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%.

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.

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.

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.

Multi-mechanism efficiency enhancement in growing Ga-doped ZnO as the transparent conductor on a light-emitting diode.

The combined effects of a few mechanisms for emission efficiency enhancement produced in the overgrowth of the transparent conductor layer of Ga-doped ZnO (GaZnO) on a surface Ag-nanoparticle (NP) coated light-emitting diode (LED), including surface plasmon (SP) coupling, current spreading, light extraction, and contact resistivity reduction, are demonstrated. With a relatively higher GaZnO growth temperature (350 °C), melted Ag NPs can be used as catalyst for forming GaZnO nanoneedles (NNs) through the vapor-liquid-solid growth mode such that light extraction efficiency can be increased. Meanwhile, residual Ag NPs are buried in a simultaneously grown GaZnO layer for inducing SP coupling. With a relatively lower GaZnO growth temperature (250 °C), all the Ag NPs are preserved for generating a stronger SP coupling effect. By using a thin annealed GaZnO interlayer on p-GaN before Ag NP fabrication, the contact resistivity at the GaZnO/p-GaN interface and hence the overall device resistance can be reduced. Although the use of this interlayer blue-shifts the localized surface plasmon resonance peak of the fabricated Ag NPs from the quantum well emission wavelength of the current study (535 nm) such that the SP coupling effect becomes weaker, it is useful for enhancing the SP coupling effect in an LED with a shorter emission wavelength.

Multi-section core-shell InGaN/GaN quantum-well nanorod light-emitting diode array.

The growth of a two-section, core-shell, InGaN/GaN quantum-well (QW) nanorod- (NR-) array light-emitting diode device based on a pulsed growth technique with metalorganic chemical vapor deposition is demonstrated. A two-section n-GaN NR is grown through a tapering process for forming two uniform NR sections of different cross-sectional sizes. The cathodoluminescence (CL), photoluminescence (PL), and electrolumines-cence (EL) characterization results of the two-section NR structure are compared with those of a single-section NR sample, which is prepared under the similar condition to that for the first uniform NR section of the two-section sample. All the CL, PL, and EL spectra of the two-section sample (peaked between 520 and 525 nm) are red-shifted from those of the single-section sample (peaked around 490 nm) by >30 nm in wavelength. Also, the emitted spectral widths of the two-section sample become significantly larger than their counterparts of the single-section sample. The PL spectral full-width at half-maximum increases from ~37 to ~61 nm. Such variations are attributed to the higher indium incorporation in the sidewall QWs of the two-section sample due to the stronger strain relaxation in an NR section of a smaller cross-sectional size and the more constituent atom supply from the larger gap volume between neighboring NRs.

Surface plasmon coupling for suppressing p-GaN absorption and TM-polarized emission in a deep-UV light-emitting diode.

The radiated power enhancement (suppression) of an in- (out-of-) plane-oriented radiating dipole at a desired emission wavelength in the deep-ultraviolet (UV) range when it is coupled with a surface plasmon (SP) resonance mode induced on a nearby Al nanoparticle (NP) is demonstrated. Also, it is found that the enhanced radiated power propagates mainly in the direction from the Al NP toward the dipole. Such SP coupling behaviors can be used for suppressing the transverse-magnetic (TM)-polarized emission, enhancing the transverse-electric-polarized emission, and reducing the UV absorption of the p-GaN layer in an AlGaN-based deep-UV light-emitting diode by embedding a sphere-like Al NP in its p-AlGaN layer.

Thermally induced variations of strain condition and emission behavior in flat and bendable light-emitting diodes on different substrates.

The emission behaviors of four light-emitting diodes (LEDs) of different substrate structures, including a lateral LED grown on sapphire, a vertical LED wafer-bonded onto Si (111), a bendable LED Ag-epoxied onto a flat metal, and another bendable LED Ag-epoxied onto a metal of a curved surface, under different duty cycles of current injection are compared. Their different variation trends of emission behavior with injection duty cycle are attributed to the different thermally-induced strain conditions in the epitaxial layers, which are controlled by their substrate structures, in increasing injection duty cycle or current level. The results of Raman scattering measurements during LED operation show that a stronger tensile strain is generated under heating for reducing the quantum-confined Stark effect and hence increasing emission efficiency when the epitaxial layer is not tightly bonded onto a hard substrate. Such a behavior is particularly stronger when the epitaxial layer is bent.

Growth of Highly Conductive Ga-Doped ZnO Nanoneedles.

