In this paper,the third-order nonlinear optical(NLO)properties of covalent organic framework(COF)materials with conjugated amphoteric ion structure are studied for the first time.A highly ordered crystalline ultrathin...In this paper,the third-order nonlinear optical(NLO)properties of covalent organic framework(COF)materials with conjugated amphoteric ion structure are studied for the first time.A highly ordered crystalline ultrathin films of the ionic COF material PySQ-iCOF was successfully fabricated using a solid-liquid interface method,meanwhile the building units extracted to be independent small molecule,1-PySA,were synthesized for comparative studies.Compared to 1-PySA,PySQ-iCOF possesses not only a larger conjugated system but also exhibits enhanced polarization and charge transfer capabilities.The NLO properties of PySQ-iCOF and the small molecule 1-PySA were investigated using Z-scan technique at a wavelength of 532 nm,revealing the PySQ-iCOF thin film exhibits outstanding NLO performance.Specifically,it demonstrates saturable absorption under nanosecond(ns)pulse laser irradiation(β=9.59×10^(-6) m/W),while exhibiting reverse saturable absorption under femtosecond(fs)pulse conditions(β=6.91×10^(-8) m/W).Furthermore,the PySQ-iCOF film exhibits strong negative refractive nonlinearity,−6×10^(-12) m^(2)/W for ns and -3.8×10^(-13) m^(2)/W for fs,respectively.Transient absorption spectroscopy studies indicate that the pulse-width-dependent nonlinear absorption char-acteristics of the PySQ-iCOF film originate from the generation of triplet excited states.Both nonlinear absorption coefficient and nonlinear refractive index of the PySQ-iCOF film surpass those of most reported organic materials measured under comparable conditions,which provides huge potential in all-optical manipulating and switching at the nanoscale as outstanding NLO materials.展开更多
The third-order nonlinear optical properties of water-soluble Cu Se nanocrystals are studied in the near infrared range of 700-980 nm using a femtosecond pulsed laser by the Z-scan technique. It is observed that the n...The third-order nonlinear optical properties of water-soluble Cu Se nanocrystals are studied in the near infrared range of 700-980 nm using a femtosecond pulsed laser by the Z-scan technique. It is observed that the nonlinear optical response of Cu Se nanocrystals is sensitively dependent on the excitation wavelength and exhibits the enhanced nonlinearity compared with other selenides such as ZnSe and CdSe. The W-shaped Z-scan trace, a mixture of the reversed saturated absorption and saturated absorption, is observed near the plasmon resonance band of Cu Se nanocrystals, which is attributed to the state-filling of free carriers generated by copper vacancies (self-doping effect) of Cu Se nanocrystals as well as the hot carrier thermal effect upon intense femtosecond laser excitation. The large nonlinear optical response and tunable plasmonic band make Cu Se nanocrystals promising materials for applications in ultra-fast all-optical switching devices as well as nonlinear nanosensors.展开更多
The crystal structUre of the title ligand and its copper (Ⅱ) complex was determined bysingle crystal X-ray diffraction. The electrochendcal properties and the third-order nonlinearoptical response of the ligand and i...The crystal structUre of the title ligand and its copper (Ⅱ) complex was determined bysingle crystal X-ray diffraction. The electrochendcal properties and the third-order nonlinearoptical response of the ligand and its copper (Ⅱ) complex were also studied.展开更多
Third-order nonlinear optical(NLO)materials are critical for applications such as optical limiting,all-optical switching,and ultrafast photonic devices,yet their performance remains constrained by the intricate balanc...Third-order nonlinear optical(NLO)materials are critical for applications such as optical limiting,all-optical switching,and ultrafast photonic devices,yet their performance remains constrained by the intricate balance between electronic delocalization and dimensional synergy.This study demonstrates a multidimensional assembly strategy to engineer aromatic synergy in osmium-organic π-clusters,achieving unprecedented enhancement of third-order NLO response.Guided by the concept of metal-organicπ-cluster,we design a prototypical Os3-plane unit as a foundational building block.Through horizontal covalent extension(C-C bonding)and vertical metallophilic stacking(Os─Os interactions),four hierarchical architectures(Os6-prism,Os6-plane,Os9-prism,and Os9-plane)are constructed,each exhibiting amplified NLO properties.Systematic analysis reveals that horizontal assembly enhances in-planeπ-conjugation through quasi-two-dimensionalπ-delocalization,while vertical stacking facilitates interlayerπ-orbital overlap.The novel structure,constructed via amultidimensional assembly strategy,exhibits a narrow HOMO-LUMO gap.The expandedπ-delocalization reduces exciton binding energy,promotes electron delocalization,and consequently yields a stronger third-order NLO response.The Os9-plane exhibits excellent third-order NLO response coefficient(γ=2.93×10^(7) a.u.),which is two orders of magnitude higher than that of the Os3-plane.This work establishes a paradigm of synergistic integration between multidimensional assembly and aromatic π-conjugation for enhanced NLO performance,opening new avenues for optoelectronic material design.展开更多
