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Optical Materials Express

Optical Materials Express

  • Editor: David J. Hagan
  • Vol. 3, Iss. 5 — May. 1, 2013
  • pp: 533–545
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Photo-induced refraction of nanoparticulate organic-inorganic TiO2-pHEMA hybrids

Andrii Uklein, Pavlo Gorbovyi, Mamadou Traore, Luc Museur, and Andrey Kanaev  »View Author Affiliations


Optical Materials Express, Vol. 3, Issue 5, pp. 533-545 (2013)
http://dx.doi.org/10.1364/OME.3.000533


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Abstract

We report on photoinduced modifications of the refractive index of nanoparticulate TiO2-pHEMA organic-inorganic hybrids. The samples with titania concentration ranging from 0.88·1020 to 17.6·1020 cm−3 were irradiated and analyzed with UV light at 375 nm. A reduction of the refractive index is observed in all samples. Although the photoinduced refraction was stronger in samples with higher titania concentration, its normalized value per Ti3+ center a0 = −2.4·10−23 cm3 remained constant. The change of refractive index correlates with the material photochromic response due to the accumulation of polaronic Ti3+ centers in the material.

© 2013 OSA

1. Introduction

Organic-inorganic hybrids have deserved a growing interest last decade owing to a combination of useful properties of their constituting components [1

1. P. Gómez-Romero and C. Sanchez, eds., Functional Hybrid Materials (Wiley-VCH Verlag GmbH & Co., 2003).

,2

2. L. Nicole, L. Rozes, and C. Sanchez, “Integrative approaches to hybrid multifunctional materials: from multidisciplinary research to applied technologies,” Adv. Mater. 22(29), 3208–3214 (2010). [CrossRef] [PubMed]

]. The flexibility and shaping versatility of an organic polymer and high refractive index of an inorganic component permit considering the hybrids materials for many potential applications in field of photonics [3

3. C. Sanchez, P. Belleville, M. Popall, and L. Nicole, “Applications of advanced hybrid organic-inorganic nanomaterials: from laboratory to market,” Chem. Soc. Rev. 40(2), 696–753 (2011). [CrossRef] [PubMed]

7

7. R. A. S. Ferreira, P. S. André, and L. D. Carlos, “Organic–inorganic hybrid materials towards passive and active architectures for the next generation of optical networks,” Opt. Mater. 32(11), 1397–1409 (2010). [CrossRef]

]. Among these materials, the TiO2-based hybrids are of particular interest because of their efficient photodarkening at the exposition to photons with energy above that of the band gap (hν≥3.25 eV). Conversely to the well-known chalcogenide glasses [8

8. K. Tanaka and K. Shimakawa, “Chalcogenide glasses in Japan: a review on photoinduced phenomena,” Phys. Status Solidi B 246(8), 1744–1757 (2009). [CrossRef]

,9

9. S. Ducharme, J. Hautala, and P. C. Taylor, “Photodarkening profiles and kinetics in chalcogenide glasses,” Phys. Rev. B Condens. Matter 41(17), 12250–12259 (1990). [CrossRef] [PubMed]

], which also exhibit photodarkening, the bleaching of the dark domains in hybrids can be photoinduced, without need of the annealing process [10

10. A. I. Kuznetsov, O. Kameneva, N. Bityurin, L. Rozes, C. Sanchez, and A. Kanaev, “Laser-induced photopatterning of organic-inorganic TiO2-based hybrid materials with tunable interfacial electron transfer,” Phys. Chem. Chem. Phys. 11(8), 1248–1257 (2009). [CrossRef] [PubMed]

]. Reversible photopatterning of these optically transparent materials makes them potentially suitable for 2D/3D laser structuring.

Previously, we have reported on the elaboration of TiO2 gel-based hybrids including macroscopic interpenetrating inorganic oxo-titanate, and organic poly(hydroxethyl methacrylate) pHEMA, networks [11

11. O. Kameneva, A. I. Kuznestov, L. A. Smirnova, L. Rozes, C. Sanchez, A. Alexandrov, N. Bityurin, K. Chhor, and A. Kanaev, “New photoactive hybrid organic-inorganic materials based on titanium-oxo-PHEMA nanocomposites exhibiting mixed valence properties,” J. Mater. Chem. 15(33), 3380–3383 (2005). [CrossRef]

]. These nanocomposites, obtained without shrinkage, show high transparency and mechanical stability, allowing optical-grade surface polishing, as well as high photonic sensitivity, which permit realization of 3D microstructures using femtosecond lasers [11

11. O. Kameneva, A. I. Kuznestov, L. A. Smirnova, L. Rozes, C. Sanchez, A. Alexandrov, N. Bityurin, K. Chhor, and A. Kanaev, “New photoactive hybrid organic-inorganic materials based on titanium-oxo-PHEMA nanocomposites exhibiting mixed valence properties,” J. Mater. Chem. 15(33), 3380–3383 (2005). [CrossRef]

,12

12. E. Fadeeva, J. Koch, B. Chichkov, A. Kuznetsov, O. Kameneva, N. Bityurin, C. Sanchez, and A. Kanaev, “Laser imprinting of 3D structures in gel-based titanium oxide organic-inorganic hybrids,” Appl. Phys., A Mater. Sci. Process. 84(1-2), 27–30 (2006). [CrossRef]

]. The photodarkening of the pHEMA-TiO2 hybrids results from an efficient charges separation at the organic-inorganic interface. Actually, the conduction-band (CB) electron remains localized onto the inorganic component as small polaron-like Ti3+ center, whereas the valence-band (VB) hole leaves to the polymer component. The localysed electron is responsible of the material absorption in the visible spectral range according to the process Ti3++hν(VIS)Ti4++e(CB). Recently, nanoparticulate pHEMA-TiO2 hybrids with nanoscale morphology control and record charge separation efficiency (50%) have been realized [13

