APPLIED PHYSICS LETTERS

VOLUME 81, NUMBER 10

2 SEPTEMBER 2002

Optical and magnetic measurements of p-type GaN epilayers implanted with Mn ions
Yoon Shon,a) Young Hae Kwon,b) Sh. U. Yuldashev, J. H. Leem, C. S. Park, D. J. Fu, H. J. Kim, and T. W. Kangc)
Quantum-Functional Semiconductor Research Center and Research Institute for Natural Sciences, Dongguk University, 3-26 Chungku Pildong, Seoul 100-715, Korea

X. J. Fan
Department of Physics, Wuhan University, Wuhan 430072, Peoples Republic of China

Received 28 May 2002; accepted for publication 22 July 2002 The p-type GaN epilayers were prepared by metalorganic chemical vapor deposition and subsequently Mn ions implanted. The properties of Mn ions-implanted GaN epilayers were investigated by optical and magnetic measurements. The results of photoluminescence measurement show that optical transitions related to Mn apparently appear at 2.5 eV and around 3.0 eV. It is conrmed that the photoluminescence peak at 2.5 eV is a donorMn acceptor transition. Ferromagnetic hysteresis loop was observed, and the temperature-dependent magnetization displayed a ferromagnetic behavior persisting up to 270 K. 2002 American Institute of Physics. DOI: 10.1063/1.1506778

In the area of diluted magnetic semiconductor DMS related to IIIV compound semiconductors, GaN is an excellent host material for successfully accomplishing DMS according to the computed value of the high Curie temperature.1 M. Zajac et al. reported magnetic and optical properties of GaMnN magnetic semiconductor using the ammonothermal method and obtained paramagnetic behavior. They suggested that the successful p-type doping of GaMnN may result in ferromagnetism of this material at room temperature.2 In this letter, we report the results of characteristics for Mn ion-implanted GaN epitaxial layers p type grown by metalorganic chemical vapor deposition MOCVD using energy dispersive x-ray EDX spectrometer, photoluminescence PL, atomic force microscopy AFM, and magnetic force microscopy MFM images, and superconducting quantum interference device SQUID magnetometer. The Mg-doped GaN lms were grown on c-plane sapphire (Al2 O3 ) substrates by MOCVD. Cyclopentadienyl magnesium (CP2 Mg) was employed as a p-type dopant. The thickness of the GaN:Mg epilayers is 1500 nm. In order to obtain p-GaN lms, the Mg-doped GaN lms were thermally annealed in the nitrogen atmosphere for 20 min at 800 C. The Hall measurement of GaN:Mg epilayers shows p-type conductivity and the carrier concentration is 3 1017 cm 3 . The p-type GaN epilayers grown by MOCVD were also uniformly implanted with Mn ions at an energy of 200 keV and doses of 5 1016 cm 2 . After the implantation of Mn ions, the rapid thermal annealing of p-type GaN epilayers has been performed in a owing nitrogen atmosphere and the annealing temperatures and times were varied between 700 and 950 C for 2 s and 30 s, respectively. The PL measurements
a

Electronic mail: son-yun@hanmail.net Electronic mail: sige@dongguk.edu c Author to whom correspondence should be addressed; electronic mail: twkang@dongguk.edu
b

were carried out using a 0.75 m monochromator equipped with an ultraviolet-sensitive photomultiplier tube. The excitation source was the 325 nm line of a HeCd laser with the total power of 50 mW. The measured EDX peaks displayed three peaks of Ga, N, and Mn with the molar concentrations of 47.3%, 34.9%, and 7.4%, respectively. Surface oxidation is responsible for the resolved oxygen peak near 0.6 keV. Figure 1 shows PL spectra at 14 K for as-grown, as-Mn implanted samples, and those annealed at different annealing temperatures and times. For an as-grown sample see inset of Fig. 1, the transition related to Mg appears at an energy of 2.8 eV without yellow luminescence YL transition. After the implantation of Mn ions, the as-implanted sample reveals new features. New peaks which do not appear in asgrown samples take place at an energy of 2.27, 2.50, and 3.0 eV along with a great reduction of transitions related to Mg. After the implantation of Mn ions, the GaN epilayer is damaged and a huge concentration of defects such as Ga vacancies ( V Ga), N vacancies ( V N), and Ga interstitial (GaI ) are generated.3 The existence of a large concentration of V N coincides with the result of EDX measurement showing the low concentration of N34.9%. Various and broad transitions of YL are caused by several closely spaced deep acceptor states. However, our interesting transitions are those at 2.5 and around 3.0 eV. We exclude the possibility of YL band at 2.5 eV because the apparent coexistence of the transition at 2.27 eV which is typical YL and 2.5 eV band has not been reported, to data, even though many researchers have studied GaN using various impurities.4 The new distinct peaks at 2.5 eV and around 3.0 eV exist in all the samples before and after the heat treatments. It is suggested that the transition at 2.5 eV is ( D , Mn) which means a donorMn acceptor pair transition and that around 3.0 eV is ( e , Mn) which means a conduction bandMn acceptor transition, respectively. In relation to ( e , Mn) and ( D , Mn) transitions, it is necessary to note that there are several types of Mn centers possibly formed in IIIV compounds, namely, the type of a neutral

0003-6951/2002/81(10)/1845/3/$19.00 1845 2002 American Institute of Physics Downloaded 01 Oct 2006 to 210.94.191.200. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp

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FIG. 2. Temperature dependent PL spectra of a sample annealed at 700 C for 2 s.

