Applied Surface Science 174 (2001) 306309

Ultraviolet absorption spectra of amphoteric SnO2 nanocrystallites

Junyong Kanga, Shin Tsunekawab,*, Atsuo Kasuyac
Department of Physics, Xiamen University, Xiamen 361005, PR China Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan c Center for Interdisciplinary Research, Tohoku University, Sendai 980-8578, Japan
b a

Received 2 February 2001; accepted 13 February 2001

Abstract Aqueous sols having SnO2 nanocrystalline particles less than 2 nm in mean diameter were prepared by ultra-ltration from original acidic and alkaline sols with particle diameters extending over a wide range of 0.58 nm. Blue shifts were observed in ultraviolet absorption spectra of both the sols. The relationship between energy band gap and size distribution in the original and ultra-ltrated sols suggests that the blue shifts depend on not only the particle size but also the chemical state of nanoparticle surfaces in the acidic and alkaline sols. # 2001 Elsevier Science B.V. All rights reserved. PACS: 72.80.Jc; 61.46.w; 61.82.Rx; 82.80.Ch; 82.80.Pv
Keywords: Stannic oxide; Aqueous sol; Amphoteric oxide; Blue shift; Energy band gap; Ultra-ltration; X-ray powder diffraction

Small particles of SnO2 have been widely used for gas sensors [16], transparent electrodes [7], ultraviolet (UV, photosensitive) optical bers [8]. Among many oxides, only SnO2 nanocrystalline particles are stably produced from both acidic and alkaline solutions, except for ZrO2. Oxide nanoparticles are often characterized by the changes in structural arrangement [9] and/or valency of cations [10,11]. These variations lead to the energy band change [12] and the anomalous lattice expansion [13,14]. The energy band gap is one of the most important parameters of semiconducting materials and its change results in the shift of optical absorption edge. This paper reports the blue shift measurement of UV absorption edges in SnO2 crystallites of less than 2 nm in mean diameter. Our result shows different

* Corresponding author. Tel.: 81-22-2103; fax: 81-22-2104. E-mail address: scorpion@lexus.imr.tohoku.ac.jp (S. Tsunekawa).

behaviors depending on samples prepared in acidic or alkaline sols. Aqueous sols having SnO2 crystallites of less than 7 nm in diameter were prepared by ultra-ltration with a at sheet membrane (NTU-3150, Nitto Electrical Industry) from the original acidic sol with 1.5 wt.% oxalic acid and the original alkaline sol with 0.3 wt.% ammonia, both containing SnO2 particles of sizes 0.58 nm produced by solgel and hydrothermal reaction processes [15]. UVabsorption measurements were carried out for the original and ultra-ltrated SnO2 aqueous sols using a spectrophotometer (U-2000, Hitachi) with 10 mm quartz cuvettes in the wavelength ranging from 200 to 600 nm. Size distributions in the ultra-ltrated SnO2 sols were obtained from a computer analysis (Image-Pro Plus, Media Cybernetics) of dark eld images of 1 1 0 and 1 0 1 reections observed by a transmission electron microscope (TEM: JEM-200CX, JEOL). The distributions in the original sols, however, were not determined by the

0169-4332/01/$ see front matter # 2001 Elsevier Science B.V. All rights reserved. PII: S 0 1 6 9 - 4 3 3 2 ( 0 1 ) 0 0 1 8 4 - 2

J. Kang et al. / Applied Surface Science 174 (2001) 306309

307

same method, because their sol concentrations were very high containing the nanosized particles that coagulated heavily. Hence, mean diameters of the particles in the original sols were determined by X-ray powder diffraction (XRD: Geigerex, Rigaku) method with Cu Ka irradiation for the samples which were dropped and dried on non-reective glass plates. Commercial SnO2 powder (purity of 99.9% and grain size of 2:5 0:3 mm) was used as a standard sample. Optical spectra of oxalic acid and ammonium solutions, and the original and ltrated acidic and alkaline SnO2 aqueous sols exhibit strong absorptions in the UV range as shown in Fig. 1. The absorption edges of the oxalic acid and ammonium solutions are located at 270 and 215 nm, respectively, which are consistent with previous data [16]. In order to remove the

