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IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010
Recent Advances in ZnO-Based Light-Emitting Diodes

Yong-Seok Choi, Jang-Won Kang, Dae-Kue Hwang, and Seong-Ju Park, Member, IEEE
(Invited/Review Paper)
AbstractZnO has attracted considerable attention for optical device applications because of several potential advantages over GaN, such as commercial availability of bulk single crystals and a larger exciton binding energy (60 meV compared with 25 meV for GaN). Recent improvements in the control of background conductivity of ZnO and demonstrations of p-type doping have intensied interest in this material for applications in light-emitting diodes (LEDs). In this paper, we summarize recent progress in ZnO-based LEDs. Physical and electrical properties, bandgap engineering, and growth of n- and p-type ZnO thin lms are also reviewed. Index Termsp-type ZnO, zinc oxide, ZnO-based light-emitting diodes (LEDs).
TABLE I BAND PARAMETERS OF ZnO AT 6 K
I. I NTRODUCTION N THE upcoming information, digital, and multimedia age, light-emitting diodes (LEDs) based on wide-bandgap semiconductors have drawn much attention. The high efciency, fast switching time, high color gamut, low power consumption, semipermanence, and low heat output of the LED have led to many new applications. The backlight units in liquidcrystal displays have been replaced by high-efciency LEDs. As the efciency of LEDs was further improved, many products equipped with LEDs have been reported. To meet the requirement of high-brightness LEDs for illumination, mobile appliances, automotive, and displays, it is necessary to develop new wide-bandgap semiconductors such as ZnO, which has excellent structural and physical properties compared to GaN. ZnO, furthermore, is inexpensive, relatively abundant, chemically stable, easy to prepare, and nontoxic. We already reviewed ZnO growth and doping, metal ohmic contacts, etchManuscript received June 16, 2009; revised September 23, 2009. First published November 10, 2009; current version published December 23, 2009. This work was supported in part by the Ministry of Knowledge Economy and the Korea Science and Engineering Foundation under Grant R17-2007-07801000-0 funded by the Korean government and in part by the World Class University program at the Gwangju Institute of Science and Technology (GIST) under Project R31-2008-000-10026-0 funded by the Ministry of Education, Science and Technology of Korea. The review of this paper was arranged by Editor S. Pearton. Y.-S. Choi, J.-W. Kang, and S.-J. Park are with the Department of Nanobio Materials and Electronics, GIST, Gwangju 500-712, Korea, and also with the Department of Materials Science and Engineering, GIST, Gwangju 500-712, Korea (e-mail: sjpark@gist.ac.kr). D.-K. Hwang is with Materials Research Institute, Northwestern University, Evanston, IL 60208 USA (e-mail: i.dkhwang@gmail.com). Color versions of one or more of the gures in this paper are available online at http://ieeexplore.ieee.org. Digital Object Identier 10.1109/TED.2009.2033769
ing of ZnO, and ZnO-based LEDs in a previous report [1]. In this paper, we summarize recent results of ZnO-based LEDs, which were mostly published after the previous report [1]. The organization of this review is given as follows. First, ZnO materials properties such as physical and electrical properties and bandgap engineering are described in Section II. This is followed by the growth of n- and p-type ZnO thin lms in Section III. Section IV is devoted to recent reports of ZnObased LEDs. II. ZnO M ATERIAL P ROPERTIES AND BANDGAP E NGINEERING Recently, ZnO has attracted much attention for its application to LEDs, varistors, scintillators, solar cells, and transparent electronics [2][5]. In this section, we focus on the materials properties of ZnO such as physical properties, electrical properties, and bandgap engineering. A. Physical Properties ZnO is a IIVI compound semiconductor with a hexagonal wurtzite structure whose lattice constant is 3.25 . ZnO is a direct bandgap semiconductor. The band edge at the -point is triply degenerated and split due to the effect of the crystalline electric eld and the spinorbit coupling. Table I shows the atmospheric pressure bandgap, the pressure dependence of the bandgap, the exciton binding energy, and exciton energy levels at 6 K [6]. Further, the splitting energies due to the crystalline
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CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES
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electric eld cf and the spinorbit coupling sc are 39.4 and 3.5 meV, respectively [6]. The negative value of sc is due to coupling with the Zn 3d orbital [7], [8]. ZnO has a number of advantages over GaN, the wide-bandgap semiconductor currently utilized in the short-wavelength optoelectronics industry. Some of these advantages include a large exciton binding energy (60 meV), a higher radiation hardness, simple processing due to amenability to conventional chemical wet etching, and the availability of large area substrates at relatively low material costs [9], [10]. B. Electrical Properties The electrical properties of undoped ZnO lm have been found to be n-type due to the formation of native defect. The background carrier concentration is typically 1016 1017 cm3 [11]. The electron mobility of undoped ZnO lm varies, depending on the growth method but is usually 120440 cm2 V1 s1 at room temperature [11]. The high carrier concentration achieved by n- and p-type doping is 1020 electrons cm3 and 1019 holes cm3 , respectively [12]. The carrier mobility of doped ZnO lm is relatively lower compared to that of undoped ZnO lms due to carrier scattering mechanism such as ionized-impurity scattering, polar optical-phonon scattering, acoustic-phonon scattering through deformation potentials, and piezoelectric interactions [11]. The typical value of mobility at room temperature for low n- and p-type doping is 200 and 550 cm2 V1 s1 , respectively [13]. The hole mobility is much lower than electron mobility due to the difference of effective mass and carrier scattering mechanism. C. Bandgap Engineering An important step in order to design ZnO-based LEDs is the realization of bandgap