13. P. Gorbovyi, A. Uklein, S. Tieng, O. Brinza, M. Traore, K. Chhor, L. Museur, and A. Kanaev, “Novel nanostructured pHEMA-TiO2 hybrid materials with efficient light-induced charge separation,” Nanoscale 3(4), 1807–1812 (2011). [CrossRef] [PubMed]

]. The relevant physical mechanisms involved in the photodarkening have been previously discussed in [10

10. A. I. Kuznetsov, O. Kameneva, N. Bityurin, L. Rozes, C. Sanchez, and A. Kanaev, “Laser-induced photopatterning of organic-inorganic TiO2-based hybrid materials with tunable interfacial electron transfer,” Phys. Chem. Chem. Phys. 11(8), 1248–1257 (2009). [CrossRef] [PubMed]

,14

14. N. Bityurin, A. I. Kuznetsov, and A. Kanaev, “Kinetics of UV-induced darkening of titanium-oxide gels,” Appl. Surf. Sci. 248(1–4), 86–90 (2005). [CrossRef]

,15

15. L. Museur, P. Gorbovyi, M. Traore, A. Kanaev, L. Rozes, and C. Sanchez, “Luminescence properties of pHEMA-TiO2 gels based hybrids materials,” J. Lumin. 132(5), 1192–1199 (2012). [CrossRef]

].

Because of the Kramers-Kroning relation, changes of the transmission in photochromic materials usually lead to the modification of their refraction properties. The photoinduced modifications may enable fabrication of optoelectronic devices as Bragg gratings or waveguides [16

16. A. Zakery and S. R. Elliott, “Optical properties and applications of chalcogenide glasses: a review,” J. Non-Cryst. Solids 330(1–3), 1–12 (2003). [CrossRef]

,17

17. N. Mehta, “Applications of chalcogenide glasses in electronics and optoelectronics: a review,” J. Sci. Ind. Res. (India) 65(10), 777–786 (2006).

]. In order to optimize the optical writing process, accurate measurements of photoinduced modifications of the linear refraction coefficient have to be performed. Practically, the absorption modifications are probed by transmission measurements, whereas the variations of refractive index are usually measured by microellipsometry [18

18. Q. Zhan and J. R. Leger, “Microellipsometer with radial symmetry,” Appl. Opt. 41(22), 4630–4637 (2002). [CrossRef] [PubMed]

] and/or Z-scan methods [19

19. K. Fedus and G. Boudebs, “Determination of photo-induced changes in linear optical coefficients by the Z-scan technique,” J. Opt. Soc. Am. B 26(11), 2171–2175 (2009). [CrossRef]

,20

20. M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, “Sensitive measurement of optical nonlinearities using a single beam,” IEEE J. Quantum Electron. 26(4), 760–769 (1990). [CrossRef]

]. First attempts to measure the photoinduced refraction in the gel-based TiO2 organic-inorganic hybrids were recently presented by Bityurin’s group using the phase grating method [21

21. A. Afanasiev, A. Alexandrov, N. Agareva, N. Sapogova, L. Smirnova, and N. Bityurin, “UV induced of linear and non-linear IR optical properties of dielectrics for photonic applications,” presented in FLAMN-10, St. Petersburg, Russia (2010).

], who reports positive refraction changes of + 1.6x10−24 cm3 per Ti3+ center at 1570 nm. The obtained value can be assigned to bound electrons, since free electrons produce negative contribution to the refraction. More experiments are required to verify the refraction changes in the photochromic hybrids.

In this publication we report on the photoinduced refraction measurements in novel nanoparticulate TiO2-pHEMA organic-inorganic hybrids with an improved photochromic response in the UV spectral range. The article is organized as follow: the experimental setup and sample preparation procedure are described in section 2. The theoretical formalism of the refractive index calculations is briefly presented in section 3. The experimental results and discussion of the photoinduced refractive index are given in section 4.

2. Experiment

The measurements were performed by using an original approach developed by Gayvoronsky et al. [22

22. V. Gayvoronsky, S. Yakunin, V. Nazarenko, V. Starkov, and M. Brodyn, “Techniques to characterize the nonlinear optical response of doped nematic liquid crystals,” Mol. Cryst. Liq. Cryst. 426(1), 231–241 (2005). [CrossRef]

]. This approach has some similarities with the well-known z-scan method, however in contrast to it the sample is kept in a fixed position. Actually, the hybrid samples are irradiated with TEM00 Gaussian shape laser beam. The modifications of the absorption coefficient Δα and refractive index Δn depend on the laser dose and, at least for small doses, the spatial distributions of Δα and Δn are of similar Gaussian shape. Depending on the sign of Δn, the induced phase shift results in a self-focusing (Δn>0) or a self-defocusing (Δn<0) of the laser beam. The modifications on the beam divergence are probed by measurements of the sample normalized transmittance through a small circular aperture placed on the beam propagation axis in the far field. The refractive index variations can be obtained by fitting the experimental points with theoretical expression of the on-axis transmittance in the Gaussian beam approximation.

The general synthesis scheme adopted for hybrids fabrication is described in details in [13

13. P. Gorbovyi, A. Uklein, S. Tieng, O. Brinza, M. Traore, K. Chhor, L. Museur, and A. Kanaev, “Novel nanostructured pHEMA-TiO2 hybrid materials with efficient light-induced charge separation,” Nanoscale 3(4), 1807–1812 (2011). [CrossRef] [PubMed]

]. Briefly, the titania based hybrids samples are synthetized in a three step process. Firstly, monodispersed titanium-oxo-alkoxy nanoparticles of size 5.2 nm are generated in 2-propanol solvent in a sol-gel reactor with rapid micromixing. On the second step, the solvent replacement by HEMA results in ligands exchange at the nanoparticles surface, and leads to the stable nanoparticulate precursor in a HEMA solution. On this stage, the concentration of the inorganic component is adjusted. Finally, the precursor solution is filled between two microscope plates and thermally polymerized. Five samples with different titanium oxide concentrations, 0.88x1020 (x1), 1.76x1020 (x2), 4.4x1020 cm−3 (x5), 8.8x1020 (x10) and 17.6x1020 cm−3 (x20) were prepared. The samples thicknesses were carefully measured with optical microscope in the cross-section of the irradiated zone. The characteristics of all samples are reported in Table 1

Table 1. Hybrid samples characteristics: [Ti4+] concentration, thickness (L), quantum yield ηa, photoinduced refractive index change ∆n0, density of [Ti3+] centers and refractive index modification per Ti3+ center a0a

table-icon
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. Additionally, a reference pHEMA polymer sample has been prepared.

