Polarity of (00.1) GaN epilayers grown on a (00.

1) sapphire
M. Seelmann-Eggebert, J. L. Weyher, H. Obloh, H. Zimmermann, A. Rar et al. Citation: Appl. Phys. Lett. 71, 2635 (1997); doi: 10.1063/1.120163 View online: http://dx.doi.org/10.1063/1.120163 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v71/i18 Published by the AIP Publishing LLC.

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Polarity of 00.1 GaN epilayers grown on a 00.1 sapphire

M. Seelmann-Eggebert,a) J. L. Weyher, H. Obloh, H. Zimmermann, A. Rar, and S. Porowskib)
r Angewandte Festko rperphysik, Tulla Strasse 72, 79108 Freiburg, Germany Fraunhofer Institut fu

Received 27 May 1997; accepted for publication 3 September 1997 The polarity is found to be a key parameter for the growth of high quality epitaxial GaN lms on sapphire 00.1 substrates. A model is suggested which may consistently explain the observed inuence of the process parameters on the polar orientation of the epitaxial lm. A simple etching technique is proposed for quick distinction of the lm polarity. The assignment of the etching behavior to the proper crystal structure is achieved by an analysis of the respective two-dimensional photoelectron diffraction patterns. 1997 American Institute of Physics. S0003-69519701644-6

Presently, much effort in research and development is directed towards the material system Alx Ga1 x N and Inx Ga1 x N, since these materials allow one to fabricate blue light emitting diodes and lasers.1 Despite the very large lattice mismatch of 16% to GaN, it is most common to use sapphire ( -Al2O3) of (00 1) orientation as a substrate for GaN epitaxy. To obtain high quality epilayers on these substrates one must perform carefully a sequence of growth initiation procedures.2,3 Nevertheless, a poor surface morphology, which is related to a high density of extended defects, may still frequently result.46 Guided by systematic trends observed for a large number of GaN layers grown in our metalorganic chemical vapor deposition MOCVD reactor we discovered that the polarity7 of the epilayer is a key parameter to obtain smooth and low defect density lms. Nitrogen terminated epilayers are generally found to show a rough surface morphology6 Fig. 1c comprising pyramidal grains and extended defects such as inversion domains.4,8 Conversely, gallium terminated GaN lms can be grown with atomically at surfaces Fig. 1a although under nonideal growth conditions, lms of this polarity can have a ne grained structure and/or contain micropipes Fig. 1b. Despite the apparent importance of its strict control, up to now the epilayer polarity has been only assessed by elaborate cross sectional transmission electron microscopy TEM analysis, since simple techniques for its determination were not yet at hand. However, we have recently found9 that aqueous solutions of KOH or NaOH 110 N selectively attack GaN surfaces of one polarity, whereas surfaces of the opposite polarity remain completely unaffected even by a long term exposure to this chemical agent. The polarity dependence of some etchants is a phenomenon well known from other compound semiconductors.10,11 Using a technique described below we found that the chemical active face of GaN is the one that is terminated by nitrogen atoms. If a rough GaN layer Fig. 1c is of nitrogen termination it can be chemomechanically Ch-M polished to atomically smooth perfection Fig. 1d with use of a KOH solution. A brief polishing 23 min with a 10 wt % KOH solution is sufa

cient to atten a surface with an initial RMS roughness as large as 400 Figs. 1c and 1d. Subsequent free-etching in the same solution results in a facetted surface structure.9 Conversely, sample surfaces which are gallium terminated Figs. 1a and 1b are resistant to both free-etching and Ch-M polishing. Hence, the two polarity orientations are easy to distinguish by simple inspection of their behavior upon etching: a nitrogen termination becomes evident by either smoothening of a rough surface upon Ch-M polishing or roughening of a smooth surface by facet formation upon free-etching. Regarding earlier attempts to determine the polarity of 00.1 GaN surfaces controversal results have been reported in the literature. Convergent beam electron diffraction CBED was used to determine the polarity of 00.1oriented heteroepitaxial GaN lms8 and single crystals.5,12 The results of Refs. 5 and 12 are inconsistent, although in both cases they were based on a comparison of calculations

Electronic mail: Seelmann@iaf.fhg.de High Pressure Institute, Polish Academy of Science, 01-142 Warsaw, Poland.

