Tailoring of optical properties of LiNbO 3 by ion implantation

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SMR/1758-14 "Workshop on Ion Beam Studies of Nanomaterials: Synthesis, Modification and Characterization" 26 June - 1 July 2006 Tailoring of Optical Properties of LiNbO3 by ion implantation Cinzia SADA Department of Physics University of Padova Padova, Italy

Tailoring of optical properties of LiNbO 3 by ion implantation Dr Cinzia Sada Physics Department,, University of Padova G.G. Bentini,, M. Bianconi, M. Chiarini IMM-CNR di Bologna N. Argiolas,, M. Bazzan,, P. Mazzoldi Physics Department,, University of Padova

Outline The material Optical properties Linear (LO) and nonlinear (NLO) optical response Exploitation of ion implantation for nanoclusters formation Exploitation of ion implantation for waveguides formation Applications: optical modulator for gas tracing Exploitation of ion implantation in photonics Photonic structures Realisation and characteristics Applications

The material C axis <001> Nb P s Lithium Niobate (LiNbO 3 ) O Li Nb Ferroelectric with a spontaneous polarization P s =0.71 C/m 2 parallel to the c- axis Due to its large Electro-Optic and Acousto-Optic coefficients, LiNbO 3 is used for optical applications: Li 1.Optical modulators 2.Pockel Cells switches, 3.Integrated waveguides 4.Second harmonic generation

Optical properties Linear optical properties Ordinary refractive index n o Extraordinary refractive n e (E c axis) (E // c axis) Negative birifrangence (at 633n) Transmission: 80% in the range 350nm-4000nm n e =2.2219 n o =2.2878 Nonlinear optical properties χ (2) =2d d=non linear optical coefficient d 31 (pm/v) d 33 (pm/v) d 22 (pm/v) LiNbO 3-5.95-34.4 4.08

Ion Implantation on LiNbO 3 LiNbO 3 LO properties NLO properties Induced NLO properties Optical waveguides Modification of the local composition and structure to confine the light Metal nanocluster in LiNbO 3 Application in nanotech Application in integrated optics

Applications of ion implantation on LiNbO 3 Local doping with passive elements (metals, H,He,..) 1 0 1 0 0 0 1 0 Input Signal λ X:LiNbO 3 Output Signal λ Optical modulation Ti:LiNbO 3 O:LiNbO 3 H:LiNbO 3 Optical recording Fe:LiNbO 3 Cu:LiNbO 3 Local doping with active elements (rare earths ) Input Signal λ Amplification and lasing Output Signal λ Er:LiNbO 3 Er:glass/SiO 2

Applications of ion implantation on LiNbO 3 Native nonlinear properties Signal λ PPLN LiNbO 3 Second Harmonic Laser at λ/2 Blue-green wavelenth for Optical recording Induced nonlinear properpies ON configuration Off configuration Input Optical Switch Output Input Optical Switch Output

Induced nonlinear properties Ion implantation of metals in LiNbO 3 for realisation of metal nanoparticles Works reported in literature: implantation of Au, Ag, Cu in the KeV region Best results obtained on Cu:LiNbO 3

Induced nonlinear optical properties Cu- implanted at E=60KeV I=10-50 µa/cm 2

Induced nonlinear optical properties Cu- implanted at: E=60KeV I=10-50 µa/cm 2 Non spherical nanocluster D=10nm Sub-picosecond nonlinear response

Linear optical properties Ion implantation of: heavy elements (Si 30KeV), medium light (C,O,N 3-5MeV) light elements (H, He 0.5-1MeV) to modify locally the refractive index of the medium and guarantee the light confinement Waveguides for integrated optics

Linear optical properties: waveguide Light confinement in optical waveguides n waveguide -n substrate >0 Total internal reflection n atmosphere θ 2 θ 3 θ 2 n waveguide n substrate

Integrated optics: optical waveguide How to prepare an optical waveguide Standard approach Introduction of suitable dopant Alternative approach Modification of the surrounding Methods: Thermal diffusion Ion exchange Ion implantation =n>n substrate =n<n substrate =n substrate =n substrate Methods: Ion implantation

