CA2013813A1

CA2013813A1 - Nonlinear optical materials

Info

Publication number: CA2013813A1
Application number: CA002013813A
Authority: CA
Inventors: Meyer H. Birnboim; Arthur E. Neeves
Original assignee: Individual
Current assignee: Individual
Priority date: 1989-04-04
Filing date: 1990-04-04
Publication date: 1990-10-04
Also published as: EP0466810A1; AU5438990A; US5023139A; JPH04504314A; WO1990011890A1; EP0466810A4

Abstract

ABSTRACT

Particles comprising a core surrounded by at least one shell wherein at least one of the core or one of the shells is a metal and at least one of the core or one of the shells is a dielectric material which exhibits a third order nonlinear response. The "shell" of a metal particle may be the adjacent region of a medium in which said particle is suspended, said medium having a third order nonlinear response. In a preferred embodiment, the particles are suspended in a dielectric medium that may be linear or may exhibit a third order nonlinear response. Enhancement of the effective ?(3) of the particles and suspensions result from the concentration of the electric field in and around the particles at the plasmon resonance frequency of the metal.

Description

NONLINEAR OPTICAL MATERIALS
The present invention relates to optical devices formed by metallic particles suspended in a medium, and more particularly, to such devices which exhibit third order 5 non-linear susceptibility.
Nonlinear composite materials are central to optical domain computing as real time holographic and bistable memory materials, as optical correlator materials, as phase conjugator materials and as thresholding materials. A number of fast response time polymeric and semiconductor materials have emerged t~at have electronic nonlinear mechanisms in the picosecond and subpicosecond time scale. However the small magnitude of the optical nonlinearity requires a high laser density to utilize these materials. The consequent power dissipation limits the utilization of these materials.
Optical phase conjugation has been measured from dilute linear suspensions of nonlinear nanospheres in degenerate four wave mixing experiments. In "Phase Conjugation In Liquid Suspensions Of Microspheres In The Diffusive Limit,"
31 Phys. Rev. A. 2375 (1985), Rogovin and Sari attributed the apparent third order optical susceptibility, X(3), to a slow electrostrictive mechanism for dielectric spheres in a dilute suspension. See also Smith et al., "Four-wave mixing in an artificial Kerr medium," 6 Optics Letters 284 (1985), and Neeves et al., "Polarization selective optical phase conjugation in a Kerr-like medium," 5 Opt. Soc. Am., B 701 (1988~. These suspensions suffer from slow response time and grating instabilities that give rise to a poor signal to noise ratio.
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On the other hand, in ~Optical Nonlinearities of Small Metal Particles: Surface-Mediated Resonance And Quantum Size l Effect," 3 J. Opt. Soc. Am. B 1647 (1986), Hache et al.
attributed the apparent ~(3) of metal spheres in a dilute suspension in a linear dielectric medium to a fast electronic mechanism. See also Ricard et al. "Surface-mediated 5 enhancement of optical phase conjugation in metal colloids,"
10 Optics Letters 511 (1985). For this case the effective ~(3) is enhanced at the surface mediated plasmon resonance frequency.
Some metallic suspensions therefore have a fast response 10 and an effective optical nonlinearity with large ma~nitude.
However, due to the large dielectric loss, the figure of merit for nonlinear composite materials is relatively poor;
The figure of merit is defined as the ratio of ~(3) to the optical absorption for the material.
The present invention is directed to a particle or particles comprising a core surrounded by at least one shell wherein at least the core or one of the shells is a metal and at least the core or one of the shells is a dielectric material which exhibits a nonlinear optical response. The 20 core and the shells are also referred to as the "layers" of the particle. Thus, at least one of the layers of the particle is a metal and at least one of the layers which are not metal is made of dielectric material which exhibit a third order nonlinear response. The particles may be any 25 shape, but they are usually nanoparticles, i.e., have dimensions on the order of nanometers.
A nanoparticles of the present invention will exhibit an effective third order nonlinear response. The effective third order nonlinear response is the response of the 3 particle considered as a whole and results from the third order nonlinear response of its constituent core and shells.
At one or more optical frequencies the particle exhibits an ' , ' '.

"enhanced" third order nonlinear response. That is, its 1 effective third order nonlinear response is much greater than the sum of the nonlinear responses of each of the core and shells separately at the same optical frequency.
"Nonlinear" as the term is used in the present invention 5 refers to the optical response of a material. Nonlinear optical response occurs when a material exhibits hyperpolarization on a molecular level. Theoretically all materials can exhibit hyperpolarization and thus nonlinear optical responses. However the intensity of radiation 10 required to hyperpolarize a material distinguishes them into well defined categories of "linear" and "nonlinear"
materials, known to those skilled in the art.
The present invention is also directed to a composite material comprising a plurality of particles in a 15 medium, each of said particles comprising a core surrounded by a shell, one of said core and shell comprising a dielectric material exhibiting a third order nonline,ar optical response and the other of said core and shell being a metal. The materials of the invention may comprise the 20 layered particles described above in a medium where the medium is either linear or nonlinear. The composite m,aterial may also be formed with a unitary metallic particle in a nonlinear medium where the medium surrounding the particle acts as the shell layer.
The enhanced third order nonlinear response of the particles of the present invention at one or more optical frequencies arises when one of the metal layers mediates a plasmon resonance. The condition for plasmon resonance of the metal layer depends on order, number, shape and the 30 dimensions of the particle's layers, the material of the layers, as well as the nature of the medium surrounding the particle. The one or more optical frequencies at which the particle exhibits enhanced nonlinear response and, necessarily, at which any one of the metal-dielectric layers 35 exhibits plasmon resonance is referred to as the plasmon resonance frequency of the particle.
At the plasmon resonance, the electric field of the incident light concentrates in and around the particle.
"Concentration" of the electric field refers to the intensity ~: , ..
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of the light in and around the particle with respect to the l intensity of light in and around an identical particle without the metal layer exhibiting plasmon resonance. The concentrated electric field in the particle layers serves to increase their degree of polarization and therefore their 5 nonlinear optical response. Thus, the nonlinear optical response of the particle is enhanced as that term is defined above.
The enhanced third order nonlinear response results in an increased polarization. Those skilled in the art 10 attribute the increased polarization to a number of different mechanisms; the response of different types of materials being more or less attributed to these different mechanisms.
For example, metals exhibit an increased polarization predominantly due to an electronic mechanism. Other 15 materials exhibit an increased polarization due to an excitonic mechanism or thermal mechanism or others. Some exhibit an electrostrictive mechanism.
Considering the specific particle ~ith a metal core and a nonlinear dielectric shell, the "shell" may be the 20 immediately adjacent portion of a nonlinear dielectric medium or matrix in which a metal nanoparticle is suspend,ed. The enhancement of ~(3) takes place in a localized region that for a nanosphere extends into the medium by approximately two particle diameters. Thus, the particle can be thought of as 25 a core and shell suspended in a medium, the shell and medium being the same nonlinear dielectric material.
The present invention provides a particle with enhanced third order nonlinear susceptibility, fast response time and an enhanced ~igure of merit. The enhanced ~(3) and figure of 30 merit for the electronic mechanism of the particles of the present invention have been determined theoretically and have experimental support. It also has the added feature of enhancing the third order nonlinear susceptibility of the suspension medium in the vicinity of the material.