The experimental setup used for measurements of the absorption and refraction kinetics is shown in Fig. 1
Fig. 1 Experimental setup: SFS – spatial filtering system, Sp is a beam splitter, S – sample, D1 and D2 are photodiodes. The beam waist position is taken as the origin of the axis z.
. A UV laser diode at 375 nm (from Oxxius) with a single mode fiber output delivers, a TEM00 beam of 0.5 mW cw power after spatial filtering system (SFS) and collimation. This beam interacts with the sample at normal incidence, and the transmitted beam is analyzed by two photodiodes (D1 and D2). A beam splitter (Sp), positioned immediately after the sample, reflects a small part of the beam to photodiode D1, which monitors the total transmitted power. A wide aperture lens (L), positioned as close as possible to the beam splitter (Sp), was used to collect the transmitted light. The photodiode D2 measures the transmitted power through a small diaphragm (ra=225μm) placed in far field and monitors the convergence/divergence of the beam due to the photoinduced refractive index variations in the sample. The sample is placed at the position ZS after the beam waist that was found at the position ZW from the SFS. The distance between the sample and diaphragm is d=60cm and the typical intensity of 280 mW/cm2 has been used to irradiate the samples.

3. Theoretical formalism of the refraction measurements

Assuming a Gaussian beam propagating along the +zdirection and the coordinate origin being at the Gaussian beam waist, the electric field incident on the sample is written:
Ee(r,z)=E0w0w(z)exp[r2w2(z)ikr22R(z)]exp[iϕ(z)]
(1)
where E0denotes the on-axis electric fields amplitude, r is the radial coordinate, z is the sample position and R(z)=z[1+(z0/z)2] stands for the wave front radius of curvature. The phase term ϕ(z) contains all the radially uniform phase variations. The sample is considered as thin with a thickness L smaller than the Rayleigh range (L<z0). Consequently, any changes of the laser beam profile induced by linear diffraction phenomena can be neglected, which was experimentally supported by the propagating beam analysis. Moreover, we suppose that (i) photoinduced modifications are uniform in the direction z of the beam propagation inside the sample and (ii) their radial distribution corresponds to the spatial profile of the beam intensity at the sample position z = zS. Thus, we can write:
Δn(r,D)=Δn0(D)exp[2r2w2(zS)]Δα(r,D)=Δα0(D)exp[2r2w2(zS)]
(2)
where Δn0 and Δα0 are respectively photoinduced variations of the on-axis refractive index and absorption coefficients and D is the irradiation dose.

wm02=w2(z)/(2m+1),dm=kwm02/2,Rm2= d [1  g/(g2+ d2/dm2) ]1θm= tan1[(d/dm)/g],wm2=wm02(g+d2/dm2)andg = 1 + d/R(z)

Equation (4) describes sufficiently thin and low absorbing samples. With an increase of both thickness and absorbance, the deviation from Eq. (4) appears. This deviation between the experiment and modeling will be considered as a criterion of the above formalism applicability.

Finally, we define the normalized on-axis transmittance:
T(D)=PonaxisPtotal=0ra|Ea(r,z,D)|2rdr0|Ea(r,z,D)|2rdr
(5)
where ra is the aperture radius. This normalization Eq. (5) permits distinguishing the refraction component of the field variation on the beam propagating in an absorbing medium. Experimentally, the powers Pon-axis and Ptotal are measured separately, and the photoinduced variation of refractive index Δn0(D) is obtained by fitting the experimental normalized on-axis transmittance with the theoretical expression of T(D) given by Eq. (5).

4. Results and discussion

It’s worth to notice that the usual Z-scan approach is not appropriate for measurements of the refraction modifications in materials with high sensitivity to photodarkening and long relaxation. Indeed, consistent Z-scan traces necessary for measurement of Δn0(D) at a given irradiation dose D require a fresh zone of the sample to be irradiated for each position Z. This needs in turn a complicated optical alignment, which would assure no axial beam deviation and conservation of laser dose during the lateral (r) and longitudinal (Z) sample displacements. The method proposed in the present article, allows to measure Δn0(D) with a large range of irradiation doses in the same experimental geometry. Moreover, its sensitivity is high. In our experimental conditions, as we will show, we were able to measure variations of 1% of the normalized on-axis transmittance. Taking into account the diaphragm radius (ra=225μm) this corresponds to a phase shift |Δϕ0|33mrad. Consequently, the minimum measurable optical path length variation is Δn0L=Δϕ0λ/2πλ/190.