engineering to create barrier layers and quantum wells (QWs) in device structures. Recently, Cdx Mgy Bez Zn1xyz O alloys have attracted much attention because their optical devices operate in the UV and visible region. CdO is an n-type semiconductor with a direct bandgap of 2.22.6 eV and an indirect one at 0.81.3 eV [14][16]. When compared to ZnO, the CdO has a different crystal structure: a cubic rocksalt structure with a lattice constant of 4.69 . CdO has been used to grow Cdx Zn1x O alloys that are expected to achieve low energy bandgaps. Because the ionic radius of Cd2+ (0.74 ) is close to that of Zn2+ (0.60 ), the wurtzite phase, which is a stable phase of ZnO, is expected to be conserved when a rocksalt-structured CdO is alloyed. Because of the large lattice mismatch and the difference in crystal structure between CdO and ZnO, however, the thermodynamic solubility limit of Cd is 2 mol% [17]. Makino et al. [17] reported that the bandgap could be tuned to the lower energy side by 0.3 eV at x = 0.07 in comparison with that of ZnO. Shigemori et al. [18] reported that plasma-assisted metalorganic chemical vapor deposition (MOCVD) enabled the growth of CdZnO with a Cd composition of 69.7% and a bandgap of 1.85 eV. On the other hand, the larger bandgap of MgZnO alloys compared to ZnO will enable its use for the growth of multiple QWs optical devices operating in the UV region. MgO has a stable rocksalt structure with
a lattice constant of 4.22 . According to the phase diagram of the ZnOMgO binary system, the thermodynamic solubility limit of MgO in ZnO is less than 4 mol% due to large lattice mismatch and the difference in crystal structure [19]. In spite of a large structural dissimilarity between ZnO and MgO, the growth of MgZnO with a Mg composition of 51% (bandgap of 4.44 eV) has been reported and used for fabrication of solarblind optical detectors [20], 2-D electron gas MgZnO/ZnO heterostructures [21], and transistors [22]. Ohtomo et al. [23] reported that the solid solubility of MgO in ZnO is 33 mol% for the thin-lm alloys grown under metastable conditions. Above 33%, MgO was reported to segregate from the wurtzite MgZnO lattice limiting its maximum bandgap to 3.9 eV. To overcome the problem with phase segregation of Mg from the MgZnO alloys, Ryu et al. [24] proposed the BeZnO alloy, which has much larger energy bandgap. BeO has a wurtzite structure with a bandgap of 10.6 eV. Since BeO and ZnO share the same hexagonal symmetry, phase segregation is not detected in BeZnO alloys. Ryu et al. reported that the Be concentration is varied over the entire range from 0 to 100 mol% without any phase segregation. III. D OPING OF ZnO A. n-Type ZnO The as-grown ZnO material is unintentionally n-type, and it is widely believed that intrinsic defects such as the zinc interstitial (Zni ) and oxygen vacancy (VO ) are source of donors in ZnO [25]. Vanheusden et al. [26] reported that the free carrier concentration was much larger than VO in their samples, and Look et al. [27] suggested that Zni rather than VO is the dominant native shallow donor in ZnO materials. It was also suggested that hydrogen atoms were incorporated to form hydrogen-related donors, such as a substitutional hydrogen (HO ) and an interstitial hydrogen (Hi ), which resulted in an increase in the donor concentration of ZnO [28], [29]. Intentional n-type doping has been accomplished using group III elements such as Al, Ga, and In, which can easily substitute Zn ions. Many groups have attempted doping with Al, Ga, and In for applications to n-type layers in light-emitting devices as well as transparent ohmic contacts. Doping method with Al [30], Ga [31], and In [32] can produce highly conducting n-type ZnO lms with a carrier concentration of > 1020 cm3 range. The group VII elements F and Cl, which substitute oxygen ion, have also been suggested for n-type dopants. Gordon [33] reported F-doped ZnO grown by chemical vapor deposition (CVD) with a resistivity of 4 104 cm. Chikoidze et al. [34] grew Cl-doped ZnO lms by the MOCVD method. B. p-Type ZnO In order to develop ZnO-based LEDs, the most important issue is the fabrication of low-resistivity p-type ZnO. Because unintentionally undoped ZnO shows typically n-type properties, acceptors may be compensated by native defects such as Zni , VO , or background impurities such as hydrogen. VO in ZnO makes deep donor level located at 1.0 eV below the
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bottom of the conduction band and can compensate acceptors in p-type ZnO [35]. Zni also makes shallow donor level located at 30 meV below the bottom of the conduction band [27]. Atomic hydrogen is well known to behave as an exclusive shallow donor in bulk ZnO [28], [29]. Hydrogen is ubiquitous and can easily be incorporated in ZnO during the crystal growth. To grow p-type ZnO, the acceptor concentration should be higher than the unintentional donor concentration. The acceptors in ZnO include group I elements such as Li [36][40], Na [41], Cu [42], and Ag [43], [44], Zn vacancies, O interstitial, and group V elements such as N [39], [45][75], P [71], [76][89], As [90][94], and Sb [95][99]. p-type doping in ZnO may be possible by substituting either group I elements (Li, Na, and K) for Zn sites or group V elements (N, P, As, and Sb) for O sites. It has been believed that the most promising dopants for p-type ZnO are the group V elements, although theory suggests some difculty in achieving a shallow acceptor level [100]. Recently, another p-type doping mechanism was proposed for group V elements (P, As, and Sb). P, As, and Sb substitute Zn sites, forming a donor, then it induces two Zn vacancy acceptors as a complex form (PZn 2V Zn , AsZn 2V Zn , and SbZn 2V Zn ) [101], [102]. However, the choice of p-type dopant and growth technique remains controversial and the reliability of p-type ZnO and the doping mechanism are still subjects of debate. Nitrogen has been used to p-type dopant due to similar ionic radius compared to oxygen and availability of gas source such as N2 , N2 O, NO, NO2 , and NH3 . Wang et al. [75] reported on the growth of p-type ZnO thin lms prepared by oxidation of Zn3 N2 thin lms deposited by dc-magnetron sputtering. Unfortunately, reliability of N-doped p-type ZnO is still problematic