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The composite material of the present invention may be formed with a plurality of particles consisting of a metallic 1 core surrounded with a nonlinear dielectric shell material and suspended in a nonlinear dielectric medium. The field in the vicinity of each of the particles is larger than the mean field through the structure. Since each region of the 5 structure has independent intrinsic ~(3) nonlinearities, this results in an enhancement of the optical nonlinearity from each component of the suspension as a consequence of the localized electric field effect. The "enhancement" of the composite material may therefore be considered as the ratio of ~(3) for a homogeneous suspension medium to ~L(3) for a suspension medium with the particle suspended therein. By suitable matching of the core, shell and suspension medium dielectric functions, the resonance will exhibit broad band enhancement.
The enhancement of ~(3) takes place in a localized region that, for a spherical particle, extends to about two particle diameters. While the enhancement can be enormous in this localized region for each particle, the effective enhancement of the composite material is reduced by the concentration effect when averaged over the entire material.
Nevertheless, enhancements of 104 for the material are predicted even after averaging.
Thus, the composite ma~erial of the present invention, when the suspension medium is a nonlinear dielectric, can be 5 conceptualized as a multiple of the particles with another "shell" surrounding the outermost shell of the particle with dielectric permittivity equal to that of the suspension medium.
The composite material of the present invention can also 3 be formed with optical particles consisting of a nonlinear dielectric core surrounded with a metallic shell and suspended in a nonlinear dielectric medium. With this structure a large spectral resonant ' `

frequency range can be achieved through adjustment of shell thickness even with a single metal and still derive large field enhancement. Again, the particles exhibit increased polarization one or more resonant frequencies in the optical spectrum and, as a result, the effective third order nonlinear susceptlbility of the suspension is enhanced at 5 those resonant fre~uencies.
The nanoparticles of the present invention are not limited to any particular geometric configuration. The particles may comprise, for example, a spherical core with spherical shells, an ellipsoidal core with ellipsoidal shells or a cylindrical core with cylindrical shells. These are referred to as nanospheres, nanoellipsoids and nanocylinders, i.e., spheres, ellipsoids and cylinders with dimensions on the order of nanometers. The underlying concept of the invention is that a uniform optical field in a homogeneous 5 material can be converted to a non-uniform optical field by replacing the homogeneous structure by an equivalçnt inhomogeneous structure. The field is localized and further enhanced by a surface mediated plasmon resonance. Nonlinear effects in the structure can be enhanced relative to the homogenous structure.
In the accompanying drawings, Figures 1-3, not to scale, show particle of the present invention.
Figure ~, also not to scale, shows a composite material of the present invention.
Figures 5a and 5b show the electric field ratio in the core of the composite material for the first preferred embodiment.
Figures 6a and 6b show the electric field ratio in and around a particle of the composite material for the first 3 preferred embodiment.

Figures 7a and 7b show the enhancement factor of X(3) versus particulate concentration for the first preferred 1 embodiment.
Figures 8a and 8b show the electric field ratio in the core of the composite material particles of the second preferred embodiment.
Figures 9a and 9b show the electric field ratio in and around a particle of the composite material for the second preferred embodiment.
Figures lOa and lOb show the enhancement factor of X(3) versus particulate concentration for the second preferred 10 embodiment.
Referring to Figure 1, a particle 10 of the present invention is shown, not drawn to scale. The particle lO is a nanosphere and consists of a core 12 of radius r1, and dielectric permittivity e1 surrounded by one shell 14 of 15 radius r2 and dielectric permittivity e2. In one embodiment, the core 12 is a metal and the shell 14 is a dielectric material which exhibits a third order nonlinear response. In a second embodiment, the shell 14 is a metal and the core 12 is a dielectric material exhibiting a third order nonlinear 20 response.
In both embodiments, the particle exhibits an effective third order nonlinear response which is enhanced at one or more frequencies of incident optical light.
In Figure 2, another embodiment of a particle 16 of the 5 present invention is shown, again not to scale. The particle 16 is a nanoellipsoid with core 18 of dielectric permittivity e1 and shell 20 of dielectric permittivity e2. The core 18 may be a metal and the shell 20 may be a dielectric exhibiting a nonlinear optical response, or vice versa. The 3 shape asymmetry with high curvature will further enhance the localized field and gives rise to three non-degenerate resonant modes.

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Referring to Figure 3, a particle 22 with multiple shells is shown, again not to scale. The particle 22 is a 1 nanosphere with a core and three shells 26, 28, 30 of dielectric permi~tivity ~ 2~ e3 and ~4 respectively, and radii rl, r2, r3 and r4 respectively. The core 24 and shells 26, 28 and 30 comprise the layers of partLcles. At least one 5 of the layers is a metal, and at least one of the layers is a dielectric materlal exhibiting a third order nonlinear response. In one embodiment layers 26 and 28 are metals and layers 26 and 30 are nonlinear dielectrics. In another embodiment layers 26 and 30 are metals while layers 24 and 28 10 are nonlinear dielectrics. In this embodiment a number of plasmon surface resonances of the metals will give rise to a number of surface resonance frequencies of the material, excluding the degenerate cases for certain shell thicknesses or e adjustments.
The particles of the present invention are not limited to any particular number of shells or order of metal or dielectric among the shells. Also, the shape of the multiple shelled particles may be spherical, ellipsoidal, cylindrical or other shape. The core of the particle may be a metal and 20 all of the surrounding shells may be nonlinear dielectric material or vice versa. Furthermore, a "superlattice"
configuration of multiple shells is part of the present invention. That is, the adjacent layers of the particle alternate between metal and nonlinear dielectric material.
25 In this embodiment, the metal layers will be relatively thin compared to the dielectric layers.
In the ensuing description, the particles, described in themselves above, are used to fabricate composite materials of the present invention. More specifically, the composite 3 materials comprise suspensions of the particles described above. In other words, the particles themselves are surrounded by a medium itself having a dielectric permittivity. The medium is a dielectric material which may or may not exhibit a nonlinear optical response.