A novel soluble π-conjugated polymer, poly [（3-acetylpyrrole-2, 5-diyl） p-（N, N-dimethylamino） azobenzylidene] （PAPDMAABE）, was synthesized by condensation of 3-acetylpyrrole with 4-aldehyde-4＇-dimethylaminoaz...A novel soluble π-conjugated polymer, poly [（3-acetylpyrrole-2, 5-diyl） p-（N, N-dimethylamino） azobenzylidene] （PAPDMAABE）, was synthesized by condensation of 3-acetylpyrrole with 4-aldehyde-4＇-dimethylaminoazobenzene （ADMAA）. The chemical structure of PAPDMAABE was characterized by Fourier transform infrared spectroscopy （FTIR）, ^1H-NMR, and UV-Vis-NIR spectra. Transmission electron microscope （TEM） analysis for PAPDMAABE indicates that part of PAPDMAABE is in crystal state, due to the short-range order of the polymer. Thermogravimetric analysis （TGA） curve shows that the polymer has good thermal stability and its decomposition temperature is 248℃. The optical band gap of PAPDMAABE obtained from the optical absorption spectrum is about 1.73 eV. The resonant third-order nonlinear optical property of PAPDMAABE at 532 nm was studied using degenerate four-wave mixing （DFWM） technique. The resonant third-order nonlinear optical susceptibility of the polymer is about 7.48×10^-8 esu.展开更多
The optical wave breaking （OWB） characteristics in terms of the pulse shape, spectrum, and frequency chirp, in the normal dispersion regime of an optical fiber with both the third-order dispersion （TOD） and quinti...The optical wave breaking （OWB） characteristics in terms of the pulse shape, spectrum, and frequency chirp, in the normal dispersion regime of an optical fiber with both the third-order dispersion （TOD） and quintic nonlinearity （QN） are numerically calculated. The results show that the TOD causes the asymmetry of the temporal- and spectral-domain, and the chirp characteristics. The OWB generally appears near the pulse center and at the trailing edge of the pulse, instead of at the two edges of the pulse symmetrically in the case of no TOD. With the increase of distance, the relation of OWB to the TOD near the pulse center increases quickly, leading to the generation of ultra-short pulse trains, while the OWB resulting from the case of no TOD at the trailing edge of the pulse disappears gradually. In addition, the positive （negative） QN enhances （weakens） the chirp amount and the fine structures, thereby inducing the OWB phenomena to appear earlier （later）. Thus, the TOD and the positive （negative） QN are beneficial （detrimental） to the OWB and the generation of ultra-short pulse trains.展开更多
We quantitatively investigate the third-order optical nonlinear response of Co-doped ZnO thin films prepared by magnetron sputtering using the Z-scan method. The two-photon absorption and optical Kerr effect are revea...We quantitatively investigate the third-order optical nonlinear response of Co-doped ZnO thin films prepared by magnetron sputtering using the Z-scan method. The two-photon absorption and optical Kerr effect are revealed to contribute to the third-order nonlinear response of the Co-doped ZnO films. The nonlinear absorption coefficient β is determined to be approximately 8.8 × 10-5 cm/W and the third-order nonlinear susceptibility X（3） is 2.93 × 10-6 esu. The defect-associated energy levels within the band gap are suggested to be responsible for the enhanced nonlinear response observed in Co-doped ZnO films.展开更多
UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing g...UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.展开更多
Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of...Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 10<sup>7</sup> atomic units (10<sup><span style="color:#4F4F4F;font-family:-apple-system, " font-size:14px;white-space:normal;background-color:#ffffff;"="">-</span>33</sup> esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH<sub>3</sub>)<sub>2</sub> or -NHCH<sub>3</sub>) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.展开更多
The study of nonlinear optical responses in the mid-infrared(mid-IR)regime is essential for advancing ultrafast mid-IR laser applications.However,nonlinear optical effects under mid-IR excitation are rarely reported d...The study of nonlinear optical responses in the mid-infrared(mid-IR)regime is essential for advancing ultrafast mid-IR laser applications.However,nonlinear optical effects under mid-IR excitation are rarely reported due to the lack of suitable nonlinear optical materials.The natural van derWaals heterostructure franckeite,known for its narrow bandgap and stability in air,shows great potential for developing mid-IR nonlinear optical devices.We have experimentally demonstrated that layered franckeite exhibits a broadband wavelength-dependent nonlinear optical response in the mid-IR spectral region.Franckeite nanosheets were prepared using a liquid-phase exfoliation method,and their nonlinear optical response was characterized in the spectral range of 3000 nm to 5000 nm.The franckeite nanosheets exhibit broadband wavelengthdependent third-order nonlinearities,with nonlinear absorption and refraction coefficients estimated to be about 10^(-7)cm/W and 10^(-11)cm^(2)/W,respectively.Additionally,a passively Q-switched fluoride fiber laser operating around a wavelength of 2800 nm was achieved,delivering nanosecond pulses with a signal-to-noise ratio of 43.6 dB,based on the nonlinear response of franckeite.These findings indicate that layered franckeite possesses broadband nonlinear optical characteristics in the mid-IR region,potentially enabling new possibilities for mid-IR photonic devices.展开更多
