Improved electroluminescence from silicon nitride light emitting devices by localized surface plasmons

Improved electroluminescence from silicon nitride light emitting devices by localized surface plasmons Dongsheng Li, * Feng Wang, Changrui Ren, and Deren Yang State Key Laboratory of Silicon Materials and Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, China *mselds@zju.edu.cn Abstract: Enhanced electroluminescence (EL) from SiN x light emitting devices (LEDs) with an ITO/SiO 2 /SiN x /Ag/p/p + -Si/Al structure was observed. Comparing to SiN x LEDs without Ag islands layer, those with Ag islands layer could conduct a higher injection current and extract light more efficiently due to the roughness of Ag islands film. Moreover, the localized surface plasmons induced by Ag islands enhanced the radiative efficiency of LEDs, resulting in the EL enhancement of ~14. By the combination enhancement on light extraction efficiency, radiative efficiency, and current-injection efficiency, the external quantum efficiency of EL from SiN x LEDs was improved by at least one order of magnitude. 2012 Optical Society of America OCIS codes: (230.2090) Electro-optical devices; (310.6860) Thin films, optical properties; (250.5403) Plasmonics. References and links 1. L. Pavesi, L. Dal Negro, C. Mazzoleni, G. Franzò, and F. Priolo, Optical gain in silicon nanocrystals, Nature 408(6811), 440 444 (2000). 2. M. Wang, D. Yang, D. Li, Z. Yuan, and D. Que, Correlation between luminescence and structural evolution of Si-rich silicon oxide film annealed at different temperatures, J. Appl. Phys. 101(10), 103504 (2007). 3. M. Wang, J. Huang, Z. Yuan, A. Anopchenko, D. Li, D. Yang, and L. Pavesi, Light emission properties and mechanism of low-temperature prepared amorphous SiN x films. II. Defect states electroluminescence, J. Appl. Phys. 104(8), 083505 (2008). 4. F. Iacona, D. Pacifici, A. Irrera, M. Miritello, G. Franzò, F. Priolo, D. Sanfilippo, G. Di Stefano, and P. G. Fallica, Electroluminescence at 1.54 µm in Er-doped Si nanocluster-based devices, Appl. Phys. Lett. 81(17), 3242 3244 (2002). 5. D. Li, X. Zhang, L. Jin, and D. Yang, Structure and luminescence evolution of annealed Europium-doped silicon oxides films, Opt. Express 18(26), 27191 27196 (2010). 6. Y. Q. Wang, Y. G. Wang, L. Cao, and Z. X. Cao, High-efficiency visible photoluminescence from amorphous silicon nanoparticles embedded in silicon nitride, Appl. Phys. Lett. 83(17), 3474 3476 (2003). 7. B.-H. Kim, C.-H. Cho, S.-J. Park, N.-M. Park, and G. Y. Sung, Ni/Au contact to silicon quantum dot lightemitting diodes for the enhancement of carrier injection and light extraction efficiency, Appl. Phys. Lett. 89(6), 063509 (2006). 8. T.-C. Tsai, L.-Z. Yu, and C.-T. Lee, Electroluminescence emission of crystalline silicon nanoclusters grown at a low temperature, Nanotechnology 18(27), 275707 (2007). 9. B.-H. Kim, R. F. Davis, C.-H. Cho, and S.-J. Park, Effect of injection current density on electroluminescence in silicon quantum dot light-emitting diodes, Appl. Phys. Lett. 95(15), 153103 (2009). 10. B.-H. Kim, C.-H. Cho, J.-S. Mun, M.-K. Kwon, T.-Y. Park, J. S. Kim, C. C. Byeon, J. Lee, and S.-J. Park, Enhancement of the external quantum efficiency of a silicon quantum dot light-emitting diode by localized surface plasmons, Adv. Mater. 20(16), 3100 3104 (2008). 11. F. Wang, D. Li, D. Yang, and D. Que, Enhancement of light-extraction efficiency of SiN x light emitting devices through a rough Ag island film, Appl. Phys. Lett. 100(3), 031113 (2012). 12. Z. T. Kang, B. K. Wagner, J. Parrish, D. Schiff, and C. J. Summers, Enhancement of white luminescence from SiN x films by surface roughening, Nanotechnology 18(41), 415709 (2007). 13. B.-H. Kim, R. F. Davis, C.-H. Cho, and S.-J. Park, Enhanced performance of silicon quantum dot light-emitting diodes grown on nanoroughened silicon substrate, Appl. Phys. Lett. 95(7), 073113 (2009). 14. D. Li, J. Huang, and D. Yang, Enhanced electroluminescence of silicon-rich silicon nitride light-emitting devices by NH 3 plasma and annealing treatment, Physica E 41(6), 920 922 (2009). (C) 2012 OSA 1 June 2012 / Vol. 2, No. 6 / OPTICAL MATERIALS EXPRESS 872

