Surface plasmon coupling effects on the förster resonance energy transfer from quantum dot into rhodamine 6G.

Rhodamine 6G (R6G) molecules linked CdZnSeS/ZnS green-emitting quantum dots (QDs) are self-assembled onto Ag nanoparticles (NPs) for studying the surface plasmon (SP) coupling effect on the Förster resonance energy transfer (FRET) process from QD into R6G. SP coupling can enhance the emission efficiency of QD such that FRET has to compete with QD emission for transferring energy into R6G. It is found that FRET efficiency is reduced under the SP coupling condition. Although R6G emission efficiency can also be enhanced through SP coupling when it is directly linked onto Ag NP, the enhancement decreases when R6G is linked onto QD and then the QD-R6G complex is self-assembled onto Ag NP. In particular, R6G emission efficiency can be reduced through SP coupling when the number of R6G molecules linked onto a QD is high. A rate-equation model is built for resembling the measured photoluminescence decay profiles and providing us with more detailed explanations for the observed FRET and SP coupling behaviors.

Combined effects of surface plasmon coupling and Förster resonance energy transfer on the light color conversion behaviors of colloidal quantum dots on an InGaN/GaN quantum-well nanodisk structure.

By forming nanodisk (ND) structures on a blue-emitting InGaN/GaN quantum-well (QW) template, the QWs become close to the red-emitting quantum dots (QDs) and Ag nanoparticles (NPs) attached onto the sidewalls of the NDs such that Förster resonance energy transfer (FRET) and surface plasmon (SP) coupling can occur to enhance the efficiency of blue-to-red color conversion. With a larger ND height, more QWs are exposed to open air on the sidewall for more QD/Ag NP attachment through QD self-assembly and Ag NP drop casting such that the FRET and SP coupling effects, and hence the color conversion efficiency can be enhanced. A stronger FRET process leads to a longer QD photoluminescence (PL) decay time and a shorter QW PL decay time. It is shown that SP coupling can enhance the FRET efficiency.

Important role of surface plasmon coupling with the quantum wells in a surface plasmon enhanced color-converting structure of colloidal quantum dots on quantum wells.

To improve the color-conversion efficiency based on a quantum-well (QW) light-emitting diode (LED), a more energy-saving strategy is needed to increase the energy transfer efficiency from the electrical input power of the LED into the emission of over-coated color-converter, not just from LED emission into converted light. In this regard, the efficiency of energy transfer of any mechanism from LED QW into the color-converter is an important issue. By overlaying blue-emitting QW structures and GaN templates with both deposited metal nanoparticles (DMNPs) and color-converting quantum dot (QD) linked synthesized metal nanoparticles (SMNPs) of different localized surface plasmon (LSP) resonance wavelengths for producing multiple surface plasmon (SP) coupling mechanisms with the QW and QD, we study the enhancement variations of their internal quantum efficiencies and photoluminescence decay times. By comparing the QD emission efficiencies between the samples with and without QW, one can observe the advantageous effect of QW coupling with LSP resonances on QD emission efficiency. Also, with the LSP resonance wavelengths of both DMNPs and SMNPs close to the QW emission wavelength for producing strong SP coupling with the QW and hence QD absorption, a higher QD emission or color-conversion efficiency can be obtained.

Emission behaviors of colloidal quantum dots linked onto synthesized metal nanoparticles.

With two different residual surfactants, four different metal nanoparticles (NPs), including two Au NPs and two Ag NPs are synthesized for linking with red-emitting CdZnSeS/ZnS colloidal quantum dots (QDs) to enhance QD emission efficiency. Those metal NPs are first connected with amino polyethylene glycol thiol of different molecular weights to avoid aggregation and make them positively charged. They can attract negatively charged QDs for inducing surface plasmon (SP) coupling such that either QD absorption or emission and hence overall color conversion efficiency can be enhanced. The enhancement of QD emission efficiency is evaluated through the comparison of time-resolved photoluminescence behaviors under different QD linkage conditions. Such results are confirmed by the measurement of the emission quantum efficiency of QD. It is found that by linking QDs onto Ag NPs, the QD emission efficiency is more enhanced, when compared with Au NPs. Also, depending on the synthesis process, the residual surfactant of citrate leads to a relatively large increment in QD emission efficiency, when compared to the surfactant of cetrimonium chloride. A more enhanced QD emission efficiency is caused by a higher QD linkage capability and a stronger SP coupling effect.

