APPLIED PHYSICS LETTERS

VOLUME 83, NUMBER 10

8 SEPTEMBER 2003

Raman scattering in ZnO thin lms doped with Fe, Sb, Al, Ga, and Li
C. Bundesmann,a) N. Ashkenov, M. Schubert, D. Spemann, T. Butz, E. M. Kaidashev,b) M. Lorenz, and M. Grundmann
Universitat Leipzig, Fakultat fur Physik und Geowissenschaften, Institut fur Experimentelle Physik II, Linnestrae 5, 04103 Leipzig, Germany

Received 8 May 2003; accepted 22 July 2003 Polarized micro-Raman measurements were performed to study the phonon modes of Fe, Sb, Al, Ga, and Li doped ZnO thin lms, grown by pulsed-laser deposition on c-plane sapphire substrates. Additional modes at about 277, 511, 583, and 644 cm 1 , recently assigned to N incorporation A. Kaschner et al., Appl. Phys. Lett. 80, 1909 2002 , were observed for Fe, Sb, and Al doped lms, intentionally grown without N. The mode at 277 cm 1 occurs also for Ga doped lms. These modes thus cannot be related directly to N incorporation. Instead, we suggest host lattice defects as their origin. Further additional modes at 531, 631, and 720 cm 1 seem specic for the Sb, Ga, and Fe dopants, respectively. Li doped ZnO did not reveal additional modes. 2003 American Institute of Physics. DOI: 10.1063/1.1609251

Wurtzite-type ZnO and its compounds are interesting materials for optoelectronic devices for operation in the blue and UV spectral region. Recent research interest is focused on p-type ZnO, because reproducible p-type doping is still a challenge. Nitrogen incorporation is seen as the most prospective pathway to produce p-type conductivity. Because control of the electrical conductivity behavior of ZnO is not fully understood in general, we have grown Fe, Sb, Al, Ga, and Li doped thin lms in order to study the inuence of the individual dopants on the free-charge-carrier properties. Raman spectroscopy is a versatile technique for fast and nondestructive study of dopant incorporation, particularly when impurity-induced modes can be traced back to individual constituents and their concentration, as demonstrated for example with Mg and As in hexagonal and cubic GaN.1 Recently, Kaschner et al.2 reported on Raman measurements of N doped ZnO thin lms, which were deposited by chemical vapor deposition on GaN templates grown on c-plane sapphire. The authors observed additional modes AMs , and explained the occurrence as local vibrational modes due to vibrating nitrogen-related complexes. A relation between the intensities of the observed AMs and the amount of incorporated N was deduced, suggesting its use for determination of nitrogen incorporation by Raman spectroscopy. In this work we report on Raman studies of Fe, Sb, Al, Ga, and Li doped ZnO thin lms, which were grown intentionally without nitrogen incorporation. In addition, we report on studies of Ga doped lms grown under NO2 atmosphere, and ZnO lms deposited from a target containing Li3 N, which we expected to reveal large N incorporation. The result of our study is i the need for revision of previous mode assignment related to N, ii the existence of additional modes seemingly related to specic dopants, iii the existence of additional modes tentatively related to intrinsic host lattice defects. All thin lms were prepared by multistep pulsed laser
a

Author to whom correspondence should be addressed; electronic mail: bundesm@physik.uni-leipzig.de b On leave from: Rostov-on-Don State University, Mechanics and Applied Mathematics Research Institute, Rostov-on-Don 344090, Russia.

deposition on 10 10 0.5 mm3 sized c-plane sapphire 0001 substrates.3 The polycrystalline laser targets were prepared by ball milling 710 g ZnO 5N together with 0.5 g Fe2 O3 , 0.05 g Sb2 O3 , 0.050.1g Al2 O3 , 0.010.5 g Ga2 O3 , or 0.5 g Li3 N powder, cold pressing, and subsequent target sintering. One of the studied Ga doped lms was grown under N2 O atmosphere, all others under pure O2 atmosphere. The typical lm thickness lies between 0.8 and 1.6 m. The thin lms were characterized by x-ray diffraction and ion beam analysis using Rutherford backscattering RBS , particle induced x-ray emission PIXE , and particle induced gamma-ray emission PIGE . The typical dopant concentration of the Fe, Sb, Al, Ga, and Li doped thin lms was 8%, 0.5%, 2%, 0.5%5%, and up to 17%, respectively, compared to oxygen. The N incorporation in all lms, including those grown with the ZnO/Li3 N target, and under the NO2 atmosphere, was found below the RBS detection limit of 23 at. %. Micro-Raman scattering experiments were performed using a DILOR XY800 spectrometer with a spectral resolution of 4 cm 1 in the wavenumber range from 230 to 760 cm 1 . The 514.53 nm line of an Ar -ion laser was used for excitation and the incident laser power was 40 mW. The spectra were recorded in the z(xy)z and z(xx)z top , as well as in the x(zy)x , x(zz)x , and x(y y)x edge backscattering congurations. The letters before and after the parentheses show the direction of the incident and scattered light, while the letters inside the parentheses show their polarization.4 The z direction of the laboratory coordinate system is normal to the sample surface and parallel to the lm and substrate c axis. Bands in Raman spectra were analyzed by determining their center wave numbers. The estimated wave number error is at least half of the spectral resolution ( 2 cm 1 ). Wurtzite-type ZnO belongs to the space group C 4 v with 6 two formula units in the primitive cell. The optical phonons at the point of the Brillouin zone belong to the following irreducible representation:5
opt

1A 1 2B 1 1E 1 2E 2 .

