This action might not be possible to undo. Are you sure you want to continue?
A. Cretì, A. Taurino, D. Valerini, C. Martucci, F. Quaranta, M. Lomascolo, P. Siciliano and R. Rella
Institute for Microelectronics and Microsystems IMM-CNR, Via per Monteroni, 73100 Lecce, Italy email@example.com
Abstract— The optical response at room temperature of ZnO nanostructures, grown by controlled vapour phase deposition, to low concentrations of NO2 gas mixed in dry-air has been investigated. In particular the quenching in the emission signal, due to the interactions between oxidizing gas molecules and sample surface, has been monitored in excitonic and defect band, as a function of NO2 gas concentration. The dynamic responses and the resulting calibration curves, obtained for each emission band, have been compared. Furthermore responses of nanorods with different size and nanostructures with different exotic shape have been discussed in order to clarify the role of the morphology and/or dimensions and structural quality. In particular we have correlated the growth conditions and the resulting structural and optical properties of the samples, highlighting their role in the optical sensing response.
The ZnO nanostructures have been used as active material in optical sensing measurements of NO2 gas in dry air. In particular the changes induced by the gas molecules in FE and D emission band intensity have been discriminated. II. EXPERIMENTAL
Zinc oxide results material of great interest in electronic and optoelectronic applications for UV light emitting diodes, lasing media and sensing. In particular ZnO micro/ nanostructures of high quality and different shape have been taken in investigation for high-performance gas sensors, due to their good properties such as sensitivity, rapid response and fast recovery. Notwithstanding the electrical measurements monitoring in sensing applications is widely exploited, at present few papers report on optical sensing in ZnO material [1,2]. In our work, we explore the possibility to detect the presence of NO2 gas at room temperature, by measuring the PL quenching/restoring in presence /absence of gas. The high quality samples allows us to exploit the optical response to gas, at room temperature, both for excitonic (FE) and defect (D) emission band, rather than the only defect one as usually reported. It results that the defect band shows a smaller response than the FE band one, in the all investigated samples. We have grown high quality ZnO nanostructures on different substrates and with different shapes by means of vapor phase deposition (VPD). The high crystal quality has been deduced by Photoluminescence (PL) at low temperature (7K) and X-ray diffraction (XRD) measurements.
ZnO nanostructures investigated in this paper have been grown on indium tin oxide (ITO) and sapphire substrates, by VPD growth technique, in a conventional furnace with horizontal quartz tube (25 mm inner diameter). Zn 5N pure granular source was placed in a tungsten crucible and inserted in the furnace at room temperature. The substrate was placed in front of / or next to the crucible, varying the distance. Ar 5N was used as carrier gas with a flux of 1 Nl/min. The temperature ramp started after five minutes of gas flux. The furnace was heated up to 600°C in 10 min, maintained at this temperature during the deposition time and then slowly cooled down to room temperature. The ITO and sapphire substrates were preliminarily coated with a 3 nm gold film deposited by e-beam evaporation. A JEOL 6500F Scanning Electron Microscope was used to analyze the surface morphology of the samples and X-ray diffraction measurements were performed in the ϑ-2ϑ geometry by using the CuKα excitation line (λ=1.5402 Å) of a Rigaku diffractometer. Photoluminescence (PL) measurements at low temperature (7K), have been carried out by He-Cd laser (325 nm), at low pump intensity ( ~ 5 meV), and dispersed by an 0.3 m focal length monocromator TRIAX 320 equipped with a cooled GaAs photomultiplier operating in photon-counts mode. Finally, for the sensing measurements, the samples were placed inside an aluminum sealed chamber in which they were exposed to the detectable gas or dry air. The gas mixing station consists of a mass flow controller (Brooks Instruments 5850S) equipped with three mass flow meters/controller (operating in the range 2.5-50 ml/min) and a system of teflon pipelines and switching valves. All the optical sensing measurements were performed at room
1-4244-2581-5/08/$20.00 ©2008 IEEE
IEEE SENSORS 2008 Conference
III. as expected from the SEM image. in order to acquire the baseline for the successive analysis of the optical response to the NO2 gas. coming from defect and excitonic bands. The total flow was kept constant at 50 ml/min.2) is dominated by two main peaks. in the response phase and in the restoring process. 3 shows the low temperature (7K) PL spectra of the investigated samples. The presence of these peaks demonstrates the misorientation of the nanorods with respect to the z axis of the wurtzite structure. In the all spectra the signal ranges between the visible range (green-orange) and the UVregion. temperature. The crystal quality of the samples has been investigated by means X-ray diffraction (XRD) and photoluminescence measurements at low temperature (7K). The sample 1#. RESULTS AND DISCUSSIONS In this work we have investigated four different samples: sample 1# and 2#. but at a reduced distance of 10 mm and maintaining the furnace temperature at 600°C for 60 min. MC 2000. placing the substrate next to the crucible and maintaining the same experimental growth conditions of sample 2# and 3#. 