Chinese Optics, Volume. 15, Issue 4, 640(2022)
Research progress on nonlinear optics of polyvinylidene fluorid and its copolymers films
![Schematic illustration of the Z-scan technique. (a) The principle of the Z-scan technique: Ⅰ-the wavefront deformation of Gaussian beam when entering nonlinear materials, Ⅱ-the Z-scan experimental apparatus in which the ratio D2/D1 is recorded as a function of the sample position Z, D1 and D2 are photodetectors[20]; (b) setup for second and third harmonic generation by means of the Maker fringe technique[21]; (c) the principle of barycentric scan technique[24]](/Images/icon/loading.gif){kind=icon}
Fig. 1. Schematic illustration of the Z-scan technique. (a) The principle of the Z-scan technique: Ⅰ-the wavefront deformation of Gaussian beam when entering nonlinear materials, Ⅱ-the Z-scan experimental apparatus in which the ratio D2/D1 is recorded as a function of the sample position Z, D1 and D2 are photodetectors[20]; (b) setup for second and third harmonic generation by means of the Maker fringe technique[21]; (c) the principle of barycentric scan technique[24]
Fig. 3. Schematic illustration of classical research on nonlinear optics of PVDF and its copolymer optical thin films. (a) Sample geometry and orientation for SHG measurements on PVDF film. The direction of the laser beam propagation corresponds to
Fig. 4. NLO properties of PVDF/metallic oxide nanocomposites films. (a) The transmittance of PMMA/PVDF-ZnO nanocomposites[78]; (b) linear absorption coefficient spectra of PVDF/ZnO/CuO nanocomposites[81]; (c) plots (direct band gap) for PVDF pristine and PVDF-ZnO Nanocomposites[73]; (d) the normalized transmittance as a function of sample position in open-aperture Z-scan for PVDF/ZnO nanocomposites [74]
Fig. 5. NLO properties of PVDF/low-dimensional carbon materials films. (a) Optical limiting graphs for PVDF/RGO films with different concentrations of RGO[93]; (b) transmittance of pristine PVDF and PVDF-RGO nanocomposites[100]; (c) transparency camera image for PVDF/MWCNT composites films[101] with different concentration of MWCNT: (ⅰ) pure PVDF, quality score is (ⅱ) 1%, (ⅲ) 2%, (ⅳ) 5%; (d) transmittance of the modified CQDs/PVDF nanocomposite films before and after 200 h of UV exposure[104]
Fig. 6. NLO properties of PVDF films doped with inorganic nonmetallic crystals, metallic salts, and composite fillers. (a) Schematics of TTTT(PVDF) configuration on HNTs[107]; (b) SEM micrographs of PVDF@SiO2@S1[113]; (c) transmittance of the PVDF/ HNTs films with Overlaid Z-scan curves[107]; (d) refractive index for pure PVDF and Li4Ti5O12/PVDF nanocomposites[111]; (e) direct bandgap of the MoS2 doped in PVDF nanocomposite samples[117]; (f) FTIR spectrums of TiO2@MWCNTs/PVDF composites[123]