FIG. 1. Surface morphology of epitaxial GaN layers a smooth surface RMS roughness r 0.2 0.8 nm, b grainy surface ( r 25 nm), c rough surface with hexagonal hillocks ( r 40 nm), d surface c after mechanochemically polishing ( r 0.4 nm) as observed in differential interference contrast images. The marker bar represents 10 m. The HSXPD determination of polarity revealed that a and b are gallium terminated, c and d are nitrogen terminated. The roughness was determined by AFM. 1997 American Institute of Physics 2635

Appl. Phys. Lett. 71 (18), 3 November 1997

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FIG. 2. Stereographic HSXPD patterns as measured with Mg K excitation for two different GaN epilayers. a Ga 3d photoelectrons of sample 1, b Ga 3d of sample 2, c N 1s photoelectrons of sample 1, d N 1s of sample 2. The surface of the sample on the left right had a smooth rough appearance.

with the experimental CBED and obtained for single crystals from the same source High Pressure Research Centre, Warsaw, Poland. Those single crystal platelets always show one smooth surface and a rough surface on the reverse side.13 Ponce et al.5 identied the smooth surface to be Ga terminated, whereas the results of Lilienthal et al.12 suggest that this surface is nitrogen terminated. With the objective to resolve the ambiguities regarding polarity assignment, we employed hemispherically scanned x-ray photoelectron diffraction HSXPD which has been proven to be capable of determining the polarity of compound semiconductor surfaces.11 Using HSXPD we investigated epilayers grown by MOCVD on sapphire 00.1 under various conditions. We also analyzed GaN bulk single crystals for which, in agreement with the results of Lilienthal,12 we found that the smooth surface of the high pressure grown single crystalline GaN platelets is of nitrogen termination.14 In contrast, the epilayers with smooth surfaces obtained by MOCVD growth showed generally a gallium termination. It is worth noting that the termination of the surface could not be assessed by simple polar X-ray photoelectron spectroscopy XPS scans, since for both polar orientations the GaN lms generally showed an excess of gallium at the surface owing to the presence of a thin galliumoxide layer or a tendency for preferential removal of nitrogen upon in situ sputter or plasma cleaning. HSXPD proved to be insensitive to such interfering effects. HSXPD has the advantage that the structural information on the near neighbors conveyed in the angular dependent diffraction features is independently obtained for the gallium and the nitrogen atoms. A recently developed analytical tool, the combined holographic real space imaging by superimposed dimer functions algorithm CHRISDA,15 is applied for the analysis of the HSXPD patterns. CHRISDA is a Fourier related transform which combines the holographic aspects and the strong forward scattering features incorporating triangulation for sections of lattice planes.15 For a given set of emitter positions chosen on the
2636 Appl. Phys. Lett., Vol. 71, No. 18, 3 November 1997

FIG. 3. CHRISDA analysis of the Ga 3d pattern of Fig. 2b left column and the N 1s pattern of Fig. 2d right column. The analysis was based on three possible emitter positions below a scatterer plane as shown in the insert. a and b show angular overlap integral in dependence of the distance between emitter and a scatterer plane pattern with 30 contributing scatterers. c and d show occupation probability proles of the scatterer planes as derived from a and b, respectively. e and f show the nominal stacking sequence along 00.1 wurtzite in terms of the three emitterscatterer congurations. The joint occupation density expected for the two nonequivalent Ga emitters in the unit cell is plotted e for the N face and f for the Ga face.

