Yaxin Zhai

Crafting Core/Graded Shell-Shell Quantum Dots with Suppressed Re-absorption and Tunable Stokes Shift as High Optical Gain Materials.

The key to utilizing quantum dots (QDs) as lasing media is to effectively reduce non-radiative processes, such as Auger recombination and surface trapping. A robust strategy to craft a set of CdSe/Cd(1-x)Zn(x)Se(1-y)S(y)/ZnS core/graded shell-shell QDs with suppressed re-absorption, reduced Auger recombination rate, and tunable Stokes shift is presented. In sharp contrast to conventional CdSe/ZnS QDs, which have a large energy level mismatch between CdSe and ZnS and thus show strong re-absorption and a constrained Stokes shift, the as-synthesized CdSe/Cd(1-x)Zn(x)Se(1-y)S(y)/ZnS QDs exhibited the suppressed re-absorption of CdSe core and tunable Stokes shift as a direct consequence of the delocalization of the electron wavefunction over the entire QD. Such Stokes shift-engineered QDs with suppressed re-absorption may represent an important class of building blocks for use in lasers, light emitting diodes, solar concentrators, and parity-time symmetry materials and devices.

Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies

Transient and CW spectroscopies unravel giant Rashba splitting in 2D hybrid perovskite multilayers. Two-dimensional (2D) layered hybrid organic-inorganic halide perovskite semiconductors form natural “multiple quantum wells” that have strong spin-orbit coupling due to the heavy elements in their building blocks. This may lead to “Rashba splitting” close to the extrema in the electron bands. We have used a plethora of ultrafast transient, nonlinear optical spectroscopies and theoretical calculations to study the primary (excitons) and long-lived (free carriers) photoexcitations in thin films of 2D perovskite, namely, (C6H5C2H4NH3)2PbI4. The density functional theory calculation shows the occurrence of Rashba splitting in the plane perpendicular to the 2D barrier. From the electroabsorption spectrum and photoinduced absorption spectra from excitons and free carriers, we obtain a giant Rashba splitting in this compound, with energy splitting of (40 ± 5) meV and Rashba parameter of (1.6 ± 0.1) eV·Å, which are among the highest Rashba splitting size parameters reported so far. This finding shows that 2D hybrid perovskites have great promise for potential applications in spintronics.

Singlet fission of hot excitons in π-conjugated polymers

We used steady-state photoinduced absorption (PA), excitation dependence (EXPA(ω)) spectrum of the triplet exciton PA band, and its magneto-PA (MPA(B)) response to investigate singlet fission (SF) of hot excitons into two separated triplet excitons, in two luminescent and non-luminescent π-conjugated polymers. From the high energy step in the triplet EXPA(ω) spectrum of the luminescent polymer poly(dioctyloxy)phenylenevinylene (DOO-PPV) films, we identified a hot-exciton SF (HE-SF) process having threshold energy at E≈2ET (=2.8 eV, where ET is the energy of the lowest lying triplet exciton), which is about 0.8 eV above the lowest singlet exciton energy. The HE-SF process was confirmed by the triplet MPA(B) response for excitation at E>2ET, which shows typical SF response. This process is missing in DOO-PPV solution, showing that it is predominantly interchain in nature. By contrast, the triplet EXPA(ω) spectrum in the non-luminescent polymer polydiacetylene (PDA) is flat with an onset at E=Eg (≈2.25 eV). From this, we infer that intrachain SF that involves a triplet–triplet pair state, also known as the ‘dark’ 2Ag exciton, dominates the triplet photogeneration in PDA polymer as Eg>2ET. The intrachain SF process was also identified from the MPA(B) response of the triplet PA band in PDA. Our work shows that the SF process in π-conjugated polymers is a much more general process than thought previously.

Laser action and photoexcitations dynamics in PbI 2 films

We have grown high quality PbI2 films by thermal evaporation. We obtained in these films two amplified spontaneous emission (ASE) lines around ~2.23 eV at relatively low pump excitation threshold using 10 ns pulsed laser, along with a broad photoluminescence (PL) band that results from trapped electron and hole (e-h) pairs in shallow traps. We discuss the two ASE lines as due to the anisotropic PbI2 crystal structure. In addition, we also studied the ultrafast transient response of photoexcitations in the PbI2 films using a broadband pump-probe correlation spectroscopy in the broad spectral range of 0.3-2.4 eV with 150 fs time resolution. The transient photomodulation spectrum is dominated by two photoinduced absorption bands and a stimulated emission band that agrees with the obtained ASE band. We ascribed the low threshold laser action in PbI2 films as due to the e-h confinement in ‘quantum wells’ like structures formed between the main 2H-PbI2 crystalline and other polytypes with lower optical gap.