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2. Experimental section SiN x LEDs with an ITO/SiO 2 /SiN x /Ag/p/p + -Si/Al multilayer structure, as shown in Fig. 1(a), were prepared for EL investigation. A boron doped p-type epitaxial silicon layer on a heavily doped p-type (100) silicon wafer was employed as a substrate, where the thickness and resistivity of the epitaxial layer were 11.4 µm and 2.5 Ω cm, respectively. Ag was deposited on the substrate by an electron beam evaporation (EBE) system (the original thickness of Ag layer was ~10 nm read from a film thickness monitor), and then annealed in argon atmosphere at 400 C for 120 seconds to form islands film, as shown in Fig. 1(b). According to incomplete statistics, the average dimension of Ag nanoparticles was ~70 nm in diameter, as shown in Fig. 1(c), where most of them were in the range of 50-80 nm. The average surface distance (d) between Ag nanoparticles and the surface coverage (η SC ) of them were about 26 nm and ~55.0%, respectively. The SiN x film of about 60 nm was deposited on the Ag islands film by plasma-enhanced chemical vapor deposition (PECVD). The reactant gas sources were nitrogen-diluted 10% silane and ammonia gas. And the flow rate of the nitrogen-diluted 10% silane and ammonia were maintained at 100 sccm and 30 sccm, respectively. The plasma power, growth temperature, and deposition pressure were fixed at 20 W, 300 C, and 16 Pa, respectively. After the SiN x deposition, a SiO 2 layer of 25 nm was evaporated on the SiN x film by EBE system. At last, an indium tin oxide (ITO) electrode of about 100 nm was sputtered on the SiO 2 through a mask to define the device area. An Al layer of 150 nm was evaporated on the back of silicon substrate. We also prepared the reference devices without Ag islands film using the same process. Due to the roughness of underneath Ag islands layer, the sequent deposited SiN x and ITO layers also became rough, as shown in Figs. 1(d) and 1(e). The area root-mean-square roughness (R rms ) of ITO electrode for the devices with Ag islands film was estimated in the range of 5-10 nm from the measurement of atomic force microscope (AFM, not shown here). However, the SiN x and ITO layers (as shown in Fig. 1(f)) for SiN x LEDs without Ag islands layer were flat (R rms <2 nm) comparing with the one with Ag islands layer. To measure the absorbance of a SiN x /Ag multilayer, we also prepared a SiN x /Ag/quartz structure film under the same deposited condition with the LEDs. Fig. 1. (a) The schematic of the devices we fabricated. (b) Scanning electron microscopy (SEM) image of Ag islands film. (c) Dimension distribution of Ag nanoparticles. SEM images of (d) SiN x film deposited on Ag islands film, (e) ITO electrode of the device with Ag islands layer, and (f) ITO electrode of the reference device. The EL and PL spectra of SiN x -based LEDs were recorded by an Acton SpectraPro-2500i monochrometer coupled to a photomultiplier tube driven by a dc power source and a 325 nm He-Cd laser, respectively. The absorption of films was measured by a HITACHI U-4100 spectrophotometer. The current-voltage (I-V) characteristics of devices were measured by a Keithley 4200 SCS semiconductor parameter analyzer. (C) 2012 OSA 1 June 2012 / Vol. 2, No. 6 / OPTICAL MATERIALS EXPRESS 874

3. Results and discussion Fig. 2. (a) EL spectra and (b) EL enhancement factor (I Ag/I R) of both SiN x LEDs with and without Ag islands layer, where I Ag and I R stand for the EL intensities of devices with and without Ag, respectively. (c) Integrated EL and (d) efficiency curves as a function of the applied voltage for both SiN x LEDs. Both SiN x LEDs with and without Ag islands film emit a broad band EL from 400 to 750 nm. EL spectra of both SiN x LEDs were measured as a function of the injection current, as shown in Fig. 2(a). It is obviously that the intensity of EL from both SiN x LEDs increases gradually with the injection current. However, the SiN x LEDs with Ag islands layer can inject current higher than 40 ma, while the reference SiN x LEDs are broken down if the injection current is higher than 25 ma. Under the same injection current, the EL intensity of SiN x LEDs with Ag islands film is always higher than that of the reference devices. Moreover, the EL spectrum shape and main peak position of the two SiN x LEDs