2# (b). Furthermore the nanorods of sample 3# have a significantly larger diameter and a much wider size dispersion (ranging between 250 and 500 nm). 1 a). 1b) and 1c)). than the one of sample 2#. due to defect 310 . The same growth conditions were used for sample 3#. The XRD spectrum of sample 1# (Fig. provides that the sample has to be preliminary expose to a flow of dry air. nanostructures of exotic shape (Fig. suggesting a worse structural quality of the sample. Finally the comparison between sample 3# and sample 4# shows that the intensity of the sapphire peaks is quite different for the two samples. which averaging diameter results to be Figure 2: XRD spectra of sample 1# (a). In this case the PL. Fig. carried out by He-Cd laser (325 nm). was recorded during a minimum period of time (10min) necessary to reach an almost equilibrium signal.a) 1μm) c) 1μm) b) 1μm) d) 1μm) Figure 1: SEM image of the ZnO nanostructures of sample 1# (a). Fig. The variation in the integrated PL signal of the sample under exposure to NO2 gas. Finally. has been obtained with the substrate placed in front of the crucible at a distance of 22 mm and maintaining the furnace temperature for 30 min. it consists of a poor density of nanorods randomly dispersed on the surface of the substrate. 2# (b).4#. grown on sapphire substrate. 2 show the theta-2theta x-ray diffraction spectra obtained respectively from sample 1# . 3# (c) and 4# (d). The sample 2# has been also obtained with the ITO substrate placed in front of the crucible. This would indicate a higher thickness of the deposited film in the case of the substrate placed next to the crucible. complarable with sample 1#. Both samples exhibit nanorods with a shape similar to sample 1#. some differences can be observed: the spectrum of sample 2# evidences secondary peaks of higher intensity in comparison with the other two samples. grown on ITO substrate and sample 3# and 4#. This demonstrates that the crystallinity of the substrate influences the structural properties of the ZnO films. in order to analyse also the reversibility of the interaction processes. Nevertheless. In particular the samples 2# and 3# grew on a ZnO bulk layer of few microns thickness. being comparable with the intensity of the 002 ZnO main peak in the case of sample 3# and almost half of the 002 peak for sample 4#. The nanorods have an hexagonal section with a tapered tip and an average diameter of (130± 20) nm. (120 ± 20) nm. namely the 100 and 002 of the ZnO wurtzite structure. The procedure for testing the optical gas sensing properties of the nanostructured ZnO films. As shown by the SEM image in Fig. 3# (3) and 4# (d). In particular the visible signal.1 m focal length Avantes spectrometer mod.1 d) have been obtained on sapphire substrate. The other three spectra show a very intense 002 peak indicating a good structural quality of the relevant ZnO films. has been dispersed by an 0. but in this case a very high density has been achieved (see Fig.
correlating the features to the growth conditions. A detailed analysis of excitonic band spectra shows a more structured spectrum in the sample 3#. in spite of many cycles at gas concentration of 115 pmm. 5).4#. see also Fig. act as electron trapper. The response signal is detected for different gas concentration values ranging from 20 ppm to 115 ppm. ZnO nanostructures result able to detect NO2 by PL quenching measurements because the oxidizing gas interacting with the optical sensing surface. and its response increases as the crystal quality increases.Figure 3: Comparison between PL spectra of samples 1# . due to the quenching of the PL intensity during the interaction processes with the gas molecules. further investigation has to be carried out particularly on exotic shape samples. in the two emission bands has been measured. to improve the sample preparation. Figure 4: Typical dynamics responses due to the quenching of PL intensity during the interaction with NO2 gas molecules relative to the excitonic and defect band emission of sample 3# emission band. This behaviour is not clear. The response of sample 2# and 3# are larger than the 1# one in the case of excitonic band before the signal saturation (see Fig. attributed usually to oxygen vacancies (green emission) and interstitial oxygen (orange emission) . Nevertheless in this case anomalous effect after some NO2 exposure cycles appears. shows a sensing response comparable to the one of sample 2# and 3#. in accordance with the x-ray spectra. 311 . In the sample 4# the signal increases with respect to the baseline. This indicates the high structural quality of the samples. but it results comparable in the case of defect one. Repeatability and reproducibility in the optical sensing response in fact has been obtained only in ZnO nanowires. The comparison between their responses. we have performed optical sensing test on different samples 1# . 