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The medium may be a liquid or a solid, and the solid may have a matrix structure. In the following description, the term "suspension" is equivalent to the term "material" and the term "suspension medium~ is equivalent to the term "medium."
Referring to Figure 4, a composite material 32 of the present invention is shown. The composite material 32 comprises particles 34 suspended in suspension medium 36.
In the first preferred embodiment, the particles 34 of the material 32 consists of nanospheres, i.e., spheres with dimensions on the order of 10 8 or 10 9m, with a metallic core, el, clad with a nonlinear shell material, e2, and suspended in a nonlinear medium, ~3. Light of a frequency~)R
incident on the material satisfies the surface-mode resonance for the material and is further described below. The nanosphere must be chosen such that scattering does not significantly affect the figure of merit. Normally in three dimensional structures this means that all three dimensions of the nanoparticle must be much less than the wavelength of the incident light. For structures of essentially two or one dimension, only the two or one dimension must satisfy this condition.
The field in the interior and vicinity of the particles 34 is larger than the mean field through the material 32.
Since each region of the material 32 has independent intrinsic ~(3) nonlinearities, this results in an enhancement of the optical nonlinearity from each component of the suspension 32 as a consequence of the localized electric field effect.
The structure of the particles enables separation of the functions of the requisite negative dielectric permittivity provided by the metal from the intrinsic nonlinearity to be enhanced that can be provided by the metal or by any of the dielectrics.

The material therefore has enhanced third order nonlinear susceptibility at at least one optical wavelength. In the 1 following treatment, suspensions are sufficiently dilute so that interparticle effects may be neglected. It is noted that at higher concentrations the field enhancement may be increased or decreased, but higher concentrations may 5 promote intrinsic optical bistability in the composite material. The spatial dependence of the field strength for homogeneous optical particles for which the dielectric permittivity may be real, complex, and dispersive is described first, followed by consideration of the 10 enhancements of phase conjugation expected from the electrostrictive contribution and from the electronic contribution to ~(3) as a function of particle concentration.
The electric field distri~ution E1, E2 and E3 is 15 calculated for each region of the material, e1, e2 and e3, within the electrostatic approximation relative to the electric field Eo far from the particle and is plotted for some specific parameters in Figures 6a and 6b, described below. The field outside the particle is equivalent to that 20 of a dipole of moment p, with an effective complex dielectric constant ~eff p = ~ n~ ~3 ~ C~e~) Eo (1) (e~ 2 (~ [r~ ~ t2) ~ 2~ Lr ~3 3o ~, :

The condition for suxface~mode resonance G~R is defined for the composite by ~ e~ (3) The theoretical dielectric function, ~ for a metallic core that exhibits anomalous dispersion with the requisite negative real component of the dielectric permittivity of the core e1' re~uired to satisfy the surface resonance condition may be represented in the frequency range of interest by the classical Drude free electron or alternatively by a combined Drude free electron model in combination with the Lorentz oscillator model for the bound electron contribution. Gold particles at optical energies that exceed the threshold of 2 eV for interband transitions, 5 re~uire a dielectric function that must include both the free electron (intraband) and the bound electron (interband~
contributions. Above this threshold energy the form of the curve of the imaginary component of the dielectric permittivity of the core, e~, in particular, depends on the specific band structure of the material. The values,for the parameters ~p, plasmon frequency, ~0, bound electron fre~uency, rf, free electron decay time, and rb, bound electron decay time, in the combined model are based on the fit to the experimental data, including the size dependence 5 of qrf. Aluminum is a material whose dielectric properties are well described by the free electron model in the ultraviolet except for a weak bound contribution near 1.5 eV.
The choice of values for the parameters ~p and ~rf in the Drude model are based on fit to experimental data.
3 The magnitude of the electric field in the core region of the particle with gold and with aluminum cores are shown in figures 5a and 5b as a function of frequency with the ratio r1/r2 as a parameter and with r1 fixed at 5nm.

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- :' ' ' -Figures 5a and 5b show the ratio of the electric field in the core E1 to the electric field far from the structure Eo as the ratio of core to shell radius rl/r2 varies from 0.1 to 1.0 with r1=5 nm. Figure 5a is for a gold core and Figure 5b is for an aluminum core. The resonance frequency,~)R~ may be shifted by altering the shell thickness to provide "tunability." When the permittivity ~2 is greater than ~3, then the resonance ~r is shifted to lower frequency with increasing shell thickness; conversely if ~2 is less than ~3, then the resonance ~R is shifted to higher frequency with increasing shell thickness. Resonant enhancement of the electric field is inversely related to el~; this key material parameter will optimize the enhancement. The spatial distribution of the magnitude of the electric field ratio for each region is shown in figure 6a and 6b. The enhancement may also be improved by adjusting the temperature for minimum 15 e~.
Figures 6a and 6b show the ratio of electric field in each region of the material relative to Eo as a function of the distance from the center of the particle. The solid line is for electric field measurements parallel to Eo and the dashed line is for measurement perpendicular to Eo~ In Figure 6a the core is gold, el/eo = 5.3 + i2.5, ~2/eO = 2.5, and ~3/~o=1~7~ In Figure 6b, the core is aluminum, e1/eO=

-2.5+iO.042, e2/eO=1.2 and e3/eo = 1.7.
The electric field distribution concentrated in the 5 neighborhood of the particle will affect the optical nonlinear behavior of the suspension. For an electrostrictive mechanism, a microparticle suspension subject to an optical field develops an e~fective ~L(3) due to electrostrictive forces proportional to the square of the 3 polarizability and hence dipole moment. The increase in dipole moment of the particle at resonance given by equations 1, 2 and 3 will result in a substantial increase in the effective third order optical nonlinearity. A particle with a polystyrene or silica shell and with a gold core or with an ~.. .