are different. The reference LEDs contain one band located at about 600 nm, while the EL spectra of SiN x LEDs with Ag islands layer emit at main band peak located at ~550 nm. In order to show clearly, the EL intensity of SiN x LEDs without Ag islands film was multiplied twice. The blueshift of EL main peak by the addition of Ag islands film may result from its improved carrier injection, as carriers, especially for holes, can be injected into a higher energy level along the band tails of SiN x due to the enhanced local electrical fields surrounding Ag nanoparticles [22,23]. This blueshift of EL peak was also observed by increasing the injected current in our early works [3]. The EL enhancement factor (I Ag /I R ) is shown as a function of the injection current in Fig. 2(b). I Ag and I R are the EL intensities from SiN x LEDs with and without Ag islands layer, respectively. Due to the weak signal/noise ratio of EL from the reference devices, the spectrum shape of EL enhancement factor is not smooth but quite rough. The EL enhancement factor of ~14 is observed at ~550 nm at a current of 25 ma, as shown in Fig. 2(b). As higher intensity current can be injected, the output intensity of SiN x LEDs with Ag islands layer is expected to be improved much more. Figure 2(c) gives the integrated EL intensity of both SiN x LEDs as a function of the applied voltage. No EL signals can be detected under a low voltage for the reference devices. The turn-on voltage decreases significantly by the addition of Ag islands film. Besides, the output intensity of SiN x LEDs with Ag islands layer increases much faster than that of the reference devices. At the applied voltage of 6 V, the integrated EL intensity of SiN x LEDs with Ag islands layer is about 480 times stronger than that of the reference devices. Considering the difference of the injection currents, the ratio of the integrated EL intensity to the injection current as a function of the applied voltage for both LEDs is shown (C) 2012 OSA 1 June 2012 / Vol. 2, No. 6 / OPTICAL MATERIALS EXPRESS 875

in Fig. 2(d). The external quantum efficiency (η EQE ) is defined by the ratio of the light output power (P out ) to the injected current (I) [10,11], and the integrated EL intensity is in direct proportion to the P out. Consequently, the EQE can be compared quantitatively by the comparation of the ratio of the integrated EL intensity to the injection current under a same voltage or current. Clearly, the external quantum efficiency of SiN x LEDs with Ag islands layer is enhanced much more compared with the reference devices. And the external quantum efficiency of SiN x LEDs with Ag layer increases with the applied voltage, while that of the reference ones decreases. Comparing the EQE of both devices at a same applied voltage, an improvement of EL efficiency of at least one order of magnitude can be obtained by the addition of Ag islands films, as shown in Fig. 2(d). Fig. 3. (a) Normalized extinction spectra of Ag islands film and SiN x film on the Ag layer deposited on quartz. (b) PL spectra of single SiN x film and Ag/SiN x structure, inset is the PL enhancement factor. Fig. 4. Current-voltage (I-V) characteristics of SiN x LEDs with Ag layer and the reference devices. The enhanced EL intensity of SiN x LEDs with Ag islands layer was expected as increasing the radiative recombination rate by coupling excitons to SPs. In order to understand the detail mechanism of enhancement from SPs, the extinction spectra and PL spectra of SiN x films with and without Ag islands layer were characterized, as shown in Fig. 3. The normalized extinction spectra shown in Fig. 3(a) are attributed to the localized surface plasmon resonance (LSPR) of Ag islands film. The resonance absorption peak of Ag islands is located at about 460 nm while after depositing SiN x on Ag layer it shifts to about 555 nm due to the large dielectric constant of SiN x film. Of course, the resonance peak of Ag islands in our metalinsulator-semiconductor (MIS) devices should redshift more considering the larger dielectric constant of silicon substrate than that of quartz. Moreover, we note that the resonance (C) 2012 OSA 1 June 2012 / Vol. 2, No. 6 / OPTICAL MATERIALS EXPRESS 876