Spatial range of the plasmonic Dicke effect in an InGaN/GaN multiple quantum well structure.

The plasmonic Dicke effect means a cooperative emission mechanism of multiple light emitters when they are simultaneously coupled with the same surface plasmon (SP) mode of a metal nanostructure to achieve a higher collective emission efficiency. Here, we compare the enhancements of emission efficiency among a series of SP-coupled InGaN/GaN quantum-well (QW) structures of different QW period numbers to show an emission behavior consistent with the plasmonic Dicke effect. The relative enhancement of overall emission efficiency increases with QW period number until it reaches a critical value, beyond which the enhancement starts to decrease. This critical QW period number corresponds to the effective depth range of the plasmonic Dicke effect in a multiple-QW system. It also represents an optimized QW structure for maximizing the SP coupling effect. Internal quantum efficiency and time-resolved photoluminescence are measured for comparing the enhanced emission efficiencies of blue and green QW structures with different QW period numbers through SP coupling induced by surface Ag nanoparticles.

Simulation study on light color conversion enhancement through surface plasmon coupling.

A theoretical model together with a numerical algorithm of surface plasmon (SP) coupling are built for simulating SP-enhanced light color conversion from a shorter-wavelength radiating dipole (representing a quantum well - QW) into a longer-wavelength one (representing a quantum dot - QD) through QD absorption at the shorter wavelength. An Ag nanoparticle (NP) located between the two dipoles is designed for producing strong SP couplings simultaneously at the two wavelengths. At the QW emission wavelength, SP couplings with the QW and QD dipoles lead to the energy transfer from the QW into the QD and hence the absorption enhancement of the QD. At the QD emission wavelength, SP coupling with the excited QD dipole results in the enhancement of QD emission efficiency. The combination of the SP-induced effects at the two wavelengths leads to the increase of overall color conversion efficiency. The color conversion efficiencies in using Ag NPs of different geometries or SP resonance behaviors for producing different QD absorption and emission enhancement levels are compared.

Color conversion efficiency enhancement of colloidal quantum dot through its linkage with synthesized metal nanoparticle on a blue light-emitting diode.

Four surface-modified and, hence, positively charged metal nanoparticles (NPs) of different localized surface plasmon (LSP) resonance wavelengths are synthesized for linking with negatively charged, red-emitting colloidal CdZnSeS/ZnS quantum dots (QDs) on the top surface of a blue-emitting InGaN/GaN quantum well (QW) light-emitting diode (LED) through electro-static force. The metal NP-QD linkage leads to a short distance between them for producing their strong surface plasmon (SP) coupling, such that QD absorption and emission can be enhanced. Meanwhile, the small p-GaN thickness in the LED results in strong SP coupling between the LSP resonance of metal NP and the QWs of the LED, leading to enhanced QW emission and, hence, stronger QD excitation. All those factors together result in the increase of the color conversion efficiency of the QD.

AlGaN nano-shell structure on a GaN nanorod formed with the pulsed MOCVD growth.

An AlGaN/GaN multi-shell structure on a GaN nanorod (NR) is formed by using the self-catalytic pulsed growth process of metalorganic chemical vapor deposition with Ga and Al/N supplies in the first and second half-cycles, respectively. With Al supply, a thin AlGaN layer is precipitated near the end of a growth cycle to form the AlGaN/GaN structure. Because of the lower chemical potential for GaN nucleation, when compared with AlN, a GaN layer is first deposited in a growth cycle. AlGaN is not precipitated until the AlN nucleation probability becomes higher when the catalytic Ga droplet is almost exhausted. Because the Al adatoms on the NR sidewalls hinder the upward migration of Ga adatoms for contributing to the Ga droplet at the NR top, the size of the Ga droplet decreases along growth cycle leading to the decrease of GaN layer thickness at the top until a steady state is reached. In this process, the slant facet of an NR changes from the (1-102)-plane into (1-101)-plane. To interpret the observed growth behaviors, formulations are derived for theoretically modeling the AlN nucleation probability, NR height increment in each growth cycle, and the time of exhausting the Ga droplet in a cycle.

Control of pore structure in a porous gold nanoparticle for effective cancer cell damage.

