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Formation of highly oriented nanopores via crystallization of amorphous
Nb2O5 and Ta2O5
R. Nakamura,1,a) M. Ishimaru,2 K. Sato,3 K. Tanaka,4 H. Nakajima,5 and T. J. Konno3
Department of Materials Science, Graduate School of Engineering, Osaka Prefecture University,
Gakuen-cho 1-1, Naka-ku, Sakai 599-8531, Japan
Department of Materials Science and Engineering, Kyushu Institute of Technology, Tobata, Kitakyushu,
Fukuoka 804-8550, Japan
Institute for Materials Research, Tohoku University, Katahira 2-1-1, Sendai 980-8577, Japan
The Institute of Scientific and Industrial Research, Osaka University, Mihogaoka 8-1, Ibaraki,
Osaka 567-0047, Japan
The Wakasa Wan Energy Research Center, Tsuruga, Fukui 914-0192, Japan
(Received 5 August 2013; accepted 9 September 2013; published online 25 September 2013)
Formation of self-oriented and -elongated nanopores in annealed amorphous Nb2O5 and Ta2O5 was
analyzed by transmission electron microscopy. Along with their crystal growth, nanopores were
spontaneously elongated in the a-axis direction perpendicular to the longitudinal b axis of the
orthorhombic structures with strong anisotropy. In addition, the effect of tungsten on the nanovoid
formation in annealed amorphous Nb2O5 and Ta2O5 was also studied. Additive tungsten atoms of a
few atomic percent into Nb2O5 and Ta2O5 were found to make the aspect ratio of nanopores larger.
Electron diffraction experiments revealed that the crystallized regions including elongated
nanopores possess a variety of periodicity in the b-axis direction. This structural flexibility in the
crystal growth of strong anisotropic structures seems to play an important role on the unidirectional
growth of nanopores. V C 2013 AIP Publishing LLC. []

INTRODUCTION fabricating highly ordered nanoporous transition-metal
oxides of not only Ta2O5 but also Nb2O5, whose orthorhom-
Porous oxides have attracted extensive attention as func-
bic structure is also strongly isotropic.8 Fabrication of such
tional materials in categories such as ion exchange, molecular
highly oriented nanoporous Ta2O5 and Nb2O5 enables the
separation, catalysis, chromatography, and energy storage,
application as electronics and sensor devices to expand con-
because their properties can be vastly improved by increasing
siderably. For example, the dielectric property of Ta2O5
the surface-to-volume ratio.1,2 Typical nanoporous oxides,
(Ref. 9) and the power conversion efficiency of Nb2O5 as a
such as mesoporous silica3 and transition metal oxides,4 are
dye-sensitized solar cell material10 can be improved by pro-
fabricated by chemical synthesis routes which combine the
viding large surface areas in order to increase high specific
use of a template and an etching process. Such chemical syn-
charge and electron diffusion length. Therefore, for the better
thesis techniques are based on the concept of creating spaces
understanding of the formation mechanisms of self-oriented
by eliminating the nano-sized templates. In our research, on
nanopores, comprehensive studies for Nb2O5 as well as
the other hand, a bottom-up technique to produce nanoporous
Ta2O5 are required. The first purpose of the present work is
structures through the accumulation of atomic level spaces is
to characterize the formation behavior of nanopores in
employed. Amorphous Al2O3 (a-Al2O3), WO3 (a-WO3), and
annealed amorphous Nb2O5 by transmission electron micros-
Ta2O5 (a-Ta2O5) were found to become nanoporous structures
copy (TEM).
as a result of structural change and crystallization by anneal-
The self-organization of nanopores by the present tech-
ing in air.5,6 The evolution of nanopores originates in the
nique, as mentioned above, originates in the structural fea-
accumulation of amounts of atomic level spaces existing at
tures of amorphous and crystalline matrices and in dynamic
loosely bonded regions of the amorphous oxides, whose den-
behavior during structural changes towards crystallization,
sities are 20%–30% lower than those of their counterpart crys-
suggesting that the properties of nanopores such as size, den-
talline phases.
