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Japanese Journal of Applied Physics Vol. 44, No. 21, 2005, pp.

L 643–L 645 #2005 The Japan Society of Applied Physics

JJAP Express Letter

Blue Light-Emitting Diode Based on ZnO
Atsushi TSUKAZAKI1 , Masashi KUBOTA2 , Akira OHTOMO1 , Takeyoshi O NUMA2;3 , Keita O HTANI4 , Hideo O HNO4 , Shigefusa F. CHICHIBU2;3 and Masashi K AWASAKI1 Ã,y
1 2

Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Ibaraki 305-8573, Japan 3 NICP, ERATO, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012, Japan 4 Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication, Tohoku University, Sendai 980-8577, Japan (Received April 19, 2005; accepted April 21, 2005; published May 11, 2005)

A near-band-edge bluish electroluminescence (EL) band centered at around 440 nm was observed from ZnO p–i–n homojunction diodes through a semi-transparent electrode deposited on the p-type ZnO top layer. The EL peak energy coincided with the photoluminescence peak energy of an equivalent p-type ZnO layer, indicating that the electron injection from the n-type layer to the p-type layer dominates the current, giving rise to the radiative recombination in the p-type layer. The imbalance in charge injection is considered to originate from the lower majority carrier concentration in the p-type layer, which is one or two orders of magnitude lower than that in the n-type one. The current-voltage characteristics showed the presence of series resistance of several hundreds ohms, corresponding to the current spread resistance within the bottom ntype ZnO. The employment of conducting ZnO substrates may solve the latter problem. [DOI: 10.1143/JJAP.44.L643]
KEYWORDS: ZnO, light-emitting diode, thin film, pulsed laser deposition, self-absorption

The recent success of p-type doping in ZnO has opened a door to realize practical application of blue and ultraviolet (UV) light-emitting diodes (LED), which can be an alternative to those based on III-nitrides.1,2) Comparing with nitrides, ZnO has significant advantages from following reasons; (1) abundant mineral sources of Zn, (2) commercial availability of large area and high quality single crystal substrates3–5) and (3) large exciton binding energy particularly advantageous for making highly efficient lasers.6–10) However, the device structure of the LEDs reported previously had not been optimized in such ways as thick and opaque top electrode and asymmetric bottom electrode structure.1) The previous device had square-shaped mesa structure with a glide type bottom electrode, giving rise to inhomogeneous current path within the n-type bottom current spread layer. These factors restricted us from observing electroluminescence (EL) spectrum intrinsic to the p–i–n junction; the detected light was limited to that coming from aside of the opaque top electrode close to the ion-etched walls of the mesa structure. Here, we have optimized the device structure to solve these problems by employing a semi-transparent top electrode and coaxial ringshaped structure for the bottom electrode. The EL spectra were dominated by the near-band-edge emission in the ptype layer, which can be attributed to the donor-acceptor pair (DAP) luminescence related with doped nitrogen similar to that in Mg doped p-type GaN.11) We identify the near-future challenges for improving the device performance based on the results. The ZnO p–i–n homojunction structure was grown on lattice-matched (0001)ScAlMgO4 (SCAM) substrates by laser molecular-beam epitaxy in 1 Â 10À6 Torr of oxygen. For nitrogen doping, a radio frequency radical source was used with the input power of 350 W and nitrogen flow of 5 Â 10À6 Torr as a background equivalent pressure. A semiconductor laser beam ( ¼ 808 nm) was employed to
Ã

Au 100 nm Ni 10 nm Au (5 nm) Ni (5 nm)

p-ZnO (150 nm)
Au (100 nm) Ti (10 nm) i-ZnO (10 nm)

n-ZnO (400 nm) ZnO buffer (100 nm) SCAM

Fig. 1. Schematic cross-sectional view of a ZnO p–i–n homojunction diode. Semi-transparent Au (5 nm)/Ni (5 nm) electrode is used for the contact to p-type ZnO layer.