The third-order optical nonlinearity of two sandwich-type phthalocyaninato and porphyrinato europium com- plexes, including double- and triple-deckers （Eu[Pc（OC5H11）8]2, Eu2（Pc）（TPP）2, Pc=phthalocyanine, TPP=5,...The third-order optical nonlinearity of two sandwich-type phthalocyaninato and porphyrinato europium com- plexes, including double- and triple-deckers （Eu[Pc（OC5H11）8]2, Eu2（Pc）（TPP）2, Pc=phthalocyanine, TPP=5, 10, 15, 20- tetraphenylporphyrinate）, was investigated by using the femtosecond time-resolved optical Kerr gate method at 830 nm wavelength. Their second-order hyperpolarizability is estimated to be 0.74× 10^-30esu and 3.0× 10^-3esu respectively. This exhibits an evident enhancement in comparison with 0.47×10^-30esu for one-decker Eu（Pc）（acac） （acac=acetylacetonate）, which is also measured under the same conditions. The enhancement is attributed to the introduction of lanthanide metal to the large π-conjugated system, intermacrocycle interaction and two-photon resonance etc.展开更多
A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] (POPNBE), was synthesized by a five-step reaction. As a result of introducing a long acyl to pyrrole at 3-position, the poly...A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] (POPNBE), was synthesized by a five-step reaction. As a result of introducing a long acyl to pyrrole at 3-position, the polymer can be easily solved in polar solvents and be processed into films. The chemical structures of the intermediates and POPNBE were characterized by FTIR, 1H NMR, and UV-Vis-NIR spectrometries. The absorption band in the range of 400-600 nm in the UV-Vis-NIR spectrum is due to the π-π * band gap transition. The optical band gap of POPNBE obtained from the optical absorption is about 1.72 eV. The resonant third-order nonlinear optical property of POPNBE at 532 nm was studied by using the degenerate four-wave mixing(DFWM) technique. The resonant third-order nonlinear optical susceptibility of POPNBE is about 3.42×10 -8 esu.展开更多
A novel Schiff base ligand (HL) derived from S-methyldithiocabazate and pmethoxylbenzaldehyde was prepared and characterized. The Schiff base ligand acts as a single negatively charged bidentate ligand fondng D-M-D ty...A novel Schiff base ligand (HL) derived from S-methyldithiocabazate and pmethoxylbenzaldehyde was prepared and characterized. The Schiff base ligand acts as a single negatively charged bidentate ligand fondng D-M-D type comPlex (D=donor, M=metal). Single crystal X-ray diffraction analysis of the copper(Ⅱ) complex established that the geometry around Cu (Ⅱ) is square-planar with two equivalent M-N and M-S bonds. The two phenyl rings and the coordinated plane are almost in one plane fotheng an electronic delocalization system. Their thirdorder response was also studied.展开更多
Nonlinear optical （NLO） properties of anatase TiO2 with nanostructures of nanopaxticle （NP）, nanowire （NW） and annealed nanowire （NWA） are studied by open-aperture and closed-aperture Z-scan techniques with a ...Nonlinear optical （NLO） properties of anatase TiO2 with nanostructures of nanopaxticle （NP）, nanowire （NW） and annealed nanowire （NWA） are studied by open-aperture and closed-aperture Z-scan techniques with a fem- tosecond pulsed laser at wavelengths of 532 nm and 780 nm simultaneously. At 532 nm, when increasing excitation intensity, NLO absorption of TiO2 NPs transforms from saturable absorption to reverse-saturable absorption. However, NWs and NWAs exhibit the opposite change. At 780nm, all samples show reverse-saturable absorption, but have different sensitivities to excitation intensity. Due to the larger surface-to-volume ratio of NPs and less defects of NWAs by annealing, nonlinear optical absorption coet^icients follow the order NPs≥ NWs≥ NWAs. The results also show that these shape and annealing effects axe dominant at low excitation intensity, but do not exhibit at the high excitation intensity. The NLO refractive index of NPs shows a positive linear relationship with the excitation intensity, whereas NW and NWAs exhibit a negative linear relationship. The results could provide some foundational guidance to applications of anatase TiO2 in optoelectronic devices or other aspects.展开更多