sity, or morphology are expected to be manipulated by modi-
Among the oxides described above, Ta2O5 exhibits a
fying amorphous and/or crystalline microstructures. One of
unique pore-formation behavior.6 Highly oriented and elon-
the possible routes for the purpose must be to introduce addi-
gated nanopores are spontaneously formed along with the
tive elements. In a previous work,11 we examined the effect
crystallization into orthorhombic b-Ta2O5, whose unit cell
of a third element, tungsten, on the pore formation in a-
(a ¼ 0.389 nm, b ¼ 4.029 nm, c ¼ 0.620 nm (Ref. 7)) is
Al2O3. The addition of tungsten into a-Al2O3 is effective for
strongly anisotropic. The pores are elongated in the a-axis
inducing larger and denser pores than in a-Al2O3 without
direction perpendicular to the longitudinal b axis of the
tungsten. The enhancement of pore formation is due to the
orthorhombic structure. The finding raises the possibility of
structural change of a-Al2O3; the introduction of tungsten
atoms makes amorphous structure more disordered, resulting
E-mail: in the decrease in density, i.e., the increase in atomic level

0021-8979/2013/114(12)/124308/6/$30.00 114, 124308-1 C 2013 AIP Publishing LLC

The beam incidence is to [014] direction. (a ¼ 0. The relationship between pore and crystal orienta- structure of thin films remains amorphous up to 773 K at an tions in orthorhombic Nb2O5 is in good agreement with that annealing time of 1 h while crystallized regions appear in in orthorhombic Ta2O5. simulated on the basis of the Nb2O5) prepared by sputtering. self- analyzed quantitatively using a Digital Micro-Luminography elongated and oriented nanopores are formed (d). The phology during the annealing of amorphous Nb2O5 (a. EXPERIMENTAL PROCEDURE Thin films of amorphous Nb2O5 (a-Nb2O5) and Ta2O5 (a-Ta2O5) were prepared by radio-frequency sputtering a crystalline oxide target with 99. Phys.12. the formation behavior of nanopores in annealed amorphous Nb2O5 and Ta2O5 con- taining tungsten atoms was also examined by analyzing the atomic structure of the amorphous oxides in terms of pair distribution function (PDF) and the crystallographic proper- ties after annealing by TEM. On the terns were recorded on an imaging plate (Eu2þ doped other hand.624 nm (Ref. The structure. tungsten is inevitably introduced into the deposited oxide films. c ¼ 0. 1(c). the concentration of which was aimed for a few at. for 1 h. In the present work. J. The changes in its morphology and structure were exam- ined by a Hitachi H-800 type TEM and a JEOL JEM-3000F TEM at 300 kV. b ¼ 4. (b) 773 K. pores in the crystallized region show a tendency to BaFBr). as can be seen in self-organized nanopores can be attributed to the strong . images were acquired within the detector angle between 60 and 210 mrad. (c) 823 K. 8)). Appl. The NaCl on which the 15–30 nm thick oxide thin film was deposited was put into distilled water.379 nm. A typical example of changes in morphology and structure of a- dark-field (HAADF) detector. %.124308-2 Nakamura et al. The effect of tungsten on the pore formation behav- ior in Nb2O5 and Ta2O5 must be clarified from a scientific perspective and also in terms of the potential applications of these materials. As a halo-patterns from the as-deposited amorphous samples were result of crystallization at a high temperature of 923 K. The direction of an as-deposited thin film of a-Nb2O5. The tilt series of Z-contrast Nb2O5 during annealing in air: (a) as-deposited. a elongated pores is parallel to the a axis. 1(a). The intensities of interface of the crystallized phase tend to be elongated. as is the case with at 773 K. In evaporating a grain of the oxides on a tungsten coil as a heating source. The Fig.392 nm.13 The composition was analyzed by the TEMs Figure 2 shows the BFIs (a) and SAED patterns (b) of equipped with an energy dispersive X-ray spectrometer fully crystallized Nb2O5 films. where an array of elongated nanopores appears. Ltd). FDL5000. Atomic number contrast (Z-contrast) images of scanning TEM (STEM) were obtained using a FEI Titan 80-300 TEM operating at 300 kV with a high-angle annular FIG.6 indicating that the formation of the the amorphous matrix at 823 K for 1 h. fraction intensities for PDF analysis were measured at cryo- It is particularly noteworthy that the pores near the front of genic temperature using a cooling holder. Resistive heating deposition was also used for preparing a-Nb2O5 and a-Ta2O5 thin films including tungsten. electron dif- aggregate and grow larger than those in the amorphous region. 