Also at Combinatorial Material Science and Technology (COMET), Tsukuba, Ibaraki 305-0044, Japan. y E-mail address: kawasaki@imr.tohoku.ac.jp

heat the backside of the substrate susceptor. The device structure is schematically shown in Fig. 1. First, an 100-nmthick ZnO buffer layer was deposited at 650 C on the substrate and annealed in-situ at 1000 C in 1mTorr of oxygen for 1 h.12) All of the successive layers were grown in a layer-by-layer growth mode as verified by persistent intensity oscillation of reflection high-energy electron diffraction. As a bottom contact and current spread layer, a 400-nm-thick n-type ZnO doped with Ga was deposited, of which doping concentration was 2 Â 1018 cmÀ3 . After the undoped ZnO layer was deposited, p-type ZnO was grown by repeated temperature modulation (RTM) technique.1) A key to realize p-type ZnO was revealed to keep both high nitrogen concentration ($1020 cmÀ3 ) and low defect density. The former requires low temperature (400 C) deposition,13) whereas the latter favors high temperature (1000 C) crystal growth as clearly revealed by positron annihilation and timeresolved photoluminescence experiments.14) RTM technique effectively overcomes this dilemma. By repeating the growth of an approximately 15-nm-thick ZnO:N at low temperature followed by the high temperature annealing and subsequent growth of an 1-nm-thick ZnO at high temperature,1) p-type layers having hole concentrations higher than 1016 cmÀ3 were reproducibly obtained.

L 643

Phys. No. indicated by thick arrow) corresponds to the absorption threshold of the p-type ZnO. respectively. The two contact probes attached on the top and bottom electrodes are visible in Fig. which is presumably due to the DAP recombination. higher-energy cut-off wavelength of the EL spectra (390 nm. Therefore. one of the possible reasons would be a considerable downshift of the valence bands due to the repulsion with the localized N acceptor levels. which was also fabricated by the lift-off technique. 0 (b) = 293K 60 PL intensity (arb. 2(a). These Au/Ni and Au/Ti electrodes provide with good ohmic contacts for p-type and n-type ZnO layers. Additionally. 3(a) as a function of forward current. Photoluminescence (PL) and transmittance spectra of the identical p-type ZnO:N layer and a PL spectrum of the undoped ZnO are shown in Fig..  equals =2 for the vertical reflection discussed herein. Therefore. The circular-shaped mesa with 300 mm in diameter was then fabricated by photolithography and Ar ion milling. Bottom electrode attached to the exposed n-type ZnO:Ga layer was made of Au (100 nm)/Ti (10 nm) with a ring shape. semi-transparent Au (5 nm)/Ni (5 nm) was deposited by evaporation.L 644 Jpn. 3(b). As shown. (a) 40 Wavelength (nm) 700 600 500 400 (a) T = 293 K EL intensity (arb. the near-band-edge emission at the p–i–n junction would be absorbed by the p-type overlayer even if it exists. 2(b).0 2. It is also noteworthy that overall spectral line shape of the EL resembles that of the PL band observed for the p-type ZnO:N except for the spectral modulations. a weak shoulder is found in the spectra at around 610 nm. these three maxima are considered to be multiple internal reflection fringes of the EL band at 440 nm. which are broadened due to the heavy doping. 12 and 16 mA.0 Photon energy (eV) 3.units) 100 80 Transmittance for p-ZnO PL from 60 ZnO 40 Transmittance (%) On the top of the p-type ZnO layer. which was also found in the PL spectrum of the p-type ZnO:N. 420 and 500 nm. 3. Vol. The spectra are seen to exhibit three independent peaks at 395.5 3. Otherwise these emissions would be self- . The observation of the higher energy emissions means that electrons are injected deep into the p-type layer. TSUKAZAKI et al. where d ¼ 620 nm is the total ZnO layer thickness of the LED. and blue emission through the semi-transparent portion of the electrode is clearly seen in Fig. The unexpected observation in the EL spectra was the appearance of higher energy tail extending above the bandgap of ZnO (> 3:3 eV). An arrow indicates the energy of sharp cut-off corresponding to the absorption edge of p-type ZnO top layer. The three wavelengths pointed out above (420. respectively. J. wavelength in the material. 2. indicating that most of the radiative recombination occurs in the p-type layer. These structures can be explained as a convolution of light modulations due to the LED structure on the fundamental blue EL band centered at around 440 nm in the p-type ZnO layer. (a) EL spectra at 293 K taken from the top of the device with feeding direct forward bias current of 8. since those emissions should be generated in the region close to the surface. 500 and 610 nm) satisfy Bragg’s multiple reflection conditions 2d sin  ¼ mð=nÞ. Thickness of the undoped and p-type films are 1 mm and 500 nm.15) Evidence to support this assignment are that the normalized spectral line shape of the EL was nearly independent of the forward current and ZnO layers are transparent for the broad EL band. 3(b). 44. EL spectra of the p–i–n LED are shown in Fig. Optical microscope images of the device taken (a) under illumination and (b) in dark with feeding a direct forward bias current of 5 mA.5 0 Fig. Thick Au (100 nm)/Ni (10 nm) top contact (100 mm in diameter) was formed by the lift-off technique. respectively. m is positive integer. (b) PL spectra at 293 K of undoped and p-type ZnO layers (dotted lines) and transmission spectrum (broken line) of ptype ZnO layer. The origin is not clear at present. Appl. as shown in Fig. =n is the 40 20 20 PL from p-type ZnO:N 0 2. Figures 2(a) and 2(b) show photographs of the devices taken under illumination and with feeding a direct forward bias current of 5 mA in dark.units) 30 I = 16 mA 20 12 mA 10 8 mA (b) 300µm Fig. However. as follows. 21 (2005) Express Letter A.

