Jialei Liu

Synthesis of novel nonlinear optical chromophore to achieve ultrahigh electro-optic activity

A new diene-conjugated chromophore WJ1 was synthesized with high yield of 36% through an H-bonding induced Vilsmeier reaction. By simple guest-host doping, a large electro-optic efficiency of 337 pm V(-1) at 1310 nm and excellent temporal stability at 75 °C have been achieved in poled films of WJ1/APC with a high loading density of 40 wt%.

Recent advances in polymer electro-optic modulators

In this brief review, nonlinear optical (NLO) chromophores widely used in electro-optic (EO) devices are summarized according to their EO coefficients. The advances of EO modulators based on organic materials in high bandwidth and low half wave voltages (Vπ) are discussed. The review is mainly devoted to the following aspects: (1) verification of high frequency operation and reduction of Vπ for all polymer waveguide EO modulators; (2) structures and advantages of sol–gel waveguide EO modulators; (3) principles and developments of silicon–organic hybrid (SOH) EO modulators. All the considerations are illustrated by the architecture of the devices and the used physical and chemical principles are explained in detail. Further means of improvement of their parameters are indicated.

Enhanced electro-optic coefficient (r33) in nonlinear optical chromospheres with novel donor structure

The synthesis and characterization of new push-pull chromophores A and B, from tricyanofuran (TCF) electron withdrawing and various electron donating moieties, have been demonstrated to compare the roles of donors in electro-optic performance. The crystal structure analyses of the intramolecular hydrogen bond, molecular coplanarity and π–π interactions reveal that A forms cross-stacking, while B forms antiparallel dimer packing, which indicates weaker intermolecular interactions of A than B. Also, the photophysical properties, solvatochromic behavior and Density Functional Theory (DFT) calculations were also investigated. In electro-optic activities, the doped films-A containing chromophore A display an r33 value of 36 pm V−1 at the saturated doping concentration of 40 wt%, while the doped films-B containing B show a maximum r33 value of 16 pm V−1 at the saturated concentration of 25 wt%. High loading density and high r33 value indicate that the chromophore A with julolidinyl-based donor can efficiently reduce the interchromophore electrostatic interactions and enhance the macroscopic optical nonlinearity, showing that chromophore A with julolidinyl-based donor has promising applications in nonlinear optical (NLO) materials.

Synthesis and optical nonlinear property of Y-type chromophores based on double-donor structures with excellent electro-optic activity

New Y-type chromophores FTC-yh1 and FTC-yh2 containing bis(N,N-diethyl)aniline as a novel electron-donor, thiophene as a π-conjugated bridge and tricyanofuran (TCF) as an acceptor have been synthesized and systematically investigated in this paper. Density functional theory (DFT) was used to calculate the HOMO–LUMO energy gaps and first-order hyperpolarizability (β) of these chromophores. These chromophores showed better thermal stability with their decomposition temperatures all above 240 °C. Most importantly, the high molecular hyperpolarizability of these chromophores can be effectively translated into large electro-optic (EO) coefficients (r33) in poled polymers. The doped film-A containing 25 wt% chromophore FTC-yh1 displayed a value of 149 pm V−1 at 1310 nm, and the doped film-B containing FTC-yh2 showed a value of 143 pm V−1 at the concentration of 25 wt%. These values are almost four times higher than the EO activity of usually reported traditional single (N,N-diethyl)aniline nonlinear optical (NLO) chromophores FTC. High r33 values indicated that the double donors of the bis(N,N-diethyl)aniline unit can efficiently improve the electron-donating ability and reduce intermolecular electrostatic interactions, thus enhancing the macroscopic EO activity. These properties, together with the good solubility, suggest the potential use of the new chromophores as advanced material devices.

Synthesis of novel nonlinear optical chromophores: achieving excellent electro-optic activity by introducing benzene derivative isolation groups into the bridge

Three novel second order nonlinear optical (NLO) chromophores based on julolidinyl donors and tricyanofuran (TCF) acceptors linked together via modified polyene π-conjugation with rigid benzene derivative steric hindrance groups (chromophore CL1 and CL2) or unmodified polyene π-conjugation (chromophores CL) moieties as the bridges have been synthesized in good overall yields and systematically characterized. Density functional theory (DFT) was used to calculate the HOMO–LUMO energy gaps and first-order hyperpolarizability (β) of these chromophores. Besides, to determine the redox properties of these chromophores, cyclic voltammetry (CV) experiments were performed. Compared with CL, after introducing benzene derivative steric hindrance groups into the bridge, chromophores CL1 and CL2 had good thermal stabilities with high thermal decomposition temperatures which were 32 °C and 24 °C higher than chromophore CL, respectively. Most importantly, the introduction of rigid steric hindrance groups can effectively reduce dipole–dipole interactions to translate their relatively small β values into bulk high EO activities. By doping chromophores CL, CL1 and CL2 with a high loading of 45 wt% in APC, EO coefficients (r33) of up to 121, 197 and 202 pm V−1 at 1310 nm can be achieved, respectively. The r33 values of new chromophores CL1 and CL2 were about 1.6 times of chromophore CL. The high r33 value, good thermal stability and high yield suggest the potential use of the new chromophores in an nonlinear optical area.

