Correlation between saturation magnetization and surface morphological features in Zn1xCrxO thin films

Y. M. Hu, S. S. Li, and C. H. Chia Citation: Appl. Phys. Lett. 98, 052503 (2011); doi: 10.1063/1.3549696 View online: http://dx.doi.org/10.1063/1.3549696 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v98/i5 Published by the American Institute of Physics.

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APPLIED PHYSICS LETTERS 98, 052503 2011

Correlation between saturation magnetization and surface morphological features in Zn1xCrxO thin lms
Y. M. Hu,a S. S. Li, and C. H. Chia
Department of Applied Physics, National University of Kaohsiung, Kaohsiung 81148, Taiwan

Received 30 December 2010; accepted 8 January 2011; published online 1 February 2011 The effect of chromium doping on the defect-induced ferromagnetism of Zn1xCrxO lms was investigated in this study. X-ray diffraction and x-ray photoelectron results conrm Cr substitution at Zn sites in the ZnO host lattice. A parabolic dependence of the saturation magnetization on the stoichiometric variable x was observed. Photoluminescence and magnetic results indicate that magnetic moments in Zn1xCrxO lms stem from Zn vacancies on the lm surface or at grain boundaries. As the variation in saturation magnetization is consistent with that in surface morphology, the ferromagnetism in Zn1xCrxO lms is sensitive to the morphological modication caused by Cr doping. 2011 American Institute of Physics. doi:10.1063/1.3549696 Throughout the last decade, zinc oxide ZnO doped with minute amounts of transition metal TM elements has been intensively investigated as a promising diluted magnetic semiconductor for potential spintronic device applications.1,2 Although room temperature ferromagnetism RTFM has often been observed in this material, no consensus has been reached regarding the coupling mechanism or the origin of the magnetic moments. Theoretical calculations originally predicted that free charge carriers are necessary for the ferromagnetic coupling among dispersive TM ions.3,4 Subsequent experiments, however, have shown RTFM in insulating TM-doped ZnO.5,6 Based on the bound magnetic polaron BMP model, Coey et al. proposed that a spin-split impurity band due to the overlap of BMPs enables a ferromagnetic coupling via the s-d exchange interaction.7 While the impurity band model might explain the coupling mechanism in TM-doped ZnO with a low carrier concentration, there is disagreement regarding the type of native defect that promotes the ferromagnetic order. RTFM in Cr-doped ZnO, for example, has been separately attributed to three types of defects: oxygen vacancies VO ,8 zinc vacancies VZn ,9 and zinc interstitials Zni .10 Several researchers have recently reported RTFM in undoped or nonmagnetic-element-doped ZnO,1113 implying that the magnetic moments arise solely from native defects. In view of this, one might suspect that the saturation magnetization Ms of TM-doped ZnO is closely related to the concentration of determinant defects irrespective of the TM ions. The correlation between Ms and defect concentration has already been proposed by several other researchers.1315 However, there exists a clear dependence of Ms on x for Zn1xTMxO lms deposited under the same conditions.16,17 TM doping also seems to inuence the concentration of determinant defects. In this report, the correlation between Ms and the surface morphological features of Zn1xCrxO thin lms is presented and discussed. We observed that minute amounts of Cr x 0.026 bring about a decrease in Ms, but a further increase in x instead leads to an increase in Ms. In particular, the variation in Ms is consistent with a change in
a

Author to whom correspondence should be addressed. Electronic mail: ymhu@nuk.edu.tw.