[Ti3+]=[Ti4+]01+ηbσbηaσa.(1exp((ηaσa+ηbσb)hν.D))
(8)

The kinetics of the total transmittance at 375 nm is plotted in the Fig. 3(a) as a function of the UV irradiation dose for all hybrids samples. As expected, the absorption increases both with the titania concentration and UV irradiation dose. According to the model discussed above and the assumption about the absorption coefficient uniformity along the z direction proposed in section 3, the transmittance curves can be described by the usual Beer-Lambet law, assuming that each produced Ti3+ center replaces one Ti4+:
T =Ptotal(D)Ptotal(D=0)exp((σbσa)[Ti3+]L)
(9)
where L is the sample thickness and the density [Ti3+] is given by Eq. (8). The quantum efficiencies ηa and ηb involved in the calculation of [Ti3+] are free parameters which can be obtained from the fit of the experimental data by Eqs. (8) and (9). The theoretical transmission curve of sample X10, is plotted by dark solid line in Fig. 3(a). An excellent agreement with the experimental curve supports the approximation of a uniform distribution of the absorbing species along the laser beam propagation. The obtained quantum efficiencies ηa for the charge separation process are ranging from 13.5% to 16.5% excepted for the sample X5 for which ηa=7%. A less efficient polymerization in sample X5 may account for this difference. The quantum efficiency ηb of the inner photoeffect process is ranging from 1.5% to 2.5% for all samples. The values of ηa are reported in Table 1. It’s worth to remark that the obtained charges separation efficiency is considerably smaller than that measured with photoexcitation at 355 nm (ηa50%) [13

13. P. Gorbovyi, A. Uklein, S. Tieng, O. Brinza, M. Traore, K. Chhor, L. Museur, and A. Kanaev, “Novel nanostructured pHEMA-TiO2 hybrid materials with efficient light-induced charge separation,” Nanoscale 3(4), 1807–1812 (2011). [CrossRef] [PubMed]

]. This may be explained by the activation barrier that the photoinduced hole has to overcome in order to escape the inorganic component. The holes remained into the inorganic component likely recombine with the CB electrons with the probability 1-ηa.

The photoinduced modifications of the absorption coefficient Δα0=(σbσa)[Ti3+] are proportional to the number density of localized electrons [Ti3+] and cross sections difference. The number density [Ti3+] is calculated using quantum efficiencies ηa and ηb obtained from the fit of total transmittance curves with Eqs. (8) and (9).

With knowledge of the total sample transmittance, the on-axis transmittance provides information about modifications of the refractive index. In the present experiment, the normalized on-axis transmittance T(D) decreases with the UV irradiation dose in all hybrid samples as shown in Fig. 3(b). This reduction of on-axis transmittance corresponds to the negative variations of the refractive index (Δn0<0), since the samples were positioned after the beam waist.

The experimental data permit evaluation of the photoinduced refractive index according to the formalism described in section 3. The fits of the normalized on-axis transmittance of samples X1 and X10 by Eq. (5) are plotted as dash curves in Fig. 5(b)
Fig. 5 Variations of refractive index Δn0 (a) and normalized on-axis transmittance (b) of hybrid samples X1 and X10 versus the UV irradiation dose. On (b) the dashed lines represent the fits of on axis transmittance by Eq. (5).
. In these fits the refractive index modification Δn0(D) is supposed to vary linearly with the Ti3+ concentration Δn0=a0[Ti3+]. Consequently, the only free parameter in the Eq. (5) is the factor a0which represents the refractive index variation per Ti3+ center. An excellent agreement with the experiment is obtained for sample X1 in the whole range of laser doses 0 < D < 60 J/cm2. On the other hand, the normalized on-axis transmittance of sample X10 can be satisfactory fitted by Eq. (5) in a restricted range of laser doses 0 < D < 20 J/cm2 responsible for the linear regime of the photodarkening. As discussed in section 3, the total sample absorption of ≤10% (see Fig. 3) sets limit of applicability of the proposed formalism. This is in agreement with [20

20. M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, “Sensitive measurement of optical nonlinearities using a single beam,” IEEE J. Quantum Electron. 26(4), 760–769 (1990). [CrossRef]

], where non-linear absorption in optical media has been considered.

The variations of the refractive index Δn0(D) of samples X1 and X10 are reported in Fig. 5(a). Typical values Δn00.67104 in sample X1 at D = 60 J/cm2 and Δn04104 in sample X10 at D = 20 J/cm2 were obtained.

The proposed method of the refractive index variation measurements is valid in the Gaussian phase shift approximation when both distributions of Δn(r,D) and Δα(r,D) reproduce the Gaussian spatial profile of the laser beam. Indeed, due to the saturation of the Ti3+ concentration, the Δn(r,D) profile becomes progressively flat when the irradiation dose increases. Experimentally, this results in a decrease of the photoinduced divergence and an underestimation of the normalized on-axis transmittance calculated by the Eq. (5). This effect is observed in the sample X10 when D > 20 J/cm2. For this reason, we were unable to calculate the refractive index changes in the range of a strong material darkening. However, to have an idea about the refractive index modification in sample X10 at higher doses, we have plotted the expected variation of Δn0(D) as a dot line in Fig. 5(a). A pure numerical approach allowing calculating the electric field Ea(r,z,D) in the aperture plane and taking into account real modifications of the Δn(r,D) profile is currently under consideration in our group. This should allow measuring the refractive index modification beyond the Gaussian phase shift approximation.

The refractive index Δn0(D)modifications have been measured in samples X2, X5 and X20 using the above described procedure. For the sake of comparison, we report in Table 1 the values of Δn0(D) measured in all samples for the same reference irradiation dose D10J/cm2. As expected because of a stronger absorbance, Δn0(D) increases with the titania concentration in the hybrid samples. To account for the increased number of the photoinduced centers, the photoinduced refraction can be normalized on their number density. The relevant density of the photoinduced Ti3+ centers for the reference dose together with the refractive index variation per Ti3+ center a0=Δn0/[Ti3+] are also reported in Table 1. As Fig. 6
Fig. 6 Photoinduced refractive index modification per Ti3+ center a0=Δn0/[Ti3+].
shows, this parameter appears to be almost independent on the titania concentration in the considered samples. Its mean value a02.41023cm3is indicated by a dot line in Fig. 6.