Enhanced emissive and lasing characteristics of nano-crystalline MAPbBr3 films grown via anti-solvent precipitation

Control of the nano-scale crystal size distribution in films of organic-inorganic lead-tri-bromide perovskites is achieved through a recently reported solution-based, anti-solvent treatment method [H. Cho et al., Science 350, 1222 (2015)]. The treated films are shown to be high quality, optically smooth with excellent emissive and optical gain properties including higher photoluminescence yield and reduced threshold for laser action. The improved lasing is shown to originate from a synergistic combination of a reduction in waveguide losses and a decrease in the non-radiative decay rate of the excited state population, compared to untreated films. The net gain is increased by a factor of two upon anti-solvent treatment and reaches a respectable value of ≈300 cm−1.

Magnetic properties of periodically organized cobalt frameworks

Periodically organized magnetic cobalt frameworks have been fabricated by a combination of colloidal self-assembly and electrochemical deposition. The ordered cobalt frameworks have a closed-packed face-centered-cubic inverse opal structure and are fabricated as micrometer-thick films. The size and density of the cobalt crystallites that compose the cobalt frameworks can be modified by a thermal annealing step following the electrodeposition. Comparison of the magnetic properties (studied by magneto-optical Kerr effect (MOKE) spectroscopy) of as-deposited and annealed samples reveals strong impact of the annealing process. Fitting the obtained MOKE response to a modified Langevin model reveals optimum values of coercivity, pinning site density, and inter-domain coupling for samples that are thermally annealed at 440 °C.

Colour selective control of terahertz radiation using two-dimensional hybrid organic inorganic lead-trihalide perovskites

Controlling and modulating terahertz signals is of fundamental importance to allow systems level applications. We demonstrate an innovative approach for controlling the propagation properties of terahertz (THz) radiation, through use of both the excitation optical wavelength (colour) and intensity. We accomplish this using two-dimensional (2D) layered hybrid trihalide perovskites that are deposited onto silicon substrates. The absorption properties of these materials in the visible range can be tuned by changing the number of inorganic atomic layers in between the organic cation layers. Optical absorption in 2D perovskites occurs over a broad spectral range above the bandgap, resulting in free carrier generation, as well as over a narrow spectral range near the bandedge due to exciton formation. We find that only the latter contribution gives rise to photo-induced THz absorption. By patterning multiple 2D perovskites with different optical absorption properties onto a single device, we demonstrate both colour selective modulation and focusing of THz radiation. These findings open new directions for creating active THz devices.All-optical approaches to modulate signals are of wide interest. Here the authors demonstrate the use of two-dimensional perovskites on silicon for optically controlling the propagation and attenuation of terahertz radiation in the visible by changing the number of atomic layers.

Magnetic field effect in organic light emitting diodes based on donor-acceptor exciplexes showing thermally activated delayed fluorescence

A new type of organic light-emitting diode (OLED) has emerged that shows enhanced operational stability and large internal quantum efficiency approaching 100%, which is based on exciplexes in donor-acceptor (D-A) blends having thermally activated delayed fluorescence (TADF) when doped with fluorescent emitters. We have investigated magnetoelectroluminescence (MEL) and magneto-conductivity in such TADF-based OLEDs, as well as magnetophotoluminescence (MPL) in thin films based on the OLEDs active layers, with various fluorescence emitters. We found that both MEL and MPL responses are thermally activated with substantially lower activation energy compared to that in the pristine undoped D-A exciplex host blend. In addition, both MPL and MEL steeply decrease with the emitters’ concentration. This indicates the existence of a loss mechanism, whereby the triplet charge-transfer state in the D-A exciplex host blend may directly decay to the lowest, non-emissive triplet state of the additive fluorescent emitter molecules.

Optical and magnetic probes of hot singlet exciton fission in π-conjugated polymers for organic photovoltaic applications

We used steady state and picosecond transient photoinduced absorption (PA), excitation dependence (EXPA(ω)) spectrum of the triplet exciton PA band, and its magneto-PA (MPA(B)) response to investigate singlet fission (SF) of hot-excitons into two separated triplet excitons in luminescent π-conjugated polymers. From the high energy step in the triplet EXPA(ω) spectrum of poly(dioctyloxy)-phenylenevinylene (DOO-PPV) films, we identified a hot-exciton SF (HE-SF) process having threshold energy at E≈2ET (=2.8 eV, where ET is the energy of the lowest lying triplet exciton), which is about 0.8 eV above the lowest singlet exciton energy. The picosecond transient PA with 3.1 eV pump excitation shows that in DOO-PPV film a triplet exciton is generated at time, t<500 ps. However the ultrafast triplet generation is missing in DOO-PPV solution, indicating that the HE-SF is predominantly interchain in nature. The HE-SF process was confirmed by the triplet MPA(B) response for excitation at E>2ET, which shows a typical SF response. Our work shows that the SF process in π-conjugated polymers is a much more general process than thought previously.