114.9% purity. electron diffraction patterns (c). and (d) 923 K for 1 h. a number of spheri- intensities of selected-area electron diffraction (SAED) pat- cal nanopores can be seen. The amorphous oxide on the Pt grid was subjected to heat-treatment in an electric furnace in air at 773–1023 K for 1 h. in particular. no void-contrast can be detected in mentally obtained diffraction patterns (b). conform to the experi- image (BFI) of Fig. As shown in the bright field orthorhombic structure model (c0 ). 1. The structure of RESULTS AND DISCUSSION crystallized Nb2O5 was identified as orthorhombic Nb2O5 Figure 1 shows a typical change in structure and mor.11 A cleavage NaCl crystal was used as the substrate. and 3D reconstruction was performed by using the INSPECT3D software package (FEI Co. On the other hand. 124308 (2013) spaces. and then the floating thin film was mounted onto a platinum grid. To avoid contamination. per- high density of spherical nanopores with an average diameter pendicular to the longitudinal b axis of the orthorhombic around 3 nm appears in a-Nb2O5 annealed at 773 K (b). Some of the crystallized specimens after annealing were coated with carbon to reduce the effects of charging at TEM observations. after annealing at 873 K (EDS). and therefore. In the amorphous region of (c).

a different Figure 3 shows a low-energy portion of energy-dispersive feature of pore formation can be recognized: the pores in the X-ray spectra of as-deposited a-Nb2O5 (a) and a-Ta2O5 (b).11 tungsten is self-evaporated into the preferential a-axis direction in Ta2O5-W is more pro- the Nb2O5 and Ta2O5 thin films from a tungsten coil used as a nounced compared to that in Ta2O5 without W. As is the case with resistive Fig. A pro. the atomic arrange. the diffraction pattern of ing nanopores at the boundary between amorphous and Figs. As a result. 7 and 8). heating source. reveals clearly that the elongation of nanopores toward heating deposition of Al2O3. % in Ta2O5-W. Appl. Phys. 5. Energy-dispersive X-ray spectra of as-deposited amorphous (a) Nb2O5-W and (b) Ta2O5-W. Fourier power spectrum. i. However. nanopores. Again. The overall picture of pore crystalline phase in the amorphous matrix. 114. Figure 4(e) shows the high- ment towards the long-periodic b-axis in the (100) plane is resolution TEM image of crystallized Ta2O5-W and its more difficult than the a. nal b axis of the orthorhombic structures. the horizontal direction. % in a-Nb2O5-W and 2 at. the concentra- tion of W is probably around 5 at. 1 and 2) and Ta2O5 (Ref. BFI (a) and SAED patterns (b) of the fully crystallized Nb2O5 film Nb2O5-W and Ta2O5-W. elongate in the a-axis direction perpendicular to the longitudi- pores show a tendency to grow unidirectionally.e.. W. oxides without W. and they elongate along slow growth of (001) plane. which provides the growing nano. Although it is hard to determine precisely the concentration of tungsten because of large difference in atomic number between metal and oxygen ions. nano. prepared by sputtering. 3.6 shown in peaks are observed in both oxides.124308-3 Nakamura et al. The W M and L between fully crystallized Ta2O5-W and Ta2O5. (001) electron diffraction pattern (cf. Figures 4(a)–4(d) show the BFIs of after annealing at 873 K for 1 h. The c-axis is almost perpendicular to the amorphous Nb2O5-W and Ta2O5-W after annealing at photograph. the samples are denoted as FIG. 124308 (2013) FIG. cal nanopores around 3 nm is formed in the a-Nb2O5-W annealed at 823 K (a) and a-Ta2O5-W at 923 K (c) and then anisotropy of orthorhombic structure of the pentoxides.and c-axes. oxides with W have higher aspect ratio than those in the prepared by resistive heating deposition. It was found that a large amount of spheri- model of orthorhombic Nb2O5 (c0 ). The comparison in reconstructed 3D image rays of Pt in a-Ta2O5 (b) come from the grid. 2. (c) Electron diffraction patterns simulated from the structure 823–973 K for 1 h. The spectrum is consistent with the pores with enough time to absorb free volume as well as exist. . The characteristic X.6 The growth of the formation behavior in Nb2O5-W and Ta2O5-W is consistent (100) plane is limited due to the long periodic structure of the with that of Nb2O5 (Figs. they grow into elongated and oriented shapes after crystalliza- posed mechanism is corporative growth of pores along with tion at 873 K (b) and 973 K (d). 6) without b-Ta2O5 unit along the b-axis direction. it was confirmed that the nanopores crystalline phases as crystal growth occurs. The bright domains correspond to ture of Nb2O5 as well as Ta2O5 allows for the faceted and less densely regions. J. The strong isotropic na. Hereafter.