A dmit2- salt: bis(tetraethylammonium)bis(1,3-dithiole-2-thione-4,5-dithiolato)cadium (CADMIT) was synthesized. The Optical Kerr Effect (OKE) signal of its acetonitrile solution was measured by femtosecond optical Ker...A dmit2- salt: bis(tetraethylammonium)bis(1,3-dithiole-2-thione-4,5-dithiolato)cadium (CADMIT) was synthesized. The Optical Kerr Effect (OKE) signal of its acetonitrile solution was measured by femtosecond optical Kerr gate technique. Using CS2 OKE signal as reference signal measured under identical conditions, the third-order optical nonlinear susceptibility, c(3), of the sample solution was obtained to be about 2.98 x 10-14 esu at the concentration of 1.57 x 10-3 M. The second-order hyperpolarizability of its molecular was estimated to be as large as 1.23 x 10-32 esu. Its response time was about 195 fs, which is believed to be the contribution from the delocalized electrons.展开更多
The third-order optical nonlinearities of [（CH3）4N]Au（dmit）2 （dmit = 4,5-dithiolate-1,3-dithiole-2-thione） at 532 nm and 1064 nm are investigated using the Z-scan technique with pulses of picoseconds duration. T...The third-order optical nonlinearities of [（CH3）4N]Au（dmit）2 （dmit = 4,5-dithiolate-1,3-dithiole-2-thione） at 532 nm and 1064 nm are investigated using the Z-scan technique with pulses of picoseconds duration. The Z-scan spectra reveal a strong nonlinear absorption （reverse saturable absorption） and a negative nonlinear refraction at 532 nm. No nonlinear absorption is observed at 1064 nm. The molecular second-order hyperpolarizability γ for the [（CH3）4N]Au（dmit）2 molecule at 532nm is estimated to be as high as （2.1 ±0.1） × 10^-31 esu, which is nearly three times larger than that at 1064 nm. The mechanism responsible for the difference between the results is analysed. Nonlinear transmission measurements suggest that this material has potential applications in optical limiting.展开更多
Colloidal Au and poly（vinylpyrrolidone） （PVP） composite thin films are fabricated by spin-coating method. Linear optical absorption measurements of the Au/PVP composite films indicate an absorption peak around 530...Colloidal Au and poly（vinylpyrrolidone） （PVP） composite thin films are fabricated by spin-coating method. Linear optical absorption measurements of the Au/PVP composite films indicate an absorption peak around 530 nm due to the surface plasmon resonance of gold nanoparticles. Nonlinear optical properties are studied using standard Z-scan technique, and experimental results show large optical nonlinearities of the Au/PVP composite films. A large value of χ^（3）/α up to 0.56× 10-^10esu·cm is obtained, which is comparable to the best values reported in metal/oxlde composite films.展开更多
A series of glasses with high Bi2O3 content of Bi2O3-B2O3-WO3 ternary system were chosen and prepared .Their densities and linear refractive indices increase with increasing WO3 content. The optical band gaps Eopt of ...A series of glasses with high Bi2O3 content of Bi2O3-B2O3-WO3 ternary system were chosen and prepared .Their densities and linear refractive indices increase with increasing WO3 content. The optical band gaps Eopt of glasses obtained from ultraviolet absorption edges decreases with increase of WO3 content. Z-scan technique was carried out to investigate the third-order nonlinear optical properties of the glasses. It is found that the nonlinear refraction γ increases with decreasing the optical band gap Eopt, since an increase of WO3 content can promote the non-bridging oxygen ion content, and the highest γ value of samples is 1.173×10-14 cm2/W. The results show that these glasses are potential materials in the application of third-order nonlinear optics field.展开更多
The optical nonlinearities of an Ag nanoparticle array are investigated by performing Z-scan measurements at the selected wavelengths （400, 600, 650, and 800 nm）. The nonlinear refraction index in the resonant regi...The optical nonlinearities of an Ag nanoparticle array are investigated by performing Z-scan measurements at the selected wavelengths （400, 600, 650, and 800 nm）. The nonlinear refraction index in the resonant region （around 400 nm） exhibits a significant enhancement by two orders compared with that in the off-resonant region （around 800 nm））, and exhibits an sign alternation of the resonant nonlinear absorption, which results in a negligible nonlinear absorption at a certain excitation intensity. Moreover, a low degree of nonlinear absorption was measured at the edges of the resonant region （600 and 650 nm）, which is attributed to the competition of the saturated absorption and the two-photon absorption processes.展开更多
The fully oxidized state of polyaniline (PANI), pernigraniline (PN), was synthesized by oxidation of the emeraldine base form of PAM dissolved in NMP solvent with m-chloroperoxybenzoic acid. The resulted PN was charac...The fully oxidized state of polyaniline (PANI), pernigraniline (PN), was synthesized by oxidation of the emeraldine base form of PAM dissolved in NMP solvent with m-chloroperoxybenzoic acid. The resulted PN was characterized by FTIR and UV-Visible spectra. The third-order nonlinear optical properties of PN in concentrated sulfuric acid (PN/H2SO4) were measured by a degenerated four wave mixing (DFWM) method. The results obtained suggest that the soliton-pair intermediate state associated with the degenerated state does not play a major role in the third order nonlinear optical properties of PANI.展开更多
基金the National Natural Science Foundation of China(22171076)Jing Li at the Technical Institute of Physics and Chemistry,Chinese Academy of Sciences(CAS),for his measurement of dynamic processes.