10 minutes are need to reaches an equilibrium value of the response and to restore the signal. resulting in a reduced PL signal. but no saturation effect of signal is present either at high gas concentration. It is important to note that the excitonic band shows a larger PL reduction than the defect band in all the investigated samples. shows a constant response in both band (of about 10 % and 4% in excitonic and defect band respectively) and a restoring signal comparable to the baseline. FXB transition  and also the first excited states FXAB  are visible. The sample with exotic shape 4#. shows contrasting results. causing the decrease of charge-carriers which can recombine radiatively. confirming the better crystal quality of the sample 3#. Nevertheless in the case of sample 4#. as expected. due to the band-edge emission of the ZnO. we have monitored the optical sensing response due to the defect band (usually reported) and of the excitonic band.4#. 5). in all cycle. . The sensing measurement is based on the variation of the PL emission due to gas/surface interaction (adsorption). Preliminary study on different samples with morphology comparable to the one of sample 4#. The measurements performed on sample 2# and 3# show a linear response as a function of gas concentration. The different diameter doesn’t affect the interaction mechanism with the gas molecules. detected at low temperature (7K). as shown in the Fig. 4 where only the response of sample 3# is reported as an example. morphological shape and crystal quality) of the sample in the surface-gas interaction mechanism and. The calibration curves of sample 2# and 3# are almost the same. The dynamic response of the analysed samples. is smaller (3 order of magnitude) than the UV signal. The dynamic response of sample 1# in the two emission band (not shown) is linear only at low concentration and it shows evident saturation effect at high gas concentration (70 ppm. We observe that in the case of low gas concentration (20 ppm). In fact the sample 4#. where besides the typical bound exciton D0X and the free exciton FXA transitions. In order to exploit the variation in the optical properties of nanostructures in optical sensing applications. due to high optical quality. In our samples. allows us to study the role of different features (dimensions.
On the contrary. Lett.H. Kawasaki. ACKNOWLEDGEMENT Figure 5: Comparison between the calibration curves of sample 1# and 3# we can attribute its larger stability at high gas concentration to the higher thickness of the film and to the larger surface to volume ratio. Sberveglieri. 8. but the larger response. D. particularly at high gas concentration. 301-307. the larger drift with respect the baseline value. “ Room-temperature gas sensing based on visible photoluminescence properties of metal oxide nanobelts “.Yu and Z. 585-     In this paper we have investigated the optical sensing properties of ZnO nanostructures.PLNO2/PLdry-air. 5 the response is calculated by considering the variation in the PL signal in dry air (PLdry-air) and in the presence of NO2 gas (PLNO2) respectively. C. Xu. „ Emission from the higher-order excitons in ZnO films grown by laser molecular-beam epitaxy ”. 2006. Shen. 114.W. pag. which result more stable. Li. The optical sensing measurements of ZnO nanostructures with exotic shape in fact result constant in both band even if the sample is exposed at high gas concentration for more time.K. IV. 208-213. This effect could be overcome in the case of thicker films. Faglia. 84. Baratto. 2006 and references therein. Actuators B vol. in all samples. “Synthesis and characterization of semiconducting nanowires for gas sensing”. A: Pure Appl. G Sberveglieri and L Zanotti. “Catalyst-free pulsedlaser-deposited ZnO nanorods and their room temperature photoluminescence properties” Appl. CONCLUSIONS We thank Flavio Casino and Giovanni Montagna for their technical help. Tsukazaki. REFERENCES  H. Liu. Y. M. G. Lett. 2004 A Bismuto. In particular we show the excitonic and defect band responses of sample 1# and 3#.X. Sens. X. Chia. G Faglia. The saturation effect in both band of sample 1# is clearly evident. and M. J. the sample 3# (or 2#) shows a linear behaviour in the investigated concentration range. G. Calibration curves are reported in Fig. C Baratto. Koinuma. 2007. T. “A novel method for improving the performance of ZnO gas sensors” Sens. Opt. It results that regular shape (exagonal nanowires) and high crystal quality ensures a high response to gas sensing. C. The excitonic band shows a larger response than the defect one. M. A. In particular we have 312 . Opt. Comini. 053110-13. as a function of NO2 gas concentration. T. pag. The interaction processes with the gas in fact results irreversible. Appl. Actuators B vol. 4. A. 121. Segawa and H. Vomiero. Phys. The role of thickness and/or exotic shape has to be clarified. Ong.sample1# sample 3# Excitonic band correlated the sensing response to NO2 gas molecules to the shape and to the crystal quality of the samples. P Maddalena. Ohtomo. 88. A. pag. Z. 3858-61. V. namely the quenching of emission signal is not restorable. Jiang. Ponzoni and A. Ferroni. by using the relation ΔR/R=PLdry-air . Makino. E Comini. C. An higher sensitivity is evidenced in the case of excitonic band of the sample 3# respect to the defect band. S Lettieri. M. In the Fig. Phys. Cui. E.Liu.
This action might not be possible to undo. Are you sure you want to continue?
We've moved you to where you read on your other device.
Get the full title to continue reading from where you left off, or restart the preview.