28 nm. Phys. 6. Appl. resulting in the enhancement of pore formation. respectively. we performed two types of analyses from the viewpoint 0. 4.14 The peak position and intensity of oxides. respectively.38 nm.13 Both amorphous oxides have similar atomic-bond properties: the first and second peaks To discuss the effect of W on the pore formation behav- corresponding to Nb(or Ta)-O and O-O are located around ior. which is more disordered and has a lower den- sity (larger atomic level spaces) than the amorphous solids. The size of reconstructed region of (a) and (b) ons attract O2 ions rather than lower valence Al3þ cations. The FIG. Figures 6(a) and 6(b) show the atomic PDF of the PDF for a-Nb2O5 and a-Ta2O5 agree well with those of a-Nb2O5-W and a-Ta2O5-W.11 The short-range atomic configurations of amor- phous Al2O3 containing W are similar to those of a pseudo- liquid state.12. 124308 (2013) FIG. J. and (c) at 923 K and (d) 973 K for Ta2O5-W. the charge state of W is close to that for . the addition of W into the oxides induces no remarkable change in amorphous structure. Atomic pair distribution function g(r) of as-deposited amorphous Nb2O5 (a) and Ta2O5 (b) with and without tungsten atoms. the introduction of W must disorder the state of coordination and bond-length in amor- FIG.20 nm and 0. The detailed proce- Ta2O5-W and its Fourier power spectrum. as-deposited a-Nb2O5 and a-Ta2O5 with and without W. and the double peaks for of structural properties: one is pair distribution analysis of Nb-Nb (or Ta-Ta) around 0. 5. BFIs of amorphous Nb2O5 and Ta2O5 containing W after annealing PDF was obtained by analyzing the SAED patterns taken in air for 1 h: (a) at 823 K and (b) 873 K for Nb2O5-W. dures of RDF analysis using electron diffraction techniques are described elsewhere. In Al2O3. 114.11 It seems that the difference in the effect of W on the amorphous struc- ture of these oxides arises from the conformity of ionic prop- erties in the matrices. (e) A high-resolution TEM image of crystallized from the region of 300 nm in diameter. Reconstructed 3D images of elongated nanopores included in the crystallized Ta2O5-W at 973 K (a) and Ta2O5 at 1023 K (b) observed by phous Al2O3 because the higher valence of W5þ or W6þ cati- HAADF-STEM tomography.124308-4 Nakamura et al. is 209 nm  295 nm  98 nm and 115 nm  189 nm  74 nm. The atomic the amorphous oxides with and without W and the other is distribution in a-Ta2O5 is almost consistent with that the comparison of lattice spacing between the crystalline reported by Bassiri et al. even though there is somewhat discrepancy in film thickness due to different sample prepa- ration processes. Therefore. On the other hand. which is different clearly from the effect of W on the structure of a-Al2O3.33 and 0.