the surface morphology due to Cr doping. These results might elucidate the role of the Cr dopant and demonstrate the effect of Cr doping on the magnetic properties of Cr-doped ZnO thin lms. Zn1xCrxO 0 x 0.097 thin lms with thicknesses of about 350 nm were deposited on c-plane sapphire substrates at 400 C by sputtering ZnO 99.99% and/or Cr 99.99% targets in an ultrahigh vacuum system at a pressure of 2.6 Pa. Ultrapure 99.999% Ar and O2 gases were introduced at ow rates of 50 and 20 sccm, respectively, via two independent mass ow controllers. The crystal structure was examined by x-ray diffraction XRD with Cu K radiation = 1.5406 . Chemical bonding states and compositions of the lms were analyzed by x-ray photoelectron spectroscopy XPS with Mg K radiation h = 1253.6 eV . The surface morphology of the lms was examined by thermal eld emission scanning electron microscopy TF-SEM with an electron beam energy of 15 keV. The surface roughness was analyzed by using atomic force microscopy AFM in contact mode. Room temperature photoluminescence RTPL spectra were recorded at an excitation wavelength of 325 nm with a He-Cd laser. Magnetic properties were probed by magnetic property measurement system/superconducting quantum interference device/vibrating sample magnetometer dc magnetometery Quantum Design . Figure 1 a shows XRD -2 scans of Zn1xCrxO thin lms on a logarithmic scale. All of the lms have a highly c-axis-oriented wurtzite structure as evidenced by the prominent ZnO 002 peak. Neither Cr nor its oxide phases were observed. The inset of Fig. 1 a displays the variation in the c-axis lattice constant Lc with different x values. The Lc value was calculated directly from the ZnO 002 peak position using Braggs law. Clearly, the Lc values of Cr-doped ZnO lms are all smaller than those of undoped ZnO lms and increase with x. The contraction of Lc conrms Cr substitution at Zn sites mainly due to the smaller ionic radius of Cr2+ compared to Zn2+, while the slight increase in Lc with increasing x implies excess Cr at unoccupied or interstitial sites in the ZnO host lattice. Figure 1 b displays the XPS spectra of Cr 2p core levels in Zn1xCrxO lms. The multi-peak-tting results showed that the asymmetric Cr 2p3/2 state in Zn1xCrxO lms is comprised of two peaks, Cr2+ 576 eV and Cr3+
2011 American Institute of Physics

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052503-2

Hu, Li, and Chia

Appl. Phys. Lett. 98, 052503 2011

FIG. 3. Color online PL spectra of Zn1xCrxO lms at RT. FIG. 1. Color online a XRD -2 scans of Zn1xCrxO lms on a logarithmic scale. S designates the peak from the sapphire substrate. The inset illustrates the variation in the calculated Lc values with different x values. b The Cr 2p core level XPS spectra of Zn1xCrxO lms with different x values.

577.4 eV , for x 0.026 and of three peaks, Cr2+, Cr3+, 578.5 eV , for x 0.046. Evidently, some Cr and Cr6+ atoms occupy substitutional Zn sites as evidenced by the Cr2+ signal in all of the Cr-doped ZnO lms. The remaining Cr ions are in a 3+ valence state for x 0.026 but in 3+ and 6+ states for x 0.046. It appears that excess Cr atoms occupy vacant octahedral Cr3+ and tetrahedral Cr6+ sites sequentially in the ZnO host lattice, and the high-valency Cr ions are precursors for secondary oxide phases, such as the antiferromagnetic Cr2O3 and ZnCr2O4 Ref. 18 phases and the paramagnetic PM CrO3 phase.19 The TF-SEM images of Fig. 2 illustrate the surface morphological changes due to Cr doping. As Fig. 2 a shows, spherical grains are compactly distributed over the surface of the undoped ZnO lm. Cr doping might reduce grain size, blur grain boundaries, and give the surface a sanded appearance as seen in Figs. 2 b 2 d . In contrast, a quite different pattern with distinct grains was obtained for the lm with x = 0.097 as displayed in Fig. 2 e . The AFM micrograph in Fig. 2 f clearly shows a pattern of prominent and large grains. Although the cause of the unique pattern is unknown at this time, the presence of hexavalent Cr as evidenced by the XPS results seems to play a role. Figure 3 displays the RT-PL spectra of Zn1xCrxO lms. The undoped ZnO lm exhibits a sharp near-band-edge

NBE emission at 3.25 eV with a full-width-at-halfmaximum of approximately 103 meV. With increasing x, the nonradiative recombinations due to an increase in dopant concentration results in a rapid quenching of the NBE emission. The VO-related emission at around 2.4 eV Ref. 20 is absent in all of the lms deposited under an oxygen atmosphere. There is also an emission shoulder centered at 3.08 eV for the Zn1xCrxO lms with x 0.026. A theoretical calculation reported in the literature has predicted that the VZn level is located 0.3 eV above the valence band.21 The emission shoulder may be assigned to a transition from the conduction band to the VZn level. The PL results demonstrate that, for the Zn1xCrxO lms with x 0.026, the VZn concentration decreases with increasing x. Figure 4 a shows the M-H curves of Zn1xCrxO lms at RT, wherein the diamagnetic contribution from the sapphire substrate has been subtracted from the raw data. All of the lms exhibited a dominant PM response. After subtracting a positive slope PM response for each curve, we observed a weak FM signal for all of the lms Fig. 4 b . Certainly, the weak FM in the undoped ZnO lm results from neither the substrate nor the Cr dopant. The obtained Ms 0.4 emu/ cm3 is comparable with the reported value 0.5 emu/ cm3 for ZnO nanoparticles.22 A theoretical calculation has already predicted that a Zn vacancy in ZnO may result in the formation of 2.0 B local moment.23 Wang et al. predicted from