Comparison of second-order nonlinear optical chromophores with D–π–A, D–A–π–A and D–D–π–A architectures: diverse NLO effects and interesting optical behavior

Four second-order nonlinear optical chromophores with D–π–A, D–A–π–A and D–D–π–A architectures have been synthesized and systematically characterized. Chromophores A and C have been synthesized with an additional acceptor (–CN) or donor group (thiophene) on the π bridge, termed the D–A–π–A and D–D–π–A configurations. D–π–A structural chromophores B and D were chosen as reference compounds for comparison. The results show that incorporation of the –CN group could increase poling efficiency possibly due to reduced intermolecular dipole–dipole interactions which results in comparable r33 values (48 pm V−1). An r33 value of 45 pm V−1 was obtained for the film C/APC suggesting significant site isolation. Compared with the D–π–A structural chromophores B and D, chromophores A and C demonstrated similar or enhanced NLO effects and better optical transparency.

Plasma density behavior with new graphite limiters in the Hefei Tokamak-7

A new set of actively cooled toroidal double-ring graphite limiters has been developed in the Hefei Tokamak-7 (HT-7) [X. Gao et al., Phys. Plasmas 7, 2933 (2000)] for long pulse operation. The extension of operational region and density behavior with graphite (C) limiters have been studied in this paper. Extended high-density region at the high plasma current low-qa was obtained. The density profile with the C limiter was studied to compare with the previous molybdenum (Mo) limiter. The critical density of multifaceted asymmetric radiation from the edge (MARFE) onset is observed in the region of Zeff1∕2fGW=0.9∼1.2, where fGW=n¯e∕nGW. (Here n¯e is the maximum line average electron density and nGW is the Greenwald density.) Under the same injected power, the critical density of MARFE onset with the new C limiter is much higher than the previous Mo limiter.

Pressure-induced crystallization in a bulk amorphous Zr-based alloy

Crystallization of multi-component on amorphous Zr-based alloy (Zr41Ti14Cu12.5Ni9Be22.5Cl) is investigated at different pressures and temperatures. We have previously found that the primary crystallization temperature decreases with increasing pressure below 6 GPa, and the crystallization follows a different process under high pressure when compared to that at ambient pressure. In this work, pressure-induced crystallization is observed by in situ X-ray diffraction (XRD) using synchrotron radiation in a diamond anvil cell at similar to25 GPa and room temperature. This phase transition between amorphous and crystalline is reversible and the crystallized sample returns to the amorphous state during decompression. The mechanism for pressure-induced crystallization is discussed. We suggest that the crystallized phases under high pressure are interstitial solid solution phases formed from the amorphous matrix without long-range atomic rearrangements

Auxiliary donor for tetrahydroquinoline-containing nonlinear optical chromophores: enhanced electro-optical activity and thermal stability

A series of chromophores FTC, L1 and L2 have been synthesized based on three different types of electron donors, including diethylaminophenyl, tetrahydroquinolinyl and N-(4-dimethylaminophenyl) tetrahydroquinolinyl groups respectively, with the same thiophene bridges and strong tricyanovinyldihydrofuran (TCF) acceptors. In particular, the donor part of the chromophore L2 was modified with an additional donor N-(4-dimethylaminophenyl) substituent, resulting in enhanced thermal stability and electro-optic activity. Cyclic voltammetry measurements showed that chromophore L2 had a smaller energy gap than chromophore L1 due to the additional donor. Moreover, density functional theory calculations suggested that the molecular quadratic hyperpolarizability (μβ) value of chromophore L2 is 29% and 44% larger than that of chromophores L1 and FTC, respectively. The doped film containing the chromophore L2 showed an r33 value of 100 pm V−1 at the concentration of 25 wt% which is much higher than the EO activity of the chromophore L1 (57 pm V−1) and two times higher than that of the traditional chromophore FTC (39 pm V−1).

Synthesis and optical properties of new fluorinated second-order nonlinear optical copolymers: an attempt toward the balance between solubility and long-term alignment stability

A new fluorinated co-polyarylate (P) was synthesized by interfacial polymerization of 1,1-bis(4-hydroxyphenyl)-1-phenyl-2,2,2-trifluoroethane (BPAPF) and diphenolic acid (DPA) with isophthaloyl chloride (IPC). P1–P3, containing different concentrations of tricyanofuran (TCF) accepter chromophores, were obtained by the esterification reaction between P and chromophore 1 catalyst by DCC and DPTS. The obtained co-polyarylates were characterized and evaluated by UV-Vis, 1H NMR, FT-IR, GPC, DSC and TGA. All the co-polyarylates P1–P3 exhibited excellent thermal stability, film forming ability and good electro-optic (EO) activity. The largest r33 value of the copolymers is 52 pm V−1 at the wavelength of 1310 nm, when the concentration of chromophore 1 is 18 wt%.