inuences of oxalic acid and ammonia in SnO2 sols on the spectra, UV absorptions of oxalic acid and ammonium solutions were measured at pH 2:5 and 10.5, respectively, as the references to the acidic and alkaline sols of nearly the same pH. Distinct blue shifts are exhibited in the spectra of both the ultraltrated acidic and alkaline SnO2 sols, comparing with the original sols in Fig. 1. Optical transition of SnO2 crystals has been known to be a direct type [17]. In this case, an absorption coefcient a is expressed as ahn G hn Eg 1=2 =hn [18]. Plots of (a(hn))2 against hn are obtained from the absorbance data shown in Fig. 1, using the relation a logI0 =I =d , where I0 and I are the light intensities before and after transmission, and d the light path length, 10 mm in our case (see Fig. 2). The value

Fig. 1. Absorbance a logI0 =I spectra with 10 mm quartz cuvettes: (a) the original (solid) and ltrated (dash) acidic SnO2 sols together with oxalic acid solution (dot) as a reference, and (b) the original (solid) and ltrated (dash) alkaline SnO2 sols together with ammonium solution (dot) as a reference.

Fig. 2. Plots of (a(hn))2 vs. hn for (a) the original (left) and ultraltrated (right) acidic SnO2 sols, and (b) the original (left) and ultra-ltrated (right) alkaline SnO2 sols. Energy band gaps Eg are obtained from the extrapolation to a 0.

308

J. Kang et al. / Applied Surface Science 174 (2001) 306309

Fig. 4. XRD patterns obtained for SnO2 in 99.9% puried powder (a), the original acidic sol (b), and the original alkaline sol (c).

obtained for submicron-sized samples with lattice strains given by Hall [19,20]:
Fig. 3. Histograms for size distributions obtained by a computer analysis of dark eld TEM images of ultra-ltrated SnO2 nanoparticles in (a) acidic and (b) alkaline sols.

b cos y

of hn extrapolated to a 0 represents the energy band gap Eg. It is found that the band gaps in the ltrated sols are larger than those in the relevant original sols. Size distributions of SnO2 nanocrystalline particles in the ultra-ltrated sols are shown in Fig. 3. About 99% of particles in both the ltrated acidic and alkaline sols are distributed in a diameter range less than 6 nm. Mean diameters are determined to be 1.6 nm for the acidic sol and 1.1 nm for the alkaline sol from the histograms. Mean diameters of nanoparticles in the original sols are obtained from XRD powder patterns. The patterns are shown in Fig. 4, where the full width at half maximum (FWHM) of the nanoparticles is found to be more than 10 times as large as that of the standard powder. The mean diameters are determined by Hall's method. The following equation has been

l 2Z sin y; (1) D where D is the particle diameter, l the X-ray wavelength Cu Ka 0:1542 nm, Z the lattice strain, y the Bragg angle, and b the FWHM estimated by the following equation:   p b1=2 bP b ; (2) 0:89 180

where b1/2 and bP are the FWHMs obtained for nanocrystallites and micron-sized powders, respectively. bP is almost constant, 0.258 for all the diffraction peaks of the standard sample in the present diffraction range. Therefore, the mean diameter is obtained by extrapolating the above b cos ysin y plot to sin y 0. The diffraction patterns shown in Fig. 4 give the mean diameter and the lattice strain of SnO2 nanocrystallites as 3.3 nm and 1.2% for the original acidic sol, and 3.8 nm and 3.3% for the original alkaline sol, respectively.