due to low solubility of nitrogen and the formation of NNrelated complexes in ZnO [13], [103]. Aoki et al. [76] reported P-doped p-type ZnO lm by expose Zn3 P2 lm to excimer laser radiation in high pressure nitrogen or oxygen ambient. Similar results were obtained by Lee et al. [77], who also transformed a Zn3 P2 layer on ZnO/sapphire to p-type ZnO by laser annealing. Kim et al. [78] prepared p-type ZnO thin lms showing hole concentrations of 1017 1019 cm3 by sputtering a ZnO target doped with P2 O5 at high temperatures followed by a thermal annealing process. The possibility of p-type doping with large group V elements, such as As and Sb, has also been explored by Limpijumnong et al. [102] using the rst-principles calculation. Ryu et al. [90], [91] reported the formation of As-doped p-type ZnO lms grown by hybrid beam deposition on GaAs and sapphire substrates. The Sb-doped p-type ZnO lm was rst achieved by exposing an Sb lm deposited on ZnO lm to KrF excimer laser radiation [95]. However, the residual Sb metal lm on top of the ZnO layer and the nonuniformity of Sb doping might be a potential problem for device performance. Xiu et al. [96] fabricated Sb-doped p-type ZnO lms by a molecular beam epitaxy (MBE) and reported p-type conductivity with a very low resistivity of 0.2 cm, a high carrier concentration of 1.7 1018 cm3 , and a high Hall mobility of 20.0 cm2 V1 s1 . In contrast to p-type doping of ZnO lm, p-type doping of ZnO nanostructures has been difcult and rarely achieved. Recently, p-type conduction in ZnO nanowires was reported by using N or P as the dopant by a simple CVD method [104], [105]. Xiang et al. [104] conrmed p-type
TABLE II S URVEY OF THE E LECTRICAL P ROPERTIES OF p-T YPE D OPED ZnO T OGETHER W ITH THE D OPANT, PL P EAK , AND S UBSTRATE
conductivity of P-doped p-type ZnO nanowires by temperature dependent photoluminescence (PL) and measurement of ZnO nanowire back-gate eld-effect transistors at room temperature. The calculated eld-effect mobility and hole concentration for a quasi-1-D system are 1.7 cm2 V1 s1 and 2.2 107 cm1 , respectively. Table II is a survey of dopants, growth technique, substrates, and electrical properties of p-type ZnO. IV. ZnO-BASED LEDs A. Heterojunction LEDs ZnO is very attractive for blue/UV LEDs and hightemperature/transparent electronics. However, ZnO-based LEDs have suffered from the lack of reproducible and highquality p-type material. A number of studies have reported on the heterojunction LEDs using n-type ZnO deposited on p-type materials of GaN, Si, and conducting oxides.
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TABLE II (Continued.)
TABLE II (Continued.)
Rogers et al. [106] fabricated an n-ZnO/p-GaN:Mg heterostructure on a c-Al2 O3 substrate. A ZnO layer was grown on top of the p-type GaN layer using pulsed laser deposition (PLD) in oxygen ambient with a KrF excimer laser (248 nm). I V characteristics exhibited nonlinear rectifying behavior with a forward-bias voltage of 3.3 V, which corresponds to the bandgap of ZnO. The electroluminescence (EL) emissions from the n-ZnO/p-GaN heterostructure under forward bias at room temperature show a single peak with a max at 375 nm. Yang et al. [107] also fabricated heterojunction LEDs with a n-ZnO/p-GaN structure on a c-Al2 O3 substrate. For the growth of the heterojunction, a 620-nm-thick Mg-doped p-type GaN layer was deposited on the c-Al2 O3 substrate using MOCVD
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Fig. 1. EL spectra of an n-ZnO/p-Al0.12 Ga0.88 N heterostructure LED at 300 and 500 K (Ic = 20 mA) [108].
and a deposition of 750-nm-thick undoped n-type ZnO layer was followed using the same MOCVD system. Based on the results of X-ray diffraction and atomic force microscopy, it was concluded that the obtained n-ZnO/p-GaN heterojunction structure was structurally in high quality. The EL spectra exhibited two peaks centered at 410 and 470 nm. A comparison of EL and PL spectra of the n-type ZnO and p-type GaN layers showed that two EL emission peaks were attributed to a radiative recombination in both n-type ZnO and p-type GaN layers. Alivov et al. [108] fabricated n-ZnO/p-AlGaN heterojunction LEDs, taking advantage of the fact that AlGaN is also well matched to ZnO and can be doped p-type. A layer of n-type ZnO with a thickness of 1 m was grown on the p-type Al0.12 Ga0.88 N using CVD stimulated by RF-discharge plasma. The devices exhibited a rectifying diode-like behavior with a threshold voltage of 3.2 V, a high reverse breakdown voltage of almost 30 V, and a small reverse leakage current of 107 A at room temperature. As shown in Fig. 1, under forward bias, the device showed intense UV EL with a peak emission near 389 nm (3.19 eV) and a full-width at half-maximum (FWHM) of 26 nm with no other emission bands. This emission was found to be stable at temperatures up to 500 K and was shown to originate from recombination within ZnO due to large conduction band offset. To improve optical characteristics with ZnO-based heterojunction LEDs, double and triple heterostructure LEDs were demonstrated [109], [110]. Ohashi et al. reported a ZnObased double heterostructure system that consisted of an n-type ZnO cap layer, an n-type Mg0.12 Zn0.88 O cladding layer, an n-type Zn1x Cdx O emission layer, and an N-doped p-type Mg0.12 Zn0.88 O barrier layer on p-type 4H-SiC substrates [109]. The PL emission energies of red-region Zn1x Cdx O lms indicated almost a constant value of 1.9 eV. As shown in Fig. 2, EL spectra under current injection showed that the emissions of blue and red are coming from different places. When the injection current level is as low as 40 mA, blue emissions coming from the p-type 4H-SiC substrate were observed. On the other hand, when a higher current of around 120 mA was injected, the red emission appears. Osinsky et al. [110] fabricated a p-n junction LED that has a MgZnO/ZnO/AlGaN/GaN
Fig. 2. EL spectra of ZnO-based double heterojunctions under current injection [109].