basis of symmetry considerations CHRISDA yields a set of respective occupation probability distributions OPDs as a function of the distance of the scatterer plane to the emitter below. These OPDs can be directly compared with the stacking sequence and distance of the planes in the nominal crystal lattice. Figure 2 shows two sets of HSXPD patterns obtained for epitaxial GaN samples which were Ga terminated left column and nitrogen terminated right column, respectively. Pronounced differences between the respective patterns of the N 1s and Ga 3d photoelectrons allows one to clearly discriminate between the two polar orientations. For the right column of Fig. 2, Fig. 3 shows the result of the CHRISDA analysis top and center row in comparison with the nominal stacking of planes in the wurtzite structure along the 00.1
Seelmann-Eggebert et al.

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axis bottom row. In the occupation density proles of Figs. 3e and 3f both nonequivalent emitters in the unit cell have been taken into account and the origin has been placed at a gallium and a nitrogen atom, respectively. If the analyzed layer has a nitrogen termination, for each column agreement between the probability distributions in the center and the occupation density at the bottom is expected, while for a gallium terminated surface a crosswise correspondence should exist. The rst stage of CHRISDA top row involves the analysis of the angular overlap between the experimental pattern and the simplied basis patterns calculated for a planar section containing 30 scatterers with the emitter positions indicated in the insert. The center row presents a rened analysis after elimination of potential ambiguities related to small nonorthogonality effects of these basis patterns. The excellent agreement for both the N 1s and the Ga 3d photoelectrons between the experimental probability distributions and the nominal occupation density gives clear evidence that the analyzed sample has a wurtzite structure and that the respective polarity corresponds to a termination by nitrogen atoms. Regarding the factors which determine the constitution of the polarity of the growing lm we observed that the pretreatment of the substrate surface has a signicant effect. An initial nitridation step performed by exposing the clean substrate to NH3 for a period of 13 min was found to reduce the Al2O3 and to result in the formation of AlN islands,3 which are likely to extend over several monolayers into the substrate. These AlN islands were present in the hexagonal phase, formed in registry with the oxygen sublattice of the substrate, and had a polarity which implied a termination by nitrogen atoms. Serving as nucleation seeds for the buffer layer growth these AlN seeds pass on their crystalline properties not only to the buffer as revealed by HSXPD but also to the subsequently grown epitaxial lm.3 Hence, GaN lms when grown on a nitridated sapphire 00.1 surface, predominantly consisting of unipolar domains with nitrogen termination. Such lms showed a strong tendency towards surface roughening during growth. Conversely, single crystalline lms which were gallium terminated could be obtained only when, for initiation of growth, all traces of ammonia had been removed from the MOCVD reactor and the heat cleaned sapphire surface was exposed exclusively to the trimethylgallium precursor. These surfaces were found to be of signicantly higher chemical stability and generally showed an excellent surface morphology over the entire 2 in. wafer if the epilayers were grown at sufciently high temperature T 950 1000 C, see Fig. 1a. Occasionally, we could observe macroscopic regions of differing polarity on a single wafer. Showing different surface morphologies by their mirrorlike or diffusely reecting appearance these regions were easy to distinguish. The occurrence of inversion domains in the lms was mainly attributed to poor process control during substrate cleaning and the very initial stage of the nucleation process preceding buffer growth. These observations can be consistently explained in the framework of a simple model for the mechanism of polarity selection for the growing lm. Assuming that deposition starts with gallium atoms on a sapphire 00.1 surface terminated by oxygen atoms, and applying Paulings second rule,
Appl. Phys. Lett., Vol. 71, No. 18, 3 November 1997