J. Kang et al. / Applied Surface Science 174 (2001) 306309 Table 1 Energy band gaps Eg and mean diameters of SnO2 nanocrystalline particles in different aqueous sols, where Z is the lattice strain of the particles Aqueous sol Acidic sol Original Filtrated Alkaline sol Original Filtrated Eg (eV) 3.80 4.40 4.23 4.61 Mean diameter (nm) 3.3 (Z 1:2 102 ) 1.6 3.8 (Z 3:3 102 ) 1.1

309

assisted by Core Research for Evolutional Science and Technology (CREST) of Japan Science and Technology Corporation. The authors would like to thank Mr. S. Yamamoto of Taki Chemical Co. for his supplying of the original sols. References
[1] M. Nitta, M. Haradome, J. Elect. Mater. 8 (1979) 571. [2] N. Yamazoe, J. Fuchigami, M. Kishikawa, T. Seiyama, Surf. Sci. 86 (1979) 335. [3] S.G. Ansari, P. Borojerdian, S.R. Sainkar, R.N. Karekar, R.C. Aiyer, S.K. Kulkarni, Thin Solid Films 295 (1997) 271. [4] J.M. Herrmann, J. Disdier, A. Fermandez, V.M. Jimenez, J.C. Sanchezlopes, Nanostruct. Mater. 8 (1997) 675. [5] S.R. Davis, A.V. Chadwick, J.D. Wright, J. Mater. Chem. 8 (1998) 2065. [6] C. Nayral, T. Ould-Ely, A. Maisonnat, B. Chandret, P. Fau, L. Lescouzeres, A. Peyre-Lavigne, Adv. Mater. 11 (1999) 61. [7] T. Arai, J. Phys. Soc. Jpn. 15 (1960) 916. [8] G. Brambilla, V. Pruneri, L. Reekie, Appl. Phys. Lett. 76 (2000) 807. [9] S. Tsunekawa, S. Ito, T. Mori, K. Ishikawa, Z.-Q. Li, Y. Kawazoe, Phys. Rev. B 62 (2000) 3065. [10] S. Tsunekawa, R. Sivamohan, S. Ito, A. Kasuya, T. Fukuda, Nanostruct. Mater. 11 (1999) 141. [11] S. Tsunekawa, T. Fukuda, A. Kasuya, Surf. Sci. 457 (2000) L437. [12] S. Tsunekawa, T. Fukuda, A. Kasuya, J. Appl. Phys. 87 (2000) 1318. [13] S. Tsunekawa, R. Sahara, Y. Kawazoe, K. Ishikawa, Appl. Surf. Sci. 152 (1999) 53. [14] S. Tsunekawa, K. Ishikawa, Z.-Q. Li, Y. Kawazoe, A. Kasuya, Phys. Rev. Lett. 85 (2000) 3440. [15] H. Nishikura, S. Yamamoto, Y. Terao, Japan Patent H3-3607 for the alkaline sols, 1991; Private communication with Mr. S. Yamamoto for the acidic sols. [16] H. Ley, B. Arends, Z. Phys. Chem. B 17 (1932) 177. [17] J. Robertson, J. Phys. C 12 (1979) 4767. [18] X.K. Zhao, J.H. Fendler, J. Phys. Chem. 95 (1991) 3716. [19] W.H. Hall, J. Inst. Met. 75 (1950) 1127. [20] W.H. Hall, Proc. Phys. Soc. A 62 (1949) 741.

The energy band gaps and mean particle diameters obtained from above analyses are summarized in Table 1. From this table, it can be seen that (1) nanoparticles in the original alkaline sol have larger strain and band gap than those in the original acidic sol, and (2) the size dependence of the band gap of nanoparticles in the alkaline sols is weaker than that in the acidic sols. This is similar to the previous result shown in ceria nanoparticles and thin lms [12]. The fact that SnO2 crystalline particles in the original alkaline sol have rather large strain, despite of rather large particle size, suggests a difference of surface states between those in the acidic and alkaline sols. More detailed analyses of the XRD patterns and the TEM images will be reported elsewhere. X-ray photoelectron spectroscopic analyses are underway in order to reveal surface states of the crystallites such as surface composition and valency. Acknowledgements This work was partly supported by National Natural Science Foundation and the Natural Science Foundation of Fujian Province of China, and was partly