m. non-oriented pores. of W. In the preceding paper. the elongation of pores with a larger aspect ratio is promoted by the addition of tungsten. and Nb2O5-W. 8). tungsten. indicating that the periodicity is The experimentally obtained SAED patterns ((a) and (b)) are not flexible but limited. It is cal example of SAED patterns taken from the regions which probable that solute tungsten atoms diffuse to be distributed to the forefront of growing crystalline phase at the amorphous-crystalline boundary. periodicity represents superstructures along As shown in Figs. As a result. 13. (c) Electron diffraction patterns simulated from the structure model of orthorhombic Nb2O5 (c0 ). inset of Fig. 8. clarify deeply the effect of third element. Appl. monly in the oriented and non-oriented crystallized regions lated from the orthorhombic models (c0 ). Under such a condition. Phys. simu.e. The spacing of fun. FIG. Ta5þ and Nb5þ so that W atoms dissolve into amorphous contain oriented (a) and non-oriented (b) pores in Ta2O5-W. 124308 (2013) FIG.6 Discussion on the latter effect. 9(a)). Nb2O5. i. occur variably during the crystal growth in the amorphous cating that the lattice spacing of the basic unit cell and the matrix. and Ta38WO98..366 nm. 114. respectively. A zoomed diffrac. smoothly in the elongated direction of a-axis along by rhombic structures are maintained in spite of the introduction absorbing atomic level spaces and existing spherical pores. J. In the non-oriented ides with and without W after the full crystallization. 4 and 5. crystal and pore growth. and superlattice reflections. Figure 9 compares a typi. Nb2O5 and Ta2O5 with the short-range order being The streaks appear sharply from the oriented regions (see the maintained. 7) and [001] for Ta2O5 (Fig. The direc- tion of incident electron beam is [001]. indi. 15 and 16)). is 8. Comparison of SAED patterns taken from the region including ori- nents both at the surface and in the matrices is required to ented pores (a) and non-oriented pores (b) in Ta2O5-W. a ¼ 0. Ta22W4O67. of Ta2O5. kinetic properties such as diffusion of compo- FIG. 9. the streaks are very weak and beam incidence was identically set to be in the [014] for the additional spots are scattered around the fundamental Nb2O5 (Fig. Comparison of SAED patterns of fully crystallized Nb2O5 with (a) and without (b) tungsten atoms.389 nm.. the damental and superlattice reflections of Nb2O5 and Ta2O5 is atomic arrangement towards the long-periodic b-axis must almost consistent with that of Nb2O5-W and Ta2O5-W. In the oriented region. on the other hand. Stephenson and Roth17–19 the substructure (e. additive tungsten atoms enhance [010] with multiplicities (m) of the unit length of b-axis of the self-elongation of pores. Comparison of SAED patterns of fully crystallized Ta2O5 with (a) and without (b) tungsten atoms. on the tion spot for enclosed point is at the upper-right corner. a synergy effect between the strong isotropic structure and crystal growth has been consid- ered to be important factors for the formation of oriented and elongated nanopores in Ta2O5. These tendencies can be seen com- in good agreement with the diffraction patterns (c). The direction of incident electron beam is [014]. which can be attributed to a wide variety Figures 7 and 8 compare the SAED patterns of pentox. (c) Electron diffraction patterns simu- lated from the structure model of orthorhombic Ta2O5 (c0 ). 7. and 19 for with spherical. . Ta30W2O81.124308-5 Nakamura et al. pores are likely to grow periodicity in the direction of longitudinal b-axis of ortho.g. of periodicity in the b-axis direction. reported that the periodicity in the b-axis direction of ortho- c ¼ 0. respectively.620 nm for Ta2O5 (Refs. Here. rhombic Ta2O5 varies according to the concentration of tung- The fully crystallized samples contain partly the grains sten: the value of multiplicities. b ¼ 0. The regions (b). providing multiple perio- dicities and then higher variability of atomic arrangements during crystal growth.