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Appl. Phys. Lett., Vol. 83, No. 10, 8 September 2003

Bundesmann et al.

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FIG. 1. Polarized micro-Raman spectra obtained in the scattering geometries z(xy)z a , z(xx)z b , x(y y)x c , x(yz)x d , and x(zz)x e for the Fe doped ZnO thin lm on c-plane sapphire. Dotted and dashed lines indicate the wave numbers of possible ZnO and sapphire modes, respectively. Solid lines denote additional modes.

FIG. 2. Polarized micro-Raman spectra in the x(y y)x scattering conguration for undoped, Ga, Al, Sb, and Fe doped ZnO thin lms on sapphire. The ZnO:Ga* lm was grown in N2 O atmosphere, all other samples were grown in O2 atmosphere. Triangles denote additional modes.

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Both A 1 and E 1 modes are polar and split into transverse TO and longitudinal optical LO phonons, all being Raman and infrared active. The two nonpolar E 2 modes (E (1) , 2 E (2) ) are Raman active only. The B 1 modes are infrared and 2 Raman inactive silent modes . Figure 1 shows Raman spectra in ve different scattering congurations for a Fe doped ZnO thin lm. Polarized Raman spectra for undoped ZnO thin lms on c-plane sapphire and for single crystals were discussed in detail previously.6 The ZnO E (2) phonon mode occurs at 438 cm 1 , and the 2 line at 332 cm 1 was assigned to multiple-phonon processes, and occurs in ZnO thin lms as well. The lines at 379, 417, 430, 447, 576, and 749 cm 1 belong to sapphire modes. The two strong bands at 584 and 644 cm 1 were not detected for pure ZnO, and partially overlap with sapphire (E g :576 cm 1 , A 1g :645 cm 1 ) and ZnO E 1 (LO): 587 cm 1 modes. These lines are identied as AMs, because the bands are present in scattering congurations, where the respective ZnO and sapphire modes are symmetry forbidden. Consider, for instance, the structure at 584 cm 1 : The ZnO A 1 (LO) (575 cm 1 ) and E 1 (LO)(587 cm 1 ) modes are allowed in the z(xx)z and x(zz)x scattering congurations, respectively. The A 1 (LO) mode has not yet been observed in ZnO thin lms, likely because it is subsumed by the strong sapphire E g mode. The E 1 (LO) mode was previously detected only as a weak feature in thin lms.6 The sapphire mode at 576 cm 1 is not allowed in the x(zz)x conguration,7 appears weakly in the x(y y)x and x(yz)x congurations, and is strongest in the two top congurations. Here the sapphire mode at 576 cm 1 was found as a sideband of the strong band centered at 584 cm 1 in the

two top scattering congurations, whereas the mode at 584 cm 1 is found in all ve scattering congurations. Hence, this mode cannot be assigned to the host ZnO or to the sapphire lattice, and must be an AM. Similar arguments hold for the mode at 644 cm 1 . Another ve AMs, well separated from ZnO and sapphire modes, appear at 277, 513, 624, 713, and 720 cm 1 in the spectra of the Fe doped ZnO thin lm. Figure 2 summarizes Raman spectra in the x(y y)x scattering conguration for Fe, Sb, Al, Ga, doped and undoped ZnO thin lms. In this geometry the contributions due to AMs is most prominent. All AMs identied here for the Fe, Sb, Al, and Ga doped lms, as discussed below, are listed in Table I. Interestingly, several ZnO lms deposited from the target containing Li3 N, which contain up to 17% Li and for which we expected the largest N incorporation, did not reveal any contributions due to AMs in the wave number range studied here. In Fig. 2, AMs at about 277, 511, 583, and 644 cm 1 appear in the spectra of the Fe, Sb, and Al doped thin lms, as well as in the spectra of the Ga doped sample grown in N2 O atmosphere, while only the mode at 277 cm 1 appears in the spectra of the Ga doped lm grown in O2 atmosphere. Previous Raman experiments on the N doped ZnO thin lms grown by chemical vapor deposition on GaN templates revealed distinct AMs at 275, 510, 582, 643, and 856 cm 1 , 2,8 which agree very well with AMs found here within the abovementioned error limit. The mode at 856 cm 1 , which was low in scattering intensity,2 lies outside the wave number range studied here. The Ga content in the samples studied in Ref. 2 was not specied. A linear relation between the scattering intensities of the AMs and the N content was reported.2 However, the AMs at 277, 513,

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Appl. Phys. Lett., Vol. 83, No. 10, 8 September 2003 TABLE I. Dopant concentration and wave numbers of the observed additional modes in Fe, Sb, Al, Ga, doped ZnO thin lms grown by PLD on c-plane sapphire in O2 atmosphere. For comparison, values for N doped ZnO lms grown by chemical vapor deposition on GaN templates from Ref. 2 are included. No additional mode was found in the ZnO thin lms containing up to 17% Li. Dopant concentration % 8 0.5 2 0.55 0.1 277 277 276 277 277 275 513 511 509 512 510 531

Bundesmann et al.