For the experimental viewpoint, the refractive index modification results from the photoexcitation of titania nanoparticles and is correlated with the material photodarkening. Therefore, since the photoexcitation process results in the electron localization on Ti4+ center and hole transfer to organics, both organic and inorganic components of the hybrid material could contribute to the observed modification of refraction. The possible mechanisms are discussed below.

n21n2+2=4π3ρβ
(10)

Actually, a decrease of refractive index in silica-based organic-inorganic hybrid material under UV-light irradiation has been previously reported by Park et al. [23

23. J. U. Park, W. S. Kim, and B. S. Bae, “Photoinduced low refractive index in a photosensitive organic–inorganic hybrid material,” J. Mater. Chem. 13(4), 738–741 (2003). [CrossRef]

]. The effect was assigned to changes of the organic component polarizability resulting from the decomposition of methacryl chains and subsequent evaporation of carbonyl groups. In our case, the organic component of the hybrids is transparent in UV-A spectral region and cannot be decomposed by 375-nm photons. Moreover, the refraction modifications are reversible and no modification of volume sample has been observed after the irradiation. Therefore, the organic component may contribute to the refractive index variation only via a decrease of its polarizability as a result of the hole transfer from titania nanoparticles [10

10. A. I. Kuznetsov, O. Kameneva, N. Bityurin, L. Rozes, C. Sanchez, and A. Kanaev, “Laser-induced photopatterning of organic-inorganic TiO2-based hybrid materials with tunable interfacial electron transfer,” Phys. Chem. Chem. Phys. 11(8), 1248–1257 (2009). [CrossRef] [PubMed]

]. Indeed, the polarizability of -OEMA groups on the inorganic nanoparticle surface is explained by the mesomeric effect, as shown in Fig. 7
Fig. 7 Charges distribution on -OEMA groups.
below:

The presence of a double carbon bond in conjugation with a carboxylic group (α-position) may have a significant impact on the charges distribution when an electric field is applied. On the other hand, the hole transfer cancels the right-most configuration, which decreases the group polarizability. Although an exact place of the hole localization in not known, the organic polymerization is not complete in these hybrids [6

6. D. J. Kang and B.-S. Bae, “Photo-imageable sol-gel hybrid materials for simple fabrication of micro-optical elements,” Acc. Chem. Res. 40(9), 903–912 (2007). [CrossRef] [PubMed]

,8

8. K. Tanaka and K. Shimakawa, “Chalcogenide glasses in Japan: a review on photoinduced phenomena,” Phys. Status Solidi B 246(8), 1744–1757 (2009). [CrossRef]

] and non-polymerized -OEMA functional groups may remain at the organic-inorganic interface.

Finally, photoinduced permanent modifications of the refractive index have been reported in a large variety of materials as chalcogenide glass, oxide glass or polymers [8

8. K. Tanaka and K. Shimakawa, “Chalcogenide glasses in Japan: a review on photoinduced phenomena,” Phys. Status Solidi B 246(8), 1744–1757 (2009). [CrossRef]

,23

23. J. U. Park, W. S. Kim, and B. S. Bae, “Photoinduced low refractive index in a photosensitive organic–inorganic hybrid material,” J. Mater. Chem. 13(4), 738–741 (2003). [CrossRef]

,28

28. T. Keiji, “Photo-induced phenomena in chalcogenide glass: Comparison with those in oxide glass and polymer,” J. Non-Cryst. Solids 352(23–25), 2580–2584 (2006).

]. They are used to realize optical devices like wave guides, photonic structures, optical switches, etc …. Typical reported values of photoinduced refractive changes ranges from 10−4 to 10−1. In the presented experiments the maximum refractive index modification −5·10−4 is found in sample X20 at the UV irradiation dose of 10 J/cm2. Although, this value is sufficient to implement waves guide in our hybrids materials [29

29. A. Ljungstrom and T. Monro, “Observation of light-induced refractive index reduction in bulk glass and application to the formation of complex waveguides,” Opt. Express 10(5), 230–235 (2002). [CrossRef] [PubMed]

,30

30. L. Merhari, Hybrid Nanocomposites for Nanotechnology: Electronic, Optical, Magnetic And Biomedical Applications (Springer, 2009).

], it’s worth to remark that the Ti3+ concentration of the considered hybrid samples can attain 13% of the available Ti atoms [8

8. K. Tanaka and K. Shimakawa, “Chalcogenide glasses in Japan: a review on photoinduced phenomena,” Phys. Status Solidi B 246(8), 1744–1757 (2009). [CrossRef]

,10

10. A. I. Kuznetsov, O. Kameneva, N. Bityurin, L. Rozes, C. Sanchez, and A. Kanaev, “Laser-induced photopatterning of organic-inorganic TiO2-based hybrid materials with tunable interfacial electron transfer,” Phys. Chem. Chem. Phys. 11(8), 1248–1257 (2009). [CrossRef] [PubMed]

]. Consequently, the photoinduced change of the refractive index could be much stronger. Assuming the refractive index change per Ti3+ center a02.41023cm3, the maximum modification of the refractive index in sample X20 could attain Δn0,max0.005. This estimation, which needs to be confirmed experimentally, makes the TiO2-pHEMA hybrid material performance comparable with those of chalcogenide and oxide glasses. Moreover, the photopatterning in the hybrids is reversible, which may permit repetitive recording.

The present results indicate that the photosensibilty of our nanoparticulate hybrids is sensitive to the excitation photon energy: the quantum yield of charges separation attains 15% at 375 nm, which is considerably lower than previously reported 50% at 355 nm [13

13. P. Gorbovyi, A. Uklein, S. Tieng, O. Brinza, M. Traore, K. Chhor, L. Museur, and A. Kanaev, “Novel nanostructured pHEMA-TiO2 hybrid materials with efficient light-induced charge separation,” Nanoscale 3(4), 1807–1812 (2011). [CrossRef] [PubMed]

]. Moreover, the titania absorbance strongly increases with an increase of photon energy above bandgap of 3.24 eV (380 nm). Accordingly, photopatterning of the hybrids at the shorter wavelengths would increase of the structure contrast and process efficiency. We notice that the use in the present study of a laser diode emitted at 375 nm is explained by its perfect Gaussian spatial beamshape, essential for the refraction measurements.

