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Journal of Luminescence 108 (2004) 385388

Room-temperature excitonic lasing from ZnO single nanobelts

Kazuki Bando*, Taiki Sawabe, Koji Asaka, Yasuaki Masumoto
Institute of Physics, University of Tsukuba, Tsukuba 305-8571, Japan

Abstract Excitonic lasing from ZnO single nanobelts was observed at room temperature, which was due to excitonexciton scattering processes appearing under intense light excitation. Morphologies of the nanobelts are rectangular shapes, so that crystalline facets of the nanobelts acted as laser-cavity mirrors. Therefore, mode spacings corresponding to cavity lengths of the respective nanobelts were observed in luminescence spectra. Lasing from ZnO single nanobelts at room temperature and their lasing properties are reported. r 2004 Elsevier B.V. All rights reserved.
Keywords: Nanowire; Nanobelt; Excitonic lasing; ZnO

1. Introduction Nanocrystals of semiconducting oxide materials have received much attention in recent years, because it is expected that they can be applied to short-wavelength optical devices and excitonic devices operating at room temperature. In particular, the exciton binding energy in ZnO (59 meV) is so large that ZnO can be applied to laser devices based on excitonic processes. The excitonic processes can result in lasing at lower threshold than that of the electronhole plasma which is a driving force of lasing for most semiconductor lasers. To lower the threshold further, the use of nanostructures can contribute to the connement of the excitons. One-dimensional nanostructures have been recently investigated with respect to
*Corresponding author. Tel.: +81-29-853-4350; fax: +8129-853-6618. E-mail address: bando@sakura.cc.tsukuba.ac.jp (K. Bando).

oxide materials including ZnO. The nanowire which has a cylindrical morphology has been already presented as a one-dimensional nanostructure [1]. Belt-like nanostructures (the so-called nanobelts), whose cross-sections are rectangular shapes, have been recently grown [2]. Excitonic lasing from ZnO nanowires at room temperature has been reported [3,4] in which lasing has occurred by an excitonexciton scattering process. It is noteworthy that this lasing occurs without an external cavity, because crystalline facets of both ends of the nanowire act to form a cavity. As the morphology of nanobelts is different from that of the well-known nanowires, it can be expected that the cavity modes formed in nanobelts would be different from those in nanowires. In this work, we observed excitonic lasing from the ZnO nanobelts at room temperature arising from an excitonexciton scattering process. In addition, we report on the lasing-cavity mode formed and on the lasing properties.

0022-2313/$ - see front matter r 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jlumin.2004.01.081

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2. Experimental ZnO nanobelts can be grown by using various methods [2,57]. In our work, the ZnO nanobelts were simply grown by thermal evaporation of the ZnO powder without catalysts, which is similar to the method reported in Ref. [2]. The ZnO powder was heated on ceramic boats in a furnace at 1450 C for 3 h in owing Ar gas at 50 sccm. The aggregate of ZnO nanobelts, which is a white wool-like product, adhered onto a ceramic tube which was simultaneously inserted in the furnace. In order to separate the aggregate into single nanobelts, it was mixed in ethanol, treated by sonication and dispersed onto copper substrates by drop-casting the ethanol containing the nanobelts. The nanobelts were observed by using scanning electron microscopy (SEM) (HITACHI S-4300). Fig. 1 shows a SEM image of the assynthesized wool-like products which were put onto the copper substrates without dispersing. The morphology of the products obtained from the SEM observation agrees with that of nanobelts which have been reported already [2,57]. Belt-like morphological images were observed, and growth of ZnO nanobelts was clearly conrmed. Photoluminescence (PL) from the single nanobelts under weak and intense excitation conditions were obtained by using either a continuous wave (CW) HeCd laser (325 nm) or the fourth-harmonic generation output (266 nm) of a pulsed

Nd:YAG laser (8 ns, 10 Hz) as excitation sources, respectively. PL images of the single nanobelts were enlarged by using a long-distance microscope to detect PL from only a single nanobelt from those dispersed on the substrate, and the PL was detected by using a monochromator and a liquid nitrogen-cooled CCD. In order to measure the PL spectra, single nanobelts whose crystalline facets were of good quality, were selected, because it was expected that the nanobelts with good crystalline facets could act as self-formed cavities and result in successful lasing.

3. Results and discussion Fig. 2 shows the excitation-intensity dependence of PL spectra at room temperature. The inset shows the SEM image of the single nanobelt whose PL spectra are shown in Fig. 2. The dimensions of the selected nanobelt are about 10 mm in length,

RT Single Nanobelt Nd:YAG Laser FHG (266nm) Luminescence Intensity (a.u.) I0 ~ 500kW/cm2 PS

P 2 3 5 5 3.0 3.1 3.2 3.3 Photon Energy (eV) I0 0.75I0 0.69I0 0.64I0 0.59I0 He-Cd Laser 3.4

Fig. 1. SEM image of the aggregate of the ZnO nanobelts on the substrate.