Fig. 7. Quantum chemical calculation for PVDF and its copolymers films. (a) Snapshot of a Ag/PVDF1250 nanocomposites simulation cell. Silver atoms are shaded gray, fluorine blue, carbon red, and hydrogen green[131]; (b) the normal reflectance (
Table 1. Optical characteristics of PVDF and its copolymer films
View tableView in ArticleTable 1. Optical characteristics of PVDF and its copolymer films
Refractive index second-harmonic coefficients Intrinsic Birefringences[ 51 ]Coherent wavelength gFibers α（Ⅱ） β（Ⅰ） γ（Ⅲ） a: Preparation with Spin-coating; b: Preparation with LB method; c. Calculations based on the formalism of Hughes and Sipe; d: Calculations based on Bunn, Denbigh (C-C, C-H) and Denbigh (C-F); e: Calculations based on Bunn, Denbigh (C-C, C-H) and Vogel(C-F); f: Calculations based on Denbigh (C-C, C- H) and LeFevre and LeFevre (C-F). g: Birefrigence of Melt-Spun PVDF Fibers before (above) and after (below) the poled films (Clod-Drawing, Elongated-40%) a1.42[51]a1.425[46]a1.41−1.49[54]b1.408[71]b1.404−1.540[68]a1.99[69]a1.4−1.9[55] d33: 0.22 pm/V [52]d31: 0.05 pm/V[52]b−35 pm/V[55]bd33: −40 pm/V[60]； bd33: −20±2 pm/V[60 ]； cd33: 1.66 pm/V[70]cd31: 2.01 pm/V[70] 0.0302 d0.0236 0.030773 0.001022 30 μm[46]37 μm (±3 μm)[52] e0.0236 0.030773 0.001022 0.0387 f0.0950 0.1132 0.0739 c0.0082[70] electro-optic coefficients(EO) Elasto-optic coefficients quadratic electro-optic coefficients $\left| {r_{51}^x } \right|$ [50]0.10×10−12 mV−1 $ \left| {\mathop \pi \nolimits_{11}^E - \left( {{\raise0.7ex\hbox{${\mathop n\nolimits_2^3 }$} \mathord{\left/ {\vphantom {{\mathop n\nolimits_2^3 } {\mathop n\nolimits_1^3 }}}\right.} \lower0.7ex\hbox{${\mathop n\nolimits_1^3 }$}}} \right)\mathop \pi \nolimits_{12}^E } \right| $ [50]3.6×10−12m2N−1 $ \left| {\mathop g\nolimits_{44}^x } \right| $ 0.02 m4C−2 [50] [70] 0.23×10−12 mV−1 21 m4C−2[59] $\left| {r_{42}^x } \right|$ [50]0.21×10−12 mV−1 $ \left| {\mathop h\nolimits_{55}^x } \right| $ 6.8×10−23 m2V−2[50] [70] 1.78×10−12 mV−1 4.11×10−18 m2V−2[59] $ \left| {\mathop r\nolimits_{13}^x - \left( {{\raise0.7ex\hbox{${\mathop n\nolimits_2^3 }$} \mathord{\left/ {\vphantom {{\mathop n\nolimits_2^3 } {\mathop n\nolimits_1^3 }}}\right.} \lower0.7ex\hbox{${\mathop n\nolimits_1^3 }$}}} \right)\mathop r\nolimits_{23}^x } \right| $ [50]0.38×10−12 mV−1 $ \left| {\mathop \pi \nolimits_{21}^E - \left( {{\raise0.7ex\hbox{${\mathop n\nolimits_2^3 }$} \mathord{\left/ {\vphantom {{\mathop n\nolimits_2^3 } {\mathop n\nolimits_1^3 }}}\right.} \lower0.7ex\hbox{${\mathop n\nolimits_1^3 }$}}} \right)\mathop \pi \nolimits_{22}^E } \right| $ [50]1.8×10−12 m2N−1 $ \left| {\mathop g\nolimits_{13}^x - \left( {{\raise0.7ex\hbox{${\mathop n\nolimits_2^3 }$} \mathord{\left/ {\vphantom {{\mathop n\nolimits_2^3 } {\mathop n\nolimits_1^3 }}}\right.} \lower0.7ex\hbox{${\mathop n\nolimits_1^3 }$}}} \right)\mathop g\nolimits_{23}^x } \right| $ [50]0.01 m4C−2 [70] 1.48×10−12 mV−1 $ \left| {\mathop h\nolimits_{13}^x - \left( {{\raise0.7ex\hbox{${\mathop n\nolimits_2^3 }$} \mathord{\left/ {\vphantom {{\mathop n\nolimits_2^3 } {\mathop n\nolimits_1^3 }}}\right.} \lower0.7ex\hbox{${\mathop n\nolimits_1^3 }$}}} \right)\mathop h\nolimits_{23}^x } \right| $ [59]26×10−23 m2V−2