An almost constant value of a0 reported in the Fig. 6 shows that the photoinduced refractive index modification per elementary e-/h+ pair excitation is not influenced by the inorganic nanoparticles concentration. This evidences the large organic/inorganic internal interface of these hybrids which is maintained until the highest nanoparticles loading (correspondent to the interparticles distance close to their size). The nanoparticulate hybrids can be considered as open structure materials, which functional properties are defined by internal interface.

5. Conclusion

We report on measurements of photoinduced modifications of the linear optical refraction coefficient of nanoparticulate pHEMA-TiO2 organic-inorganic hybrids at 375 nm. The samples with titania concentration ranging from 0.88·1020 (X1) to 17.6·1020 cm−3 (X20) were prepared and analyzed. The photoinduced phase shift was obtained from the evolution of the normalized on-axis sample transmittance as a function of the UV irradiation dose. The reduction of the refractive index with the increase of the UV irradiation dose was observed in all hybrids. The refraction per Ti3+ center a0=Δn.0/[Ti3+]2.4(±0.5)1023cm3 was found almost independent on titania concentration. Both organic and inorganic components of the hybrid can contribute to the refractive changes. The strongest variation of Δn=5104 in the linear sample absorbance regime has been measured in X20 sample with the highest concentration of TiO2 nanoparticles. At high irradiation doses close to the photodarkening saturation, the refraction index variations could attain −0.005, which makes these materials candidates for applications in optoelectronics.

Acknowledgments

The financial supports of the ANR French grant ANR-07-BLAN-0299-02 and of the LABEX SEAM are kindly acknowledged.

References and links

1.

P. Gómez-Romero and C. Sanchez, eds., Functional Hybrid Materials (Wiley-VCH Verlag GmbH & Co., 2003).

2.

L. Nicole, L. Rozes, and C. Sanchez, “Integrative approaches to hybrid multifunctional materials: from multidisciplinary research to applied technologies,” Adv. Mater. 22(29), 3208–3214 (2010). [CrossRef] [PubMed]

3.

C. Sanchez, P. Belleville, M. Popall, and L. Nicole, “Applications of advanced hybrid organic-inorganic nanomaterials: from laboratory to market,” Chem. Soc. Rev. 40(2), 696–753 (2011). [CrossRef] [PubMed]

4.

R. Houbertz, G. Domann, C. Cronauer, A. Schmitt, H. Martin, J. U. Park, L. Fröhlich, R. Buestrich, M. Popall, U. Streppel, P. Dannberg, C. Wächter, and A. Bräuer, “Inorganic–organic hybrid materials for application in optical devices,” Thin Solid Films 442(1–2), 194–200 (2003). [CrossRef]

5.

R. Reisfeld, A. Weiss, T. Saraidarov, E. Yariv, and A. A. Ishchenko, “Solid-state lasers based on inorganic–organic hybrid materials obtained by combined sol–gel polymer technology,” Polym. Adv. Technol. 15(6), 291–301 (2004). [CrossRef]

6.

D. J. Kang and B.-S. Bae, “Photo-imageable sol-gel hybrid materials for simple fabrication of micro-optical elements,” Acc. Chem. Res. 40(9), 903–912 (2007). [CrossRef] [PubMed]

7.

R. A. S. Ferreira, P. S. André, and L. D. Carlos, “Organic–inorganic hybrid materials towards passive and active architectures for the next generation of optical networks,” Opt. Mater. 32(11), 1397–1409 (2010). [CrossRef]

8.

K. Tanaka and K. Shimakawa, “Chalcogenide glasses in Japan: a review on photoinduced phenomena,” Phys. Status Solidi B 246(8), 1744–1757 (2009). [CrossRef]

9.

S. Ducharme, J. Hautala, and P. C. Taylor, “Photodarkening profiles and kinetics in chalcogenide glasses,” Phys. Rev. B Condens. Matter 41(17), 12250–12259 (1990). [CrossRef] [PubMed]

10.

A. I. Kuznetsov, O. Kameneva, N. Bityurin, L. Rozes, C. Sanchez, and A. Kanaev, “Laser-induced photopatterning of organic-inorganic TiO2-based hybrid materials with tunable interfacial electron transfer,” Phys. Chem. Chem. Phys. 11(8), 1248–1257 (2009). [CrossRef] [PubMed]

11.

O. Kameneva, A. I. Kuznestov, L. A. Smirnova, L. Rozes, C. Sanchez, A. Alexandrov, N. Bityurin, K. Chhor, and A. Kanaev, “New photoactive hybrid organic-inorganic materials based on titanium-oxo-PHEMA nanocomposites exhibiting mixed valence properties,” J. Mater. Chem. 15(33), 3380–3383 (2005). [CrossRef]

12.

E. Fadeeva, J. Koch, B. Chichkov, A. Kuznetsov, O. Kameneva, N. Bityurin, C. Sanchez, and A. Kanaev, “Laser imprinting of 3D structures in gel-based titanium oxide organic-inorganic hybrids,” Appl. Phys., A Mater. Sci. Process. 84(1-2), 27–30 (2006). [CrossRef]

13.

P. Gorbovyi, A. Uklein, S. Tieng, O. Brinza, M. Traore, K. Chhor, L. Museur, and A. Kanaev, “Novel nanostructured pHEMA-TiO2 hybrid materials with efficient light-induced charge separation,” Nanoscale 3(4), 1807–1812 (2011). [CrossRef] [PubMed]

14.

N. Bityurin, A. I. Kuznetsov, and A. Kanaev, “Kinetics of UV-induced darkening of titanium-oxide gels,” Appl. Surf. Sci. 248(1–4), 86–90 (2005). [CrossRef]

15.