For tumor treatment, compared with gold nanoparticles (NPs) of other geometries, a porous gold NP (PGNP) has the advantages of stronger localized surface plasmon resonance (LSPR) due to the pore nanostructures and a larger surface area to link with more drug or photosensitizer (PS) molecules for more effective delivery into cancer cells. Different from the chemical synthesis methods, in this paper we demonstrate the fabrication procedures of PGNP based on shaped Au/Ag deposition on a Si substrate and elucidate the advantageous features. PGNPs fabricated under different conditions, including different deposited Au/Ag content ratios and different alloying annealing temperatures, are compared for optimizing the fabrication condition in terms of LSPR wavelength, PS linkage capability, and cancer cell damage efficiency. It is found that within the feasible fabrication parameter ranges, the Au/Ag content ratio of 3:7 and alloying annealing temperature at 600 °C are the optimized conditions. In comparing with widely used gold NPs of other geometries, PGNP fabricated under the optimized conditions can be used for achieving a significantly higher linked PS molecule number per unit gold weight.

Different surface plasmon coupling behaviors of a surface Al nanoparticle between TE and TM polarizations in a deep-UV light-emitting diode.

The formulations and numerical algorithms of a three-level model for studying the Purcell effect produced by the scattering of an air/AlGaN interface and the surface plasmon (SP) coupling effect induced by a surface Al nanoparticle in a two-polarization emission system to simulate the transverse-electric- (TE-) and transverse-magnetic- (TM-) polarized emissions in an AlxGa1-xN/AlyGa1-yN (y > x) quantum well (QW) are built. In reasonably selected ranges of Al content for an AlGaN QW to emit deep-ultraviolet (UV) light, the enhancement (suppression) of TE- (TM-) polarized emission is mainly caused by the SP-coupling (interface-scattering) effect. Different from a two two-level model, in the three-level model the TE- and TM-polarized emissions compete for electron in the shared upper state, which is used for simulating the conduction band, such that either interface-scattering or SP-coupling effect becomes weaker. In a quite large range of emission wavelength, in which the intrinsic emission is dominated by TM polarization, with the interface-scattering and SP-coupling effects, the TE-polarized emission becomes dominant for enhancing the light extraction efficiency of a deep-UV light-emitting diode.

Coupling of a light-emitting diode with surface plasmon polariton or localized surface plasmon induced on surface silver gratings of different geometries.

A metal grating on top of a light-emitting diode (LED) with a designed grating period for compensating the momentum mismatch can enhance the surface plasmon polariton (SPP) coupling effect with the quantum wells (QWs) to improve LED performance. Here, we demonstrate the experimental results showing that the induced localized surface plasmon (LSP) resonance on such a metal grating can dominate the QW coupling effect for improving LED performance, particularly when grating ridge height is large. The finding is illustrated by fabricating Ag gratings on single-QW, green-emitting LEDs of different p-type thicknesses with varied grating ridge height and width such that the distance between the grating ridge tip and the QW can be controlled. Reflection spectra of the Ag grating structures are measured and simulated to identify the SPP or LSP resonance behaviors at the QW emission wavelength. The measured results of LED performances show that in the LED samples under study, both SPP and LSP couplings can lead to significant enhancements of internal quantum efficiency and electroluminescence intensity. At the designated QW emission wavelength, with a grating period theoretically designed for momentum matching, the LSP coupling effect is stronger, when compared with SPP coupling.

Efficiency enhancement of light color conversion through surface plasmon coupling.

The efficiency enhancement of light color conversion from blue quantum well (QW) emission into red quantum dot (QD) emission through surface plasmon (SP) coupling by coating CdSe/ZnS QDs on the top of an InGaN/GaN QW light-emitting diode (LED) is demonstrated. Ag nanoparticles (NPs) are fabricated within a transparent conductive Ga-doped ZnO interlayer to induce localized surface plasmon (LSP) resonance for simultaneously coupling with the QWs and QDs. Such a coupling process generates three enhancement effects, including QW emission, QD absorption at the QW emission wavelength, and QD emission, leading to an overall enhancement effect of QD emission intensity. An Ag NP geometry for inducing an LSP resonance peak around the middle between the QW and QD emission wavelengths results in the optimized condition for maximizing QD emission enhancement. Internal quantum efficiency and photoluminescence (PL) decay time measurements are performed to show consistent results with LED performance characterizations, even though the QD absorption of PL excitation laser may mix with the SP-induced QD absorption enhancement effect in PL measurement.

Further emission efficiency improvement of a commercial-quality light-emitting diode through surface plasmon coupling.