Table 2. Linear optical and nonlinear optical parameters of PVDF/MO (metallic oxide) nanocomposites films
View tableView in ArticleTable 2. Linear optical and nonlinear optical parameters of PVDF/MO (metallic oxide) nanocomposites films
Nonlinear optical parameters Note：P-PVDF, 1- ac activation energy (Eac), 2-dc activation energy (Edc), Ed-Direct band gap, Ei-Indirect optical band gap, n-linear refractive index (λ≈633 nm), Ea-optical activation energy, Ef-Fermi energy, n2-nonlinear refractive index (cm2/W×10−13), β-nonlinear absorption coefficient (two-photon, cm/W×10−8), α-linear absorption coefficient, transmittance, εr-dielectric constant, χ(3)-third order nonlinear optical susceptibility(10-6esu), Leff-effective length of the sample(10−3 cm), ΔΦ0-the nonlinear phase shift, k-the extenction coeffecient (λ≈633 nm), p-average polarizability (C2 m2J−1×10−39), β′-first hyperpolarizability(C3 m3J−2×10−51), ᴧ-anisotropy (C2 m2J−1×10−39), V-ZnO: ZnO doped with vanadium, S- ZnO: ZnO doped with sulfur, Dy-ZnO:ZnO doped with dysprosium. Samples Leff β εr n2 ΔΦ0 Ed (eV) Ei (eV) Ea(eV) |χ(3)| P/ZnO [ 81 ]1.051[ 81 ]0.2339~0.30405[ 73 ]1.942[ 81 ]17.58~2.064[ 73 ]3.15~4.91[ 81 ]−1.624[ 81 ]−4.562~ 12.22[ 73 ]0.181[ 81 ]0.147~ 0.29[ 74 ]5.57~4.95[ 73 ]3.24[ 81 ]4.76~3.35[ 73 ]1.16[ 73 ]0.7145[ 73 ]P/ZnO/CuO [ 81 ]0.862 4.740 — −3.220 0.294 — — — 1.4039 Samples β' εr n p Ed (eV) Ef (eV) ᴧ P/ZrO2[ 69 ]3396.8~26.10 3.97~5.83 1.99~2.41 1.62~7.27 1.53~5.89 2.94~0.76 0.34~9.29 Linear optical parameters Samples εr n k Samples T εr P/CrO2[ 83 ]2.77−5.83 1.395~1.43 0.005~0.03 P/Gd2O3: Eu3+[ 89 ]82%~85% 7~7.5 P/PPO/POPOPGd2O3:Eu3+[ 89 ]75%~77% 12~15 Samples[ 82 ]α εr Ed (eV) Samples[ 76 ]α Ed (eV) Ei (eV) P/PEO-Al2O3 0.99 3.56~6.35 4.91 P/PMMA-V-ZnO 0.88~0.60[ 78 ]2.8 2.5 P/PEO-SnO2 0.99 2.7~4.68 4.62 P/PMMA-S-ZnO 0.82~0.60[ 78 ]3.0 2.8 P/PEO-TiO2 0.982 3.08~5.05 3.53 P/PMMA-Dy-ZnO 0.78~0.60[ 78 ]2.5 2.2 Samples α n Ed (eV) Ei (eV) k(10−2) T εr P/PMMA-ZnO [ 78 ]0.975~0.602 [ 78 ]0.83~0.40[ 76 ]1.29~1.54[ 78 ]5.22~5.75[ 78 ]2.9[ 76 ]2.6[ 78 ]0.018~0.06[ 78 ]35%~40%[ 78 ]2.37~1.67[ 78 ]P/PMMA [ 78 ]0.44[ 78 ]0.50~0.35[ 76 ]1.21~1.22[ 78 ]5.85[ 78 ]4.4[ 76 ]3.7[ 76 ]0.01[ 76 ]65%~70%[ 76 ]1.46[ 76 ]Samples α εr Ed (eV) Ea(eV) Samples α La2O3/P-TrFE[ 85 ]0.968~0.996 163 3.15~2.80 10.20~0.15；20.84~0.41 P/Nd2O3[ 88 ]0.90 — Fe3O4/P-HFP[ 87 ]0.90
Table 3. Linear optical and nonlinear optical parameters of PVDF/low-dimensional carbon materials nanocomposites films
View tableView in ArticleTable 3. Linear optical and nonlinear optical parameters of PVDF/low-dimensional carbon materials nanocomposites films