Standard approach Increase of the refractive index in the doped region Implanted ion concentration Dopant implantation profile depth Refractive index Refractive index profile depth

Ion implantation of light elements Refractive index behaviours of He implanted optical waveguides in LiNbO 3, KTiOPO 4 and Li 2 B 4 O 7 P. Bindner et al, NIMB 142 (1998) 329-337

Ion implantation: alternative approach Interaction of the medium light elements with the material Surface Damage Substrate Surface damage due to the electronic energy loss ions End of range damage due to the nuclear energy loss Waveguide End Of Range Damage

Ion implantation of medium light elements High implant fluences of medium light elements increase the surface damage Higher damage with increasing atomic number of the implanted species Questions 1. Origin of the surface damage 2. Dependence of the surface; damage on the implantation conditions.

Ion Implantation: i) The energy lost by electronic interaction mostly generates localised colour centres and/or few structural isolated defects. These defects can be easily annealed at lower temperatures than the more complex defect clusters generated at the End-of-Range by nuclear interaction. ii) This is a general trend rather independent of the target material. iii) The energy lost by Nuclear interaction, generates collision cascades and large defect clusters.

Ion implantation of medium light elements Surface damage N D Φ = 1 exp Φ c n N D Φ Φ C defects density in the region nearby the surface fluence critical fluence Φ c =(3.1±0.6) 10 14 /cm 2 n=(2.75±0.25), 220 Threshold 220 ev/å n=1 1-D defect n=1.5 2.5 2-D defects n=3-4 3-D defects

Ion implantation of medium light elements End of range damage Linear dependence of the end of range damage up to a threshold value that depends on the implanted species

Ion implantation of medium light elements Above a give threshold in the electronic energy loss the surface damage occurs The overlap between the damage due to the electronic regime and the nuclear one give the final damage profile

Ion implantation: alternative approach Structural modification relative lattice mismatch d/d d=d film -d substrate d= d substrate C:LiNbO 3 Surface region: d/d<0.0002 End of range (EOR): peak: d/d~0.00255 O:LiNbO 3 Surface region: peak at d/d~0.0025 End of range damage peak at d/d~0.0035

Ion implantation: alternative approach Optical properties The variation in the refractive index can be due to the following contributions: Variation in the optical refraction due to composition and ion polarizability Variation in the molar volume Variation in the spontaneous polarization Variation due to the structural modification Elasto-optic effect n R n V n P n ε n tot = n R + n V + n P + n ε

Ion implantation Effect of implantation on the optical properties 6 5 Electronic Stopping Regime End-of-Range % Decrement in Refractive Index 4 3 2 1 0-1 n e n o 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 Damage Depth (µm)

Results of ion implantation Compositional analysis Refractive index SIMS Yield (Counts/s) 10 6 Li C O 10 5 Nb 10 4 n e 2.24 2.22 2.20 2.18 C:LiNbO 3 3.9MeV 6*10 14 at*cm -2 10 3 2.16 10 2 0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 Depth (µm) 2.14 0 1 2 3 4 Depth (µm) C excess in the EOR region, LiNbO 3 composition unaltered Low optical losses <3dB/cm)

Optical waveguide O:LiNbO 3 waveguide Optical Mode 3 inch Losses < 3dB/cm Laser Light coupling Guida planare

Ion implantation of medium light elements Ion implantation combined with photolitographic process can be used to prepare optical circuit and devices One of the most important application is the optical modulator: the input signal is modulated by interference effect due to the different refractive index value in the two optical branches Constant Refractive index n 1 0 1 0 0 0 1 0 Optical signal λ Refractive index n(v) varied in a controlled way NEED of realizing channel patterns Output signal λ

Ion Implantation of medium light elements Implanted ions Mask n 1 n 2 Mask n 0 Substrate n 0 Substrate n 1 > n 0 n 1 n 2 < n 0 n 2 n 0 Substrate n 0 Substrate