文摘In this paper,the third-order nonlinear optical(NLO)properties of covalent organic framework(COF)materials with conjugated amphoteric ion structure are studied for the first time.A highly ordered crystalline ultrathin films of the ionic COF material PySQ-iCOF was successfully fabricated using a solid-liquid interface method,meanwhile the building units extracted to be independent small molecule,1-PySA,were synthesized for comparative studies.Compared to 1-PySA,PySQ-iCOF possesses not only a larger conjugated system but also exhibits enhanced polarization and charge transfer capabilities.The NLO properties of PySQ-iCOF and the small molecule 1-PySA were investigated using Z-scan technique at a wavelength of 532 nm,revealing the PySQ-iCOF thin film exhibits outstanding NLO performance.Specifically,it demonstrates saturable absorption under nanosecond(ns)pulse laser irradiation(β=9.59×10^(-6) m/W),while exhibiting reverse saturable absorption under femtosecond(fs)pulse conditions(β=6.91×10^(-8) m/W).Furthermore,the PySQ-iCOF film exhibits strong negative refractive nonlinearity,−6×10^(-12) m^(2)/W for ns and -3.8×10^(-13) m^(2)/W for fs,respectively.Transient absorption spectroscopy studies indicate that the pulse-width-dependent nonlinear absorption char-acteristics of the PySQ-iCOF film originate from the generation of triplet excited states.Both nonlinear absorption coefficient and nonlinear refractive index of the PySQ-iCOF film surpass those of most reported organic materials measured under comparable conditions,which provides huge potential in all-optical manipulating and switching at the nanoscale as outstanding NLO materials.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11274302,11474276 and 11674240
文摘The third-order nonlinear optical properties of water-soluble Cu Se nanocrystals are studied in the near infrared range of 700-980 nm using a femtosecond pulsed laser by the Z-scan technique. It is observed that the nonlinear optical response of Cu Se nanocrystals is sensitively dependent on the excitation wavelength and exhibits the enhanced nonlinearity compared with other selenides such as ZnSe and CdSe. The W-shaped Z-scan trace, a mixture of the reversed saturated absorption and saturated absorption, is observed near the plasmon resonance band of Cu Se nanocrystals, which is attributed to the state-filling of free carriers generated by copper vacancies (self-doping effect) of Cu Se nanocrystals as well as the hot carrier thermal effect upon intense femtosecond laser excitation. The large nonlinear optical response and tunable plasmonic band make Cu Se nanocrystals promising materials for applications in ultra-fast all-optical switching devices as well as nonlinear nanosensors.
文摘The crystal structUre of the title ligand and its copper (Ⅱ) complex was determined bysingle crystal X-ray diffraction. The electrochendcal properties and the third-order nonlinearoptical response of the ligand and its copper (Ⅱ) complex were also studied.
基金supported by the National Natural Science Foundation of China(22571298,U23A2095,and 92161105)the Postdoctoral Fellowship Program(Grade C)of China Postdoctoral Science Foundation under Grant Number GZC20241834.
文摘Third-order nonlinear optical(NLO)materials are critical for applications such as optical limiting,all-optical switching,and ultrafast photonic devices,yet their performance remains constrained by the intricate balance between electronic delocalization and dimensional synergy.This study demonstrates a multidimensional assembly strategy to engineer aromatic synergy in osmium-organic π-clusters,achieving unprecedented enhancement of third-order NLO response.Guided by the concept of metal-organicπ-cluster,we design a prototypical Os3-plane unit as a foundational building block.Through horizontal covalent extension(C-C bonding)and vertical metallophilic stacking(Os─Os interactions),four hierarchical architectures(Os6-prism,Os6-plane,Os9-prism,and Os9-plane)are constructed,each exhibiting amplified NLO properties.Systematic analysis reveals that horizontal assembly enhances in-planeπ-conjugation through quasi-two-dimensionalπ-delocalization,while vertical stacking facilitates interlayerπ-orbital overlap.The novel structure,constructed via amultidimensional assembly strategy,exhibits a narrow HOMO-LUMO gap.The expandedπ-delocalization reduces exciton binding energy,promotes electron delocalization,and consequently yields a stronger third-order NLO response.The Os9-plane exhibits excellent third-order NLO response coefficient(γ=2.93×10^(7) a.u.),which is two orders of magnitude higher than that of the Os3-plane.This work establishes a paradigm of synergistic integration between multidimensional assembly and aromatic π-conjugation for enhanced NLO performance,opening new avenues for optoelectronic material design.
基金the National Natural Science Foundation of China for financial support of this work(No.60277002).