Kawasaki and H.1) This reduction in the threshold voltage might be due to the increased hole concentration in p-type ZnO. 4) J. F. Physics of Semiconductors. Yu. L. 4 (2005) 42. Maeda. K. Zamfirescu. Ohtomo. TSUKAZAKI et al. the current does not show exponential increase as V is increased. Ohno. 105 (1998) 399. Koinuma: Appl. T. 20 (2005) S78. Sci. which is much lower than that reported previously (7 V). 8) D. Koinuma. Uedono. Sota and M. 20 (2005) S67. Kawasaki. Fuke. Technol. Nemeth: Semicond. Koinuma and Y. Tsukazaki. S. ed. we have reported on the bluish EL spectra observed through the semi-transparent top electrode attached to the p-type ZnO of a p–i–n LED. Z. M. Niikura and T. Kawasaki. Sumiya. A. Singapore. Hiramatsu: J. 7) P. Sumiya for fruitful discussion and help for experiments. the integrated EL intensity between 320 and 720 nm linearly increased with the current. C. making the color of the emission more bluish.. C. Vol. 12) A. Wong. Formation of single. F. W. Harsch: Solid State Commun. This factor can be eliminated by employing heavily doped thicker lateral conducting layer (currently n-type ZnO doped with 1018 cmÀ3 of Ga has a conductivity of 10À2 cm with a carrier concentration of 1018 cmÀ3 and a mobility of 100 cm2 VÀ1 sÀ1 ). Haboeck. 72 (1998) 3270. Makino. F. Dworzak: Phys. Lett. This resistance value is in the same order as that measured between bottom electrodes of adjusted devices. 4. Scheffler and R. H. M. A. Tsukazaki. A. 20 (2005) S49. 4. Kawasaki and H.Jpn. Technol. is supported by a JSPS fellowship. A. Y. Sci. presumably that through DAP. the use of conducting ZnO substrate (about 1 cm is available) and backside contact of electrode will reduce the series resistance to 1 and provide with much simpler device structure. Segawa: Solid State Commun. B. A. K. T. K. G. 20 (2005) S1. K. C. In summary. G. as shown by the closed circles in Fig. Segawa: Appl. J. Tsukazaki. Amano. 9) Z.2 eV observed in the previous LED1) is completely eliminated in the present LED.or double heterostructures containing p-type (Mg. Y. S. Integrated EL intensity (arb. Zimmermann (World Scientific. although any data of hole concentration for this particular or equivalent quality p-type ZnO layers are not available. K. Hofmann. Y. 1453. S. Lumin. Sizelove. Phys. 83 (2003) 2784. 103 (1997) 459. and (3) surface control of ZnO substrates to mimic the surface of annealed ZnO buffer layer on SCAM. Jones. 21 (2005) Express Letter A. Lett. Segawa: in 23rd Int. Ohtomo. Phys. To obtain the near-band-edge UV emissions. Wong. Technol.units) 20 5000 Although finite EL was observed at lower currents. A. absorbed. M. Cantwell and W. F. However. M. indicating that current-spread resistance in n-type ZnO:Ga limits the current. Makino. Phys. M. Goto: Appl. Technol. Sato. Kawasaki: Semicond. M. Current–voltage characteristics (solid line) of the ZnO p–i–n LED and forward bias current dependence of integrated EL intensity (closed circle). H. Strassburg and M. the EL intensity is still weak and nonradiative recombination through the defects seems to dominate the power consumption. Ohtomo. Ohtani. M. Heating effect seems to induce the saturation behavior at higher current region than 16 mA. Hoffmann. 