L. Museur, P. Gorbovyi, M. Traore, A. Kanaev, L. Rozes, and C. Sanchez, “Luminescence properties of pHEMA-TiO2 gels based hybrids materials,” J. Lumin. 132(5), 1192–1199 (2012). [CrossRef]

16.

A. Zakery and S. R. Elliott, “Optical properties and applications of chalcogenide glasses: a review,” J. Non-Cryst. Solids 330(1–3), 1–12 (2003). [CrossRef]

17.

N. Mehta, “Applications of chalcogenide glasses in electronics and optoelectronics: a review,” J. Sci. Ind. Res. (India) 65(10), 777–786 (2006).

18.

Q. Zhan and J. R. Leger, “Microellipsometer with radial symmetry,” Appl. Opt. 41(22), 4630–4637 (2002). [CrossRef] [PubMed]

19.

K. Fedus and G. Boudebs, “Determination of photo-induced changes in linear optical coefficients by the Z-scan technique,” J. Opt. Soc. Am. B 26(11), 2171–2175 (2009). [CrossRef]

20.

M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, “Sensitive measurement of optical nonlinearities using a single beam,” IEEE J. Quantum Electron. 26(4), 760–769 (1990). [CrossRef]

21.

A. Afanasiev, A. Alexandrov, N. Agareva, N. Sapogova, L. Smirnova, and N. Bityurin, “UV induced of linear and non-linear IR optical properties of dielectrics for photonic applications,” presented in FLAMN-10, St. Petersburg, Russia (2010).

22.

V. Gayvoronsky, S. Yakunin, V. Nazarenko, V. Starkov, and M. Brodyn, “Techniques to characterize the nonlinear optical response of doped nematic liquid crystals,” Mol. Cryst. Liq. Cryst. 426(1), 231–241 (2005). [CrossRef]

23.

J. U. Park, W. S. Kim, and B. S. Bae, “Photoinduced low refractive index in a photosensitive organic–inorganic hybrid material,” J. Mater. Chem. 13(4), 738–741 (2003). [CrossRef]

24.

B. R. Bennett, R. A. Soref, and J. A. Del Alamo, “Carrier-induced change in refractive index of InP, GaAs and InGaAsP,” IEEE J. Quantum Electron. 26(1), 113–122 (1990). [CrossRef]

25.

N. A. Deskins and M. Dupuis, “Electron transport via polaron hopping in bulk TiO2: a density functional theory characterization,” Phys. Rev. B 75(19), 195212 (2007). [CrossRef]

26.

R. Ulbricht, E. Hendry, J. Shan, T. F. Heinz, and M. Bonn, “Carrier dynamics in semiconductors studied with time-resolved terahertz spectroscopy,” Rev. Mod. Phys. 83(2), 543–586 (2011). [CrossRef]

27.

R. G. Hunsperger, Integrated Optics (Springer, 2009).

28.

T. Keiji, “Photo-induced phenomena in chalcogenide glass: Comparison with those in oxide glass and polymer,” J. Non-Cryst. Solids 352(23–25), 2580–2584 (2006).

29.

A. Ljungstrom and T. Monro, “Observation of light-induced refractive index reduction in bulk glass and application to the formation of complex waveguides,” Opt. Express 10(5), 230–235 (2002). [CrossRef] [PubMed]

30.

L. Merhari, Hybrid Nanocomposites for Nanotechnology: Electronic, Optical, Magnetic And Biomedical Applications (Springer, 2009).

OCIS Codes
(160.4670) Materials : Optical materials
(160.4760) Materials : Optical properties
(160.5320) Materials : Photorefractive materials
(160.4236) Materials : Nanomaterials

ToC Category:
Nanomaterials

History
Original Manuscript: January 2, 2013
Revised Manuscript: February 7, 2013
Manuscript Accepted: February 7, 2013
Published: April 1, 2013

Virtual Issues
Hybrid Organic-Inorganic Materials for Novel Photonic Applications (2013) Optical Materials Express

Citation
Andrii Uklein, Pavlo Gorbovyi, Mamadou Traore, Luc Museur, and Andrey Kanaev, "Photo-induced refraction of nanoparticulate organic-inorganic TiO2-pHEMA hybrids," Opt. Mater. Express 3, 533-545 (2013)
http://www.opticsinfobase.org/ome/abstract.cfm?URI=ome-3-5-533


