NO2 OPTICAL SENSING IN ZNO NANOSTRUCTURES

A. Cret, 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 protected]
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

I.

INTRODUCTION

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 600C 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 -2 geometry by using the CuK excitation line (=1.5402 ) 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

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a) 1m)

c) 1m)

b)

1m)

d)

1m)

Figure 1: SEM image of the ZnO nanostructures of sample 1# (a), 2# (b), 3# (3) and 4# (d).

temperature. In this case the PL, carried out by He-Cd laser (325 nm), has been dispersed by an 0.1 m focal length Avantes spectrometer mod. MC 2000. The procedure for testing the optical gas sensing properties of the nanostructured ZnO films, provides that the sample has to be preliminary expose to a flow of dry air, in order to acquire the baseline for the successive analysis of the optical response to the NO2 gas. The total flow was kept constant at 50 ml/min. The variation in the integrated PL signal of the sample under exposure to NO2 gas, coming from defect and excitonic bands, was recorded during a minimum period of time (10min) necessary to reach an almost equilibrium signal, in the response phase and in the restoring process, in order to analyse also the reversibility of the interaction processes. III. RESULTS AND DISCUSSIONS In this work we have investigated four different samples: sample 1# and 2#, grown on ITO substrate and sample 3# and 4#, grown on sapphire substrate. The sample 1#, 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. As shown by the SEM image in Fig. 1 a), it consists of a poor density of nanorods randomly dispersed on the surface of the substrate. The nanorods have an hexagonal section with a tapered tip and an average diameter of (130 20) nm. The sample 2# has been also obtained with the ITO substrate placed in front of the crucible, but at a reduced distance of 10 mm and maintaining the furnace temperature at 600C for 60 min. The same growth conditions were used for sample 3#. Both samples exhibit nanorods with a shape similar to sample 1#, but in this case a very high density has been achieved (see Fig. 1b) and 1c)). Furthermore the nanorods of sample 3# have a significantly larger diameter and a much wider size dispersion (ranging between 250 and 500 nm), than the one of sample 2#, which averaging diameter results to be

Figure 2: XRD spectra of sample 1# (a), 2# (b), 3# (c) and 4# (d).

(120 20) nm, complarable with sample 1#. In particular the samples 2# and 3# grew on a ZnO bulk layer of few microns thickness. Finally, placing the substrate next to the crucible and maintaining the same experimental growth conditions of sample 2# and 3#, nanostructures of exotic shape (Fig.1 d) have been obtained on sapphire substrate. The crystal quality of the samples has been investigated by means X-ray diffraction (XRD) and photoluminescence measurements at low temperature (7K). Fig. 2 show the theta-2theta x-ray diffraction spectra obtained respectively from sample 1# - 4#. The XRD spectrum of sample 1# (Fig.2) is dominated by two main peaks, namely the 100 and 002 of the ZnO wurtzite structure. The presence of these peaks demonstrates the misorientation of the nanorods with respect to the z axis of the wurtzite structure, as expected from the SEM image. The other three spectra show a very intense 002 peak indicating a good structural quality of the relevant ZnO films. Nevertheless, some differences can be observed: the spectrum of sample 2# evidences secondary peaks of higher intensity in comparison with the other two samples, suggesting a worse structural quality of the sample. This demonstrates that the crystallinity of the substrate influences the structural properties of the ZnO films. Finally the comparison between sample 3# and sample 4# shows that the intensity of the sapphire peaks is quite different for the two samples, 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#. This would indicate a higher thickness of the deposited film in the case of the substrate placed next to the crucible. Fig. 3 shows the low temperature (7K) PL spectra of the investigated samples. In the all spectra the signal ranges between the visible range (green-orange) and the UVregion. In particular the visible signal, due to defect

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Figure 3: Comparison between PL spectra of samples 1# - 4#, detected at low temperature (7K).