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aluminum core with rl/r2=0.5 will experience an enhancement of 18 or of 7200 in the effective ~(3) over that of a pure l polystyrene or pure silica particle; the corresponding enhancements in phase conjugate reflectivity would be 330 and 5x107, respectively. For gold shelled or aluminum shelled particLes, the effective ~(3) can be enhanced by 104 at 500nm with a time constant reduction factor of 10.
The electronic mechanism calculation for the particle is an extension of prior art treatments of metallic particles in a linear dielectric. The mean polarization and dielectric permittivity, e, of the composite considered as a homogeneous medium are related through D = eÉ = eoE+p with the polarization p=~x~)E ~ ~Ox~>~ t ~DX ~ 3 (4) ~:
If this is expressed as P = P~ + PNL and e = eL + e, then pNL=~eE with ~e =~eo~(2)E+eox 3)E2. The e represents the field dependent perturbation of the medium treated as a continuum with E as the mean field; if ~e is now considered as a function of the material composition variables,, where the subscripts 1, 2, 3 refer to the core, shell and medium respectively 3~ S~ S~ ( 5 ) The el, e2, e3 are the field dependent variations of each material component of the material obtained from the respective 3 nonlinear susceptabilities by ~q = eo~q(3)Eq2 with the localized field factors flq = Eq/Eo and q = 1, 2, 3.

.~, The dielectric constitutive equation for a dilute suspension of particles with no shell is taken as the l Maxwell-Garnett form, which to the first order in p becomes ~ = ~3 ~ 3~ ~3 'F I (6) where ~eff = el/~3; whereas for the case of a dilute suspension of composite particles, Xeff is given by equation 3. The three partial derivatives required for equation 5 lO become a ~
a~ q ,~ ~3 ~ or q,= 1,2. (7a) -= ~, 3~O (~$2~~ ~e~~2~ (7b) ~3 (Ke~

The equivalent homogeneous field E is obtained by integration over the inhomogeneous sample to define a space averaged f3, E=f3 Eo~ The total nonlinear polarization then becomes 3 _ PNI_=~~ 3~2q ~1~ %~ Eo3 (8a) ' ', ., . ~'1 ' . .. ..

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-h re the ~ ~ are space averaged over the qth region. For a 1 DFWM experiment in an isotropic medium in which the forward, back and probe input beamS Ef' Eb, Ep are all polarized in the same z direction, and since Eo = Ef + Eb + Ep, the z component of nonlinear polarization reduces to PZN~ = 3/~ ~OXZZZZ Ef~ Eb ~pz (8b) For this system the z component of field is dominant; so that the averages in equation 8a are taken over the z component of electric field to yield P~L ~ ~o~ ~ f2~ ~1 ~ X ~3)F~ Eb ~p (8c) where ~q(3) = 3/4 ~zzzz with ~=1..3. The intensity of the phase conjugate signal and hence reflectivitv is proportional to the square of PNL. The range of applicability of this dilute suspension theory is estimated at 10% by volume for 20 nm gold cored particles. This estimate is based,on the criterion that the field E3 should decay to within 5% of Eo at the mean interparticle distance.
The results of the field concentrated in the neighborhood of the particle on the phase conjugate 5 reflectivity for each combination of nonlinear core, shell, and suspension medium can be determined from figures 7a and 7b for the given sample parameters. Figures 7a and 7b show the concentration dependence of the enhancement factor for the phase conjugate amplitude for the core, shell and outer 3 region. The solid lines are for r1/r2 = 0.5 and the dashed lines are for rl/r2 = 1Ø Figure 7a has a gold core and Figure 7b has an aluminum core; the dielectric permittivities are as described in Figures 6a and 6h. The product field : -, . - - ::
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_nhancement factor of equation 8 is plotted in these figuresas a function of particle concentration, and can be used to l examine various structures. By way of illustration similar figures are used to examine a few specific examples. In the ultraviolet at 200 nm., a 0.2% particulate concentration with an alurninum core and nonlinear urea shell, with r1/r2=0.9, 5 suspended in a fused silica medium would exhibit an effective ~(3)=0.9xlO 7esu compared to a homogeneous urea sample with ~(3)=lxlO 12esu, and conjugate beam reflectivity enhancement of 0.8x101. In the visible at 488 mn., a nonlinear fluorescein doped borosilicate glass exhibits a (slow) lO ~(3)=lesu, whereas the fluorescein adsorbed to gold spheres at the same concentration should exhibit an effective ~(3)=4esu at the same speed, corresponding to a reflectivity enhancement of 16. Such samples might be prepared by using the metallic nanospheres as nucleating sites for controlled 15 crystal qrowth or polymer adsorption sites.
Thus, as demonstrated above, in the present invention the electric fieïd both interior and in the exterior neighborhood of the particle is increased at the plasmon resonance. The increased field is then utilized for 20 enhancement of the intrinsic third order nonlinear susceptabilities of the core, shell and neighbor~ood or localized suspension medium. The increased electric field in the regions, and the resulting enhanced intrinsic third order nonlinear susceptibilities of the regions give rise to an 25 enhanced effective third order nonlinear susceptibility of the material. This enhanced effective third order nonlinear susceptibility may be attributed partially to an electrostrictive mechanism acting on the material and partially to an electronic, excitonic, or any other intrinsic 3 nonlinear mechanism acting on the material.