triple heterostructure. Energy band diagrams of the LED structure incorporating piezoelectric and spontaneous polarization elds were simulated, revealing a strong hole connement near the n-ZnO/p-AlGaN. Electron-beam-induced current measurements conrmed the presence of a p-n junction located at the n-ZnO/p-AlGaN interface. The triple heterostructure p-n junctions showed rectifying characteristics with a threshold voltage of 3.2 V and a UV light emission at 390 nm. Experimental spectral dependence of the photocurrent conrmed the excitonic origin of the optical transition at 390 nm. Light emissions measured up to 650 K provided additional conrmation of the excitonic nature of the optical transitions in the devices. Mares et al. reported visible EL from a hybrid n-MgZnO/CdZnO/p-GaN LED heterostructure with a single Cd0.12 Zn0.88 O QW [111]. PL measurements showed strong luminescence centered at 430 nm with an FWHM of 90 nm without any low-energy defect luminescence. The measured EL spectra also showed no signicant defect luminescence bands in the EL emission, which is indicative of the highquality growth. EL spectra showed, however, higher energy emission than PL. Mares et al. demonstrated that PL spectra differ from the EL emission due to spatially indirect optical transitions between the electrons conned in the QW and holes accumulated at the GaN/CdZnO interface. Heterojunction LEDs have been constructed mostly by depositing n-type ZnO or n-type MgZnO on various p-type semiconductor layers. However, there have been several attempts to fabricate the heterojunction LEDs constructed by depositing p-type ZnO on various n-type semiconductor layers. Mandalapu et al. [112] fabricated heterojunction LEDs by growing Sb-doped p-type ZnO layer on an n-type Si substrate. A thin undoped ZnO lm was grown at low temperature on n-type Si (100) substrate as a buffer layer, followed by Sbdoped ZnO layer at a higher temperature by MBE. The resultant thicknesses of undoped and Sb-doped ZnO layers are 50 and 370 nm, respectively. Finally, thermal activation of the Sb dopant was performed in situ in vacuum at 800 C for 30 min. The I V characteristics showed a rectifying behavior
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Fig. 3. (a) Temperature-dependent EL spectra obtained at an injection current of 110 mA. EL from LED is obtained at 9, 50, 100, 200, and 300 K. (b) Temperature-dependent EL spectra in the UV region only [112].
Fig. 4. (a) I V characteristics of a p-ZnO/n-GaN heterostructure illustrating the rectifying behavior. Inset: I V characteristics of Ti/Al and NiO/Au metal contacts on n-GaN and p-ZnO lms. (b) EL spectrum of a p-ZnO/n-GaN heterostructure at an injection current of 60 mA [113].
with a higher leakage current at both higher temperatures and higher biases, which is possibly attributed to the band alignment of wide-bandgap p-type ZnO and narrow-bandgap n-type Si. Fig. 3(a) shows the EL spectra obtained from LEDs at an injection current of 110 mA at different temperatures. The nearband edge (NBE) emission at 381 nm was observed. The other peaks around 485, 612, and 671 nm related to intrinsic defects were also observed. Fig. 3(b) shows the spectra focusing on the UV region only. With increasing temperature, both the small UV peak and the NBE emission redshift and appear as a single peak at higher temperatures due to the temperatureinduced bandgap variation. The intensity of emissions drops throughout the spectra with increasing temperature, which is typical due to the increase in nonradiative recombination at higher temperatures. The intensity of UV peaks is low compared to deep-level emissions probably due to low radiative efciency and self-absorption effect induced by deep levels. Hwang et al. [113] reported on the growth and device properties of p-ZnO/n-GaN heterojunction LEDs. A GaN buffer layer was deposited on a (0001) sapphire substrate, followed by deposition of an n-type GaN layer by MOCVD. After the growth of the n-type GaN layer, a P-doped ZnO layer was deposited by an RF-magnetron sputtering system. To activate the p-type dopant, a rapid thermal annealing (RTA) process
was adopted at a temperature of 800 C under a N2 ambient. Fig. 4(a) shows rectifying characteristics of a p-ZnO/n-GaN heterojunction with a threshold voltage of 5.4 V, and the inset of Fig. 4(a) shows the I V characteristics of the Ti/Al and NiO/Au metal contacts on n-type GaN and p-type ZnO lms, respectively, indicating that good ohmic contacts are formed on both electrodes. The PL spectra showed emission peaks of n-type GaN and p-type ZnO at 365 and 385 nm, respectively. Fig. 4(b) shows the EL spectrum of a heterostructure at an injection current of 60 mA. The EL emission peak at 409 nm was attributed to the recombination of holes and electrons in the p-type ZnO region. A comparison of EL and PL spectra of the p-type ZnO layer shows that the EL emission peak appears at a lower energy region around 409 nm rather than at 385 nm. This lower energy EL emission peak is attributed to the band offset of 0.13 eV at the p-type ZnO and n-type GaN interface. Table III is a survey of structure, method, and emission color of ZnO-based heterojunction LEDs [106][121]. B. Heterojunction LEDs With ZnO Nanostructures The optical devices using ZnO nanostructures have attracted much attention due to their optical properties arising from quantum connement such as enhanced radiative recombination of carriers. The research for application to LEDs using the ZnO nanostructures has focused on 1-D nanostructure
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TABLE III S URVEY OF S TRUCTURE , M ETHOD , AND E MISSION C OLOR OF ZnO BASED H ETEROJUNCTION LEDs
TABLE IV S URVEY OF S TRUCTURE , M ETHOD , AND E MISSION C OLOR OF H ETEROJUNCTION LEDs W ITH ZnO NANOSTRUCTURES
due to the crystal orientation of ZnO. Various approaches for growing ZnO nanostructures have been developed by many means, such as MOCVD [122][124], CVD [125], the solution method [126][128], electrodeposition [129], PLD [130], and the vapor-phase transport method [131]. However, the difculties also exist here due to the absence of a stable and reliable p-doping method in the fabrication of heterojunction LEDs using ZnO nanostructures. Therefore, most of heterojunction devices using ZnO nanostructure have been realized from different p-type materials such as p-type GaN [122][124], [130], Si [126], NiO [127], and p-type polymers [125], [128], [129]. The properties of heterojunction LEDs with ZnO nanostructures are summarized in Table IV together with the LED structure, the growth method of ZnO nanostructures, and the emission peak position [122][131]. As a promising approach for LEDs using ZnO nanostructures, 1-D ZnO nanostructure/p-GaN heterojunction structures were suggested by several groups because these materials
