NANO LETTERS

Anisotropic Light Scattering in Nanoporous Materials: A Photon Density of States Effect

Andrey A. Lutich, Sergey V. Gaponenko,*, Nikolai V. Gaponenko, Igor S. Molchan, Vitalii A. Sokol, and Vitali Parkhutik
Institute of Molecular and Atomic Physics, National Academy of Sciences, F. Skaryna AVe 70, Minsk 220072 Belarus, Department of Microelectronics, Belarusian State UniVersity of Informatics and Electronics, Minsk, P. BroVka Str., 6, 220027 Belarus, and Material Science Department, Technical UniVersity of Valencia, Paseo de Viaducto 1, 03801 Spain
Received March 9, 2004; Revised Manuscript Received July 21, 2004

2004 Vol. 4, No. 9 1755-1758

ABSTRACT
Similar to spontaneous emission of photons and inelastic (Raman) scattering, elastic (Rayleigh) scattering of light is controlled by spectral and spatial distribution of photon density of states, DOS (density of electromagnetic modes). However, to date Rayleigh scattering in nanoporous media has not become the subject of discussion in the context of photon DOS effects. In this paper, we consider light scattering in porous materials in the context of spectral, spatial, and angular redistribution of photon DOS in materials with pores whose size and spacing are of the order of light wavelength. The DOS effect results in predictable and controllable modification of scattering and can be purposefully used in certain light harvesting and illumination systems. A possible role of the effect in the cornea of eye is outlined for seeing at grazing incidence of light beams with respect to an eye pupil.

Photon density of states, DOS (density of electromagnetic modes) appears in a number of formulas describing emission of photons by matter. First of all, it appears in the Planks formula for spectral density of equilibrium (thermal) electromagnetic radiation. The density of equilibrium electromagnetic radiation is the product of photon energy, BoseEinstein distribution function, and photon DOS value. Second, photon DOS is known to appear in the expression for the lifetime of excited atoms, molecules, and solids since spontaneous emission of photons is viewed as stimulated emission with stimulating photons coming from zero-point oscillations of electromagnetic field.1 Third, photon DOS can be found as a factor in formulas describing inelastic (Raman) scattering of photons by molecules and solids.2 Finally, photon DOS factor is in the expression for the probability of elastic (Rayleigh) scattering of photons.3 Similar to inelastic scattering, elastic scattering in terms of quantum electrodynamics is considered as virtual excitation of matter with subsequent photon emission. Elementary photon emission is considered as a result of interaction of an excited (actually or virtually) quantum system with electromagnetic zero-field fluctuations. Accordingly, the spontaneous emis* Corresponding author. E-mail: gaponen@imaph.bas-net.by. National Academy of Sciences. Belarusian State University of Informatics and Electronics. Technical University of Valencia. 10.1021/nl049620e CCC: $27.50 Published on Web 08/06/2004 2004 American Chemical Society

sion rate, the probability of inelastic and elastic scattering of photons, is proportional to photon DOS. In a homogeneous space, the scattering rate W for photons with frequency into elementary solid angle d reads W() ) I()|V|2D()(42)-1 d (1)

where I() is the incident photon flux, V is the matrix element for photon emission, and D() is photon DOS. In a continuous medium, photon DOS D() is expressed by the formula D() ) 2n3/22c3 (2)

where c is the speed of light in vacuum and n is the refractive index of a medium under consideration (see, e.g., refs 1 and 2 and refs therein for more detail on DOS in various media). Noteworthy, the well-known 4 dependence of scattering probability, which is responsible for the blue sky color and sunset/sunrise redness, occurs essentially from the contribution of D() in the form of eq 2. In complex media such as dense sols, matrices with pores, cavities, or inclusions of guest materials, the D() function modifies at frequencies that correspond to photon wavelengths of the order of a characteristic material inhomogeneity size. A quarter-wave

Figure 1. Schematic drawing of a porous alumina sample.

