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Sound-Driven Piezoelectric Nanowire-Based Nanogenerators

By Seung Nam Cha, Ju-Seok Seo, Seong Min Kim, Hyun Jin Kim, Young Jun Park,* Sang-Woo Kim,* and Jong Min Kim
The desire for completely self-powered electronics has led to a continuously increasing amount of related research over the last decade.[1] Along with the dramatic advances in nanotechnology and low power consumption electronics, wireless and maintenance-free multifunctional nanodevices that can be used anywhere at any time have attracted much attention.[24] However, these devices require their own power sources in spite of their nanometer size and low power consumption. In most cases, the power source is a conventional electrochemical battery. Even if the battery has a huge capacitance, it has a limited lifetime, and the miniaturization of devices limits the size of battery, resulting in short battery lifetimes. In addition, the battery must be occasionally recharged. Thus, it is highly desirable for wireless devices and even required for body-implanted medical systems to be sustainable without requiring a battery or recharging process. In these regards, a number of approaches for self-powering systems by scavenging energy from environments using photovoltaic,[5] thermoelectric,[6] and piezoelectric phenomena[7] have been intensively explored. Among them, very recent innovative research has been intensively carried out to convert external mechanical stimuli such as atomic force microscope tip-induced deformation,[8] body movements,[9,10] gas ow,[11] and ultrasonic wave[12,13] into electricity, resulting in wireless self-powered systems. Such a piezoelectric power generation aims to capture the normally wasted energy surrounding a system and converts it into usable energy for operating electrical devices. However, the number of mechanical energy sources used in previous works are articial ones or hard to be supplied continuously. The sound (noise or even music) that always exists in our everyday life and environments has been overlooked as a source for piezoelectric power generation despite the fact that it is a form of mechanical energy. There should be a way to turn sound energy from speech, music or noise into electrical power. Thus, sound power can be used for various novel applications including mobile phones that can be charged during conversations and sound-insulating walls near highways that generate electricity from the sound of passing vehicles. The latter development would have the additional benet of reducing noise levels near highways by absorbing the sound energy of vehicles. Here, we report the rst power-generating performance of sound-driven nanogenerators based on piezoelectric ZnO nanowires. Figure 1a and b show a schematic diagram of an integrated nanogenerator with piezoelectric ZnO nanowires and a crosssectional eld-emission scanning electron microscopy (FE-SEM) image of vertically well-aligned ZnO nanowire arrays (acting as a piezoelectric active layer), respectively. The nanowires were grown using a thermal chemical vapor deposition (CVD) system via a vapor-liquid-solid mechanism on an n-type GaN thin lm (acting as a bottom electrode)-deposited sapphire substrate.[14] It was found that there are no additional peaks other than (0002) and (0004) peaks of ZnO in X-ray diffraction measurements (not shown), indicating good alignment of the ZnO nanowires along the c-axis direction on GaN. A palladium gold (PdAu)coated polyethersulfone (PES) substrate were used as both a top electrode and a vibration plate and placed above the ZnO nanowire arrays. The integrated device was then sealed at the edges to prevent physical and chemical damage. The average length and diameter of the ZnO nanowires were 10 m and 150 nm, respectively. The integrated nanogenerator was then connected to a measurement system. Figure 1c shows plots of the input signal generating the sound wave and the output voltage obtained from the integrated nanogenerator. The converted electrical energy from the sound wave was displayed on the oscilloscope as a voltage in the alternating current (AC) mode, following the frequency of the sound wave with the sinusoidal mode electrical input with a small phase difference. This phase difference between the signals is due to the impedance of the intrinsic capacitance and reactance within the piezoelectric circuit. The intensity of the input sound was 100 decibel (dB) (102 W m2 at 100 Hz), and the amplitude of the output voltage was 50 mV. Sound is a regular mechanical vibration that travels through matter as a waveform. Longitudinal sound waves (compression waves) transmitted through the ambient air are made up of waves of alternating pressure deviations from the equilibrium pressure, causing local regions of compression and rarefaction. When a sound wave strikes the PdAu-coated exible PES substrate acting as the top electrode, it causes the exible substrate to vibrate. This mechanical vibration of the exible substrate generated by the sound wave is directly transferred to the

[] Dr. S. N. Cha, Dr. S. M. Kim, Dr. H. J. Kim, Dr. Y. J. Park, Dr. J. M. Kim Frontier Research Laboratory Samsung Advanced Institute of Technology Yongin, Gyeonggi, 446712 (Republic of Korea) E-mail: youngjunpark@samsung.com J.-S. Seo, Prof. S.-W. Kim School of Advanced Materials Science and Engineering SKKU Advanced Institute of Nanotechnology (SAINT) Center for Human Interface Nanotechnology (HINT) Sungkyunkwan University Suwon, 440746 (Republic of Korea) E-mail: kimsw1@skku.edu