FIG. 2. Color online a e Magnied top-view TF-SEM micrographs of the Zn1xCrxO lms with x = 0, 0.016, 0.026, 0.046, and 0.097, respectively. f AFM micrograph with a scanning area of 3 3 m2 for the lm with x = 0.097.

FIG. 4. Color online a M-H curves of Zn1xCrxO lms at RT. After subtracting a PM response for each curve, the hysteresis loops are displayed in b .

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052503-3

Hu, Li, and Chia

Appl. Phys. Lett. 98, 052503 2011

rst-principles calculations that Zn vacancies tend to reside on the lm surface and that the magnetic moments arising from unpaired 2p electrons at O sites surrounding VZn might couple ferromagnetically if they are adjacent.24 In this study, the PL result indicates the existence of VZn in the undoped ZnO lm. A Hall measurement revealed that the undoped ZnO lm has poor conductivity, i.e., a high resistivity of 10.1 cm and an extremely low carrier concentration of 5.6 1014 cm3. We deduce that the dominant PM response arises from isolated Zn vacancies, while the weak RTFM results from clustered Zn vacancies, in which the induced magnetic moments may couple ferromagnetically without a need for charge carriers, on the lm surface or at grain boundaries. In particular, Ms of Zn1xCrxO lm decreases with increasing x and nearly vanishes for x = 0.026 as displayed in Fig. 4 b . The variation in Ms is exactly in accordance with the change in surface morphology shown in Figs. 2 a 2 c . Considering that the Zn vacancies tend to reside either on the lm surface or at grain boundaries, one could argue that Cr doping alters the surface morphology, thereby lessening the amount of clustered Zn vacancies and leading to a loss of RTFM for x = 0.026. The incorporated Cr ions are few and far apart, acting as isolated moments. As a result, the Cr ions contribute to PM only, and the slope of the PM response increases with x see Fig. 4 a . The decrease in Ms is not due to the incorporation of Cr at Zn vacancies because of a rebuilt RTFM in Zn1xCrxO lms with x 0.026 as seen in Fig. 4 b . The rebuilt RTFM is attributed to an occurrence of clustered Zn vacancies on prominent grains with distinct grain boundaries. As previously mentioned, the existence of hexavalent Cr accompanies the presence of prominent grains, where clusters of electron-compensator Zn vacancies in the nearest neighbors of high-valency Cr might be accessible. Clear evidence is necessary to support this claim, and relevant investigation is ongoing. For x 0.026, the isolated Cr moments might be close enough to couple antiferromagnetically, thereby reducing contributions to PM as seen in Fig. 4 a . The variation in Ms with x for Zn1xCrxO lms is analogous to a parabolic dependence of Ms on the relative change in Lc reported by Schoofs et al.,15 who ascribed the variation in Lc to a change in the concentration of determinant native defects for both ZnO and Zn0.99Mn0.01O thin lms. Although a similar correlation between Ms and Lc was also observed in samples from the present study, the impact of x on Lc cannot be ignored. On the contrary, this study clearly shows an impact of x on the morphological features of the lms, which directly affects surface defects. The determinant defects on the lm surface or at grain boundaries might depend not only on the deposition method and growth ambient but also on TM doping. For this reason, the reported magnetic properties of TM-doped ZnO lms are often inconsistent and controversial. In summary, the effect of Cr doping on defect-induced ferromagnetism in Zn1xCrxO 0 x 0.097 thin lms was

investigated. The weak RTFM in undoped ZnO lms is possibly a result of clustered Zn vacancies on the lm surface or at grain boundaries. For the Cr-doped ZnO lms, the variation in Ms is consistent with the change in surface morphology due to Cr doping. On the basis of the results, we conclude that Cr doping might modify surface morphological features, leading to the variation in Ms. In addition, incorporated Cr ions either contribute to PM only or couple antiferromagnetically, depending on x. This study was nancially supported by the National Nano Device Laboratories Grant No. NDL-97-C03SG-151 and the National Science Council Grant No. NSC-99-2112M-390-006 .
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