value /4n is a reasonable scaling factor measuring the role of material inhomogeneities on photon DOS value. In a general case of an inhomogeneous dielectric with irregular structure, the local DOS value must be taken into consideration. Redistribution of the electromagnetic field inside a heterogeneous medium with respect to continuous one or to a free space is indicative of modification of the D() function. In a few model cases, e.g., dielectrics with periodic modulation of refractive index in space, so-called photonic crystals, the photon DOS can be ascribed to a complex dielectric as a characteristic of the medium. Three-dimensional photonic crystals such as colloidal close-packed structures4 and 2-dimensional photonic crystals such as mesoporous alumina5,6 became convenient model structures for investigation of modified photon DOS on optical processes. However, most of the experiments are focused on controlling (and freezing) spontaneous emission of photons (see refs 1 and 4 and refs therein). Other quantum processes in materials with modified photon DOS still remain beyond the attention of experimental physicists. Only rare experimental data are available on modified equilibrium radiation in photonic crystals7 and related model structures.8 Photon DOS effects on inelastic (Raman) and elastic (Rayleigh) scattering of photons has not been examined systematically as well. In this contribution we examine the photon DOS effect on elastic scattering of photons using porous anodic alumina as a representative material whose properties, with respect to photon DOS modification, can be qualitatively understood.

Porous anodic alumina (PAA) has been chosen as a proper material for experiments. It is known to possess well-defined submicrometer pore channels oriented normally to the surface. Under the condition of preliminary templating or adjusted etching regimes, the cylindrical pores forming a lattice in the plane normal to the pore axes can be developed.9 PAA membranes possess self-organized pores that are perpendicular to the planar sample surface (Figure 1, 2). The samples exhibit high reflection (up to 80%) with respect to visible light incident within the x-y plane and very high transmission (up to 98%) with respect to light propagating along the z-axis coinciding with pore orientation. Samples under investigation can be treated as a kind of 2-dimensional photonic crystal since high reflection for light beams in the x-y plane is indicative of strong redistribution of photon DOS, namely a decrease of DOS in the solid angle adjacent to the x-y plane and an increase of photon DOS for solid angles adjacent to the z-axis. The techniques available permit to fabricate samples up to 200 m thick with pore dimensions in the range of 10 to 500 nm. In this work we have used PAA membranes with thickness 100 m and pore displacement period 100 nm. In the experimental setup (Figure 3) the sample (membrane of porous alumina) and the detector can turn around the axis passing through the sample plane. Such a scheme permits to make experiments on light scattering by a sample at different angles of laser beam incidence as well as experiments on angular dependent transmission. Experiments were performed with two cw-light sources: a He-Ne gas laser (632 nm) and a solid-state Nd laser pumped with a semiconductor laser (second harmonic, 531 nm). With respect to normally incident light, such membranes are more transparent than any sample of a continuous dielectric (e.g., glass optical transmission 93%). Shapes of the transmission angular dependencies on angle of incidence are different for different wavelengths because the pore displacement period and light wavelength (500-600 nm) have comparable values (Figure 4). We have observed systematically anisotropic light scattering for PAA samples. Light coming at various angles with respect to the pore axis was found to be scattered predomi-

Figure 2. Electron microphotograph of the surface (left) and cross-section (right) of a porous alumina sample.
1756 Nano Lett., Vol. 4, No. 9, 2004

Figure 3. Scheme of experimental setup.

Figure 4. Transmission angular diagrams of the porous alumina membrane and ground glass for two wavelengths (632 and 531 nm). Detector is aligned along the incident laser beam propagation.