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Furthermore, it is the imaginary component of the permittivity, usually 61" of the core material, that determines the magnitude of the field enhancement of the material. The plasmon resonance ~R may be tuned by adjusting the ratio r1/r2 of the particle. That is, given r1, r2, e2 and e3, the dispersive dielectric function for the metal then 5 determines the plasmon resonant frequency ~JR (rl/r2). Thus, the plasmon resonance can be tuned through adjustment of rl/r2 .
In a second preferred embodiment, the material 32 of Figure 4 consists of nanospheres 34 with a nonlinear core, 10 e1, and metallic shell, e2, suspended in a nonlinear medium 36 e3. The use of a metallic shell instead of a metallic core in the particle overcomes the frequency range restrictions imposed by the dielectric dispersion of the metal and therefore provides for a wide range of ncnlinear materials. Calculations for gold and for aluminum shells indicate that phase conjugate reflectivity enhancements in excess of 108 can be achieved.
In the first preferred embodiment of the composite materials, i.e., metal core and nonlinear dielectric shell particles in a nonlinear medium, the useful wavelength range of adjustment was sufficiently restricted so that a different metal was re~uired for each spectral region. This can be seen in Figures 5a and 5b. The dual role of the metallic core was to provide the negative dielectric constant 5 requisite for resonance and to act as a source term for the field distribution. These functions are separated in a particle in which a metallic shell surrounds a dielectric core and is suspended in a nonlinear medium. With this model a large spectral range can be achieved through adjustment 3 or "tuning" of shell thickness even with a single metal and still derive large field enhancements.

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In the second preferred embodiment of the composite materials, light of an optical frequency ~R~ the surface-mode resonance of the material, is incident on the material, at the surface surface-mode resonance, resulting in an enhanced effective third order nonlinear susceptibility of the materia.l. In the following description the suspensions are 5 again considered to be sufficiently dilute so that interparticle effects may be neglected. It is further assumed in every case that the materials behave as linear dielectrics for the purpose of the localized electric field evaluation, and the the nonlinear dielectric properties lO contribute only to calculation of the phase conjugate field.
When intrinsic bistability considerations are involved el=el(El)~ e2=e2(E2) and ~3=e3(E3).
Calculating the electric field distribution el, e2 and E3 for each region of the material el, e2 and e3, within the 15 electrostatic approximation relative to the electric field Eo far from the particle, .:

~ q~3 Eo Icos e ~r ~ sin e e~ ~ (9a) ~2~a~2~3~b ~2= ~ OC~S e er - 3 ~b (r) ~ Sine êe (9b) ~3= ~ a 2~bb ~ 0 C05 e ~r (9c) 3o ~ a- 3~b r~ Fo si~ e ca where ~a(r)~ ~ (rl/r)3~ t ~ ~ C~-(rL/r)3~ (lOa) .
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~b(r)~ ~ (rl/r)3~ 2~(rl/~ )3~ (lOb) ~a -- ~a (~z) ( loc ~b - ~b (r~) ( lOd~

The condition for surface mediated plasmon resonance at a frequency ~R is defined for the particle by setting the real part of the complex dielectric expression in the denominator of the field equations 9 to zero.

~ a ~ b~ = (lla) If only the metallic shell, e2, is taken as complex, and P=l-(rl/r2)3, then this resonance condition becomes ~æ'Pc -3L~1~2~3~ ~ ~[~1 ~3~ . (llb) - 2 ~ 3-~' 2)/~ ~ p 3o .

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The resonance equation is solved for any ratio rl/r2 given el and ~3 to obtain the requisite negative e2'. The dispersive dielec~ric function for the metal then determines the plasmon resonant frequency ~R (rl/r2). For example, a theoretical model such as the Drude-Lorentz function for free plus bound electron contributions ~ o(~ p~ ~ ~ ~pb ~ ~ ~rb) (12) can describe the dielectric function for metallic gold or an emperical function can be fit to the experimental data. The 15 parameters of the model are ~pf and ~pb~ the free and bound plasmon frequencies; ~f and ~b' the free and bound electron decay rates; and ~O, the bound electron resonant frequency;
The resonant behavior of the electric field in the core dielectric region of the composite particles with gold and 20 with aluminum shells are shown in figures 8a and 8b with the ratio r1/r2 as a parameter. Figures 8a and 8b s~ow the magnitude of the electric filed ratio E1/Eo in the core region as a function of fre~uency. The ratio r1/r2 varies from 0.1 to 1.0 and el/co = 2.5 and e3/eo = 1 7- In Figure 8a the shell is gold and is fitted to the Drude-Lorentz model with ~p~ = 1.3 1ol6, lrf = 9 3 10-15 ~ 15 2.2 10 6. In Figure 8b the shell is aluminum and is fitted to the Drude model with ~)pf = 2.28 1016 and ~f = 6.9 10 15.
These curves illustrate the high degree of "tunability" of~)R
30 that can be attained by altering the shell thickness.
Tunability of ~3R from ultraviolet to infrared is predicted.
Comparison of figures 8a and 8b also indicate that in Figure 8a a broadband near-resonance could be obtained.

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Complementary matching of dielectric and metallic dielectric l functions could make the particles very broad-band. The magnitude of the field enhancement at resonance depends inversely on the dielectric loss at each wavelength.
Examples of the spatial distribution of the magnitude of the 5 electric field at resonance in the core, shell, and outer region for each particle is shown in figures 9a and 9b.
Figures 9a and 9b show the ratio of electric field in each region to Eo as a function of distance from the center of the particle. The solld line is for the measurement of electric lO filed taken parallel to Eo and the dashed line is for the filed taken perpendicular to Eo~ The resonant frequency in both figures is 2.8.1015 Hz. Figure 9a is a gold shell with r1/r2 = 0.83 and e2/eo = -16.77 + il.98. Figure 9b is an aluminum shell with rl/r2 = O.955 and e2/eO = -65.1 + i3.4.
15 The principle observation is that large enhancement can be attained in the core and outer region at the expense of the field in the shell due to the two metal dielectric boundary conditions.
Enhancement of the effective third order optical 20 nonlinear susceptibility ~eff(3) is a result of the field concentrated in the neighborhood of the particle'at the surface mediated resonance. Two different mechanisms for ~(3) are described, the electrostrictive mechanism and the electronic mechanism. In the electrostrictive mechanism, a 25 microparticle suspension subject to gradients in the electromagnetic field develops an effective third order optical nonlinearity due to electrostrictive forces given by t3) l~r~ 3 r ~a - ~3 ~b ~ ~
%e~ a k T ~ r2 L ~a t ~636b ~ (13) '~,:', -22~
where is the volume fraction of particles. Thus the increase in the polarizability of the particle at the plasmon 1 resonance condition will result in a substantial increase in (3) For the electronic mechanism, calculation of ~eff~3) for the particle is similar to the first preferred 5 embodiment for metallic core particles described above. The inhomogeneous material with core, shell and suspending medium dielectric permittivities, eq, and intrinsic nonlinear susceptibilities ~q(3) where q-1, 2, and 3 respectively is represented as an equivalent homogenous medium of e and 10 ~eff~3). The dielectric constitutive equation for e for a dilute suspension of composite particles is of the Maxwell-Garnett form to the first order in p.