have the same wurtzite crystal structure, relatively similar bandgap energy, and a low lattice parameter mist of 1.9%. The EL emission of 1-D ZnO nanostructure/p-GaN heterojunction structures is observed at UV, blue, green, and yellow, which is generally considered from excitonic recombination, radiative recombination related to Mg acceptor level, and ZnO defect states such as Zni and VO [122][124], [130]. Park and Yi [122] reported on a p-n heterojunction LED composed of n-type ZnO nanorod on Mg doped p-type GaN lm grown by using MOCVD. ZnO nanorod arrays were aligned vertically to the substrate surface due to the growth direction along the c-axis of ZnO. Room temperature EL spectra of n-ZnO/p-GaN nanorod heterojunction LEDs were measured at the various reverse-bias voltages because EL emission was not observed at a forward-bias voltage in the range of up to 10 V. The main emission peak of EL spectra was a wide yellow emission band centered at 2.2 eV, and the intensity increased with the reverse bias increased from 3 to 7 V. The blue emission peak at 2.8 eV and UV emission peak at 3.35 eV were revealed above reverse-bias voltage of 4 V. Jeong et al. [123] proposed p-GaN lm/ZnO nanowire/ n-ZnO lm heterojunction LEDs to improve the carrier injection efciency of nanostructured junctions. ZnO nanowire arrays of this junction device were formed on Mg-doped p-type GaN lms by MOCVD. Al-doped ZnO lms for injection of electrons into ZnO nanowire arrays were grown by RF-magnetron sputtering. Fig. 5 shows scanning electron
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Fig. 5. (a) SEM image tilted by 45 . (b) Schematic of the Mg-doped GaN lm/ZnO nanowire array/Al-doped ZnO lm structures for nanometer-sized GaN/ZnO heterojunction diode applications. Inset: Photograph of blue-light emission from the heterojunction diodes observed through a microscope at the forward current of 10 mA [123].
Fig. 7. Typical I V curve of n-ZnONR/p-CuAlO2 /p+ -Si LEDs. Inset: I V curve of n-ZnO NR/p+ -Si LEDs [131].
Fig. 6. EL spectra of (a) lm-based GaN/ZnO heterojunction diodes and (b) ZnO-nanowire-inserted GaN/ZnO heterojunction diodes [123].
microscope (SEM) images and a schematic diagram of ZnOnanowire-inserted GaN/ZnO heterojunction LEDs. Film-based ZnO/GaN heterojunction structures were also fabricated for the optical and electrical characterization of ZnO-nanowireinserted GaN/ZnO heterojunction LEDs. The EL spectra of the lm-based and ZnO-nanowire-inserted GaN/ZnO heterojunction diodes are shown in Fig. 6. The EL spectra of lm-based heterojunction show broad blue emission peaks. The blue
emission peak centered at 440 nm was enhanced and slightly shifted to 425 nm with the forward current increased to 20 mA. The enhancement and blueshift of the blue emission peaks with an increased forward current were due to the electron injection from the ZnO nanowires to the GaN lms for radiative electronhole recombination in the GaN lms. The I V characteristics of two heterojunction devices showed different leakage current at a reverse-bias voltage of 10 V and turn-on voltage due to the differences in the interface between ZnO nanowire or ZnO lms and p-type GaN. Park et al. [124] fabricated a heterojunction LED by growing ZnO nanorod on p-type GaN. The ZnO lms as electron injection layers were homoepitaxially grown by growing ZnO lms on ZnO nanorod arrays using MOCVD. This heterojunction LEDs showed asymmetry rectifying I V characteristics with a small breakdown voltage, which is due to a leakage current at the junction. An EL spectrum showed a strong peak centered at 440 nm and a broad peak around 560 nm. The blue emission from the ZnO nanorods/GaN heterojunction indicated that the emission was caused by the p-type GaN [120][122]. A visible broad peak centered at around 560 nm was related to transitions by ZnO defect states. Sun et al. [126] fabricated a p-n heterojunction LED composed of n-type ZnO nanorods and p-type Si. ZnO nanorods were grown on a p-type Si substrate by using an aqueous solution method. High-molecular-weight polymers were used to ll the space between the individual ZnO nanorods. The I V characteristics of n-ZnO nanorods/p-Si heterojunction showed a low threshold voltage under reverse bias and a high resistance under forward bias because of an inconsistent band structure at the interface and the nonideal contact. In addition, the large valence band offset (2 eV) at the interface of n-ZnO nanorods/p-Si caused easy tunneling of electrons between the electrode and ZnO nanorods. The EL spectra of LED were composed of narrow UV emission peak centered at 387 nm and broad greenish emission peak centered at 535 nm, which were related to excitonic transition and transition from a shallow donor level of VO to the valence band, respectively. The intensity of UV emission increased more quickly than that of the green emission by increasing the applied bias. Ling et al. [131] fabricated a n-ZnO nanorod/p-CuAlO2 lm heterojunction LED on p-type Si substrates. Vertically aligned ZnO nanorods grown by the vapor-phase transport method
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Fig. 9. Zinc oxide homostructural p-i-n junction shows EL in forward bias at room temperature. EL spectrum from the p-i-n junction (blue) and PL spectrum of a p-type ZnO lm measured at 300 K. The p-i-n junction was operated by feeding in a direct current of 20 mA [132].
Nadarajah et al. [129] realized exible LEDs using n-type ZnO nanowire and p-type polymer. ZnO nanowires were grown on an ITO-coated polymeric substrate by electrodeposition. The top anode contact for hole injection consisted of a thin poly(3,4ethylene-dioxythiophene) poly(styrenesulfonate) layer and a Au lm. The measured I V characteristics showed the diode characteristics and the rectication. The EL spectra of exible LED using ZnO nanowires showed a broad emission band covering the wavelength range of 5001100 nm. In addition, ZnO nanowires in this exible LED remained attached even as the substrate was bent over a curvature radius less than 10 m.