Sample ZnO:Fe ZnO:Sb ZnO:Al ZnO:Ga ZnO:Gaa ZnO:Nb

a b

Additional modes (cm 584 583 579 583 582 624 623 631 624

) 713 685 720

644 644 643 644 643

Grown in N2 O atmosphere. Reference 2.

583, and 644 cm 1 occur also in the Raman spectra of the Fe, Sb, and Al doped thin lms, and the 277 cm 1 line in the Ga doped thin lms grown in O2 atmosphere. Because no N was present during our thin lm preparation process, an assignment to N obviously cannot hold for these modes. Further support for this conclusion is the scattering intensity distribution among the AMs observed here, which differs between the Fe, Sb, Al, and Ga doped lms, and which is different from that reported in Ref. 2. For example, in the two top z(xx)z and z(xy)z congurations, the modes at 580 and 275 cm 1 were, apart from the ZnO E (2) phonon 2 mode at 437 cm 1 , the strongest features in the samples studied in Ref. 2, whereas for the Fe doped thin lm the mode at 277 cm 1 is hardly observed in the z(xy)z conguration see Fig. 1 . In the Ga doped lms grown in O2 atmosphere the AM at about 580 cm 1 cannot be separated from the sapphire E g mode at 576 cm 1 , whereas the AM at 277 cm 1 appears in the edge and top congurations. Because of the large differences in mass between dopants Fe, Sb, Al, and Ga we expect that the AMs discussed above are related to intrinsic host lattice defects, which either become activated as vibrating complexes or their concentration increases upon dopant incorporation. This assumption is supported by the fact that none of our undoped ZnO thin lms, deposited on c-plane sapphire, revealed any of the AMs discussed above. Interestingly, preliminary Raman experiments on undoped ZnO lms grown on r-plane sapphire, which exhibit lower structural quality, reveal AMs at 276, 511, and 581 cm 1 . In this respect, the fact that the Li doped thin lms did not show any of the AMs could be due to higher thin lm quality, or alternatively due to screening of the host defect vibrational complexes upon the highly mobile Li ions within the wurtzite ZnO lattice. At this point, further struc-

ture investigations and theoretical calculations are required for denite assignments. Finally, we point out that some of the AMs appear only in the spectra of ZnO thin lms with certain dopant species, such as the AM at 720 cm 1 for the Fe doped, at 531 cm 1 for the Sb doped, and at 631 cm 1 for Ga doped thin lms. These modes seem to be related to the individual dopants, and may be used as indication for their incorporation. This work was supported by the Bundesministerium fur Bildung und Forschung within the Wachstumskern INNOCIS FKZ 03WKI09 , and by the Deutsche Forschungsgemeinschaft Gr 1011/10-1 within SPP 1136 . The authors thank Ulrike Teschner for technical support during the Raman measurements.
1

G. Kaczmarczyk, A. Kaschner, A. Hoffmann, and C. Thomsen, Phys. Rev. B 61, 5353 2000 . 2 A. Kaschner, U. Haboeck, M. Strassburg, M. Strassburg, G. Kaczmarczyk, A. Hoffmann, C. Thomsen, A. Zeuner, H. R. Alves, D. M. Hofmann, and B. K. Meyer, Appl. Phys. Lett. 80, 1909 2002 . 3 E. M. Kaidashev, M. Lorenz, H. von Wenckstern, A. Rahm, H.-C. Semmelhack, K.-H. Han, G. Benndorf, C. Bundesmann, H. Hochmuth, and M. Grundmann, Appl. Phys. Lett. 82, 3901 2003 . 4 T. C. Damen, S. P. S. Porto, and B. Tell, Phys. Rev. 142, 570 1966 . 5 C. A. Arguello, D. L. Rousseau, and S. P. S. Porto, Phys. Rev. 181, 1351 1969 . 6 N. Ashkenov, B. N. Mbenkum, C. Bundesmann, V. Riede, M. Lorenz, D. Spemann, E. M. Kaidashev, A. Kasic, M. Schubert, M. Grundmann, G. Wagner, H. Neumann, V. Darakchieva, H. Arwin, and B. Monemar, J. Appl. Phys. 93, 126 2003 . Note the subtle misprint of the geometry assignment in Figs. 7 and 8. The correct assignment is obtained after exchanging x(y y)x x(zz)x . 7 G. H. Watson, Jr., W. B. Daniels, and C. S. Wang, Phys. Rev. B 52, 956 1981 . 8 X. Wang, S. Yanga, J. Wanga, M. Lia, X. Jianga, G. Dua, X. Liub, and R. P. H. Chang, J. Cryst. Growth 226, 123 2001 .

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