Fig. 2. PL spectra of a ZnO single nanobelt. The inset shows the SEM image of the single nanobelt whose PL spectra were measured. The lowest PL spectrum was obtained for weak He Cd cw laser excitation. The others were obtained by intense Nd:YAG laser excitation. For this intense excitation, PL from both spontaneous (P) and stimulated (PS) emissions due to the excitonexciton scattering process were observed.

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2 mm in width, and B100 nm in thickness. A relatively wide nanobelt was selected, because the PL intensity from the wider nanobelts is strong enough to detect. In addition, the length of the selected nanobelt was relatively short compared to that of ordinary nanobelts. It appears that long nanobelts were broken by the dispersing process of the sonication in the ethanol and cleaved facets were accidentally formed at both ends of these nanobelts. In Fig. 2, the lowest PL spectrum was obtained under weak cw excitation and is a broad PL band which consists of PL bands due to free excitons and their phonon replicas. The PL spectrum just above was obtained by the weakest of the pulsed excitations and the PL peak position is observed at lower energy than that observed for weak cw excitation. The PL band appears around 3.25 eV which is lower than the exciton resonance (B3.31 eV) by the exciton binding energy of 59 meV, indicating that spontaneous emission (P) due to exciton-recoil processes of the exciton exciton scattering appears under intense excitation. With increasing excitation intensity, three sharp peaks (PS) abruptly appear in the lower energy tail (B3.2 eV) of the spontaneous emission above an excitation threshold of I=0.69I0 (B350 kW/cm2). Considering that the PL peaks appear above a certain threshold power, it is concluded that stimulated emission occurs. Upon increasing the excitation level further, the intensity of the sharp peaks superlinearly increases and the number of peaks increases on the lower-energy side. These peaks comprise several sharp peaks whose energy spacings are constant, which clearly indicates that lasing occurs in the nanobelts. It is considered that the self-formed cavity of the nanocrystal brings about lasing in the cavity modes formed in the nanobelt. The cavity modes appear as the several peaks with constant energy spacing in the PL spectra. An important aspect is that this lasing action occurs without external mirrors and the nanolaser cavity is formed by the crystalline facets alone. It is noted that this PL from the nanobelt was detected not along the length of the nanobelt, but in the vertical direction of the substrate. Although it is considered that the cavity is formed along the length of the nanobelt, it is considered that the light emitted from the

nanobelt was scattered in every direction due to the roughness on the surface of the substrate. In actuality, the lasing was also observed along the length of the nanobelt. In order to examine the relation between the cavity and its lasing action further, PL measurements were performed with respect to several nanobelts whose lengths differed from each other. If the nanolaser cavity is formed by crystalline end facets, the peak energy spacings should be related to the energy spacings between modes formed in the nanobelts, and therefore should depend on the length of the nanobelts. In Fig. 3, the spacings are plotted as a function of the reciprocal nanobelt ! rot cavity model length 1/L. As the FabryPe should apply to the nanobelt lasing cavity, the relationship between the mode spacing and the cavity length can be evaluated by using DE=hc/ 2nL, where DE is mode spacing, h is Plancks constant, c the speed of light and L is the length of each nanobelt. Here, n is the effective refractive index expressed by n=n+E dn/dE, where the energy dispersion of the refractive index n(E) was given by Park and Schneider [8]. The solid line in Fig. 3 shows the relationship calculated by this equation. As shown in Fig. 3, the peak energy

0.014 0.012 Mode Spacing E (eV) 0.010 0.008 0.006 0.004 0.002 0.000 0.00
E = hc/2L{n+E(dn/dE)}

0.02

0.04

0.06 1/L (m)

0.08

0.10

Fig. 3. The relation between the peak energy spacing and the reciprocal nanobelt length 1/L. The solid line is the relationship given by the equation DE=hc/2L{n+E(dn/dE)}.

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spacings observed in the PL spectra of the respective nanobelts agree quantitatively with mode spacings estimated from the equation. Therefore, it is concluded that the cavity modes are formed between the two end facets of the nanobelts. In summary, we observed excitonic lasing from ZnO single nanobelts at room temperature. The nanobelts were simply grown by a thermal evaporation process in a furnace. Under cw excitation, PL from the free exciton was observed at room temperature. With an increasing level of pulsed-laser excitation, PL from an exciton exciton scattering process appeared. Stimulated emission consisting of several sharp peaks which abruptly appeared with a further increase of the level of excitation. In other words, lasing occurred within the self-formed cavity of the nanobelt. By measuring the sharp PL peaks of the lasing from the several single nanobelts, it was concluded that the cavity modes were formed between the two end facets of the nanobelts.

Acknowledgements This work was partly supported by the Sasakawa Scientic Research Grant from The Japan Science Society and Research Project and Nanoscience Special Project of University of Tsukuba. The authors are grateful to Professor Y. Ootuka of the university for the use of the SEM.

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