Repeated temperature modulation epitaxy for p-type doping and light-emitting diode based on zno

ABSTRACT Since the successful demonstration of a blue light-emitting diode (LED)1, potential materials for making short-wavelength LEDs and diode lasers have been attracting increasing

interest as the demands for display, illumination and information storage grow2,3,4. Zinc oxide has substantial advantages including large exciton binding energy, as demonstrated by

efficient excitonic lasing on optical excitation5,6. Several groups have postulated the use of p-type ZnO doped with nitrogen, arsenic or phosphorus7,8,9,10, and even p–n junctions11,12,13.

However, the choice of dopant and growth technique remains controversial and the reliability of p-type ZnO is still under debate14. If ZnO is ever to produce long-lasting and robust devices,

the quality of epitaxial layers has to be improved as has been the protocol in other compound semiconductors15. Here we report high-quality undoped films with electron mobility exceeding

that in the bulk. We have used a new technique to fabricate p-type ZnO reproducibly. Violet electroluminescence from homostructural p–i–n junctions is demonstrated at room-temperature.

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support SIMILAR CONTENT BEING VIEWED BY OTHERS LIGHT-TRIGGERED REGIONALLY CONTROLLED N-DOPING OF ORGANIC SEMICONDUCTORS Article 28 May 2025 OPERANDO ZNO RECRYSTALLIZATION FOR EFFICIENT

QUANTUM-DOT LIGHT-EMITTING DIODES Article Open access 15 May 2025 RECONFIGURABLE PHOTO-INDUCED DOPING OF TWO-DIMENSIONAL VAN DER WAALS SEMICONDUCTORS USING DIFFERENT PHOTON ENERGIES Article

14 December 2020 REFERENCES * Nakamura, S., Mukai, T. & Senoh, M. Candela-class high-brightness InGaN/AlGaN double-heterostructure blue-light emitting diodes. _Appl. Phys. Lett._ 64,

1687–1689 (1994). Article  CAS  Google Scholar  * Kinoshita, A., Hirayama, H., Ainoya, M., Aoyagi, Y. & Hirata, A. Room-temperature operation at 333 nm of Al0.03Ga0.97N/Al0.25Ga0.75N

quantum-well light-emitting diodes with Mg-doped superlattice layers. _Appl. Phys. Lett._ 77, 175–177 (2000). Article  CAS  Google Scholar  * Koizumi, S., Watanabe, K., Hasegawa, M. &

Kanda, H. Ultraviolet emission from a diamond pn junction. _Science_ 292, 1899–1901 (2001). Article  CAS  Google Scholar  * Watanabe, K., Taniguchi, T. & Kanda, H. Direct-bandgap

properties and evidence for ultraviolet lasing of hexagonal boron nitride single crystal. _Nature Mater._ 3, 404–409 (2004). Article  CAS  Google Scholar  * Bagnall, D. M. et al. Optically

pumped lasing of ZnO at room temperature. _Appl. Phys. Lett._ 70, 2230–2232 (1997). Article  CAS  Google Scholar  * Yu, P. et al. Ultraviolet spontaneous and stimulated emissions from ZnO

microcrystalline thin films at room temperature. _Solid State Commun._ 103, 459–463 (1997). Article  Google Scholar  * Minegishi, K. et al. Growth of p-type zinc oxide films by chemical

vapor deposition. _Jpn J. Appl. Phys._ 36, L1453–L1455 (1997). Article  CAS  Google Scholar  * Ryu, Y. R. et al. Synthesis of p-type ZnO films. _J. Cryst. Growth_ 216, 330–334 (2000).

Article  CAS  Google Scholar  * Look, D. C. et al. Characterization of homoepitaxial p-type ZnO grown by molecular beam epitaxy. _Appl. Phys. Lett._ 81, 1830–1832 (2002). Article  CAS 

Google Scholar  * Kim, K.-K., Kim, H.-S., Hwang, D.-K., Lim, J.-H. & Park, S.-J. Realization of p-type ZnO thin films via phosphorus doping and thermal activation of the dopant. _Appl.

Phys. Lett._ 83, 63–65 (2003). Article  CAS  Google Scholar  * Aoki, T., Hatanaka, Y. & Look, D. C. ZnO diode fabricated by excimer-laser doping. _Appl. Phys. Lett._ 76, 3257–3259

(2000). Article  CAS  Google Scholar  * Ryu, Y. R., Lee, T. S., Leem, J. H. & White, H. W. Fabrication of homostructural ZnO p-n junctions and ohmic contacts to arsenic-doped p-type ZnO.

_Appl. Phys. Lett._ 83, 4032–4034 (2003). Article  CAS  Google Scholar  * Alivov, Y. I. et al. Fabrication and characterization of n-ZnO/p-AlGaN heterojunction light-emitting diodes on

6H-SiC substrates. _Appl. Phys. Lett._ 83, 4719–4721 (2003). Article  CAS  Google Scholar  * Look, D. C. & Claflin, B. P-type doping and devices based on ZnO. _Phys. Status Solidi B_

241, 624–630 (2004). Article  CAS  Google Scholar  * Haase, M. A., Qiu, J., DePuydt, J. M. & Cheng, H. Blue-green laser diodes. _Appl. Phys. Lett._ 59, 1272–1274 (1991). Article  CAS 

Google Scholar  * Sze, S. M. _Semiconductor Devices: Physics and Technology_ Ch. 12 (Wiley, New York, 1986). Google Scholar  * Chia, C. H. et al. Confinement-enhanced biexciton binding

energy in ZnO/ZnMgO multiple quantum wells. _Appl. Phys. Lett._ 82, 1848–1850 (2003). Article  CAS  Google Scholar  * Ohtomo, A et al. Mg_x_Zn1−_x_O as a II–VI widegap semiconductor alloy.