Nonlinear optical parameters Note：P-PVDF, Ed-direct band gap, Ei-indirect optical band gap, n-linear refractive index (λ≈633 nm), n2-nonlinear refractive index (cm2/W×10−10), β-Nonlinear absorption coefficient (two-photon, cm/GW), α-linear absorption coefficient, T-transmittance (λ≈633 nm), χ(3): third-order nonlinear optical susceptibility (10−11 esu), Imχ(3); The imaginary part of third-order nonlinear optical susceptibility (10−11 esu), Pth-optical limiting threshold power (MW/cm2). samples β n2 Pth Imχ(3) |χ(3)| P/RGO[ 99 ]195−400 3.410−6.270 8.4−7.84 6.19−12.95 6.2−12.96 Linear optical parameters samples α n Ed (eV) Ei (eV) T P/RGO[ 100 ]83%−99% 1.8−2.2 5−4.3 4.4−3.2 30%−1% PVDF/CQDs[ 105 ]90%−98.5% 1.22−1.55 2.96−5.00 1.16−4.32 4%−12% samples T P-OH@CQDs/PVA [ 104 ]88%(300−800 nm) PVDF/MWCNT[ 101 ]0（5%CNT）、22%（2%CNT）、48%（1%CNT）
Table 4. Linear optical and nonlinear optical parameters of PVDF/inorganic nonmetallic crystalline materials nanocomposites films
View tableView in ArticleTable 4. Linear optical and nonlinear optical parameters of PVDF/inorganic nonmetallic crystalline materials nanocomposites films
Nonlinear optical parameters Note：P-PVDF, Ed−Direct band gap, Ei−Indirect optical band gap, n-Linear refractive index (λ≈633 nm), n2− nonlinear refractive index (cm2/W×10−12), T-transmittance (λ≈633 nm), χ(3): third-order nonlinear optical susceptibility (10−8esu), α-linear absorption coefficient, Pth−optical limiting threshold power (MW/cm2), Leff: the effective length (μm); Δφ0: the on-axis nonlinear phase shift at the focus; n∞: the long wavelength refractive index, λ0: the average oscillator wavelength, S0: average oscillator strength (1014 m−2), ε∞: high-frequency dielectric constant, N/m*: free carriers ratio (×1057 m−3), ωp: the plasma frequency (1014 s−1), n-Linear refractive index (λ≈633nm), k-the extension coefficient (10−3, 220 nm<λ<380 nm). samples Δφ0 Leff n2 χ3 Pristine PVDF[ 107 ]2.05 24.3 −3.13 −1.7872 P/HNT[ 107 ]0.59−2.2 13.9−20.4 1.24−4.89 1.2075−8.9922 samples n∞ λ0(nm） S0 ε∞ N/m* ωp Li4Ti5O12[ 111 ]2.78 213.62 1.47 8.15 0.472 4.09 P/Li4Ti5O12[ 111 ]3.50−7.32 269.68−291.60 1.55−6.19 15.64−74.83 3.684−35.60 8.25−11.67 Linear optical parameters Samples α Ei (eV) 200 nm<λ<400 nm 400 nm<λ<800 nm BaTiO3[ 110 ]0.99 0.684 3.6 (0.8)PVDF/(0.2)BaTiO3[ 110 ]0.999 0.997 2.9 0.6PVDF/0.4BaTiO3[ 110 ]0.999 0.999 2.4 1PVDF/5BaTiO3[ 109 ]0.9−0.5 0.2−0.5 3.85−3.3
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Yong LIU, Wei-guo LIU, Xiao-ling NIU, Ying-xue HUI, Zhong-hua DAI, Zhi-heng WANG, Wen-hao GUO. Research progress on nonlinear optics of polyvinylidene fluorid and its copolymers films[J]. Chinese Optics, 2022, 15(4): 640
Category: Review
Received: Nov. 2, 2021
Accepted: --
Published Online: Sep. 6, 2022
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