It is usually believed that surface plasmon (SP) coupling is practically useful only for improving the performance of a light-emitting diode (LED) with a low intrinsic internal quantum efficiency (IQE). In this Letter, we demonstrate that the performance of a commercial-quality blue LED with a high IQE (>80%) can still be significantly improved through SP coupling based on a surface Ag nanoparticle (NP) structure. The performance improvement of such an LED is achieved by increasing the Mg doping concentration in its p-AlGaN electron blocking layer to enhance the hole injection efficiency such that the p-GaN layer thickness can be significantly reduced without sacrificing its electrical property. In this situation, the distance between surface Ag NPs and quantum wells is decreased and hence SP coupling strength is increased. By reducing the distance between the surface Ag NPs and the top quantum well to 66 nm, the IQE can be increased to almost 90% (an ∼11% enhancement) and the electroluminescence intensity can be enhanced by ∼24%.

Exocytosis of gold nanoparticle and photosensitizer from cancer cells and their effects on photodynamic and photothermal processes.

We first illustrate the faster decrease of the photothermal (PT) effect with the delay time of laser treatment, in which the illumination of a 1064 nm laser effectively excites the localized surface plasmon (LSP) resonance of cell-up-taken gold nanoring (NRI) linked with a photosensitizer (PS), when compared with the photodynamic (PD) effect produced by the illumination of a 660 nm laser for effective PS excitation. The measurement results of the metal contents of Au NRI and PS based on inductively coupled plasma mass spectroscopy and the PS fluorescence intensity based on flow cytometry show that the linkage of NRI and PS is rapidly broken for releasing PS through the effect of glutathione in lysosome after cell uptake. Meanwhile, NRI escapes from a cell with a high rate such that the PT effect decays fast while the released PS can stay inside a cell longer for producing a prolonged PD effect. The effective delivery of PS through the linkage with Au NRI for cell uptake and the advantageous effect of LSP resonance at a PS absorption wavelength on the PD process are also demonstrated.

Enhancements of Cancer Cell Damage Efficiencies in Photothermal and Photodynamic Processes through Cell Perforation and Preheating with Surface Plasmon Resonance of Gold Nanoring.

The methods of cell perforation and preheating are used for increasing cell uptake efficiencies of gold nanorings (NRIs), which have the localized surface plasmon resonance wavelength around 1064 nm, and photosensitizer, AlPcS, and hence enhancing the cell damage efficiency through the photothermal (PT) and photodynamic (PD) effects. The perforation and preheating effects are generated by illuminating a defocused 1064-nm femtosecond (fs) laser and a defocused 1064-nm continuous (cw) laser, respectively. Cell damage is produced by illuminating cell samples with a focused 1064-nm cw laser through the PT effect, a focused 1064-nm fs laser through both PT and PD effects, and a focused 660-nm cw laser through the PD effect. Under various conditions with and without cell wash before laser illumination, through either perforation or preheating process, cell uptake and hence cell damage efficiencies can be enhanced. Under our experimental conditions, perforation can be more effective at enhancing cell uptake and damage when compared with preheating.

Method for enhancing the favored transverse-electric-polarized emission of an AlGaN deep-ultraviolet quantum well.

An AlGaN quantum well (QW) structure of a deep-ultraviolet (UV) light-emitting diode (LED) needs to be well designed for controlling its band structure such that the heavy-hole (HH) band edge becomes lower than the split-off (SO) band edge and hence the transverse-electric (TE) polarization dominates the emission for achieving a higher light extraction efficiency. Here, we report the discovery of un-intentionally formed high-Al AlGaN nano-layers right above and below such a QW and their effects on the QW for changing the relative energy levels of the HH and SO bands. The comparison between the results of simulation study and polarization-resolved photoluminescence measurement confirms that the high-Al layers (HALs) represent the key to the observation of the dominating TE-polarized emission. By applying a stress onto a sample along its c-axis to produce a tensile strain in the c-plane for counteracting the HAL effects in changing the band structure, we can further understand the effectiveness of the HALs. The formation of the HALs is attributed to the hydrogen back-etching of Ga atoms during the temperature transition from quantum barrier growth into QW growth and vice versa. The Al filling in the etched vacancies results in the formation of an HAL. This discovery brings us with a simple method for enhancing the favored TE-polarized emission in an AlGaN deep-UV QW LED.

Dependencies of surface plasmon coupling effects on the p-GaN thickness of a thin-p-type light-emitting diode.