Kung et al.16 suggested that the top site on the Ga atom is the energetically favorable position for subsequent nitrogen adsorption. Consequently, a lm polarity should be established which has a cation termination in the bilayers forming the epitaxial lm. However, if upon the initial nitridation of the sapphire surface the oxygen atoms in the top layer are largely replaced by nitrogen atoms, the underlying Al atoms experience these nitrogen atoms in exactly the opposite conguration and nitrogen terminated bilayers can become the planar units in subsequent layer growth. These conceptual considerations are merely inuenced by the fact that above 900 C the sapphire surface is found to be, at least partially, terminated by a layer of Al atoms.3,17 In summary, we have found a strong correlation between surface morphology and the termination of the surface. To obtain smooth GaN lms by MOCVD it is necessary to ensure that a gallium termination is established in the initial stages of lm formation. Using a KOH based etching process we suggest a simple and quick procedure to analyze and distinguish the two polar orientations of 00.1 wurtzite type GaN lms and crystals. ller for the atomic The authors would like to thank S. Mu force microscope AFM measurements and P. Meisen for technical assistance. One of the authors J.L.W. acknowledges support by Grant No. NATO HTECH. EV 960986.

S. Nakamura, M. Senoh, S. Nagahama, N. Iwasa, T. Ymada, T. Matsushita, H. Kiyoku, and Y. Sugimoto, Appl. Phys. Lett. 68, 2105 1996. 2 S. Keller, B. P. Kemmer, Y.-F. Wu, B. Heyring, D. Kapolneck, J. S. Speck, U. K. Mishra, and S. P. Denbaars, Appl. Phys. Lett. 68, 1525 1996. 3 M. Seelmann-Eggebert, H. Zimmermann, H. Obloh, R. Niebuhr, and B. Wachtendorf, Mater. Res. Symp. Proc. 468, 193 1997. 4 J. L. Rouviere, M. Arlery, R. Niebuhr, K. H. Bachem, and O. Briot, MRS Internet J. Nitride Semicond. Res. 1, 33 1996. 5 F. A. Ponce, D. P. Bour, W. T. Young, M. Saunders, and J. W. Steeds, Appl. Phys. Lett. 69 1996. 6 Final Report of the Brite-Euram II EC-Project BRE2-CT93-0526 1996. 7 A close relation between the polarity of the 00.1 crystal face and a surface terminating atomic layer is established if the ideal wurtzite lattice is truncated by a plane cutting only a single bond per atom. In this sense, we describe the polarity of a crystal face in terms of a surface termination. 8 ` re, and M. Arlery, Appl. Phys. Lett. 69, 2480 B. Daudin, J. L. Rouvie 1996. 9 ller, I. Grzegory, and S. Porowski, J. Cryst. Growth J. L. Weyher, S. Mu 182 1997. 10 J. L. Weyher, in Handbook on Semiconductors, edited by S. Mahajan Elsevier, Amsterdam, 1994, Vol. 3, p. 1005. 11 M. Seelmann-Eggebert and H. J. Richter, J. Vac. Sci. Technol. B 9, 1861 1991. 12 Z. Liliental-Weber, C. Kisielowski, S. Ruvimov, Y. Chen, J. Washburn, I. Grzegory, M. Bockowski, J. Jun, and S. Porowski, J. Electron. Mater. 25, 1545 1996. These authors use a denition for the polar orientation which differs from the conventional one used here. 13 G. Novak, S. Krukowski, J. Grzegory, S. Porowski, J. M. Baranowski, K. Pakula, and J. Zak, MRS Internet J. Nitride Semicond. Res. 1, 5 1996. 14 ` re, J. L. Weyher, M. Seelmann-Eggebert, and S. Porowski, J. J. L. Rouvie Cryst. Growth submitted for publication. 15 M. Seelmann-Eggebert, Surf. Sci. 377 379, 1094 1997; Phys. Rev. B 55, 15 842 1997. 16 P. Kung, C. J. Sun, A. Saxler, H. Ohsato, and M. Razeghi, J. Appl. Phys. 75, 4515 1994. 17 M. Gautier, J. P. Durand, L. Pham Van, and M. J. Guittet, Surf. Sci. 250, 71 1991. Seelmann-Eggebert et al. 2637

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