48–49 (1991) 666. A. Yoshida. Yu. Zeuner. The authors thank S. 1) A. 14) S. H. A. Shen and T. 15) A. Chen. Ohtomo. M. M. Makino. Koinuma and Y. Segawa. The emission is assigned as a radiative recombination in the p-type ZnO. Chia. A. Fuke. C. Koinuma and M. Tang. T. 13) M. Technol. (2) successful doping of (Mg. Bagnall. Figure 4 shows the bias voltage (V) and the integrated EL intensity as a function of forward current bias (I). No. We identify near future challenges as follows: (1) improving the hole concentration above 1018 cmÀ3 in p-type ZnO. Fukuda: Semicond. Appl. Ohtomo. H. the Asahi Glass Foundation and the inter-university cooperative program of the IMR. G. Reynolds. Tang. it is necessary to have higher hole concentration (> 1018 cmÀ3 ) in the p-type ZnO to turn on the hole injection into the undoped active regions. Litton. A. Yu. Sumiya. 5) D. T.4 V. K. Phys. U. Alves. C. Wong. Sci. Akasaki. T. Y. Koyama. 10) T. This work was supported by MEXT Grant (Creative Scientific Research 14GS0204 and 21st Century COE program ‘‘Promotion of Creative Interdisciplinary Materials Science for Novel Functions’’). M. M. Cantwell. Y. 20 (2005) S45. Ohtomo. . D. W. Segawa. Appl. Kito and K. H. H. Z. Koinuma: J. 3) K. J. Zhu. Kawasaki. 1996) p. I. 44. Koinuma: Semicond. H. M. Tsukazaki: Semicond. Z. Meyer. The result clearly indicated the reduced point defect density in the present material. L 645 Applied voltage (V) 15 R = 380 Ω 10 4000 3000 2000 5 1000 0 20 0 0 5 10 15 Forward current (mA) Fig. R. L. Litton. A.Zn)O may also enable one to extract the UV lights efficiently. Koida. Segawa. because we think optimizing the growth conditions by characterizing device performances would be much easier and much more straight forward. Onuma. D. Kavokin. Mater. A. L. but is limited by an ohmic resistance of 380 . R. Sci. M. Fuke. Koinuma and Y. G. Ohtomo and A. Yao. Onuma. 70 (1997) 2230. M. Y. G. Tsukazaki. which gives rise to deep penetration of the depletion layer. 6) P. Tohoku University.Zn)O into p-type to enable double-hetero structure. H. S. C. S. Kawasaki: Nat. H. Phys. T. T. M. Tang. The predominant radiative recombination in the ptype layer is due to its lower hole concentration discussed before. Ohtani. S. In the forward bias region with V above the threshold. Makino. Status Solidi B 234 (2002) R7. and M. Chichibu. It should be noted that broad yellow luminescence band centered at 2. L. K. Ohtani. T. Segawa. Chichibu and H. Chichibu. M. Nause and B. We do not routinely characterize Hall effect of p-type ZnO layers now. 2) A. Look. T. 93 (2003) 2562. K. M. A good rectification was seen with a threshold voltage of 5. Kawasaki. Tamura. Lett. P. K. Above I ¼ 7 mA. Conf. Sci. 11) I.