Figure 5. Scattering indicatrixes for different angles (R) of laser beam incidence. Light wavelength is 632 nm.

nantly in the solid angle adjacent to the pore axis. Scattering indicatrixes for different angles of incidence have been measured (Figure 5). The three petals systematically pronounced in the scattering diagrams are interpreted as follows. The two side petals result from direct transmission of incident light through the sample and from constructive interference on a set of parallel pore channels. Accordingly, the orientation of one side petal always coincides with incident beam propagation, whereas orientation of the second side petal shows mirror symmetry to incident beam with respect to the pore axis. Remarkable is the persistent central petal whose orientation correlates with pore axis independently of the angle of incidence. The central peak appears because light diffusely scatters on a porous structure under nonisotropic density of photon state conditions. The probability of light scattering in certain direction is proportional to the DOS in this direction. DOS has a maximum value in the direction along pores and a minimum in the perpendicular directions.
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Therefore, light mainly scatters in the direction along pore axes and the central peak develops. Therefore, we consider the observed anisotropic light scattering in porous alumina as a direct manifestation of photon density of states on quantum processes of photon scattering, thus complementing the discussion of photon DOS effects on spontaneous emission and inelastic scattering and extending interpretation of optical properties of nanostructured materials such as photonic solids toward classical scattering phenomena. It is reasonable to note one essential physical difference of elastic scattering of photons as compared to spontaneous photon emission and inelastic (Raman) scattering. Spontaneous emission and inelastic scattering result in photons with different frequency, which did not present in the incident light beam. For this reason elementary acts of photon emission/scattering can be understood only within the framework of quantum electrodynamics. Elastic scattering results in modification of direction and polarization of incident light and most probably can be completely understood within the framework of classical wave theory as a result of multiple scattering and interference of scattered waves. Therefore, the photon DOS concept is not necessary to describe elastic scattering in complex heterogeneous media. However, certain intuition promoted by the DOS concept can be helpful in many complex structures for which correct calculation of multiple light scattering is difficult but tentative redistribution photon DOS is qualitatively understood. Potential applications of the observed anisotropic scattering include concentration of light beams in light harvesting (e.g., solar cells) and light illumination (e.g., backlight in displays) systems. Since the effect observed in our experiments is valid for a different range of electromagnetic spectrum (e.g., microwave or radio frequency ranges) as well as for other classical waves (e.g., acoustic), porous materials with appropriate length scale of substructure can be used in these fields for focusing and spatial concentration of waves. Mammalian eye cornea is known to possess porous structure similar to PAA.10 Similar to porous alumina, porosity removes reflection at the air/cornea interface, providing superior transmission of light inside the eye. We suppose that anisotropic scattering of incident light coming at grazing incidence with respect to the direction normal to the cornea surface may assist in providing so-called side seeing by means of light concentration at the pupil coming from objects located at angles far from an eye axis. Acknowledgment. The work has been supported by INTAS grant #01-0642. References
(1) A review of photon DOS effects on spontaneous emission can be found in Barnes, W. L. J. Modern Opt. 1998, 45, 661. (2) Gaponenko, S. V. Phys. ReV. B 2002, 65, 140303 (R). (3) See, e.g., Berestetskii, V. B.; Lifshitz, E. M.; Pitaevskii, L. P. Quantum Electrodynamics; Nauka: Moskow, 1989; Chapter 6. (4) Petrov, E. P.; Bogomolov, V. N.; Kalosha, I. I.; Gaponenko S. V. Phys. ReV. Lett. 1998, 81, 77. (5) Krauss,Th. F.; De La Rue, R. M. Prog. Quantum Electron. 1999, 23, 51. (6) Gaponenko, N. V.; Davidson, J. A.; Skeldon, B. P.; Thompson, G. E.; Zhou, X.; Pivin, J. C. Appl. Phys. Lett. 2001, 76, 1006. 1757

(7) Lin, S.-Y.; Fleming, J. G.; Chow, E.; Bur, J.; Choi, K. K.; Goldberg, A. Phys. ReV. B 2000, 62, R2243. (8) Maruyama, S.; Kashiwa, T.; Yugami, H.; Esashi, M. Appl. Phys. Lett. 2001, 79, 1393. (9) Shingubara, S. J. Nanopart. Res. 2003, 5, 17.

(10) Ameen, D. B.; Bishop, M. F.; Mullen, T. M. Biophys. J. 1998, 75, 2520.

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