The molecular beam epitaxy growth of highly degenerate Ga-doped ZnO (GaZnO) nanoneedles (NNs) based on the vapor-liquid-solid (VLS) growth mode using Ag nanoparticles (NPs) as the growth catalyst is demonstrated. It is shown that when the growth substrate temperature is sufficiently high, a portion of a Ag NP can be melted for serving as the catalyst to precipitate GaZnO on the residual Ag NP and form a GaZnO NN. Record-low turn-on and threshold electric fields in the field emission test of the grown GaZnO NNs are observed. Also, a record-high field enhancement factor in field emission is calibrated. Such superior field emission performances are attributed to a few factors, including (1) the low work function and high conductivity of the grown GaZnO NNs due to highly degenerate Ga doping, (2) the sharp-pointed geometry of the vertically aligned GaZnO NNs, (3) the Ag doping in VLS precipitation of GaZnO for further reducing NN resistivity, and (4) the residual small Ag NP at the NN tip for making the tip even sharper and tip conductivity even higher.

Modulation behaviors of surface plasmon coupled light-emitting diode.

The modulation bandwidths of the light-emitting diodes (LEDs) of different mesa sizes with and without surface plasmon (SP) coupling effect are compared. Due to the significant increase of carrier decay rate, within the size range of LED square-mesa from 60 through 300 micron and the injected current-density range from 139 through 1667 A/cm², the SP coupling can lead to the enhancement of modulation bandwidth by 44-48%, independent of the variations of LED mesa size or injected current level. The enhancement ratios of modulation bandwidth of the samples with SP coupling with respect to those of the samples without SP coupling are lower than the corresponding ratios of the square-root of photoluminescence decay rate due to the increases of their RC time constants (the product of device resistance and capacitance). The increases of the RC time constants in the samples with SP coupling are attributed to the increases of their device resistance levels when the Ag nanoparticles and GaZnO dielectric interlayer are added to the LED surface for effectively inducing SP coupling.

Cu2ZnSnS4 absorption layers with controlled phase purity.

We report the synthesis and characterization of Cu2ZnSnS4 (CZTS) with controlled phase purity. The precursor was first prepared using sequential electrodeposition of Cu, Zn, and Sn in different orders. The Cu/(Sn+Zn) ratio in each stacking order was also varied. The precursor was subjected to annealing at 200°C and sulfurization at 500°C in a 5%-H2S/Ar atmosphere for the formation of CZTS. The phase evolutions during the electrodeposition and annealing stages, and the final phase formation at the sulfurization stage were examined using both x-ray diffractometry and Raman spectroscopy, both of which are shown to be complimentary tools for phase identification. Detailed growth path is therefore reported. We also demonstrate by controlling the stacking order and the Cu/(Sn+Zn) ratio, CZTS with a phase purity as high as 93% is obtained.

Phosphor-free, white-light LED under alternating-current operation.

A light-emitting diode structure, consisting of a p-GaN layer, a CdZnO/ZnO quantum-well (QW) structure, a high-temperature-grown ZnO layer, and a GaZnO layer, is fabricated. Under forward bias, the device effectively emits green-yellow light, from the QW structure, at the rim of device mesa. Under reverse bias, electrons in the valence band of the p-GaN layer move into the conduction band of the GaZnO layer, through a QW-state-assisted tunneling process, to recombine with the injected holes in the GaZnO layer, for emitting yellow-red and shallow ultraviolet light over the entire mesa area. Also, carrier recombination in the p-GaN layer produces blue light. By properly designing the thickness of the high-temperature grown ZnO layer, the emission intensity under forward bias can be controlled such that, under alternating-current operation at 60 Hz, the spatial and spectral mixtures of the emitted lights of complementary colors, under forward and reverse biases, result in white light generation based on persistence of vision.

Dependencies of the emission behavior and quantum well structure of a regularly-patterned, InGaN/GaN quantum-well nanorod array on growth condition.

To achieve green emission from the sidewall non-polar quantum wells (QWs) of a GaN nanorod (NR) light-emitting diode, regularly patterned InGaN/GaN QW NR arrays are grown under various growth conditions of indium supply rate, QW growth temperature, and QW growth time for comparing their emission wavelength variations of the top-face c-plane and sidewall m-plane QWs based on photoluminescence and cathodoluminescence (CL) measurements. Although the variation trends of QW emission wavelength by changing those growth conditions in the NR structure are similar to those in the planar structure, the emission wavelength range of the QWs on an NR is significantly shorter than that in a planar structure under the same growth conditions. Under the growth conditions for a longer NR QW emission wavelength, the difference of emission wavelength between the top-face and sidewall QWs is smaller. Also, the variation range of the emission wavelength from the sidewall QWs over different heights on the sidewall becomes larger. On the other hand, strain state analysis based on transmission electron microscopy is undertaken to calibrate the average QW widths and average indium contents in the two groups of QW of an NR. The variation trends of the calibrated QW widths and indium contents are consistent with those of the CL emission wavelengths from various portions of NR QWs.

Independent variations of applied voltage and injection current for controlling the quantum-confined Stark effect in an InGaN/GaN quantum-well light-emitting diode.