FIG. 1. PL spectra measured at 14 K for as-grown see inset, as-Mn implanted samples, and those annealed at different annealing temperatures and times.

Mn center ( A o ) is d 4 core e (tightly bound electron) 2 5 h (weakly bound hole) MnGa ( d ) h and has the property of ferromagnetic semiconductor, and it was found in some bulk GaAs:Mn samples.5,6 In the case of ( D , Mn), V N supplies donors and the above neutral Mn acceptors supply holes, which forms D A pairs. The suggestion on ( e , Mn) origin of the band at 3.0 eV can be supported by the results of temperature dependent PL spectra measurements. Figure 2 shows the temperature dependent PL spectra of a sample annealed at 700 C for 2 s. With increasing temperature, YL transitions disappear at 210 K and simultaneously D A pairs ( D , Mn) disappear gradually, but the transition related to ( e , Mn) is considerably activated. Only ( e , Mn) band exists at 270 K and disappears almost at 300 K. These results conrm the transition of ( e , Mn). Therefore we conclude that the transitions at 3.0 eV are ( e , Mn). Meanwhile, Fig. 1 shows the PL spectra of Mn ionimplanted GaN epilayers treated at different annealing temperatures for different durations. With increasing annealing temperature, most of YL decrease but ( e , Mn) and ( D , Mn) increase. Especially for ( e , Mn), the very remarkable activation of the peak related to Mn around 3.0 eV starts from an annealing temperature of 800 C for 30 s and it is well formed. This activation is caused by annealing of the defects introduced during ion implantation. The measurements of AFM and MFM images were carried out for the samples annealed at 750 C for 2 s and 850 C for 20 s, respectively. It can be deduced that the magnetic clusters in MFM image of the sample annealed at

750 C for 2 s were formed but not uniformly and satisfactorily formed. With increasing annealing temperature of 850 C for 20 s, the formation of GaMnN magnetic clusters is improved and is relatively well formed see inset of Fig. 3. The size of magnetic clusters is 200300 nm and their height is 2030 nm. These results agree with PL results that the transitions of ( e , Mn) and ( D , Mn) are noticeably activated at an annealing temperature of 850 C for 20 s in comparison with sample annealed at 750 C for 2 s see Fig. 1. The magnetic property has been characterized by SQUID magnetometer measurements Quantum Design MPMS-XL. In view of the results of PL and MFM image, Fig. 3 shows the measurement of magnetization. The measurement of hysteresis loop at 10 K was accomplished for the sample an-

FIG. 3. AFM and MFM images of Mn ion-implanted sample annealed at 850 C for 20 s see inset and hysteresis loop measured at 10 K of a sample annealed at 850 C for 20 s. Downloaded 01 Oct 2006 to 210.94.191.200. Redistribution subject to AIP license or copyright, see http://apl.aip.org/apl/copyright.jsp

Appl. Phys. Lett., Vol. 81, No. 10, 2 September 2002

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( e , Mn) around 3.0 eV start from an annealing temperature of 800 C for 30 s and is well formed. AFM and MFM images show that magnetic clusters are properly formed at an annealing temperature of 850 C for 20 s, which coincides with the PL result that the transitions of ( e , Mn) and ( D , Mn) are noticeably activated at such temperature and annealing time. The ferromagnetic hysteresis loops of the sample annealed at 850 C for 20 s was obtained and the same sample showed a ferromagnetic behavior persisting up to 270 K. This work was supported by the Quantum-Functional Semiconductor Research Center QSRC, and by a research fund of the Dongguk University, 2002 and National Natural Science Foundation of China Contract No. 50175082.
1

FIG. 4. Temperature dependent magnetization of a sample annealed at 850 C for 20 s.

nealed at 850 C for 20 s and ferromagnetic hysteresis loop was obtained. Figure 4 shows the temperature dependence of magnetization of the sample annealed at 850 C for 20 s. The sample displayed a ferromagnetic behavior persisting up to 270 K. In summary, the distinct PL peaks related to ( e , Mn) and ( D , Mn) appear apparently at 3.0 eV and around 2.5 eV, respectively. It is suggested that the transition at 2.5 eV is ( D , Mn), and not YL. The very remarkable activations of

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