absorption peak from Ag islands is just near the EL peak of SiN x LEDs. Thus, the enhancement of EL intensity can be attributed to the coupling between the dipole moment of excitons in SiN x film and localized electric field of LSPs in Ag islands film [10,11]. The PL spectra confirm this result further, as shown in Fig. 3(b). From the inset of Fig. 3(b), the maximum PL enhancement factor is about 2 at about 600 nm. It is the coupling of the dipole moment of excitons in SiN x to the local electric field of LSPs in Ag islands film that leads to an increase in the radiative recombination rate of excitons, consequently increasing the PL/EL intensity. However, the EL enhancement factor at ~600 nm and the maximum EL enhancement factor at ~500 nm are about 5 and 16, respectively, as can be seen in Fig. 2(b), while the maximum PL enhancement is only ~2. Since the EL enhancement factor is larger than the PL enhancement factor, the coupling of excitons and LSPs in Ag islands film is considered as a partial factor for the enhancement of EL intensity. Furthermore, the redshift of PL peak by the addition of Ag islands film may result from the scattering enhancement of long wavelength by LSPs, where the dipole resonance peak of LSPs has a similar wavelength with that of PL peak for the device with Ag, as shown in Fig. 3. On the other hand, considering that the existence of Ag islands in devices can enhance the inhomogeneous local electric fields at the interface between Ag layer and SiN x layer [22,23], the carrier injection efficiency would be enhanced significantly. Due to the existence of an additional path of recombination mentioned above, carriers can transfer their energies into LSPs rapidly keeping the carrier density in the luminescence layer low even though the injection level was improved significantly. Consequently, the increasing tunneling probability of carrier into SiN x film can also result in an enhanced EL intensity. Figure 4 shows the current-voltage (I-V) characteristics of SiN x LEDs with and without Ag islands layer. The EL signals from both devices can be detected when the injected current is ~5 ma, but the threshold voltage is ~3.3 V for the device with Ag layer and ~6.1 V for the reference device. The lower threshold voltage of the device with Ag layer indicates that Ag islands film can significantly enhance the carrier injection into SiN x film. However, considering the transferring of carriers between Ag nanoparticles, this enhancement of carrier injection efficiency might not be so much distinctly. Furthermore, we have noticed the roughening of SiN x and ITO films deposited on Ag islands film, which can also enhance the EL intensity of SiN x LEDs. As shown in Figs. 1(c) and 1(d), the surface roughness and crystalline grain of ITO film in the device with Ag islands layer are larger than those of ITO film in the reference device. The rougher surface of ITO can increase the transparency of ITO electrode and light extraction efficiency of the device [12,24]. In general, the roughening induced by the addition of Ag islands film plays an important role in the improvement of EL performance of SiN x - based LEDs, which not only increases the light extraction efficiency, but also enhances the carrier injection efficiency significantly. 4. Conclusion The enhancement of EL intensity and EQE are observed for SiN x -based LEDs with Ag islands film. One order magnitude of EQE enhancement is achieved in the devices. We attributed this significant increase mainly to the improvement in radiative recombination rate of excitons in SiN x, the increased carrier injection and light extraction efficiency due to the addition of Ag islands film. Our experimental results provide an alternative approach towards the fabrication of SiN x -based or Si-based LEDs with high EL extraction efficiency. And further improvement of the EL performance of SiN x -based LEDs can be achieved by the optimization of the surface coverage and/or the morphology of Ag particles. Acknowledgments We thank the National Natural Science Foundation of China (No. 61176117), 863 Program (Grant No. 2011AA050517), and the Innovation Team Project of Zhejiang Province (No. 2009R50005) for the financial support. (C) 2012 OSA 1 June 2012 / Vol. 2, No. 6 / OPTICAL MATERIALS EXPRESS 877