~ = ~3 ~ 3P ~3 ~a ~ 2~3~b (14) 20 For a degenerate four-wave mixing (DFWM) experimenlt in an isotropic medium in which the forward, back and probe input beams Ef, Eb, Ep are all polarized in the same z direction, and since Eo=Ef+Eb+Ep, the z component of nonlinear polarization reduces to ~N~ - ~ ~ ~3 f~ X ~(3) E~ E~E ~ (1S) : :
3o :- ~

:

where Xq(3) = 3/4 ~zzzz with q=1..3. The local field factors l flq~ the three concentration dependent partial derivatives f2q and the factor f3 obtained by integration over the inhomogeneous sample to define the equivalent homogeneous field E, are given relative to Eo far from the particle by ~ (r)~0 (16a) ~2~ - a~ (16b) E - ~ ~o (16c) 20 The average factors flq2 and f3 are obtained by integration on the z component of the electric field over each ~egion q of the material. The contribution from the other components of the inhomogenous field in the tensorial integration have been neglected either on the basis of small magnitude or 25 because we ignore the depolarized component of polarization.
The product enhancement factors f4q and ~eff of the total material on comparison to equation 8 are defined by 'PNL-- ~:o~QM ~ Eb~p~ ( 17) 3o : . . .

. . : , ~ ~ ` ..

(18) %e$f(3) ~ ~ ~ % (3) (19) An example of the f4q enhancement factors for composites lO with a gold shell and for composites with an aluminum shell as a function of concentration are seen in figures lOa and lOb. Figures lOa and lOb show the concentration dependence of the enhancement factor f4q for the phase conjugate amplitude for the core, shell and outer region. The solid lines are for rl/r2 = 0.5 and the dashed lines are for rl/r2 = 1.0 as in Figures 7a and 7b. The dielectric permittivities are as given in Figures 6a and 6b. Figure lOa shows a gold shell composite and Figure lOb shows an aluminum shell composite.
Thus, in the second preferred embodiment of the composite materials a metallic clad dielectric cored particle is used to increase the electric field in the core and neighboring or localized nonlinear medium at the plasmon resonance frequency. The increased field in the vicinity of 25 the particle enhances the intrinsic third order susceptibility of the core, shell and local suspension medium and therefore enhance the effective third order susceptibility for the material. Enhancements of reflectivity in excess of 108 are predicted for both 30 electrostrictive and electronic nonlinear mechanisms, with no change in the speed of the intrincic nonlinearity. The resonant frequency ~R is tunable from the ultraviolet to the infrared and complementary matching of materials can lead to a wide pass-band. The magnitude of the resonant enhancement of the field varies inversely with the metallic e~ .

. .~ 1:

.. . . -- .

The particles and materials of the present invention l have an enhanced figure of merit n. The figure of merit is given by the equation (3 ~ ~ nc ~ (20) The ~3) is the 3rd order intrinsic nonlinearity for a homogeneous material and is ~(3)eff of the composite material. ~ is the absorption of the composite material and comprises the sum of the intrinsic molecular absorbtion coefficient of the material ~m and the scattering absorption lO coefficient of the material is ~s . ~O is the effective refractive index of the material.
Since the figure of merit is thus proportional to the ratio of ~(3)eff to ~ , the optical absorption of the composite material is required in order to establish a figure 15 of merit for device utilization of the material.
In calculations using particles consisting of gold or aluminum and a nonlinear polymer such as PDA or PBA or urea and a linear medium, a figure of merit enhancement of up to 103 is predicted. Such enhancements of n have been 20 indirectly detected experimentally, as the phase conjugate signal to noise ratio for composite materials of thelpresent invention have improved.
The figure of merit is important in phase conjugate mirror (PCM~ applications, since for a DWFM PCM, R = 0.131 25 I2t(n2 ~2).
The composite materials of the present invention are not limited to the use of spherical shaped particles suspended in a medium as described above. Any geometric arrangement of particles that will result in the third order nonlinear 30 enhancement may be utili~ed. The core e1 may be metal and the shell e2 may be a nonlinear dielectric, or vice versa.
The suspension medium e3 may be linear or nonlinear dielectric material.

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In each of the above embodiments, a "metal" ccre or 1 shell of the particle includes "metal-like" or any material with a negative dielectric constant, and so can include superconductors or some materials with an anomalous dispersion or heavily doped semiconductors where free carrier 5 motion dominates the dielectric function or conducting polymers. High temperature semiconductor will exclude field in the far IR, therefore the field will be concentrated at the exterior surface, which is where the nonlinear dielectrie should be. An additional metallic shell will also cause 10 plasmon resonance enhancement of the field in the nonlinear dielectric.
The materials and particles of the present invention ~may be applied as phase conjugate mirrors or a nonlinear evanescent wave switch. Its use in biopolymer 15 characterization is also possible where the plasmon resonance would be selected to overlap any spectroscopic feature in dilute suspension, resulting in enhancement of the concentration sensitivity for deteetion. Used in a liquid scintillation eounter, metallie labelled seintillators should 20 be more effieient in photon capture.
Further, the application of the invention t~ light activated drugs is possible. If a metallic label is attached to 8-MOP, the UV dosage required for patient irradiation is reduced because radiation is localized to the required site.
Further, application of the invention to photodeteetor resolution will provide greater spatial deeoupling through field localization. Field localization would also provide higher video disc resolution.
The present invention ma~ also be applied to pulsed laser initiated nuclear fusion. The localized laser field enhancement on a scale smaller than the diffraction limit will lower laser power threshold for metallic coated nanoparticle implosion.

. ~ . - .... , ,~
.~ .

. . .