The high performance of a light-emitting diode (LED) with the total p-type thickness as small as 38 nm is demonstrated. By increasing the Mg doping concentration in the p-AlGaN electron blocking layer through an Mg pre-flow process, the hole injection efficiency can be significantly enhanced. Based on this technique, the high LED performance can be maintained when the p-type layer thickness is significantly reduced. Then, the surface plasmon coupling effects, including the enhancement of internal quantum efficiency, increase in output intensity, reduction of efficiency droop, and increase of modulation bandwidth, among the thin p-type LED samples of different p-type thicknesses that are compared. These advantageous effects are stronger as the p-type layer becomes thinner. However, the dependencies of these effects on p-type layer thickness are different. With a circular mesa size of 10 µm in radius, through surface plasmon coupling, we achieve the record-high modulation bandwidth of 625.6 MHz among c-plane GaN-based LEDs.

Structure variation of a sidewall quantum well on a GaN nanorod.

A theoretical model for evaluating the height-dependent variations of quantum well (QW) thickness and In concentration in a sidewall QW of a single- or two-section GaN nanorod (NR) is proposed. By reasonably choosing modeling parameter values, the obtained numerical results are quite consistent with the available experimental data. In particular, the model clearly demonstrates the increasing trends of QW thickness and In concentration with height on a sidewall of a single-section NR. Also, it successfully explains the larger QW thickness and higher In concentration in the upper uniform section, when compared with the lower uniform section, in a two-section NR. In this model, three III-group adatom supply sources are considered for sidewall deposition on a single-section NR, including the downward diffusion of adatoms collected on the slant facets at the NR top, the upward diffusion of adatoms collected on the NR base, and the direct adsorption of atoms on the sidewall from the vapor phase. For a two-section NR, the upward and downward diffusions of adatoms collected on the slant facets of the tapering section between the two uniform sections serve as extra adatom supply sources.

Cancer cell death pathways caused by photothermal and photodynamic effects through gold nanoring induced surface plasmon resonance.

The different death pathways of cancer cells under the conditions of the photothermal (PT), effect, photodynamic (PD) effect, and their combination are evaluated. By incubating cells with Au nanoring (NRI) either linked with the photosensitizer, AlPcS, or not, the illumination of a visible continuous laser for exciting the photosensitizer or an infrared femtosecond laser for exciting the localized surface plasmon resonance of Au NRI, leads to various PT and PD conditions for study. Three different staining dyes are used for identifying the cell areas of different damage conditions at different temporal points of observation. The cell death pathways and apoptotic evolution speeds under different cell treatment conditions are evaluated based on the calibration of the threshold laser fluences for causing early-apoptosis (EA) and necrosis (NE) or late-apoptosis (LA). It is found that with the PT effect only, strong cell NE is generated and the transition from EA into LA is faster than that caused by the PD effect when the EA stage is reached within 0.5 h after laser illumination. By combining the PT and PD effects, in the first few hours, the transition speed becomes lower, compared to the case of the PT effect only, when both Au NRIs internalized into cells and adsorbed on cell membrane exist. When the Au NRIs on cell membrane is removed, in the first few hours, the transition speed becomes higher, compared to the case of the PD effect only.

Regularly patterned multi-section GaN nanorod arrays grown with a pulsed growth technique.

The growth of regularly patterned multi-section GaN nanorod (NR) arrays based on a pulsed growth technique with metalorganic chemical vapor deposition is demonstrated. Such an NR with multiple sections of different cross-sectional sizes is formed by tapering a uniform cross section to another through stepwise decreasing of the Ga supply duration to reduce the size of the catalytic Ga droplet. Contrast line structures are observed in either a scanning electron microscopy or transmission electron microscopy image of an NR. Such a contrast line-marker corresponds to a thin Ga-rich layer formed at the beginning of GaN precipitation of a pulsed growth cycle and illustrates the boundary between two successive growth cycles in pulsed growth. By analyzing the geometry variation of the contrast line-markers, the morphology evolution in the growth of a multi-section NR, including a tapering process, can be traced. Such a morphology variation is controlled by the size of the catalytic Ga droplet and its coverage range on the slant facets at the top of an NR. The comparison of emission spectra between single-, two-, and three-section GaN NRs with sidewall InGaN/GaN quantum wells indicates that a multi-section NR can lead to a significantly broader sidewall emission spectrum.