Gu et al Nanoscale Research Letters 2011, 6:199 http://www.nanoscalereslett.com/content/6/1/199 NANO REVIEW Open Access Light-emitting diodes enhanced by localized surface plasmon resonance Xuefeng Gu1,2, Teng Qiu1*, Wenjun Zhang3, Paul K Chu3 Abstract Light-emitting diodes [LEDs] are of particular interest recently as their performance is approaching fluorescent/ incandescent tubes Moreover, their energy-saving property is attracting many researchers because of the huge energy crisis we are facing Among all methods intending to enhance the efficiency and intensity of a conventional LED, localized surface plasmon resonance is a promising way The mechanism is based on the energy coupling effect between the emitted photons from the semiconductor and metallic nanoparticles fabricated by nanotechnology In this review, we describe the mechanism of this coupling effect and summarize the common fabrication techniques The prospect, including the potential to replace fluorescent/incandescent lighting devices as well as applications to flat panel displays and optoelectronics, and future challenges with regard to the design of metallic nanostructures and fabrication techniques are discussed Introduction Light-emitting diodes [LEDs] have attracted much scientific and commercial interest since the realization of a practical LED device with emission frequencies in the visible region of the electromagnetic spectrum [1] Since then, research activities have been focusing on how to produce economical LEDs with the desired colors as well as white light sources [2] The strong demand has also driven materials technology, and new emitting materials and configurations have been proposed to enhance the performance For example, the use of a polymer instead of small molecules opens the door to flexible, large-area, and stable organic LEDs [OLEDs] [3] In the past 15 years, low-dimensional emitting devices incorporating quantum dots [QDs] and quantum wells [QWs] have been extensively investigated in order to achieve the desirable emission color and enhance device efficiency [4-10] However, LEDs suffer from inherently low efficiency due to the sometimes low internal quantum efficiency [IQE] and difficulty extracting the generated photons out of the device Although the use of electro-phosphorescent materials with proper management of both singlet and triplet excitons has brought IQE in * Correspondence: tqiu@seu.edu.cn Department of Physics, Southeast University, Nanjing 211189, People’s Republic of China Full list of author information is available at the end of the article OLEDs to almost unity [11-13], that of LEDs with inorganic emitting materials such as GaN, CdSe, and Si QDs or QWs remains unsatisfactory because nonradiative electron/hole pair recombination dominates Another channel of energy loss is total internal reflection at the emitter/air interface because of the typically high refractive index of the emitting materials Several methods have been proposed to enhance the overall efficiency of LEDs, and they include substrate modification and incorporation of scattering medium, micro-lenses, nanogratings, corrugated microstructures, photonic crystals, and so on [14-17] In spite of some efficiency enhancement, spectral changes and angle-dependent colors associated with the substrate modification techniques, the high precision needed to produce nanogratings and the high cost of photonic crystals are still challenging issues plaguing commercial applications Surface plasmon polaritons [SPPs] were first exploited to enhance the efficiency of InGaN QWbased LEDs by Okamoto et al in 2004 [18] Known as Purcell effect, when the resonant frequency of the silver SPPs overlaps the emission frequency of the InGaN QWs, the energy coupled to the SPP mode is significantly increased and thus the IQE is enhanced [19] Scattered by the rough silver film, the energy coupled to the SPP mode can be recovered as free space photons In their work, the enhanced IQE h*int © 2011 Gu et al; licensee Springer This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited Gu et al Nanoscale Research Letters 2011, 6:199 http://www.nanoscalereslett.com/content/6/1/199 Page of 12 is observed to increase 6.8 times with Ag coating, leading to a very desirable Purcell factor Fp ≈ − ηint − η∗int (1) where hint represents the original IQE Figure shows the wavelength-dependent h*int, Purcell factor, and the emission spectrum of their sample It is clear that greater enhancement can be obtained at shorter wavelengths (~440 nm) However, this wavelength does not perfectly overlap the GaN/InGaN emission peak, leaving space for better enhancement In fact, the SPP resonant energy must be in the vicinity of the emission energy in order to achieve the best enhancement This rule has since been verified by other experiments [20-23] Hence, only a small subset of LEDs can be enhanced via SPP/ emitter coupling because the SPP resonant frequency of a metal film cannot be easily tuned Another challenge is that the metal film is typically opaque, thereby making light extraction from the metal side of the device difficult It has been shown that light can be effectively extracted from the metal side by exploiting the surface plasmon cross-coupling effect, but incorporation of the appropriately scaled nanostructures is necessary [24,25] In comparison with the aforementioned technology, localized surface plasmon [LSP] offers a unique advantage in tunability; that is, the optical properties resulting from LSP can be easily varied by altering the type, size, geometry, and interparticle distance of the metallic nanoparticles [NPs] The other advantage of LSP- enhanced LEDs over SPP ones is less dissipation since the induced wave is locally confined and cannot propagate along the metal surface Furthermore, the metal layer is no longer opaque, making emission from the metal side possible, and so metallic NPs instead of a continuous metal film can be used to enhance the performance of LEDs Figure schematically shows the story of this review: incorporation of noble metallic nanoparticles into LEDs leads to a new class of highly efficient solid-state light sources (top row); in order to get considerable enhancement, the extinction band of LSP must be close to the band-gap emission energy of the LED (middle row); and this new technology has found its applications in general lighting, flat panel displays, and ultrafast optoelectronic chips (bottom row) Recent improvements combined with the low cost and easy fabrication process make localized surface plasmon resonance [LSPR]-enhanced LEDs very attractive commercially Mechanism Pioneering experimental results have confirmed the importance of overlapping between the LSPR energy and emission energy, and some of them are presented in Table The type, shape, height, and density of the NPs determine the degree of enhancement In order to explore the cause and mechanism, experiments have been conducted carefully, often excluding other possible factors which may contribute to the enhancement such as reflection from the metallic NPs, emission from the NPs themselves, increased absorption of light in photoluminescence [PL] enhancement, and quenching of defects emission However, although it is generally agreed to stem from resonant coupling between the semiconductor band-gap emission and LSP generated by the metallic NPs, the exact mechanism is still debatable In this section, we discuss two mechanisms that have been suggested to explain the resonant-coupling enhancing effect, namely, increase of IQE via emitter/plasmon coupling and increase of light extraction efficiency [LEE] by means of out-coupling of the generated photons Enhancement of IQE Figure Enhanced emission efficiency, Purcell factor, and PL spectrum of the sample These are shown as red dashed line, blue solid line, and black dotted line, respectively Nearly 100% emission efficiency can be obtained at around 440 nm; however, this does not perfectly match the emission peak Reproduced from [18] Copyright Nature Publishing Group, 2004 The local electric field and magnitude of the extinction spectrum are significantly enhanced at the LSPR frequency [26] This effect has been broadly studied and utilized in many fields such as surface-enhanced Raman spectroscopy, solar cells, and biosensors [27-30] With regard to the efficiency improvement rendered by LSPR, it is supposed that the enhanced electric field interacts with the emitting materials, increasing the spontaneous emission rate and consequently enhancing the IQE of the device This assumption can be partly verified by experiments showing that the radiative decay rate and Gu et al Nanoscale Research Letters 2011, 6:199 http://www.nanoscalereslett.com/content/6/1/199 Page of 12 Figure Noble metallic NP layer deposited on or within a conventional LED to enhance efficiency of device This new class of LEDs can be used in various compelling applications spontaneous emission rate of the light emitters can be improved in the presence of silver SPPs since the enhanced local electric field at the LSPR frequency plays a similar role as the evanescent wave induced by SPPs [31,32] An example of the IQE enhancement in LSPRenhanced LEDs is the GaN-based LED developed by Kown et al [33] The optical output power increases by 32.2% at an input current of 100 mA, and the timeresolved PL measurement shows that the PL decay time in the presence of Ag NPs is significantly reduced As a result, the spontaneous emission rate and the IQE are better Table Summary of representative experimental results showing the important relationship between the LSPR energy and emission energy in order to attain the best enhancement Emitting materials and configurations Peak emission energy (nm) InGaN/GaN multiple QW 463 Metal used Optical properties of metal layer Enhancement References Ag Transmittance exhibits absorption from 396 to 455 nm 32.2% with an 100-mA current Kwon et al [33] Fujiki et al [34] Alq3 thin film 525 Au A peak in absorption at 510 nm 20-fold InGaN/GaN QW 550 Ag A dip in transmission at about 550 nm 150% in peak intensity with a Yeh et al [36] 20-mA current InGaN/GaN QW 465 Au A dip in transmission in 511 nm 180% with a 20-mA current Sung et al [37] Organic poly 575 Ag Large absorption from 330 to 500 nm Sixfold Qiu et al [41] Si QD 600 Ag A peak in absorption at 535 nm Reaches maximum at 530 nm Kim et al [42] ZnMgO alloys 357 Pt Extinction band near 350 nm Sixfold You et al [44] ZnO film Si-on-insulator 380 1,140 Ag Ag Extinction band near 370 nm A dip in transmission at about 520 nm Threefold 2.5-fold in peak intensity Cheng et al [45] Pillai et al [48] CdSe/ZnS nanocrystals 580 Au A peak in absorption at about 600 nm 30-fold Pompa et al [53] Si QD 775 Ag A dip in transmission at 710 nm Twofold, with the peak blue shifts Biteen et al [54] GaN 440 Ag A dip in transmission at about 440 nm Twofold Mak et al [62] Gu et al Nanoscale Research Letters 2011, 6:199 http://www.nanoscalereslett.com/content/6/1/199 Page of 12 The effect of varying the distance between the active emitting region and metallic NPs on the overall device efficiency enhancement also reveals that the larger local field plays an important role Coupling and enhancing vanish as the distance is increased above a certain threshold, and the distance cannot be too small or too large If it is too small, the non-radiative quenching process dominates and most of the energy is dissipated accordingly On the contrary, if the distance is too large, the coupling effect vanishes since only the electron/hole pairs near the metallic NPs can effectively couple to increase the IQE Fujiki et al [34] have introduced a copper phthalocyanine hole transport layer in their LED structure as a spacer to avoid non-radiative quenching In order to retain the effect, a 20-nm-thick film is used and smaller enhancement is observed if the thickness is larger The experiment provides direct evidence of the role played by the higher local electric field in the IQE enhancement effect A model proposed by Khurgin et al [35] further confirms the importance of the higher local field and demonstrates that the IQE can indeed be enhanced by LSPR via the electric field/emitter interaction However, the use of NPs to enhance the IQE of LEDs is effective only when the original IQE is very low (