Application of the materials and particles of the 1 present invention to a phase conjugate S~S mirror is possible. The piezo-optical effect is proportional to the localized field squared. Thus, the threshold for SBS can be lowered by a nanoparticle of metallic clad electrooptic 5 materials.
The materials and particles of the present invention may also be used in laser velocimetry. The high scattering cross-section of composite particles at plasmon resonance permits smaller particles or lower concentrations that have 10 smaller perturbation or flow properties.
In additional, a nonlinear waveguide material may also be formed by the materials and particles of the present invention. Such a waveguide may consist of three material layers: index nl, a linear dielectric film; n2, the nonlinear 15 composite; and n3, a linear dielectric substrate. The nonlinear composite n2 can be a suspension of any of the particles or the multilayer composite structure. Enhanced nonlinearity results.
Application of the materials and particles of the 20 present invention to an extrinsic bistable or optical switch material is also possible. The composite material w~uld lie between the plane dielectric mirrors in Fabry Perot geometry.
The composition of the composite can be selected for sharpness of the plasmon resonance condition to attain high 25 switching sensitivity. Planar geometry Fabry Perot structures are also possible.
Application of the materials and particles of the present invention to an intrinsic bistable or optical switch material is also possible. The composite particles of the 30 present invention with nonlinear dielectric core suspended in - a nonlinear dielectric have intrinsic bistability. The sharper plasmon resonance and the larger ~L(3) attainable would enormously enhance the switching sensitivity. Planar geometry intrinsic bistability is also possible. Moreover, a , . . . ,~, .

Mach Zender optical switch, where one leg is a nonlinear composite, can also be fabricated with the inventive optical 1 structure. In addition, laser hardening is also possible, since a bistable material has a low level to transmit and a high level to reflect.
The materials and particles of the present invention may 5 also be used to fabricate an intensity dependent narrow bandpass filter. In a laser hardening application, a Fabry Perot configuration would be required. For SBS geometry with the composite material, there is normal transmission at low intensity and SBS at high intensity. Depending on the 10 composite choice, the filter could be made narrow band tunable or broad band tunable.
Application of the materials and particles of the present invention to a detector hardening material is also possible. Only a low intensity prescribed narrow band signal 15 will reach the detector. The detector hardening material would exhibit enormous dynamic range. The input signal would pass through a beam splitter to a DFWM phase conjugate mirror (PCM). The PCM would be designed for a low saturation level and reflectivity of one up to saturation. The phase 20 conjugate of the input is sent to the beam splitter and on to the detector only up to the threshold level. The PCM is narrow band because of the DFWM configuration.
In a nonlinear optical switching material, two prisms could be coupled by an evanescent wave through the material and 25 particles of the present invention. The wave would either be transmitted or re~lected depending on intensity.
Use of the materials of the present invention for harmonic generation is also possible. Input light of frequency would be localized in the material and particles 3 and absorbed at the plasmon resonance frequency . The material and particles would remain highly transparent at harmonics of the resonant frequency. The variables available " :
. :

in the material and particles design permit choice o~
materials to satisfy the phase matching. The relevant ~(2) and ~(3) are enhanced, so that harmonic generation at lower power levels should be possible.
Use of the materials and particles of the present invention for an optical memory material is also possible.
The particles act as huge super-dipoles at plasmon resonance.
In high concentration, the asymmetric nano particles can experience optically induced ordering or phase transitions which lead to an optical memory material.
The present invention may also be applied to an optical amplifier material by means of the usual DFWM geometry.
The materials and particles of the present invention may be applied to the following devices which utilize a third order nonlinear response: a laser frequency converter 1 device, an optical Kerr effect device, an electrooptical Kerr effect device, a four wave mixing composite device, an optical inteferometric waveguide gate device, a wide-band electrooptical guided-wave analog-to-digital converter device, an all-optical multiplexer device, an all optical 20 demultiplexer device, an optical bistable device, an optical parametric device, and an optical fiber which is clad with a transparent coating.
Furthermore, in biopolymer characterization, gold spheres are now used as labels attached to biopolymers in 2 optical and election microscopy. But, if plasmon resonance were selected to overlap any spectroscopic feature in dilute suspension, then concentration sensitivity for detection would be enhanced. This would apply to SERS, to molecular absorption spectra, to flourescence, to W and IR
spectroscopy.

. . .

The nanoparticles of the present invention may be fabricated using molecular beam epitaxy technology or 1 chemical-vapor deposition technology. Layered Al-Si and Al-GaAs nanospheres have been fabricated in this manner.
Alternatively, nanoparticles may be fabricated by spinning, coating and evaporating. A polished glass 5 substrate may be mounted on the axis of a high speed centrifuge. Two syringes provide fluid drops to the spinning surface. One syringe has a metallic plating solution, the other a nonlinear material in solution or suspension. The fluids spread and evaporate on the spinning substrate in one 10 or more layers.
Before forming the metal shell about the nonlinear dielectric core, pretreating and filling all interstitial spaces in the core with neutral space filling atoms may be desirable. The metallic coating, for example, silver, will 15 then stay on the core surface and be hindered from penetration into the core.
Similarly, a nonlinear dielectric core may be surface coated by charge adhesion of a layer of metallic nanoparticles, rather than atomic metal reduction at the 20 surface. The surface tension would keep the metallic nanoparticle, for example, gold, intact rather than atomically dispersed in the core.
The optical particles of the present invention may have a semiconductor core as a "metallic" core under the broad 25 definition of metal. More particularly, semiconductor nanocrystals of CdSxSel x may be used. Also, superconductors may be used as the metallic core.
A metallic core with a semiconductor shell may also comprise the composite particles.
3 The optical particles of the composite materials, including cores of semiconductor material such as GaAs, may be suspended in a medium consisting of silicate glass or a polymeric glass such as polystyrene to form the composite materials of the inventor.

,.

mhe nonlinear polymers such as polydiacetylene and polybenzothiazole can be used as the suspending medium of the composite materials or in the nanoparticle.
The suspending medium of the composite materials may also be a glass or crystal or some more complex 5 superstructure.
The same concepts developed herein apply to magnetic as well as electric field terms in nonlinear polarization:
DNL = ~ijk ~E + ~ijk ~ Xijk EB + ~ijkl EEE
+ ~ijkl EBB + ........................... (2) where ~i~k would be the magnetic-equivalent of ~ , and ~ijkl would be the magnetic equivalent of ~(3). The magnetic B fields are part of the optical filed or can be internal or external fields.
While the invention has been particularly shown and described with respect to illustrative and preferred embodiments thereof, it will be understood by those skilIed in the art that the foregoing and other changes in form and details may be made without departing from the spirit and 20 scope of the invention which should only be limited by the scope of the appended claims.