Fig. 8. (a) Room temperature PL spectrum of ZnO nanorods and the schematic of the light transmission path in our device (inset). (b) Room temperature EL spectra and the EL photograph (inset) of n-ZnO nanorods/p-CuAlO2/p+ -Si LED. (c) Room temperature EL spectra and the EL photograph (inset) of n-ZnO NR/p+ -Si LED [131].
C. Homojunction LEDs Tsukazaki et al. [132], [133] proposed a repeated temperature modulation technique as a reliable and reproducible way to fabricate p-type ZnO. Thin lms of ZnO and junction devices were grown by laser MBE using nitrogen as a p-type dopant. The p-i-n homojunction structure was grown in a layer-by-layer mode, keeping an atomically at interface. The I V characteristics show fairly good rectication with a threshold voltage of about 7 V. The threshold voltage is higher than the bandgap of ZnO (3.3 eV), which is mainly due to the high resistivity of the p-type ZnO layer. The EL spectrum shows luminescence from violet to green regions with multireection interference fringes. The EL spectrum apparently shows a redshift compared to exciton emission of undoped ZnO layer at 3.2 eV. This is partly due to the low hole concentration in p-type ZnO; electron injection from undoped ZnO to p-type ZnO overcomes hole injection from p-type ZnO to undoped ZnO. The PL spectrum (black) of a p-type ZnO lm is also shown in Fig. 9. The higher energy side peak around 430 nm in the EL spectrum matches well with the PL spectrum. Lim et al. [134] realized a UV emitting diode using a ZnO p-n homojunction. Ga-doped n-type ZnO layers with a
served as channels for injection of electron and optical connement. A p-type CuAlO2 lm grown by dc-magnetron sputtering was used as the hole injection layer. In addition, the free space between ZnO nanorod arrays was lled with hydrophobic poly(methyl-methacrylate) (PMMA) as an insulating and supporting layer. Fig. 7 shows rectifying I V characteristics of n-ZnO nanorods/p-CuAlO0/p+ -Si and n-ZnO nanorod/p+ -Si LEDs. The LED with the p-type CuAlO2 lm indicated a comparatively low turn-on voltage of 4 V and a high breakdown voltage above 40 V compared to the LED without p-type CuAlO2 . As shown in Fig. 8, UV (band edge) emission and greenish (defect-related) emission were observed on the room temperature PL and EL spectra of LEDs. While EL spectra of LED with a p-CuAlO2 layer showed an rising UV emission intensity with increasing injection current, as shown in Fig. 8(b), relatively intense green emission was obtained from the LED without CuAlO2 . It indicated that the p-type CuAlO2 layer can be used to improve the LED performance of ZnO/Si UV LEDs.
35
Fig. 10. EL spectra of a p-n homojunction ZnO LED operated at forward currents of 20 and 40 mA; PL spectrum of p-type ZnO obtained at room temperature [134].
Fig. 11. (a) Schematic of a ZnO LED containing Mg0.1 Zn0.9 O barrier layers for carrier connement in n-type ZnO. (b) EL spectra of the ZnO LED with Mg0.1 Zn0.9 O layers operated at forward currents of 20 and 40 mA [134].
thickness of 1.5 m were grown on a c-Al2 O3 substrate by RFsputtering deposition at 900 C, using a ZnO target mixed with 1 wt.% Ga2 O3 . For the p-n homojunction ZnO LED, a layer of p-type ZnO with a thickness of 0.4 m was grown on the n-type ZnO layer at 900 C using a ZnO target mixed with 1 wt.% P2 O5 . For the ZnO LED with carrier connement layers, two Mg0.1 Zn0.9 O epitaxial layers, each of 40 nm thickness, were deposited by cosputtering MgO and ZnO targets on n-type ZnO. The samples were subjected to an RTA process for 5 min at 800 C in a nitrogen atmosphere in order to activate the p-type ZnO layers. The LED shows clear rectication with a threshold voltage of 3.2 V, which is in good agreement with the ZnO bandgap energy of 3.37 eV. Fig. 10 shows an EL spectra of the homojunction ZnO LED, with an NBE emission at 380 nm (3.26 eV) and broad deep-level emissions at approximately 640 nm. A comparison of EL and PL spectra of the p-type ZnO lm suggests that the recombination of electrons and holes occurs mostly in p-type ZnO. The carrier diffusion lengths of the electrons in p-type ZnO and the holes in n-type ZnO were estimated to be 290.2 and 97.8 nm, respectively. As shown in Fig. 11(a), a ZnO LED with two 40-nm-thick Mg0.1 Zn0.9 O lms as the carrier connement layers and a 40-nm-thick n-type ZnO layer as the active region was grown on c-Al2 O3 . Fig. 11(b) shows EL spectra of the ZnO LED with Mg0.1 Zn0.9 O layers operated at forward currents of 20 and 40 mA. With increasing injection current, a redshift of the band edge emission was observed because of bandgap narrowing caused by heat generation. Unlike the case of the band edge emission, the deep-level emission was not blueshifted. This result indicates that the deep-level emission is from the ptype ZnO excited by UV light emitted from the conned n-type ZnO layer that does not show any deep-level emission in the PL spectrum. Ryu et al. presented results for ZnO-based UV LEDs that employ a Be0.3 Zn0.7 O layer and a BeZnO/ZnO active layer between n-type and p-type ZnO [135]. The active layer is com-
Fig. 12. EL spectrum measured at room temperature in continuous current mode of a p-n junction ZnO-based LED having a BeZnO active layer. The primary spectral emission peak is located near 363 nm and arises from localizedexciton emissions in the QWs. The secondary peak centered near 388 nm is from impurity-bound exciton emissions in ZnO [135].
posed of seven QWs for which undoped Be0.2 Zn0.8 O and ZnO form barrier and well layers, respectively. The thickness of each BeZnO barrier layer is about 7 nm, and each ZnO well layer is about 4 nm. The p-type ZnO and BeZnO layers are formed with As as the acceptor dopant while the n-type ZnO and BeZnO layers were formed with Ga as the dopant. I V measurements demonstrate p-n junction characteristics for the ZnO-based structures, featuring a high turn-on voltage and a low reversebias current as shown in the insert. Fig. 12 shows the intensity of the EL spectral output of one of the ZnO-based LEDs with increasing injection current. The peaks located near 388 nm (bound exciton) and 550 nm (green band) are the dominant features at low forward currents under 20 mA, at which the intensities of EL peaks at 388 and 550 nm have become saturated.
