Applied Physics Express 3 (2010) 022101

Dual-Color Emission in Hybrid IIINitride/ZnO Light Emitting Diodes

Gon Namkoong, Elaissa Trybus1 , Maurice C. Cheung2 , W. Alan Doolittle1 , Alexander N. Cartwright2 , Ian Ferguson1 , Tae-Yeon Seong3 , and Jeff Nause4
Electrical and Computer Engineering Department, Old Dominion University, Norfolk, VA 23529, U.S.A. 1 School of Electrical and Computer Engineering, Georgia Institute of Technology, Atlanta, GA 30332, U.S.A. 2 Department of Electrical Engineering, University at Buffalo, The State University of New York, Buffalo, NY 14260, U.S.A. 3 Department of Materials Science and Engineering, Korea University, Seoul 136-712, Korea 4 Cermet Inc., Atlanta, GA 30318, U.S.A. Received November 29, 2009; accepted January 22, 2010; published online February 12, 2010 We report dual-color production of the blue and green regions using hybrid nitride/ZnO light emitting diode (LED) structures grown on ZnO substrates. The blue emission is ascribed to the near-band edge transition in InGaN while green emission is related to Zn-related defect levels formed by the unintentional interdiffusion of Zn into the InGaN active layer from the ZnO substrates. # 2010 The Japan Society of Applied Physics DOI: 10.1143/APEX.3.022101

nO/IIInitride heterojunction semiconductors are of technological interest for the development of bright light emitting diodes (LEDs). However, the properties of ZnO/IIInitride heterojunction devices1,2) have a great potential for scientic impact. The uniqueness of ZnO has attracted interests in developing high-eciency optoelectronic devices, such as the low-threshold UV lasers3) and short wavelength LEDs.4) In particular, ZnO materials have excellent luminous eciency because of the large exciton binding energy of 60 meV ($26 meV for GaN).5) The various wavelengths of ZnO materials can be easily obtained with dierent dopants, such as ZnO:W for blue, ZnO:V for yellow and ZnO:(Y,Eu) for red emission.6) The strong luminescence and easy tuning of wavelength in ZnO will be benecial to the design of multi-wavelength LEDs. However, the lack of reliable p-type ZnO hinders the development of ZnO-based optoelectronic devices.7) Therefore, direct integration of IIInitride emitters onto ZnO via p-type GaN has the potential to produce advanced LEDs by combining strong luminescence of ZnO and lattice-matched InGaN. The use of ZnO substrates has already demonstrated the improved structural quality of IIInitride materials.810) An additional advantage is that high quality and low defect density (105 cm2 ) of ZnO substrates are available at low costs. Until now, most of the ZnO/IIInitride heterojunction devices are epitaxially grown on p-GaN1,11) or p-AlGaN templates.12) None of the studies address heterojunction device performance on ZnO substrates because p-type GaN has not been successfully grown on ZnO substrates. The lack of progress is due to the volatility of the ZnO substrates13) and the tendency for n-type compensation from oxygen. Herein, we present, for the rst time, the achievement of p-type GaN layer on ZnO and the characteristics of heterojunction ZnO/nitride LEDs. Furthermore, it is found that the careful control of impurities from ZnO into InGaN active layer can produce dual wavelengths of blue and green emissions not observed from IIInitride/ZnO heterojunction grown on p-GaN1) or p-type AlGaN templates.12) IIInitride epilayers were grown on Zn-face ZnO substrates from Cermet Inc. using molecular beam epitaxy (MBE).10) 50-nm-thick InGaN and 0.4-m-thick Mgdoped GaN were grown under metal-rich conditions. Hole