963 ability of atomic arrangement in crystal growth must be a key (1999). Sov. 7. Mater. Nakamura. T. 10 J. Domen. E. Tanaka. Hirata. Hirotsu. and J. The common feature of pore formation in Young Scientists (B) (No. D. E. J. P.. S. Acta Crystallogr. W. P. Sect. TEM observations were carried out at the Research 20 Y. J. tures. Nakajima. T. Lu. Beck. Both amorphous structure and crystallo. A. H. . J. Scr. 197 (2011). Zhuiykov. Phys. S. K. Kaner. 124308 (2013) CONCLUSION Comprehensive Analysis Center of ISIR. R. 1194 (2001). Center for Ultra-High Voltage Electron Microscopy and the 13. A portion of this study was performed under the inter- Self-oriented and -elongated growth of nanopores is university cooperative research program of the IMR. Vartuli. 178. 3308 growth using external effects. and S. 1010 (1971). Wan and D.. M. Osaka University. Rev. J. Appl. 19 N. Chem. J. B. Less-Common Met. maintained even by the addition of tungsten of a few at. 171 (2002). Solid State Chem. Rani. J. 4045 (2012). J. 64. 9 ment during crystal growth. S. and H. This work was supported by Grant-in-Aid for the case with Ta2O5. Parker. Ollivier. Takata. B 27. 8. H. Instrum. Takahara. 66. and K. Hough. J. Grey. manipulating pore morphology by designing the additive ele. I. Scr. Kondo. Ohkubo and Y. 1025 (1971). Y. Lu. Stephenson and R. Roth. B. resulting in the enhancement of I. 031904 (2011). Kalantar-zadeh. 397 (1964). 750 (1960). or on substrates with epitaxial relations. e. 3 factor enabling the unidirectional growth of nanopores. B 27. Appl. 18 N. 094201 (2003). J. Sect. J. S. and R. Nakajima. Z. tributes to the change in the variability of atomic arrange. N. tungsten. Appl. A. Lehovec. Zheng. B 250. Nakamura. 2 S. T.10 and 13 M. M. D. L. Ham. K. Rev. into the oxides enhances the formation of nanopores with a 5 R. ACS Nano 6. and P. Zvinchuk. and H. Kannan. Roth. A. and K. 7 R. S. orthorhombic structures and pore growth revealed that the vari. 445 into Nb2O5 and Ta2O5. 98. and H.20 To obtain more highly ordered nanoporous struc. Y. and T. Lee. % Nakajima. 2821 (2007). Waring. Roth. of Nb2O5 to use as dye-sensitized solar cell materials.-H. Ou. Nucl. Stephenson and R. Ishimaru. A. The highly oriented porous R. and H. 4 It was found that the addition of third element. niobium and tantalum pentoxides can be attributed to the strong isotropy of the orthorhombic structures. R. Mater. Nature 359. T. Zhao. Roth. MacLaren. 107. 17 netic fields. J. Tane. M. catalysis. Acta Crystallogr. Y. C. 182 (2012). S. Mumme. Kresge. C. Zhang. Phys. 15 K. B. Sect. 11 ments into amorphous oxides. Domen. Shudo. 110.. 3. Leonowicz. Johnson. J. Ishimaru. Sato. N. under electric and mag. Ishimaru. as is University. (2011). Hirata.. Solid-State Lett. Schmuki. M. 2. R. J.124308-6 Nakamura et al. it may be worthwhile trying to control the crystal 16 I. Sriram. S. 710 (1992). 064324 nanostructures are expected to enable the range of applica. Topics in Catalysis 19. D. C. S. 8 R. 14 in the case of Ta2O5 to use as dielectric materials9 and photo. B 27. higher aspect ratio. It seems that additive tungsten con. Mallouk. Sieber. Nakamura. (2005). R. 6 graphic properties such as lattice constant and periodicity are R. Sato. S. Phys. M. Kondo. Bhaskaran. T. Stephenson and R. Cockayne. Acta Crystallogr. tion of Nb2O5 and Ta2O5 to expand considerably: in the case 12 T. Roth. M. Crystallogr. T. Rowan. B 67. Borisenko. Field. and K. Shudo. C. unidirectional pore growth. Lett. K. Bassiri. Mater. Roth. Tohoku induced as a result of crystallization of amorphous Nb2O5. B. M. Kimizuka. A. Electron diffraction 1 analyses on the relationship between the long periodicity of C. E. H.g. Res. Chem. 1018 ACKNOWLEDGMENTS (1971). J. J10 (2005). M. J. Phys. 309 (2006). 114. G. (1970). Science 283. W. Ishimaru. 24760574). Konno. Phys. Electrochem. Takahara. Konno. Methods Phys. The results of present work suggest the possibilities of Reece. Solid State Chem. K.

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