36
Fig. 14. EL spectra of a p-n ZnO diode at room temperature, with increasing injection current from 60 to 100 mA. Inset: PL spectrum of the same device at room temperature [138].
Fig. 13. EL spectra of the ZnO LED measured at room temperature under various injection currents. Inset: Normalized EL spectra in which the blueshift of the emission peak is clearly seen [137].
The peak at 388 nm is the impurity (donor or acceptor)-bound exciton emission. The peak at 550 nm is shifted to shorter wavelengths as current injection is increased; the peak location is around 520 nm at an injection current of 50 mA. This behavior indicates impurity-involved emission such as from donor acceptor pair recombination for the 550-nm peak. The peak located near 363 nm (localized exciton) becomes the prominent spectral feature at current injection levels above 20 mA. The peak observed at 363 nm has not been previously reported for ZnO. Its emission could be from band-to-band recombination, such as from localized-exciton peaks in the active layer of the QWs, as has been observed in GaN-based LEDs. Xu et al. [136] reported on the growth of p-type ZnO thin lms by MOCVD using NO plasma as both the oxygen and nitrogen sources. N-doped ZnO thin lms were grown by the plasma-assisted low-pressure MOCVD method. ZnO homojunction has a rectifying behavior with a turn-on voltage of 2.3 V, which is a little lower than ZnO bandgap. The reduction of the turn-on voltage might be attributed both to the high defect concentration in the interface and to the low carrier concentration in the n-type side of the junction. At a forward current of 20 mA, weak luminescence was detected in the region between yellow and blue (430600 nm). As the current is increased to 40 mA, besides the emissions at the visible region, a UV emission at around 375 nm was also detected. Wei et al. [137] fabricated ZnO p-n junction LEDs on c-Al2 O3 substrates by plasma-assisted MBE. A gas mixture of N2 and O2 was used as the p-type dopant, by which the doubledonor doping of N2(O) was avoided signicantly. At a low temperature of 100 K, the I V curve of the ZnO LED showed a good rectication characteristic with a low leak current at reverse-bias voltages and a threshold voltage 4.0 V at forward bias. The p-n junction LED kept a good rectifying characteristic even at temperatures up to 300 K. Fig. 13 shows the EL spectra measured at room temperature under forward injection currents of 2.42, 2.65, 2.86, 3.09, and 3.31 mA. Under the injection
current of 2.42 mA, the emission band is located at 2.83 eV with an FWHM of 500 meV. With increasing injection current, the emission band shifted to the higher energy side. The inset shows the normalized EL spectra, which shows the peak energy of the emission band shifting from 2.83 to 2.95 eV when the injection current changed from 2.42 to 3.31 mA. The blueshift of the emission band with the injection current suggests that the EL mechanism originated from the donoracceptor pair recombination in the p-type ZnO layer. Kong et al. [138] and Chu et al. [139]showed a ZnO p-n junction grown on an n-type Si (100) substrate using MBE. A thin MgO buffer layer was deposited at 350 C to reduce the lattice mismatch between Si and ZnO, followed by 410 nm Ga-doped n-type ZnO and 410 nm Sb-doped p-type ZnO. The diode showed fairly good rectication behavior with a threshold voltage of 2.5 V. Fig. 14 shows the EL spectra obtained at different injection currents. An NBE emission at 3.2 eV starts to appear when the current is 60 mA. Afterward, the intensity of this emission increases as the injection current increases from 60 to 100 mA. Moreover, the intensity of this emission peak increases evidently at a current of 6080 mA, while it changes less signicantly at 80100 mA, which is due to the heat effect as a result of the increasing current through the diode. When injection current increases from 60 to 100 mA, the UV emission peak also slightly shifts from 385 to 393 nm. This is typical in a radiative recombination process for a direct bandgap material because heat induced by increased injection current will decrease its effective bandgap. The output power of this LED is estimated to be only 1 nW at a drive current of 100 mA. Zhao et al. [140] fabricated a ZnO homojunction on the c-plane sapphire substrate by MOCVD. Diethylzinc, trimethyl antimony, and high-purity O2 were used as Zn, Sb precursor, and oxidizer, respectively. The unintentionally doped ZnO with a thickness of 500 nm was used as an n-type layer. The Sbdoped p-type ZnO layer with a thickness of 300 nm was grown on top of the n-type ZnO layer. From the X-ray photoelectron spectroscopy spectrum, the Sb 3d3/2 peak and 3d5/2 at the binding energy of 539.3 and 530.2 eV indicated that Sb should exist as SbZn rather than SbO in the Sb-doped ZnO lm. A clear rectifying behavior of the ZnO p-n homojunction was demonstrated by the I V curve. The forward turn-on voltage and reverse breakdown voltage were 3.3 and 5.0 V, respectively. No noticeable changes in the spectrum shape were observed
37
TABLE V S URVEY OF S TRUCTURE , M ETHOD , AND E MISSION C OLOR OF ZnO-BASED H OMOJUNCTION LEDs
under injection currents of 40, 60, and 80 mA. The EL spectrum could be tted to three independent peaks centered at 3.00, 2.31, and 1.74 eV. On comparing EL spectra with the PL spectra, the emission peak at 3.0 eV on the EL spectrum is associated with NBE emission. A dominated emission peak at 1.74 eV with a high energy shoulder of 2.31 eV is observed in the EL spectra. The emission of 2.31 eV should be assigned to the intrinsic defects related emission. Considering the difference in the emission position of the EL and PL, the emission of 1.74 eV in the EL spectrum should be Sb-related deep-level emission. There have been several attempts to reduce hydrogen incorporation at or near the surface and mesa sidewall that was introduced when the LED structure was fabricated by wet etching and photolithography [141], [142]. Kim et al. [141] reported that annealing at 350 C for 5 min in O2 improved I V characteristics and EL intensity. ZnO-based LEDs were fabricated on c-plane sapphire using P-doped ZnO/Zn0.9 Mg0.1 O/ZnO/Zn0.9 Mg0.1 O/Ga-doped ZnO p-i-n structures using PLD. The LED fabrication