E-mail address: gnamkoon@odu.edu

concentration was measured to be 3 { 5 1017 cm3 for Mg-doped GaN. The indium composition of InGaN on Znface ZnO was conrmed by X-ray diraction measurement using a Phillips Xpert Pro MRD. Optical measurement was performed at room temperature (RT) using a 325 nm HeCd laser, a 405 nm pulsed diode laser (Picoquant), and the 400 nm second harmonic of a Ti:sapphire femtosecond pulsed laser (Coherent RegA-Mira). Using the femtosecond ($200 fs) pulses for excitation, the backscattered timeresolved photoluminescence (PL) spectra and decays were measured using a Hammatsu C4334 Streak Camera attached to a Chromex 250 IS spectrograph. Electroluminescence (EL) spectra were measured from a device of 350 350 m2 . Ohmic contacts of Ni/Au and Ti/Al/Ti/Au were formed on p- and n-type ZnO, respectively. The present work uses low growth temperatures of 500 550  C with a Mg to achieve p-type GaN layer on Zn-polar ZnO substrates. As-received ZnO substrate showed n-type conductivity with electron concentration of 3 1016 cm3 . To compare the device performance, a GaN pn diode was grown with similar structure on a sapphire substrate, which has 0.15-m-thick Mg-doped p-GaN layer and 1.0m-thick Si-doped n-type GaN. Hall carrier concentrations of n-type and p-type layers were estimated $1 1018 and $3 1017 cm3 for electrons and holes, respectively. The currentvoltage (IV ) characteristics of hybrid GaN/ZnO pn diodes and GaN pn diodes on sapphire substrates are shown in Fig. 1. The devices show reasonable IV characteristics, with the less mature GaN/ZnO based diode having higher reverse leakage currents. However, the IV characteristic indicates that Mg-doped GaN on ZnO is indeed a p-type conductive layer. Moreover, it is found that current density of GaN/ZnO pn diodes is $4 times larger than that of GaN pn diodes on sapphire substrates. The high current density of hybrid pn diodes can be attributed to the conductive ZnO substrates while a poor thermal conductivity (35 W/mK) of sapphires restricts the operating currents. Therefore, highly conductive ZnO substrates are promising in terms of device performance (1) providing higher current injections into the active layers and (2) more emission intensity in LEDs. For the hybrid p-GaN/n-ZnO heterojunction diodes, the forward turn-on voltage was about 2.8 V which is close to the values reported by Chuang et al.14) The ideality factor of the
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(a)

(b)

Fig. 1. IV characteristic of GaN pn junction (black) on sapphire and p-GaN/n-ZnO (red). Device size was 350 350 m2 .

Fig. 2. (a) IV characteristic and (b) EL spectra of p-GaN/In GaN/n-ZnO with different forward currents. Inset of (a) shows photoluminescence of p-type GaN/InGaN/ZnO structures measured at RT.

(a)

hybrid diodes was $5, indicating that there exist multiple transport mechanisms such as defect-assisted tunneling and carrier recombination in the space charge region. Even though we used the low growth temperature, real-time reection high-energy electron diraction (RHEED) indicates the formation of interfacial layer at the initial growth stage.10) Therefore, such an interfacial layer contains defects which may allow for tunneling path or carrier recombination during the operation of p-GaN/n-ZnO diodes. The achievement of p-type GaN on ZnO has lead us to grow and fabricate a heterojunction of p-GaN/In0:07 Ga0:93 N/ ZnO LEDs. The IV characteristics of heterostructure devices are presented in Fig. 2(a). EL at an applied current of 40 mA shows near-UV peak at 396 nm. As the applied current increases from 40 to 60 mA, the yellow emission at 560 nm shows a drastic increase in intensity. Moreover, weak blue emission at 483 nm is also observed. Near-UV emission at 396 nm can be attributed to band edge emission of the active In0:07 Ga0:93 N layer. At a higher injection current of 60 mA, the band edge emission of GaN at 360 nm appears with yellow emission at 560 nm, indicating that the radiative recombination occurs in GaN layer. The PL spectra of p-GaN/InGaN/ZnO measured at RT are shown in inset of Fig. 2(a). As seen from the gure, the PL spectrum consists of intense yellow luminescence emission with a wavelength of $550 nm. The broad yellow band is commonly observed and is attributed to Mg-related defects in Mg-doped GaN layers.15) Therefore, higher currents inject electrons from the n-ZnO to the InGaN and into the p-GaN. The EL peak at 483 nm is not clear since PL emissions of the p-GaN/InGaN/ZnO are not correlated to EL peaks. To investigate the possible origin of blue peak, a 50-nm-thick In0:07 Ga0:93 N was grown on ZnO at 515  C and was examined with transmission electron microscopy (TEM) and timeresolved PL analysis. A TEM image of the sample is shown in the inset of Fig. 3(a). The image shows that the interface between the In0:07 Ga0:93 N and the ZnO is fairly planar. The corresponding energy dispersive spectroscopy (EDS) of InGaN grown on ZnO substrates indicates that the interdiusion occurred at the interface of InGaN/ZnO substrates. Zn and O atoms indeed diused into InGaN layers and Ga and N also diused into ZnO. These impurities from ZnO can signicantly aect optical properties of the InGaN layer, and