文摘A novel soluble π-conjugated polymer, poly [（3-acetylpyrrole-2, 5-diyl） p-（N, N-dimethylamino） azobenzylidene] （PAPDMAABE）, was synthesized by condensation of 3-acetylpyrrole with 4-aldehyde-4＇-dimethylaminoazobenzene （ADMAA）. The chemical structure of PAPDMAABE was characterized by Fourier transform infrared spectroscopy （FTIR）, ^1H-NMR, and UV-Vis-NIR spectra. Transmission electron microscope （TEM） analysis for PAPDMAABE indicates that part of PAPDMAABE is in crystal state, due to the short-range order of the polymer. Thermogravimetric analysis （TGA） curve shows that the polymer has good thermal stability and its decomposition temperature is 248℃. The optical band gap of PAPDMAABE obtained from the optical absorption spectrum is about 1.73 eV. The resonant third-order nonlinear optical property of PAPDMAABE at 532 nm was studied using degenerate four-wave mixing （DFWM） technique. The resonant third-order nonlinear optical susceptibility of the polymer is about 7.48×10^-8 esu.
基金supported by the Postdoctoral Fund of China(Grant No.2011M501402)the National Natural Science Foundation of China(Grant No.61275039)+2 种基金the 973 Program of China(Grant No.2012CB315702)the Key Project of the Chinese Ministry of Education,China(Grant No.210186)the Major Project of the Natural Science Foundation supported by the Educational Department of Sichuan Province,China(Grant Nos.13ZA0081 and 12ZB019)
文摘The optical wave breaking （OWB） characteristics in terms of the pulse shape, spectrum, and frequency chirp, in the normal dispersion regime of an optical fiber with both the third-order dispersion （TOD） and quintic nonlinearity （QN） are numerically calculated. The results show that the TOD causes the asymmetry of the temporal- and spectral-domain, and the chirp characteristics. The OWB generally appears near the pulse center and at the trailing edge of the pulse, instead of at the two edges of the pulse symmetrically in the case of no TOD. With the increase of distance, the relation of OWB to the TOD near the pulse center increases quickly, leading to the generation of ultra-short pulse trains, while the OWB resulting from the case of no TOD at the trailing edge of the pulse disappears gradually. In addition, the positive （negative） QN enhances （weakens） the chirp amount and the fine structures, thereby inducing the OWB phenomena to appear earlier （later）. Thus, the TOD and the positive （negative） QN are beneficial （detrimental） to the OWB and the generation of ultra-short pulse trains.
基金Supported by National Basic Research Program of China under Grant Nos 2011CB922200 and 2013CB922303
文摘We quantitatively investigate the third-order optical nonlinear response of Co-doped ZnO thin films prepared by magnetron sputtering using the Z-scan method. The two-photon absorption and optical Kerr effect are revealed to contribute to the third-order nonlinear response of the Co-doped ZnO films. The nonlinear absorption coefficient β is determined to be approximately 8.8 × 10-5 cm/W and the third-order nonlinear susceptibility X（3） is 2.93 × 10-6 esu. The defect-associated energy levels within the band gap are suggested to be responsible for the enhanced nonlinear response observed in Co-doped ZnO films.
基金supported by the National Natural Science Foundation of China(21172161)
文摘UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.
文摘Third-order nonlinear optical (NLO) materials have broad application prospects in high-density data storage, optical computer, modern laser technology, and other high-tech industries. The structures and frequencies of Dinaphtho[2,3-b:2’,3’-d]thiophene-5,7,12,13-tetraone (DNTTRA) and its 36 derivatives containing azobenzene were calculated by using density functional theory B3LYP and M06-2X methods at 6-311++g(d, p) level, respectively. Besides, the atomic charges of natural bond orbitals (NBO) were analyzed. The frontier orbitals and electron absorption spectra of A-G5 molecule were calculated by TD-DFT (TD-B3LYP/6-311++g(d, p) and TD-M06-2X/6-311++g(d, p)). The NLO properties were calculated by effective finite field FF method and self-compiled program. The results show that 36 molecules of these six series are D-π-A-π-D structures. The third-order NLO coefficients γ (second-order hyperpolarizability) of the D series molecules are the largest among the six series, reaching 10<sup>7</sup> atomic units (10<sup><span style="color:#4F4F4F;font-family:-apple-system, " font-size:14px;white-space:normal;background-color:#ffffff;"="">-</span>33</sup> esu) of order of magnitude, showing good third-order NLO properties. Last, the third-order NLO properties of the azobenzene ring can be improved by introducing strong electron donor groups (e.g. -N(CH<sub>3</sub>)<sub>2</sub> or -NHCH<sub>3</sub>) in the azobenzene ring, so that the third-order NLO materials with good performance can be obtained.
基金supported by the National Natural Science Foundation of China(Grant No.61975055)the Natural Science Foundation of Hunan Province,China(Grant No.2023JJ30165)+1 种基金the Natural Science Foundation of Shandong Province,China(Grant No.ZR2022QF005)the Doctoral Fund of University of Heze(Grant No.XY22BS14).