started with device isolation, followed by p-mesa denition using dilute phosphoric acid solution. The resistivity of P-doped ZnO was decreased signicantly with exposure to the etchant due to incorporation of hydrogen as a donor. Although hydrogen atoms can easily diffuse into ZnO lms, they also can be driven out of the lms by thermal annealing. The annealed LEDs showed rectifying I V characteristics with a turn-on voltage of 2.2 V and an EL peak at 385 nm. Wang et al. [142] have investigated the passivation effects of dielectric materials (SiO2 and SiNx ) on ZnO LEDs. The 300-nm SiO2 lms were deposited after mesa formation. After deposition of SiO2 , there were no diode rectifying characteristics and no light emission for the as-fabricated LEDs. After annealing at 350 C, under an O2 ambient, however, diodes showed rectifying I V characteristics and EL emission at 385 nm and a broad defect band ranging from around 500 to 1000 nm at room temperature. The 350 C annealing would have signicant impact on the diode characteristics through removing the acceptors in the p-ZnO by removal of hydrogen. The annealed SiNx -passivated ZnO LEDs showed leaky diode characteristics and no light emission. The difference in I V characteristics and EL property between SiO2 - and SiNx -passivated LEDs may result from residual hydrogen in the dielectric. The SiNx -passivated LED has a signicant concentration of hydrogen left such as NH and SiH bonds, whereas no hydrogen bonding was detected either for unpassivated or SiO2 -passivated LEDs. The properties of ZnO-based homojunction LEDs are summarized in Table V, together with the structure, growth method, and emission peak position [76], [132][156]. R EFERENCES
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Yong-Seok Choi was born in Korea in 1983. He received the B.S. degree in material science and engineering in 2005 from Chonnam National University, Gwangju, Korea, and the M.S. degree in material science and engineering in 2007 from the Gwangju Institute of Science and Technology (GIST), where he is currently working toward the Ph.D. degree in material science and engineering in the Department of Materials Science and Engineering under the supervision of Prof. Park. He is also with the Department of Nanobio Materials and Electronics, GIST. His current research interests include growth of ZnO by MOCVD and ZnO-based optoelectronic devices.
Jang-Won Kang received the B.S. degree in physics in 2007 from Kyunghee University, Seoul, Korea, and the M.S. degree in material science and engineering in 2009 from the Gwangju Institute of Science and Technology (GIST), Gwangju, Korea, where he is currently working toward the Ph.D. degree in material science and engineering in the Department of Materials Science and Engineering under the supervision of Prof. Park. He is also with the Department of Nanobio Materials and Electronics, GIST. His current research interests include ZnO-based optoelectronic devices.
Dae-Kue Hwang received the B.S. degree in materials science and engineering from Chonbuk National University, Jeonju, Korea, in 2002, the M.S. and Ph.D. degrees in materials science and engineering from the Gwangju Institute of Science and Technology, Gwangju, Korea in 2004 and 2008, respectively, with a focus on ZnO light-emitting diodes (LEDs), ZnO and GaN heterojunction LEDs, transparent conducting oxide for optoelectronic devices, ZnO eld effect transistors (FETs) and ZnO nanowire FETs. He is currently a Postdoctoral Fellow with the Materials Research Institute, Northwestern University, Evaston, IL. His research interests include photonic crystal, surface plasmons for biosensor, atomic layer deposition of oxide materials, and dye-sensitized solar cells.
Seong-Ju Park (M00) was born in Korea in 1952. He received the B.S. degree in chemistry and the M.S. degree in physical chemistry from Seoul National University, Seoul, Korea, in 1976 and 1979, respectively, and the Ph.D. degree in physical chemistry from Cornell University, Ithaca, NY, in 1985. From 1985 to 1987, he was a Postdoctoral Fellow with the IBM T.J. Watson Research Center, Yorktown Heights, NY. From 1987 to 1995, he was with the Electronics Telecommunications Research Institute, Taejeon, Korea, as a Principal Researcher. In 1995, he joined the faculty of the Department of Materials Science and Engineering, Gwangju Institute of Science and Technology (GIST), Gwangju, Korea, where he is currently a Professor. He is also with the Department of Nanobio Materials and Electronics, GIST. He is the Director of the Samsung LED Research Center, GIST. He is also the Director of GIST Technology Institute, GIST. He is a member of Korean Academy of Science and Technology. He is the author or a coauthor of more than 230 refereed papers. His current research interests include growth and fabrication of GaN LEDs, Si quantum dot LEDs/Flash memory, and ZnO LEDs/TFT displays.

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IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010

Recent Advances in ZnO-Based Light-Emitting Diodes

TABLE I BAND PARAMETERS OF ZnO AT 6 K

0018-9383/$26.00 2009 IEEE

CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES

IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010

CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES

IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010

Fig. 2. EL spectra of ZnO-based double heterojunctions under current injection [109].

CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES

IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010

CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES

IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010

CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES

IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010

CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES

IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010

[6] [7] [8]

[9] [10] [11]

[12] [13] [14] [15] [16] [17]

CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES

IEEE TRANSACTIONS ON ELECTRON DEVICES, VOL. 57, NO. 1, JANUARY 2010

[122] [123] [124] [125]

[128] [129] [130]

CHOI et al.: RECENT ADVANCES IN ZnO-BASED LIGHT-EMITTING DIODES

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