu.edu.tw

FIG. 1. Color online a Scanning electron microscopy image of GaN nanorods. b Experimental setup and procedures for generating electricity by deforming a piezoelectric nanorod with a conductive atomic force microscopy AFM tip. The AFM scans across a nanorod in contact mode. c Topography image and d corresponding output current image of the nanorod arrays. e Line proles from the topography and output current images across a nanorod.

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lated well with the site of the nanorod. It implies that the output current is indeed due to the bended GaN nanorod. In order to exclude the possibility that the output current may arise from friction or contact potential, we have performed the similar experiment for a metal lm. It is found that there is no detectable signal. The energy output generated by the bended GaN rod can be roughly estimated as follows. The full width at half maximum of the current peak is about 36 nm. The tip was scanned over a single nanorod at a scanning velocity of 12 042 nm/ s. Therefore, the lifetime of the output current is 18 ms. The nanorod can be approximated as a resistor Rn and a capacitor Cn. The lifetime of the output current across the load RL, which is 1.75 M for GaN lm, is = RL + Rn Cn. For the experiment studied here, the resistance of the nanorod Rn is negligible, and the equivalent capacitance of the nanorod is therefore equal to / RL, which has a magnitude of about 10 nF. The electric power generated by the bended nanorod W CV2 / 2 C i0R 2 / 2 0 17 1.568 10 J, where i0 is the peak value of the output current. The obtained W represents the generated electric energy by one single nanorod in one single event. For a typical resonant vibrational frequency of 5 MHz for GaN nanorod with a diameter of 10 nm and length of 1 m,4 and the nanorod density of 1010 / cm2, the estimated output power density is about 0.75 W / cm2, which is quite feasible for a nanomaterial based device. As shown in Fig. 1 e , when the tip starts to deect the nanorod, the current output is observable. It sharply increases and then decreases, and it drops to zero when the deection of the nanorod approaches its maximum. This behavior is in stark contrast with that of ZnO nanorod,5 in which the output voltage is detectable only when the deection of the nanowire reaches its maximum. It drops to zero, when the nanowire is released by the AFM tip. To resolve this subtle difference, let us have a more detailed examination of the electric eld induced by the bended nanorod as well as the interface consisting of the bended nanorod and metallic contacts. In addition to its magnitude, the direction of the generated piezoelectric eld of the bended nanorod is also an important factor to inuence the current ow. Before determining the direction of the piezoelectric eld, we need to know the polarity of the nanorod, which can be judged from its resistence to H3PO4 etching.6 As shown in Figs. 2 a and 2 b , the SEM images of the surface morphologies before and after etching are compared. It clearly shows that all nanorods disappear after etching, which indicates that the base area is Ga polar for its resistance to the etching, while the nanorods are likely to be N polar for their dissolution by the H3PO4. With the outer surface being stretched and the inner surface compressed as shown in Figs. 2 c and 2 d , the deected GaN nanorod by AFM tip will create a strain eld. The created electric eld Ez is along the nanorod z direction inside the volume through the piezoelectric effect, Ez = z / d, where d is the piezoelectric coefcient along the nanorod direction. If the GaN nanorod owns the N polar, which means the nitrogen atomic layer being the top-terminating layer, the piezoelectric eld direction is parallel to the z axis at the outer surface and antiparallel to the z axis at the inner surface. With respect to the ground base contact, the electric potential of the compressed surface is negative, denoted as V, while that of the stretched side is positive, denoted as V+. At present, we did not know the exact magnitude for the voltage V, which have to be calculated based on the ionic

FIG. 2. Scanning electron microscopy image of GaN nanorods. a Before etching and b After etching. c Schematic denition of a nanorod and the coordination system. d Corresponding longitudinal piezoelectricity induced electric eld Ez distribution in the nanorod. e and g Contacts between the AFM tip and the semiconductor GaN nanorod at two reversed local contact potentials positive and negative . f Reverse and forward biased Schottky rectifying behaviors.

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charges induced by the piezoelectric effect and the surface charges caused by the boundaries. In our measurement, the bottom contact was an Ohmic contact formed by depositing indium drops to the GaN lm, and annealing the sample at 240 C for 10 min. Because the electron afnity of GaN is 4.2 eV,7 and the work function of In is 4.12 eV, there is no barrier at the interface, and the GaNIn contact is Ohmic. The work function of PtIr is 5.5 eV,8 and the electron afnity of GaN is 4.2 eV.7 Therefore, the PtIrGaN contact is a Schottky barrier and dominates the charge conduction, as shown in Fig. 2 f . We are now ready to understand the current output, as shown in Fig. 1 e . When the AFM tip is in contact with the stretched side of the nanorod, because the PtIrGaN contact is negatively biased, which corresponds to a forward-biased Schottky diode. Therefore, the output current is sharply increased as shown in Figs. 2 e and 2 f as well as in Fig. 1 e . When the AFM tip is in contact with the compressed surface of potential V+, the PtIrGaN interface in this case corresponds to a reverse-biased Schottky diode, and little current ows across the interface as shown in Figs. 2 g and 2 f , as well as in Fig. 1 e . We therefore can see that the variation of the output current can be understood quite well in terms of the coupling between piezoelectricity, semiconducting properties, and the characteristic of a Schottky diode. To further probe the property of the current output induced by the bended GaN nanorod, we have performed the measurements for the AFM tip with different scanning speeds. It was found that the magnitude of the output current increases with the scanning speed, as shown in Fig. 3. To quantitatively understand this behavior, let us consider the detailed energy transfer process. When the tip sweeps across the nanorod, the top of the nanorod will move with a speed similar to that of the tip, and the kinetic energy will transfer into the elastic energy of the bended nanorod. Under the rst-order approximation, the elastic energy is proportional

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FIG. 3. Color online Variation of current output vs scanning speed of the bended GaN nanorod. The red line is plotted according to the characteristics of the current ow in a Schottky diode given by Eq. 1 .

current output on the scanning speed can be described quite well by Eq. 1 with q / kT replaced by a tting parameter. This result therefore provides an additional evidence to support our proposed interpretation as shown above. In summary, we have conclusively demonstrated the conversion of mechanical energy into electric energy in GaN nanorods. The obtained result can be well interpreted in terms of the coupling between piezoelectricitivity, semoconducting properties, as well as the characteristic of a Schottky contact. In addition, the estimated output power is quite feasible for the application in nanomaterial based devices. In view of a wide range of applications based on nitride semiconductors, including full color displays, blue lasers, as well as high temperature and high power microelectronics, our study shown here should be very useful and timely. This work was supported by the National Science Council of the Republic of China.
1 2

to the square of the displacement of the deection S, and therefore the displacement S is linearly proportional to the scanning speed. Because the displacement S is linearly proportional to the induced potential V according to the previous reports,4 V is thus also linearly proportional to the scanning speed. The variation of the current output in terms of the scanning speed should therefore follow the expression describing the current ow in a Schottky diode, I = Is eqV/kT 1 , 1

where q is the magnitude of electronic charge, V is the applied voltage, k is the Boltzman constant, and T is the temperature. Indeed, as we can see that the dependence of the

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