A reverse-biased voltage is applied to either device in the vertical configuration of two light-emitting diodes (LEDs) grown on patterned and flat Si (110) substrates with weak and strong quantum-confined Stark effects (QCSEs), respectively, in the InGaN/GaN quantum wells for independently controlling the applied voltage across and the injection current into the p-i-n junction in the lateral configuration of LED operation. The results show that more carrier supply is needed in the LED of weaker QCSE to produce a carrier screening effect for balancing the potential tilt in increasing the forward-biased voltage, when compared with the LED of stronger QCSE. The small spectral shift range in increasing injection current in the LED of weaker QCSE is attributed not only to the weaker QCSE, but also to its smaller device resistance such that a given increment of applied voltage leads to a larger increment of injection current. From a viewpoint of practical application in LED operation, by applying a reverse-biased voltage in the vertical configuration, the applied voltage and injection current in the lateral configuration can be independently controlled by adjusting the vertical voltage for keeping the emission spectral peak fixed.

Regularly patterned non-polar InGaN/GaN quantum-well nanorod light-emitting diode array.

The growth and process of a regularly patterned nanorod (NR)- light-emitting diode (LED) array with its emission from sidewall non-polar quantum wells (QWs) are demonstrated. A pyramidal un-doped GaN structure is intentionally formed at the NR top for minimizing the current flow through this portion of the NR such that the injection current can be effectively guided to the sidewall m-plane InGaN/GaN QWs for emission excitation by a conformal transparent conductor (GaZnO). The injected current density at a given applied voltage of the NR LED device is similar to that of a planar c-plane or m-plane LED. The blue-shift trend of NR LED output spectrum with increasing injection current is caused by the non-uniform distributions of QW width and indium content along the height on a sidewall. The photoluminescence spectral shift under reversed bias confirms that the emission of the fabricated NR LED comes from non-polar QWs.

Light-emitting device with regularly patterned growth of an InGaN/GaN quantum-well nanorod light-emitting diode array.

A light-emitting device consisting of a two-dimensional regularly patterned InGaN/GaN quantum well (QW) nanorod (NR) light-emitting diode (LED) array is implemented and characterized. The NR p-i-n structure includes n-GaN NR core and essentially conformal p-GaN shell. The active regions include nonpolar sidewall QWs and polar top-face QWs. A conformal layer of transparent GaZnO of low resistivity is deposited onto the NR LED structure for spreading the injection current over the sidewalls. It is found that the blue-shift range of the output spectral peak in increasing injection current is smaller than that of a planar LED of about the same operation wavelength in a similar variation range of injection current density although it is nonzero. The small blue-shift range is attributed to the mixed emission contributions from the nonpolar sidewall QWs and polar top-face QWs.

Geometry and composition comparisons between c-plane disc-like and m-plane core-shell InGaN/GaN quantum wells in a nitride nanorod.

With the nano-imprint lithography and the pulsed growth mode of metalorganic chemical vapor deposition, a regularly-patterned, c-axis nitride nanorod (NR) array of quite uniform geometry with simultaneous depositions of top-face, c-plane disc-like and sidewall, m-plane core-shell InGaN/GaN quantum well (QW) structures is formed. The differences of geometry and composition between these two groups of QW are studied with scanning electron microscopy, cathodoluminescence, and transmission electron microscopy (TEM). In particular, the strain state analysis results in TEM observations provide us with the information about the QW width and composition. It is found that the QW widths are narrower and the indium contents are higher in the sidewall m-plane QWs, when compared with the top-face c-plane QWs. Also, in the sidewall m-plane QWs, the QW width (indium content) decreases (increases) with the height on the sidewall. The observed results can be interpreted with the migration behaviors of the constituent atoms along the NR sidewall from the bottom.

Flocculation behavior of Sphingobium chlorophenolicum in degrading pentachlorophenol at different life stages.

The cell flocculation behavior of degrading pentachlorophenol (PCP) by using Sphingobium chlorophenolicum (Flavobacterium sp., ATCC 39723) is investigated in the present paper. It is found that these Sphingobium cells can efficiently degrade PCP when the concentration of this toxic compound is below 150 ppm. These degradation rates of PCP can be facilitated with the additions of three supplementary carbons: glutamate (4.0 g/L), glucose (3.2 g/L), and cellobiose (3.05 g/L), among which the highest specific growth rate of cells is obtained when glucose is added. More importantly, in these biodegradation experiments described herein, in order to investigate the cell flocculation behavior, the temporal variations of cell size, zeta potential, and stability ratio of the cell suspension are also measured. It is found that, no matter what kind of supplementary carbon source is added, the highest stability ratio of the cell suspension can be always obtained at the end of the exponential growth phase, which can be well explained by using the results of cell size and zeta potential measurements according to the DLVO theory.