文摘The study of nonlinear optical responses in the mid-infrared(mid-IR)regime is essential for advancing ultrafast mid-IR laser applications.However,nonlinear optical effects under mid-IR excitation are rarely reported due to the lack of suitable nonlinear optical materials.The natural van derWaals heterostructure franckeite,known for its narrow bandgap and stability in air,shows great potential for developing mid-IR nonlinear optical devices.We have experimentally demonstrated that layered franckeite exhibits a broadband wavelength-dependent nonlinear optical response in the mid-IR spectral region.Franckeite nanosheets were prepared using a liquid-phase exfoliation method,and their nonlinear optical response was characterized in the spectral range of 3000 nm to 5000 nm.The franckeite nanosheets exhibit broadband wavelengthdependent third-order nonlinearities,with nonlinear absorption and refraction coefficients estimated to be about 10^(-7)cm/W and 10^(-11)cm^(2)/W,respectively.Additionally,a passively Q-switched fluoride fiber laser operating around a wavelength of 2800 nm was achieved,delivering nanosecond pulses with a signal-to-noise ratio of 43.6 dB,based on the nonlinear response of franckeite.These findings indicate that layered franckeite possesses broadband nonlinear optical characteristics in the mid-IR region,potentially enabling new possibilities for mid-IR photonic devices.
基金Project supported by the National Key Research Program of China （Grant No TG1999075209） and the National Natural Science Foundation of China （Grant Nos 10434020, 90206003 and 60378012）.
文摘The third-order optical nonlinearity of two sandwich-type phthalocyaninato and porphyrinato europium com- plexes, including double- and triple-deckers （Eu[Pc（OC5H11）8]2, Eu2（Pc）（TPP）2, Pc=phthalocyanine, TPP=5, 10, 15, 20- tetraphenylporphyrinate）, was investigated by using the femtosecond time-resolved optical Kerr gate method at 830 nm wavelength. Their second-order hyperpolarizability is estimated to be 0.74× 10^-30esu and 3.0× 10^-3esu respectively. This exhibits an evident enhancement in comparison with 0.47×10^-30esu for one-decker Eu（Pc）（acac） （acac=acetylacetonate）, which is also measured under the same conditions. The enhancement is attributed to the introduction of lanthanide metal to the large π-conjugated system, intermacrocycle interaction and two-photon resonance etc.
文摘A novel soluble π-conjugated polymer, poly[(3-octanoylpyrrole-2,5-diyl)-p-nitrobenzylidene] (POPNBE), was synthesized by a five-step reaction. As a result of introducing a long acyl to pyrrole at 3-position, the polymer can be easily solved in polar solvents and be processed into films. The chemical structures of the intermediates and POPNBE were characterized by FTIR, 1H NMR, and UV-Vis-NIR spectrometries. The absorption band in the range of 400-600 nm in the UV-Vis-NIR spectrum is due to the π-π * band gap transition. The optical band gap of POPNBE obtained from the optical absorption is about 1.72 eV. The resonant third-order nonlinear optical property of POPNBE at 532 nm was studied by using the degenerate four-wave mixing(DFWM) technique. The resonant third-order nonlinear optical susceptibility of POPNBE is about 3.42×10 -8 esu.
文摘A novel Schiff base ligand (HL) derived from S-methyldithiocabazate and pmethoxylbenzaldehyde was prepared and characterized. The Schiff base ligand acts as a single negatively charged bidentate ligand fondng D-M-D type comPlex (D=donor, M=metal). Single crystal X-ray diffraction analysis of the copper(Ⅱ) complex established that the geometry around Cu (Ⅱ) is square-planar with two equivalent M-N and M-S bonds. The two phenyl rings and the coordinated plane are almost in one plane fotheng an electronic delocalization system. Their thirdorder response was also studied.
基金Supported by the National Natural Science Foundation of China under Grant Nos 11404410 and 11504105
文摘Nonlinear optical （NLO） properties of anatase TiO2 with nanostructures of nanopaxticle （NP）, nanowire （NW） and annealed nanowire （NWA） are studied by open-aperture and closed-aperture Z-scan techniques with a fem- tosecond pulsed laser at wavelengths of 532 nm and 780 nm simultaneously. At 532 nm, when increasing excitation intensity, NLO absorption of TiO2 NPs transforms from saturable absorption to reverse-saturable absorption. However, NWs and NWAs exhibit the opposite change. At 780nm, all samples show reverse-saturable absorption, but have different sensitivities to excitation intensity. Due to the larger surface-to-volume ratio of NPs and less defects of NWAs by annealing, nonlinear optical absorption coet^icients follow the order NPs≥ NWs≥ NWAs. The results also show that these shape and annealing effects axe dominant at low excitation intensity, but do not exhibit at the high excitation intensity. The NLO refractive index of NPs shows a positive linear relationship with the excitation intensity, whereas NW and NWAs exhibit a negative linear relationship. The results could provide some foundational guidance to applications of anatase TiO2 in optoelectronic devices or other aspects.
