Bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase TiO2: Gd nanosystems

We report a comprehensive investigation of the third-order nonlinear interaction of femtosecond laser pulses with nanostructured anatase TiO2 doped with varying concentrations of gadolinium impurities. The samples were synthesized using a facile sol‒gel method. The physicochemical characteristics of...

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Main Authors: Oriparambil Sivaraman Nirmal Ghosh, Sethuraman Gayathri, Srinivasa Rao Allam, Alok Sharan, S.B. Sruthil Lal, Modigunta Jeevan Kumar Reddy, A.M. Shanmugharaj, Annamraju Kasi Viswanath
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Language:English
Published: Elsevier 2024-12-01
Series:Chemical Physics Impact
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Online Access:http://www.sciencedirect.com/science/article/pii/S2667022424002238
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author Oriparambil Sivaraman Nirmal Ghosh
Sethuraman Gayathri
Srinivasa Rao Allam
Alok Sharan
S.B. Sruthil Lal
Modigunta Jeevan Kumar Reddy
A.M. Shanmugharaj
Annamraju Kasi Viswanath
author_facet Oriparambil Sivaraman Nirmal Ghosh
Sethuraman Gayathri
Srinivasa Rao Allam
Alok Sharan
S.B. Sruthil Lal
Modigunta Jeevan Kumar Reddy
A.M. Shanmugharaj
Annamraju Kasi Viswanath
author_sort Oriparambil Sivaraman Nirmal Ghosh
collection DOAJ
description We report a comprehensive investigation of the third-order nonlinear interaction of femtosecond laser pulses with nanostructured anatase TiO2 doped with varying concentrations of gadolinium impurities. The samples were synthesized using a facile sol‒gel method. The physicochemical characteristics of the prepared samples were investigated using various analytical techniques, including XRD, SEM, TEM, SAED, UV‒Vis, PL and XPS. The average crystallite sizes of the pristine TiO2- and Gd (1, 2, and 3 %)-doped TiO2 nanoparticles were calculated to be 10.9, 9.2, 10.2 and 8.9 nm, respectively. The W-H plots also revealed average crystallite sizes in the range of 13.9, 16.6, 13.9 and 10.4 for pristine and Gd (1, 2, 3 %)-doped TiO2 nanoparticles. The lattice strain values for pristine and Gd (1, 2, and 3 %) doped TiO2 nanoparticles were computed as 0.00203, 0.00667, 0.0036 and 0.00262, respectively, from the W‒H plots. The average crystallite size was calculated to 9.2 nm from the TEM images using ImageJ software. The optical band gap values of pristine TiO2 and Gd (1, 2, and 3 %)-doped TiO2 nanoparticles were calculated to be 3.3, 3.23, 3.21 and 3.20 eV from the Kubelka–Munk function plot. The emission peaks of pristine and Gd(1,2,3 %) doped TiO2 nanoparticles were calculated as 3.2, 3.23, 3.26 and 3.32 eV from the photoluminescence spectra recorded at 330 nm photo excitation. The binding energies of the O1s, Ti2P and Gd4d peaks present in the survey scan of TiO2 nanoparticles doped with one weight percentage of Gd impurity were 528.79, 531.53, 457.53, 463.25 and 149.6 eV, respectively. The third-order nonlinear characteristics of the TiO2:Gd samples were probed using the ultrafast laser Z-scan technique. We observed that the density of bound excitons can be regulated by controlling the dopant concentration. The strong oscillatory interactions between photogenerated bound excitons, which act as dipole oscillators with large oscillating frequencies, were recorded using a single-beam femtosecond Z-scan. The third-order nonlinear susceptibility χ(3) for pristine and Gd(1,2,3 %)-doped TiO2 nanoparticles were calculated as 7.258 × 10-18, 9.4 × 10-18, 11 × 10-18 and 13 × 10-18 cm2/V2, respectively. The obtained results suggest that the thermal lensing phenomenon in nanostructured anatase TiO2 can be generated and effectively controlled using a band gap engineering technique. We determined that the small pump power in nonlinear media with controllable band fluctuations can produce large phase distortions in TiO2:Gd nanosystems. Our findings reveal that Gd doping induces controlled modification of the electronic structure of TiO2, leading to a tailored energy landscape for exciton formation and binding. These findings provide a novel approach for engineering systems of TiO2-based nanostructures for energy-efficient optical-limiting nanophotonic systems and optoelectronic-switching devices.