_Appl. Phys. Lett._ 72, 2466–2468 (1998). Article  CAS  Google Scholar  * Makino, T. et al. Band gap engineering based on Mg_x_Zn1−_x_O and Cd_y_Zn1−_y_O ternary alloy films. _Appl. Phys.

Lett._ 78, 1237–1239 (2001). Article  CAS  Google Scholar  * Takagi, T., Tanaka, H., Fujita, S. & Fujita, S. Molecular beam epitaxy of high magnesium content single-phase wurtzite

Mg_x_Zn1−_x_O alloy (_x_ ∼ 0.5) and their application to solar-blind region photodetectors. _Jpn J. Appl. Phys._ 42, L401–L403 (2003). Article  CAS  Google Scholar  * van de Walle, C. G.

Hydrogen as a cause of doping in zinc oxide. _Phys. Rev. Lett._ 85, 1012–1015 (2000). Article  CAS  Google Scholar  * Theys, B. et al. Effects of intentionally introduced hydrogen on the

electrical properties of ZnO layers grown by metalorganic chemical vapor deposition. _J. Appl. Phys._ 91, 3922–3924 (2002). Article  CAS  Google Scholar  * Tsukazaki, A. et al.

Layer-by-layer growth of high-optical-quality ZnO film on atomically smooth and lattice relaxed ZnO buffer layer. _Appl. Phys. Lett._ 83, 2784–2786 (2003). Article  CAS  Google Scholar  *

Ohtomo, A et al. Single crystalline ZnO films grown on lattice-matched ScAlMgO4(0001) substrates. _Appl. Phys. Lett._ 75, 2635–2637 (1999). Article  CAS  Google Scholar  * Koida, T. et al.

Correlation between the photoluminescence lifetime and defect density in bulk and epitaxial ZnO. _Appl. Phys. Lett._ 82, 532–534 (2003). Article  CAS  Google Scholar  * Chichibu, S. F. et

al. Emission mechanisms of bulk GaN and InGaN quantum wells prepared by lateral epitaxial overgrowth. _Appl. Phys. Lett._ 74, 1460–1462 (1999). Article  CAS  Google Scholar  * Look, D. C.,

Hemsky, J. W. & Sizelove, J. R. Residual native shallow donor in ZnO. _Phys. Rev. Lett._ 82, 2552–2555 (1999). Article  CAS  Google Scholar  * Sumiya, M. et al. Quantitative control and

detection of heterovalent impurities in ZnO thin films grown by pulsed laser deposition. _J. Appl. Phys._ 93, 2562–2569 (2003). Article  CAS  Google Scholar  * Ip, K. et al. Hydrogen

incorporation, diffusivity, and evolution in bulk ZnO. _Solid-State Electron._ 47, 2255–2259 (2003). Article  CAS  Google Scholar  * Guo, X.-L., Choi, J.-H., Tabata, H. & Kawai, T.

Fabrication and optoelectronic properties of a transparent ZnO homostructural light-emitting diode. _Jpn J. Appl. Phys._ 40, L177–L180 (2001). Article  CAS  Google Scholar  * Tsukazaki, A.

et al. Systematic examination of carrier polarity in composition spread ZnO thin films codoped with Ga and N. _Appl. Phys. Lett._ 81, 235–237 (2002). Article  CAS  Google Scholar  * Ohnishi,

T et al. Determination of surface polarity of c-axis oriented ZnO films by coaxial impact-collision ion scattering spectroscopy. _Appl. Phys. Lett._ 72, 824–826 (1998). Article  CAS  Google

Scholar  Download references ACKNOWLEDGEMENTS We thank T. Ohnishi and M. Lippmaa for measurement of coaxial impact-collision ion scattering spectroscopy. This work was supported by MEXT

Grant of Creative Scientific Research 14GS0204, MEXT Grant-in-Aid for Young Scientists 15685011, the Asahi Glass Foundation, and the inter-university cooperative program of the IMR. A.T. is

supported by a JSPS fellowship and S.F.C. is supported by the MEXT-COE21 program. AUTHOR INFORMATION AUTHORS AND AFFILIATIONS * Institute for Materials Research, Tohoku University, Sendai,

980-8577, Japan Atsushi Tsukazaki, Akira Ohtomo, Makoto Ohtani & Masashi Kawasaki * Institute of Applied Physics and Graduate School of Pure and Applied Sciences, University of Tsukuba,

Tsukuba, 305-8573, Japan Takeyoshi Onuma & Shigefusa F. Chichibu * Photodynamics Research Center, The Institute of Physical and Chemical Research (RIKEN), Sendai, 980-0845, Japan

Takayuki Makino, Shigefusa F. Chichibu & Yusaburou Segawa * Department of Electrical and Electronic Engineering, Shizuoka University, Hamamatsu, 432-8561, Japan Masatomo Sumiya & 

Syunrou Fuke * Research Institute of Electrical Communication, Tohoku University, Sendai, 980-8577, Japan Keita Ohtani & Hideo Ohno * Materials and Structures Laboratory, Tokyo Institute

of Technology, Yokohama, 226-8503, Japan Hideomi Koinuma * Combinatorial Material Science and Technology (COMET), Tsukuba, 305-0044, Japan Hideomi Koinuma & Masashi Kawasaki Authors *

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PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE CITE THIS ARTICLE Tsukazaki, A., Ohtomo, A., Onuma, T. _et al._ Repeated temperature modulation epitaxy for p-type doping and

light-emitting diode based on ZnO. _Nature Mater_ 4, 42–46 (2005). https://doi.org/10.1038/nmat1284 Download citation * Received: 28 June 2004 * Accepted: 27 September 2004 * Published: 19

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