文摘A dmit2- salt: bis(tetraethylammonium)bis(1,3-dithiole-2-thione-4,5-dithiolato)cadium (CADMIT) was synthesized. The Optical Kerr Effect (OKE) signal of its acetonitrile solution was measured by femtosecond optical Kerr gate technique. Using CS2 OKE signal as reference signal measured under identical conditions, the third-order optical nonlinear susceptibility, c(3), of the sample solution was obtained to be about 2.98 x 10-14 esu at the concentration of 1.57 x 10-3 M. The second-order hyperpolarizability of its molecular was estimated to be as large as 1.23 x 10-32 esu. Its response time was about 195 fs, which is believed to be the contribution from the delocalized electrons.
基金Project supported by the National Natural Science Foundation of China （Grant Nos 60377016 and 60476020） and the National High Technology Development Program of China （Grant No 2002AA313070）.
文摘The third-order optical nonlinearities of [（CH3）4N]Au（dmit）2 （dmit = 4,5-dithiolate-1,3-dithiole-2-thione） at 532 nm and 1064 nm are investigated using the Z-scan technique with pulses of picoseconds duration. The Z-scan spectra reveal a strong nonlinear absorption （reverse saturable absorption） and a negative nonlinear refraction at 532 nm. No nonlinear absorption is observed at 1064 nm. The molecular second-order hyperpolarizability γ for the [（CH3）4N]Au（dmit）2 molecule at 532nm is estimated to be as high as （2.1 ±0.1） × 10^-31 esu, which is nearly three times larger than that at 1064 nm. The mechanism responsible for the difference between the results is analysed. Nonlinear transmission measurements suggest that this material has potential applications in optical limiting.
文摘Colloidal Au and poly（vinylpyrrolidone） （PVP） composite thin films are fabricated by spin-coating method. Linear optical absorption measurements of the Au/PVP composite films indicate an absorption peak around 530 nm due to the surface plasmon resonance of gold nanoparticles. Nonlinear optical properties are studied using standard Z-scan technique, and experimental results show large optical nonlinearities of the Au/PVP composite films. A large value of χ^（3）/α up to 0.56× 10-^10esu·cm is obtained, which is comparable to the best values reported in metal/oxlde composite films.
基金Funded by the National Natural Science Foundation of China (No.60677015)the Science and Technology Department of Zhejiang Province (No.2007C21122)the Natural Science Foundation of Ningbo (No.2006A610020)
文摘A series of glasses with high Bi2O3 content of Bi2O3-B2O3-WO3 ternary system were chosen and prepared .Their densities and linear refractive indices increase with increasing WO3 content. The optical band gaps Eopt of glasses obtained from ultraviolet absorption edges decreases with increase of WO3 content. Z-scan technique was carried out to investigate the third-order nonlinear optical properties of the glasses. It is found that the nonlinear refraction γ increases with decreasing the optical band gap Eopt, since an increase of WO3 content can promote the non-bridging oxygen ion content, and the highest γ value of samples is 1.173×10-14 cm2/W. The results show that these glasses are potential materials in the application of third-order nonlinear optics field.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 11005088 and 11047145)the Science and Technology Project of Henan Province, China (Grant Nos. 102300410241 and 112300410021)the Scientific Research Foundation of Education Department of Henan Province, China(Grant No. 2011B140018)
文摘The optical nonlinearities of an Ag nanoparticle array are investigated by performing Z-scan measurements at the selected wavelengths （400, 600, 650, and 800 nm）. The nonlinear refraction index in the resonant region （around 400 nm） exhibits a significant enhancement by two orders compared with that in the off-resonant region （around 800 nm））, and exhibits an sign alternation of the resonant nonlinear absorption, which results in a negligible nonlinear absorption at a certain excitation intensity. Moreover, a low degree of nonlinear absorption was measured at the edges of the resonant region （600 and 650 nm）, which is attributed to the competition of the saturated absorption and the two-photon absorption processes.
基金This work was partly supported by NNSFC,Chinese Academy of Sciences and Director Foundation of the Institute of Chemistry,Academia Sinica
文摘The fully oxidized state of polyaniline (PANI), pernigraniline (PN), was synthesized by oxidation of the emeraldine base form of PAM dissolved in NMP solvent with m-chloroperoxybenzoic acid. The resulted PN was characterized by FTIR and UV-Visible spectra. The third-order nonlinear optical properties of PN in concentrated sulfuric acid (PN/H2SO4) were measured by a degenerated four wave mixing (DFWM) method. The results obtained suggest that the soliton-pair intermediate state associated with the degenerated state does not play a major role in the third order nonlinear optical properties of PANI.