Ion Implantation of medium light elements Damage Profile of a Channel Waveguide realized by High Energy Ion Implantation Au SiO x 0.025 LiNbO 3 2.24 C:LiNbO 3 3.9MeV 6*10 14 at*cm -2 Displaced Atoms (%) 0.020 0.015 0.010 0.005 n e 2.22 2.20 2.18 2.16 0.000 0.0 0.5 1.0 1.5 2.0 2.5 Depth (µm) 2.14 0 1 2 3 4 Depth (µm)

Application: optical modulator Surface Damage LiNbO 3 substrate Implanted channel Substrate End Of Range Damage Mask O 3+ 5MeV Implanted channel waveguide End Of Range Damage How to change the refractive index in one branch? Via the electro-optic effect

Electro-optic effect Change in refractive index with the applied electric field: (1/n 2 ) = r E + P E 2 Pockel effect Kerr effect Where: n= Refractive index r = Linear Electro-Optic coefficient P = Quadratic Electro-Optic Coefficient E = Applied Electric Field

Electro-optic effect Modulation of the refractive index through the applied electric field Material r (pm/v) n KTP KNbO 3 25 2.17 LiNbO 3 29 2.2 Ba 2 NaNb 5 O l5 SBN (25-75) GaAs BaTiO 3 35 56 56-1340 1.2 28 1.86 2.22 2.22 3.6 2.36

Ion implantation: application to gas tracing

Ion implantation: application to gas tracing LIMB channel White solar light NADIR channel Dispersed gas in the stratosphere Transmitted solar light (without the absorbed wavelenght)

Application to gas tracing Input Mach-Zehnder Output 750 755 760 765 770 1.0 1.0 0.8 0.8 Relative Intensity 0.6 0.4 0.2 0.6 0.4 0.2 In V Out 0.0 0.0 750 755 760 765 770 λ (nm) Different refractive index in the two branches=different phase velocity of the optical beams Reconstruction At the output, beams recombination gives light interference The interference pattern contains the information on the input signal Post analysis of the interference pattern allows the identification of the input signal, i.e gas element

Application to gas tracing High selectivity on the wavelength Position of the waveguides below the driving electrodes

Nanotech applied to LiNbO 3 Realization of periodic grating acting as wavelength filters LiNbO3 - Aria; 240 nm (50 layers) 1.0 0.9 T R R,T 0.8 0.7 0.6 0.5 Periodic structure in the nanoscale region obtained by laser irradiation: band pass filter 0.4 0.3 0.2 0.1 0.0 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 λ (µm)

Ion implantation: application in nanotech Ion implantation through a mask Chemical etching on the implanted surface Surface

Ion implantation: application in nanotech Effect of the damage on the etching rate 6000 5 MeV O 3+ Implanted LiNbO 3, 1*10 14 at / cm 2 Implanted region are chemically attached faster than unimplanted ones 5000 Depth (Å) 4000 3000 Selective etching! 2000 Virgin Material 1000 0 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 Time (h)

Ion implantation: application in nanotech Patterns obtained on LiNbO 3 by ion Implantation and selective etching

Ion implantation: application to nanotech Simulation of the electromagnetic field propagation in a Photonic Device obtained by ion implantation + selective etching

Perspectives Driving Electrodes waveguide Tunable Mirrors Tunable Resonant Cavity Obtained by periodic structures

Outline Resonant Cavity 1 0.8 0.6 0.4 0.2 4.25 4.3 4.35 4.4 4.45 4.5 Resonant Cavity, periodicity of the Photonic Structures: 600 nm Photonic Band Gap of the cavity, (Theory)

Nanotech applied to LiNbO 3 Laser beam Beam Shaper Mask Projection system Sample 5 µm Lower period can be obtained by laser irradiation

Conclusions Ion implantation is a very versatile techinique to modify the LiNbO 3 properties In combination with photolitography it allows for the relaization of optical pattern In principle any complex optical device can be realised, with tailored performances and functionalities