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References

  1. P. Gómez-Romero and C. Sanchez, eds., Functional Hybrid Materials (Wiley-VCH Verlag GmbH & Co., 2003).
  2. L. Nicole, L. Rozes, and C. Sanchez, “Integrative approaches to hybrid multifunctional materials: from multidisciplinary research to applied technologies,” Adv. Mater.22(29), 3208–3214 (2010). [CrossRef] [PubMed]
  3. C. Sanchez, P. Belleville, M. Popall, and L. Nicole, “Applications of advanced hybrid organic-inorganic nanomaterials: from laboratory to market,” Chem. Soc. Rev.40(2), 696–753 (2011). [CrossRef] [PubMed]
  4. R. Houbertz, G. Domann, C. Cronauer, A. Schmitt, H. Martin, J. U. Park, L. Fröhlich, R. Buestrich, M. Popall, U. Streppel, P. Dannberg, C. Wächter, and A. Bräuer, “Inorganic–organic hybrid materials for application in optical devices,” Thin Solid Films442(1–2), 194–200 (2003). [CrossRef]
  5. R. Reisfeld, A. Weiss, T. Saraidarov, E. Yariv, and A. A. Ishchenko, “Solid-state lasers based on inorganic–organic hybrid materials obtained by combined sol–gel polymer technology,” Polym. Adv. Technol.15(6), 291–301 (2004). [CrossRef]
  6. D. J. Kang and B.-S. Bae, “Photo-imageable sol-gel hybrid materials for simple fabrication of micro-optical elements,” Acc. Chem. Res.40(9), 903–912 (2007). [CrossRef] [PubMed]
  7. R. A. S. Ferreira, P. S. André, and L. D. Carlos, “Organic–inorganic hybrid materials towards passive and active architectures for the next generation of optical networks,” Opt. Mater.32(11), 1397–1409 (2010). [CrossRef]
  8. K. Tanaka and K. Shimakawa, “Chalcogenide glasses in Japan: a review on photoinduced phenomena,” Phys. Status Solidi B246(8), 1744–1757 (2009). [CrossRef]
  9. S. Ducharme, J. Hautala, and P. C. Taylor, “Photodarkening profiles and kinetics in chalcogenide glasses,” Phys. Rev. B Condens. Matter41(17), 12250–12259 (1990). [CrossRef] [PubMed]
  10. A. I. Kuznetsov, O. Kameneva, N. Bityurin, L. Rozes, C. Sanchez, and A. Kanaev, “Laser-induced photopatterning of organic-inorganic TiO2-based hybrid materials with tunable interfacial electron transfer,” Phys. Chem. Chem. Phys.11(8), 1248–1257 (2009). [CrossRef] [PubMed]
  11. O. Kameneva, A. I. Kuznestov, L. A. Smirnova, L. Rozes, C. Sanchez, A. Alexandrov, N. Bityurin, K. Chhor, and A. Kanaev, “New photoactive hybrid organic-inorganic materials based on titanium-oxo-PHEMA nanocomposites exhibiting mixed valence properties,” J. Mater. Chem.15(33), 3380–3383 (2005). [CrossRef]
  12. E. Fadeeva, J. Koch, B. Chichkov, A. Kuznetsov, O. Kameneva, N. Bityurin, C. Sanchez, and A. Kanaev, “Laser imprinting of 3D structures in gel-based titanium oxide organic-inorganic hybrids,” Appl. Phys., A Mater. Sci. Process.84(1-2), 27–30 (2006). [CrossRef]
  13. P. Gorbovyi, A. Uklein, S. Tieng, O. Brinza, M. Traore, K. Chhor, L. Museur, and A. Kanaev, “Novel nanostructured pHEMA-TiO2 hybrid materials with efficient light-induced charge separation,” Nanoscale3(4), 1807–1812 (2011). [CrossRef] [PubMed]
  14. N. Bityurin, A. I. Kuznetsov, and A. Kanaev, “Kinetics of UV-induced darkening of titanium-oxide gels,” Appl. Surf. Sci.248(1–4), 86–90 (2005). [CrossRef]
  15. L. Museur, P. Gorbovyi, M. Traore, A. Kanaev, L. Rozes, and C. Sanchez, “Luminescence properties of pHEMA-TiO2 gels based hybrids materials,” J. Lumin.132(5), 1192–1199 (2012). [CrossRef]
  16. A. Zakery and S. R. Elliott, “Optical properties and applications of chalcogenide glasses: a review,” J. Non-Cryst. Solids330(1–3), 1–12 (2003). [CrossRef]
  17. N. Mehta, “Applications of chalcogenide glasses in electronics and optoelectronics: a review,” J. Sci. Ind. Res. (India)65(10), 777–786 (2006).
  18. Q. Zhan and J. R. Leger, “Microellipsometer with radial symmetry,” Appl. Opt.41(22), 4630–4637 (2002). [CrossRef] [PubMed]
  19. K. Fedus and G. Boudebs, “Determination of photo-induced changes in linear optical coefficients by the Z-scan technique,” J. Opt. Soc. Am. B26(11), 2171–2175 (2009). [CrossRef]
  20. M. Sheik-Bahae, A. A. Said, T. H. Wei, D. J. Hagan, and E. W. Van Stryland, “Sensitive measurement of optical nonlinearities using a single beam,” IEEE J. Quantum Electron.26(4), 760–769 (1990). [CrossRef]
  21. A. Afanasiev, A. Alexandrov, N. Agareva, N. Sapogova, L. Smirnova, and N. Bityurin, “UV induced of linear and non-linear IR optical properties of dielectrics for photonic applications,” presented in FLAMN-10, St. Petersburg, Russia (2010).
  22. V. Gayvoronsky, S. Yakunin, V. Nazarenko, V. Starkov, and M. Brodyn, “Techniques to characterize the nonlinear optical response of doped nematic liquid crystals,” Mol. Cryst. Liq. Cryst.426(1), 231–241 (2005). [CrossRef]
  23. J. U. Park, W. S. Kim, and B. S. Bae, “Photoinduced low refractive index in a photosensitive organic–inorganic hybrid material,” J. Mater. Chem.13(4), 738–741 (2003). [CrossRef]
  24. B. R. Bennett, R. A. Soref, and J. A. Del Alamo, “Carrier-induced change in refractive index of InP, GaAs and InGaAsP,” IEEE J. Quantum Electron.26(1), 113–122 (1990). [CrossRef]
  25. N. A. Deskins and M. Dupuis, “Electron transport via polaron hopping in bulk TiO2: a density functional theory characterization,” Phys. Rev. B75(19), 195212 (2007). [CrossRef]
  26. R. Ulbricht, E. Hendry, J. Shan, T. F. Heinz, and M. Bonn, “Carrier dynamics in semiconductors studied with time-resolved terahertz spectroscopy,” Rev. Mod. Phys.83(2), 543–586 (2011). [CrossRef]
  27. R. G. Hunsperger, Integrated Optics (Springer, 2009).
  28. T. Keiji, “Photo-induced phenomena in chalcogenide glass: Comparison with those in oxide glass and polymer,” J. Non-Cryst. Solids352(23–25), 2580–2584 (2006).
  29. A. Ljungstrom and T. Monro, “Observation of light-induced refractive index reduction in bulk glass and application to the formation of complex waveguides,” Opt. Express10(5), 230–235 (2002). [CrossRef] [PubMed]
  30. L. Merhari, Hybrid Nanocomposites for Nanotechnology: Electronic, Optical, Magnetic And Biomedical Applications (Springer, 2009).

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