DOI: 10.1002/adma.201001169

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Figure 1. Sound-driven nanogenerator with piezoelectric ZnO nanowires. (a) Schematic diagram of an integrated nanogenerator in which the exible PdAu-coated PES substrate acting as both a top electrode and a vibration plate was installed above the ZnO nanowire arrays. (b) FE-SEM image of ZnO nanowire arrays on a GaN/sapphire substrate. (c) The input signal for the generation of a sound wave and the output voltage from the piezoelectric ZnO nanowire arrays due to the sound wave.

vertically aligned ZnO nanowires, causing compressing and releasing of the nanowires. The power output mechanism of the sound-driven nanogenerator is based on the coupling of the piezoelectric and semiconducting properties of ZnO. The preferred c-axis alignment of the ZnO nanowires leads to strong piezoelectric alignment with regard to the external force.[9] The sound wave is used to vibrate the top contact electrode, which generates electric potential through the vertically well-aligned ZnO nanowires in the direct compression mode. With a force applied in the direction parallel to the vertically aligned ZnO nanowires, the centers of mass of the positive and negative ions are shifted, resulting in polarization along this direction. The created piezoelectric potentials along individual nanowires have the same tendency of distribution because the ZnO nanowires are grown on the substrate with the preferred c-axis orientation. Under direct compression by the sound wave to the vertically aligned ZnO nanowires, a negative piezoelectric potential is generated on the top side while a positive piezoelectric potential is generated on the bottom side.[10] The AC output mode from the nanogenerator is due to the Schottky contact formation between the nanowires and the electrode, which acts as a capacitor.[9] The negative piezoelectric potential generated by the wave increases the conduction band and the Fermi level at the top side of the nanowires. Electrons, then ow from the top electrode to the bottom side through the external circuit and the positive potential is generated around the top PdAu electrode (Figure 2b). The potential is kept since the Schottky contact hinders the electrons from being transported through the interface. The piezoelectric potential dissipates when the external pressure on the top PES substrate is momentarily removed in the rarefaction mode of the sound wave (compressive strain is released from the nanowires) (Figure 2c). The electrons ow back via the external circuit till neutralizing the positive potential around the top electrode. Theses repeated cycles then result in the AC voltage pulses through the generator. The functional relationship of the parameters used in the sound-driven piezoelectric nanogenerator can be described as V2 P/f, where P, V, and f are the power (which is dened as the input intensity of the sound wave multiplied by the surface area), the output voltage obtained from the nanogenerator, and the frequency of the applied sound wave, respectively.[15] Under a xed frequency (100 Hz), the V2 generated from the nanogenerator is proportional to the input power applied to the nanogenerator (Figure 3a). The V2 value increased linearly within the intensity range of 03 mW m2, which can be converted to a power ranging from 0 to 0.3 W considering a device size of 1 cm2. Above this range, V2 was saturated, possibly due to the limitations of energy conversion. When the input intensity of the sound wave was held constant at 100 dB, V2 was linearly dependent on the frequency of the applied sound wave (Figure 3b). These two relationships clearly support the evidence that the piezoelectric output generated by the acoustic system follows piezoelectric-mechanical-acoustic energy conversion (i.e., piezoelectric energy is transformed into the acoustic one via the mechanical vibration).[15] Further, we performed a linear superposition test in which the two nanogenerators, Cell 1 and Cell 2, showed output voltages of 24 mV and 26 mV,

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(a)

(a)
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8 6 4 2 0

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Figure 2. Proposed mechanism for power generation in the sound-driven piezoelectric nanogenerator. (a) The as-received nanogenerator with no sound wave application. (b) Electrons ow from the top electrode to the bottom side through the external circuit by the negative piezoelectric potential generated at the top side of the ZnO nanowires under direct compression by the sound wave. At this time, the positive potential is generated around the top PdAu electrode. (c) The piezoelectric potential dissipates when the external pressure on the top PES substrate is momentarily removed in the rarefaction mode of the sound wave. Electrons ow back via the external circuit till neutralizing the positive potential around the top electrode.

200 150

Cell 1 Cell 2 Cell 1 + Cell 2

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100 50 0 -50 -100 -150 0 20 40 60 80

respectively (Figure 3c). In the linear superposition test, the output voltages of the nanogenerators were enhanced by connecting them in serial. The output voltage of 52 mV is the approximate sum of the output voltage of the individual nanogenerators. Therefore, these experimental results clearly support the hypothesis that the measured signal originated from the sound-driven piezoelectric nanogenerator rather than from the measurement system. Figure 4a shows the room temperature photoluminescence (PL) of the ZnO nanowires in the nanogenerator used in this

Time (ms)
Figure 3. (a) Output voltage vs. the input power of the applied sound wave under a xed frequency of 100 Hz. (b) Output voltage vs. the frequency of the applied sound wave. (c) Results of the linear superposition tests.