(b)

(c)

Fig. 3. (a) TEM image of InGaN on ZnO and corresponding EDS profile and (b) photoluminescence and (c) time resolved PL (TRPL) of In0:07 Ga0:93 N grown on ZnO, indicating the power law decay of It I0t 1:4 .

they can be a possible cause of the broad PL spectrum of the In0:07 Ga0:93 N/ZnO around the PL peak at 483 nm, as shown in Fig. 3(b). To deepen our understanding of this broad emission, transient measurement by time-resolved PL was performed. The intensity decay for the defects related PL is usually non-exponential and can be tted into the stretched exponential decay:16,17)
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(a)

(b)

Fig. 4. (a) Electroluminescence spectra of p-GaN/In0:14 Ga0:86 N/ZnO LEDs and (b) photographs of the LEDs at different forward currents.

"   # t  It I0 exp ;  eff or the power-law decay18) of: It I0tm ;

respectively. The photographs of the hybrid LEDs results in bluish white color because of the dual emissions of green and blue, as shown in Fig. 4(b). Non-uniform EL spectra observed in Fig. 4(b) are possibly related to the non-optimal growth and fabrication conditions, in conjunction with very rough surface of nitride/ZnO, formation of interfacial layers, and non-uniform p-type spreading layers of Au metals. In conclusion, hybrid IIInitride/ZnO LEDs were demonstrated by achieving p-type GaN on ZnO substrates. Unintentional interdiusion of the Zn and O from ZnO into InGaN layer creates multiple defect energy levels which are responsible for green emission in hybrid LEDs. Furthermore, multi-quantum well (MQW) structures in the active layer may produce bright dual wavelengths if impurities from the ZnO diusing into the InGaN active layer are carefully controlled.
Acknowledgments Distribution Statement A (Approved for Public Release, Distribution Unlimited). The publication of this article was partially supported by National Science Foundation.

where eff is the eective lifetime and  is the stretched component parameter. The potential uctuation of band-edge transition, typically present in InGaN as a result of the randomly localized indium clusters in potential wells, can be tted into the stretched exponential decay.16,17) However, it is seen from a Fig. 3(c), the PL decay near the 483 nm transition measured at RT exhibits a power-law decay that ts well with the exponent of m 1:4. The decay kinetics following the power-law decay usually represent possible tunneling driven radiative recombination via various trap centers or defect levels.1921) Since interdiusion of Zn and O into the InGaN may creates various defect levels, such as deep acceptor22) and donor defect states,23) a power-law decay in InGaN layer can be related to the radiative recombination though such defect centers. Moreover, the broad PL peaks possibly caused by Zn interdiusion proles into InGaN indicate the broadened acceptor levels.24) It should be noted that Zn is an acceptor in nitride materials and occupies deep energy state of $0:5 eV above the valence band in ternary InGaN materials, as Nakamura et al.22) indicated. Therefore, PL spectrum at 483 nm (2.57 eV) should be related to Zn-related deep acceptor states. Since interdiusion of Zn and O into InGaN active layer creates multiple defect levels, the control of indium composition can produce dual wavelengths in nitride/ZnO LEDs. For this purpose, hybrid LEDs were grown on n-type ZnO with higher indium composition of 14% in active InGaN layer. EL spectra of p-GaN/In0:14 Ga0:86 N/n-ZnO heterostructure were measured under dierent forward currents and are shown in Figs. 4(a) and 4(b). The EL spectra of heterojunction LEDs consist of two dierent wavelength spectra of blue and green emissions. At the forward current of 40 mA, green emission at 516 nm is dominant and can be attributed to Zn related band emission in InGaN. Further increase in the forward current to 60 and 100 mA increases the EL intensity. Moreover, the blue emission spectra also show the peak position shift toward the shorter wavelength from $432 nm (2.87 eV) to 411 nm (3.01 eV) as injection current increases from 60 to 100 mA,

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