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Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OF PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A particle comprising a core surrounded by a shell, one of said core and shell comprising a dielectric material exhibiting a third order nonlinear optical response and the other of said core and shell being a metal.

2. A particle as in Claim 1 wherein said core is a metal and said shell is a dielectric exhibiting a third order nonlinear optical response.

3. A particle as in Claim 2 wherein said particle exhibits an enhanced effective third order nonlinear response when light of at least one predetermined optical frequency is incident thereon.

4. A particle as in Claim 2 wherein said dielectric shell comprises a region of a dielectric medium immediately adjacent a metal core suspended in said medium, said medium exhibiting a third order nonlinear response.

5. A particle as in Claim 1 wherein said shell is a metal and said core is a dielectric exhibiting a third order nonlinear response.

6. A particle as in Claim 5 wherein said particle exhibits an enhanced effective third order nonlinear response when light of at least one predetermined optical frequency is incident thereon.

7. A particle as in Claims 1, 2 or 5 wherein said particle is a nanoparticle.

8. A particle as in Claim 7 wherein said nanoparticle is a nanosphere.

9. A particle as in Claim 7 wherein said nanoparticle is a nanoellipsoid.

10. A particle as in Claim 7 wherein said nanoparticle is a nanocylinder.

11. A particle as in Claim 1 wherein said dielectric material is one of polydiacetylene, polybenzothiazole, polystyrene and silica.

12. A particle as in Claim 1 wherein said metal has dielectric permittivity less than zero.

13. A particle as in Claim 1 wherein said metal is one of gold, aluminum and silver.

14. A particle as in Claim 1 wherein said metal is a doped semiconductor.

15. A particle as in Claims 1 wherein said metal is a superconductor.

16. A particle comprising a metal core surrounded by two or more shells, at least one of said two or more shells being a dielectric material exhibiting a third order nonlinear response.

17. A particle comprising a core surrounded by two or more shells, said core being a dielectric material exhibiting a third order nonlinear optical response, at least one of said two or more shells being a metal.

18. A particle as in Claim 16 wherein all of said two or more shells are dielectric material exhibiting a third order nonlinear response.

19. A particle as in Claim 16 wherein adjacent shells of all of said two or more shells alternate between metal and dielectric material exhibiting a third order nonlinear response.

20. A particle as in Claim 17 wherein all of said two or more shells are metal.

21. A particle as in Claim 17 wherein adjacent shells of all of said two or more shells alternate between metal and dielectric material exhibiting a third order nonlinear response.

22. A particle as in Claims 16 or 17 wherein said particle exhibits an enhanced effective third order nonlinear response when light of at least one optical frequency is incident thereon.

23. A particle as in Claims 16 or 17 wherein said metal has dielectric permittivity less than zero.

24. A particle as in Claims 16 or 17 wherein said particle is a nanoparticle.

25. A particle as in Claim 24 wherein said nanoparticle is one of a nanosphere, nanoellipsoid and a nanocylinder.

26. A composite material comprising a plurality of particles in a medium, each of said particles comprising a core surrounded by a shell, one of said core and shell comprising a dielectric material exhibiting a third order nonlinear optical response and the other of said core and shell being a metal.

27. A composite material as in Claim 26 wherein said core is a metal and said shell is a dielectric exhibiting a third order nonlinear optical response.

28. A composite material as in Claim 27 wherein said shell is a metal and said core is a dielectric exhibiting a third order nonlinear optical response.

29. A composite material as in Claim 27 wherein said material exhibits an enhanced effective third order nonlinear response when light of at least one optical frequency is incident thereon.

30. A composite material as in Claim 28 wherein said material exhibits an enhanced effective third order nonlinear response when light of at least one optical frequency is incident thereon.

31. A composite material as in Claims 26, 27 or 28 wherein each of said particles are a nanoparticle.

32. A composite material as in Claim 31 wherein each of said nanoparticles is one of a nanosphere, nanoellipsoid and nanocylinder.

33. A composite material as in Claim 26 wherein said dielectric material is one of polydiacetylene, polybenzothiazole, polystyrene and silica.

34. A composite material as in Claim 26 wherein said metal is one of gold, aluminum and silica.

35. A composite material as in Claim 26 wherein said metal is a doped semiconductor.

36. A composite material as in Claim 26 wherein said metal is a superconductor.

37. A composite material as in Claim 26 wherein said metal has dielectric permittivity less than zero.

38. A composite material as in Claim 26 wherein said medium exhibits a third order nonlinear response.

39. A composite material as in Claim 38 wherein said medium is one of polydiacetylene and polybenzothiazole.

40. A composite material as in Claim 38 wherein said medium is a polymeric glass.

41. A composite material as in Claim 26 wherein said medium is glass.

42. A composite material as in Claim 26 wherein said medium is water.

43. A composite material comprising a plurality of particles suspended in a medium, each of said particles comprising a metal core surrounded by two or more shells, at least one of said two or more shells being a dielectric material exhibiting a third order nonlinear response.

44. A composite material comprising a plurality of particles suspended in a medium, each of said particles comprising a core surrounded by two or more shells, said core being a dielectric material exhibiting a third order nonlinear optical response, at least one of said two or more shells being a metal.

45. A composite material as in Claims 43 or 44 wherein said material exhibits an effective third order nonlinear response when light of at least one predetermined optical frequency is incident thereon.

46. A composite material as in Claims 43 or 44 wherein each of said particles is a nanoparticle.

47. A composite material as in Claim 46 wherein each of said nanoparticles is one of a nanosphere, nanoellipsoid and nanocylinder.

48. A composite material as in Claims 43 or 44 wherein adjacent shells of said two or more shells alternate between metal and dielectric material exhibiting a third order nonlinear response.

49. A composite material as in Claims 43 or 44 wherein said medium exhibits third order nonlinear response.

50. A composite material as in Claims 43 or 44 wherein said metal has dielectric permittivity less than zero.

51. A composite material as in Claim 29 wherein said enhanced response occurs when K'eff + 2 = 0

52. A composite material as in Claim 30 wherein said enhanced response occurs when 2?2'? -3[-1+2?3]+2[?l+?3] -2[?1?3-?2"2)/?2']