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spelling doaj-art-9a84fcc3be7b47668ecb4f357063ed1c2025-08-20T02:48:39ZengElsevierChemical Physics Impact2667-02242024-12-01910067910.1016/j.chphi.2024.100679Bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase TiO2: Gd nanosystemsOriparambil Sivaraman Nirmal Ghosh0Sethuraman Gayathri1Srinivasa Rao Allam2Alok Sharan3S.B. Sruthil Lal4Modigunta Jeevan Kumar Reddy5A.M. Shanmugharaj6Annamraju Kasi Viswanath7Centre for Nanoscience and Technology, Pondicherry University, Puducherry 605014, India; Quantum Matter-Energy-Information Interfaces and Complex Systems Research Laboratory, BRIIC, Buddha Falls Valley Range 685503, Kerala, India; Corresponding authors.Centre for Nanoscience and Technology, Pondicherry University, Puducherry 605014, India; DRDO Industry Academia Centre of Excellence, Bharathiar University Campus, Coimbatore, 641046, IndiaDepartment of Physics, Pondicherry University, Puducherry 605014, India; Institute for Advanced Academic Research, Chiba University, Chiba 263-8522, JapanDepartment of Physics, Pondicherry University, Puducherry 605014, IndiaDepartment of Physics, Pondicherry University, Puducherry 605014, IndiaDepartment of Polymer Science and Engineering, Department of IT-Energy Convergence, Chemical Industry Institute, Korea National University of Transportation, Chungju 27469, South KoreaDepartment of Chemistry, Sri Sivasubramaniya Nadar (SSN) College of Engineering, Kalavakkam, Chennai 603110, Tamilnadu, IndiaCentre for Nanoscience and Technology, Pondicherry University, Puducherry 605014, India; Research Division, Ballari Institute of Technology and Management, Ballari 583104, Karnataka, India; Corresponding authors.We report a comprehensive investigation of the third-order nonlinear interaction of femtosecond laser pulses with nanostructured anatase TiO2 doped with varying concentrations of gadolinium impurities. The samples were synthesized using a facile sol‒gel method. The physicochemical characteristics of the prepared samples were investigated using various analytical techniques, including XRD, SEM, TEM, SAED, UV‒Vis, PL and XPS. The average crystallite sizes of the pristine TiO2- and Gd (1, 2, and 3 %)-doped TiO2 nanoparticles were calculated to be 10.9, 9.2, 10.2 and 8.9 nm, respectively. The W-H plots also revealed average crystallite sizes in the range of 13.9, 16.6, 13.9 and 10.4 for pristine and Gd (1, 2, 3 %)-doped TiO2 nanoparticles. The lattice strain values for pristine and Gd (1, 2, and 3 %) doped TiO2 nanoparticles were computed as 0.00203, 0.00667, 0.0036 and 0.00262, respectively, from the W‒H plots. The average crystallite size was calculated to 9.2 nm from the TEM images using ImageJ software. The optical band gap values of pristine TiO2 and Gd (1, 2, and 3 %)-doped TiO2 nanoparticles were calculated to be 3.3, 3.23, 3.21 and 3.20 eV from the Kubelka–Munk function plot. The emission peaks of pristine and Gd(1,2,3 %) doped TiO2 nanoparticles were calculated as 3.2, 3.23, 3.26 and 3.32 eV from the photoluminescence spectra recorded at 330 nm photo excitation. The binding energies of the O1s, Ti2P and Gd4d peaks present in the survey scan of TiO2 nanoparticles doped with one weight percentage of Gd impurity were 528.79, 531.53, 457.53, 463.25 and 149.6 eV, respectively. The third-order nonlinear characteristics of the TiO2:Gd samples were probed using the ultrafast laser Z-scan technique. We observed that the density of bound excitons can be regulated by controlling the dopant concentration. The strong oscillatory interactions between photogenerated bound excitons, which act as dipole oscillators with large oscillating frequencies, were recorded using a single-beam femtosecond Z-scan. The third-order nonlinear susceptibility χ(3) for pristine and Gd(1,2,3 %)-doped TiO2 nanoparticles were calculated as 7.258 × 10-18, 9.4 × 10-18, 11 × 10-18 and 13 × 10-18 cm2/V2, respectively. The obtained results suggest that the thermal lensing phenomenon in nanostructured anatase TiO2 can be generated and effectively controlled using a band gap engineering technique. We determined that the small pump power in nonlinear media with controllable band fluctuations can produce large phase distortions in TiO2:Gd nanosystems. Our findings reveal that Gd doping induces controlled modification of the electronic structure of TiO2, leading to a tailored energy landscape for exciton formation and binding. These findings provide a novel approach for engineering systems of TiO2-based nanostructures for energy-efficient optical-limiting nanophotonic systems and optoelectronic-switching devices.http://www.sciencedirect.com/science/article/pii/S2667022424002238Bound excitonTiO2: Gd nanosphereFemtosecond Z-ScanThermal lensing
spellingShingle Oriparambil Sivaraman Nirmal Ghosh
Sethuraman Gayathri
Srinivasa Rao Allam
Alok Sharan
S.B. Sruthil Lal
Modigunta Jeevan Kumar Reddy
A.M. Shanmugharaj
Annamraju Kasi Viswanath
Bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase TiO2: Gd nanosystems
Chemical Physics Impact
Bound exciton
TiO2: Gd nanosphere
Femtosecond Z-Scan
Thermal lensing
title Bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase TiO2: Gd nanosystems
title_full Bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase TiO2: Gd nanosystems
title_fullStr Bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase TiO2: Gd nanosystems
title_full_unstemmed Bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase TiO2: Gd nanosystems
title_short Bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase TiO2: Gd nanosystems
title_sort bound exciton engineering approach for tuning the thermal lensing phenomenon in anatase tio2 gd nanosystems
topic Bound exciton
TiO2: Gd nanosphere
Femtosecond Z-Scan
Thermal lensing
url http://www.sciencedirect.com/science/article/pii/S2667022424002238
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