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, attributed usually to oxygen vacancies (green emission) and interstitial oxygen (orange emission) [3], is smaller (3 order of magnitude) than the UV signal, due to the band-edge emission of the ZnO. This indicates the high structural quality of the samples. A detailed analysis of excitonic band spectra shows a more structured spectrum in the sample 3#, where besides the typical bound exciton D0X and the free exciton FXA transitions, FXB transition [4] and also the first excited states FXAB [4] are visible, confirming the better crystal quality of the sample 3#, in accordance with the x-ray spectra. In order to exploit the variation in the optical properties of nanostructures in optical sensing applications, we have performed optical sensing test on different samples 1# - 4#. The comparison between their responses, allows us to study the role of different features (dimensions, morphological shape and crystal quality) of the sample in the surface-gas interaction mechanism and, correlating the features to the growth conditions, to improve the sample preparation. The sensing measurement is based on the variation of the PL emission due to gas/surface interaction (adsorption). ZnO nanostructures result able to detect NO2 by PL quenching measurements because the oxidizing gas interacting with the optical sensing surface, act as electron trapper, causing the decrease of charge-carriers which can recombine radiatively, resulting in a reduced PL signal. [5]. In our samples, due to high optical quality, we have monitored the optical sensing response due to the defect band (usually reported) and of the excitonic band. The dynamic response of the analysed samples, due to the quenching of the PL intensity during the interaction processes with the gas molecules, in the two emission bands has been measured. The response signal is detected for different gas concentration values ranging from 20 ppm to 115 ppm. We observe that in the case of low gas

concentration (20 ppm), 10 minutes are need to reaches an equilibrium value of the response and to restore the 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, see also Fig. 5). The measurements performed on sample 2# and 3# show a linear response as a function of gas concentration, as shown in the Fig. 4 where only the response of sample 3# is reported as an example. The calibration curves of sample 2# and 3# are almost the same. The different diameter doesnt affect the interaction mechanism with the gas molecules. 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. 5), but it results comparable in the case of defect one. It is important to note that the excitonic band shows a larger PL reduction than the defect band in all the investigated samples, and its response increases as the crystal quality increases, as expected. The sample with exotic shape 4#, shows a sensing response comparable to the one of sample 2# and 3#, but no saturation effect of signal is present either at high gas concentration. In fact the sample 4#, 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, in all cycle, in spite of many cycles at gas concentration of 115 pmm. Nevertheless in this case anomalous effect after some NO2 exposure cycles appears. In the sample 4# the signal increases with respect to the baseline. This behaviour is not clear, further investigation has to be carried out particularly on exotic shape samples. Repeatability and reproducibility in the optical sensing response in fact has been obtained only in ZnO nanowires. Preliminary study on different samples with morphology comparable to the one of sample 4#, shows contrasting results. Nevertheless in the case of sample 4#,

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sample1# sample 3#

Excitonic band

correlated the sensing response to NO2 gas molecules to the shape and to the crystal quality of the samples. It results that regular shape (exagonal nanowires) and high crystal quality ensures a high response to gas sensing. The excitonic band shows a larger response than the defect one, in all samples, but the larger response, the larger drift with respect the baseline value. The interaction processes with the gas in fact results irreversible, particularly at high gas concentration, namely the quenching of emission signal is not restorable. This effect could be overcome in the case of thicker films, which result more stable. 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. The role of thickness and/or exotic shape has to be clarified. V.
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. Calibration curves are reported in Fig. 4. In particular we show the excitonic and defect band responses of sample 1# and 3#, as a function of NO2 gas concentration. The saturation effect in both band of sample 1# is clearly evident. On the contrary, the sample 3# (or 2#) shows a linear behaviour in the investigated concentration range. In the Fig. 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, by using the relation R/R=PLdry-air - PLNO2/PLdry-air. An higher sensitivity is evidenced in the case of excitonic band of the sample 3# respect to the defect band. IV.
CONCLUSIONS

We thank Flavio Casino and Giovanni Montagna for their technical help. REFERENCES
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In this paper we have investigated the optical sensing properties of ZnO nanostructures. In particular we have

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