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(a)
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Figure 4. (a) Room-temperature PL spectrum of the ZnO nanowires. (b) Behavior of the output voltage from the UV irradiated (365 nm wavelength) piezoelectric nanogenerators driven by sound waves (1 mW cm2 input power).

carriers in ZnO nanowires speed up the rate at which the piezoelectric potential is screened,[18] it was concluded that our ZnO nanowires with a small number of point defects grown on GaN with a negligibly low lattice mismatch to ZnO is very promising for effectively generating piezoelectric potential in the nanowires due to the mechanical stimuli of sound waves. It has been reported that the surfaces of the ZnO nanowires are apt to be covered with oxygen (O2) molecules, creating a depletion region.[18,19] As a result, this not only decreases the carrier density (due to the trapping of free electrons in the n-type ZnO nanowire), but also decreases the conductivity. Under ultraviolet (UV) light irradiation, however, oxygen is able to be detached, which results in increased conductance through the nanowires.[19] This is because the holes resulting from the electron-hole pairs generated by the UV light irradiation can migrate to the surface and recombine with O2-trapped electrons, causing their release. These electrons then contribute to the current, enhancing the conductivity of the nanowires. In addition, UV light irradiation generates photoexcited carriers into the ZnO nanowires with a direct band gap, resulting in increased free carrier concentration in the conduction band. Therefore, it is expected that it will be difcult to effectively generate piezoelectric potential in very conductive nanowires,[18] which then causes a decrease in the output voltage of the piezoelectric nanogenerators driven by the sound wave when the ZnO nanowires are exposed to UV light irradiation (Figure 4b). This result is additional evidence that the output voltage is due to the piezoelectric potential generation under sound wave irradiation. In summary, we demonstrated the sound-driven power generation using nanogenerators based on piezoelectric ZnO nanowires. The sound wave was used to vibrate the top contact electrode, which generated electric potential through the vertically well-aligned ZnO nanowires in the direct compression mode. When sound with an intensity of 100 dB was applied to the nanogenerator, an AC output voltage of about 50 mV was obtained from the nanogenerator. Systematic investigations of the generated output voltage as a function of the input power and frequency of the applied sound wave, linear superposition tests, and the observation of output voltage drop with UV light irradiation applied to the nanogenerator clearly support the notion that the measured output voltage originated from the sound-driven nanogenerator. Therefore, our results suggest that sound can be one of promising energy sources with highly efcient generators based on piezoelectric nanowires.

work. The predominant peak seen at 375 nm is usually attributed to the recombination of free excitons, while a broad deeplevel emission band with relatively weak emission intensity was also observed at about 510 nm. In general, broad deep-level emission prevails over free exciton-related emission in the ZnO nanostructures.[16] It is well known that deep-level emission is mainly due to deep states in the band gap, which originates from defects such as zinc interstitials, oxygen vacancies, and their complexes in the nanostructures.[17] It may be proposed that the relatively weak deep-level emission from our ZnO nanowires is due to the formation of a small number of point defects in the nanowires. Because the charged point defects acting as active

Experimental Section
Growth of ZnO nanowires on the GaN/sapphire substrate: ZnO nanowires were thermally grown using a horizontal quartz tube by vaporizing mixed ZnO and graphite (1:1) powder. The growth substrate used was GaN (2 m)/sapphire on which 3 nm of an Au thin lm catalyst was deposited using a thermal evaporator. The source powder and the Au-coated substrates were placed on the ceramic boat and then loaded at the center of the tube. The ZnO nanowires were synthesized at a temperature of 950 C for 20 min under argon gas (50 sccm). Characterizations: The morphological properties of the grown ZnO nanowires were examined by FE-SEM. The sound wave was generated by a speaker and a function generator (SONY Tektronix AFG310), and the intensity of the generated sound was measured by a dB meter. The nanogenerator performance in the presence of the sound wave was

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evaluated using an oscilloscope (Tektronix, TDS 7104 Digital phosphor oscilloscope). PL measurements were conducted using a He-Cd laser ( = 325 nm) for excitation. [7]

Supporting Information
Supporting Information is available from the Wiley Online Library or from the author. [8] [9]

Acknowledgements
This research was supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (20100015035, 20090077682, 33120081-D00294). Received: April 1, 2010 Published online: August 30, 2010

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