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IEEE JOURNAL OF SELECTED TOPICS IN QUANTUM ELECTRONICS, VOL. 17, NO. 4, JULY/AUGUST 2011

Properties of GaN Nanowires Grown by Molecular Beam Epitaxy

Lutz Geelhaar, Caroline Ch` ze, Bernd Jenichen, Oliver Brandt, Carsten Pf ller, Steffen M nch, Ralph Rothemund, e u u Stephan Reitzenstein, Alfred Forchel, Thomas Kehagias, Philomela Komninou, George P. Dimitrakopulos, Theodoros Karakostas, Leonardo Lari, Paul R. Chalker, Mhairi H. Gass, and Henning Riechert
(Invited Paper)

AbstractOn Si(1 1 1) and Si(0 0 1), GaN nanowires (NWs) form in a self-induced way without the need for any external material. On sapphire, NW growth is induced by Ni collectors. Both types of NWs exhibit the wurtzite crystal structure and grow in the Gapolar C-direction perpendicular to the substrate. The NW sidewalls are M-plane facets, although on the Ni-induced NWs also A-plane segments form, if the growth temperature is low. Both self-induced and collector-induced NWs are free of strain and epitaxially aligned to the substrate, but in particular the former show a signicant spread in tilt and twist caused by a mostly amorphous interfacial layer of SiN. The self-induced NWs are virtually free of extended defects, but the collector-induced NWs contain many stacking faults. The photoluminescence of the former is signicantly brighter and sharper. The spectra of single, dispersed, selfinduced NWs contain extremely sharp excitonic lines. Signicant emission is caused by excitons bound to donors close to the surface whose binding energy is reduced compared to the bulk value. In comparison, both the microstructure and optical properties of the self-induced NWs are superior. The limited material quality of the collector-induced NWs can be explained by detrimental effects of the collector. Index TermsCrystal growth, nanotechnology, semiconductor materials measurements.

I. INTRODUCTION

AN NANOWIRES (NWs) have been grown by molecular beam epitaxy (MBE) for more than ten years, although

Manuscript received September 28, 2010; revised November 12, 2010; accepted November 12, 2010. Date of publication January 28, 2011; date of current version August 5, 2011. This work was supported by the European Union through the Information Society Technologies project Nanowire-based One-Dimensional Electronics under Grant 015783 and by the Marie Curie Research Training Network Interfacial Phenomena at Atomic Resolution and multiscale properties of novel III-V SEMiconductors under Grant MRTN-CT-2004 005583. L. Geelhaar, C. Ch` ze, and H. Riechert were with Qimonda, 81730 Munich, e Germany. They are now with the Paul-Drude-Institut f r Festk rperelektronik, u o 10117 Berlin, Germany (e-mail: geelhaar@pdi-berlin.de). B. Jenichen, O. Brandt, and C. Pf ller are with the Paul-Drude-Institut f r u u Festk rperelektronik, 10117 Berlin, Germany. o S. M nch, R. Rothemund, S. Reitzenstein, and A. Forchel are with the u Technische Physik Department, Universit t W rzburg, Am Hubland, W rzburg a u u 97074, Germany. T. Kehagias, P. Komninou, G. P. Dimitrakopulos, and T. Karakostas are with the Physics Department, Aristotle University, Thessaloniki 54124, Greece. L. Lari and P. R. Chalker are with the Department of Engineering, University of Liverpool, Liverpool, L69 3GH, U.K. M. H. Gass is with the SuperSTEM, Daresbury Lab, Keckwick Lane, Daresbury, WA4 4AD, U.K. Color versions of one or more of the gures in this paper are available online at http://ieeexplore.ieee.org. Digital Object Identier 10.1109/JSTQE.2010.2098396

for a long time these efforts were largely unnoticed by most of the NW community. The pioneering work of the Kishino and Calleja groups [1], [2] attracted other scientists to work in this eld, and their number is still increasing [3][8]. In general, the synthesis of NWs is most commonly based either on catalyst seeds that collect the precursor species and induce uniaxial growth [9], [10] or on templates or prepatterned masks that guide NW growth [11]. In contrast, GaN NWs can be grown by MBE in a self-induced way, i.e., without the need for any foreign material. Given in addition the ultraclean environment of an MBE chamber, these NWs are destined to contain an extremely low impurity concentration, which may potentially lead to exciting physical phenomena [12] or novel devices [13]. Alternatively, the formation of GaN NWs during MBE can be induced by Ni islands in the vaporsolidsolid (VSS) mechanism [14], [15]. Thus, the comparison of these two types of GaN NWs offers the possibility to study the effect of the collectors on the resulting NWs. The aim of this paper is to give an overview of the typical properties of both types of GaN NWs grown by MBE. The emphasis will be on structural and optical properties, while transport and doping are reviewed elsewhere [16]. As briey pointed out earlier, there are different approaches to grow GaN NWs by MBE. The most common and oldest way is to make use of self-organization phenomena that lead to the self-induced formation of NWs. In this case, GaN is simply grown under suitable growth conditions, i.e., N is supplied in excess, and on appropriate substrates or buffer layers, and NWs form without the need for any foreign material in the form of collectors, masks, or templates. The synthesis of GaN NWs has been demonstrated in this approach on bare Si(1 1 1) [2] and Si(0 0 1) [17], on AlN [18] and SiO2 [19] buffer layers on Si(1 1 1), and on AlN [1] and low-temperature GaN [18] buffer layers on C-plane sapphire. As a slight variation, nuclei grown by metalorganic vapor phase epitaxy on R-plane sapphire have also been used as the starting surface [20]. Most studies employed Si(1 1 1) substrates, either bare or with an AlN buffer layer. There are still many open questions with respect to why and how these NWs form, but the general understanding is that one has to distinguish between the nucleation and the growth stage. During the nucleation stage, the interaction with the substrate is important [21]. Once the rst NWs have formed, the anisotropy of the GaN crystal ensures uniaxial growth [19], [22][24].

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For another approach, growth conditions have been found that enable selective-area growth of GaN by MBE on prepatterned substrates. The most successful experiments have been carried out with Ti masks on smooth GaN lms [25]. LEDs have been fabricated from such NWs [26], but information on the material properties of these NWs is scarce. As yet another alternative, Ni islands can lead on bare sapphire substrates to the formation of GaN NWs in the VSS mechanism [14], [15]. Remarkably, the required growth window is very similar to the one that is necessary for the self-induced NW growth on bare Si [27]. Thus, collector-induced NWs can be directly compared with self-induced NWs. This unique combination enables the elucidation whether collectors consisting of a foreign material have any effect on the NW properties. Taking all material systems and growth techniques into account, the majority of NWs is grown with the help of collectors, so the results presented here are highly relevant for the entire eld. II. EXPERIMENTAL GaN NWs were grown by MBE. Ga was supplied by an effusion cell and N by a RF plasma source. The Ga (N) ux was calibrated by the growth of planar layers in the N (Ga) limited regime [28] and corresponded to a planar growth rate of 0.4 (2.0) A/s unless noted otherwise. The substrate temperature was for most experiments 730 C, and for others either 755 C or 780 C, and was measured by a pyrometer. The growth duration was 76 min, and during this time, a 180-nmthick planar layer would have been grown under suitable conditions (nominal thickness). The collector-induced GaN NWs were grown on sapphire substrates. Prior to the growth of GaN, 4-A-thin Ni layers were deposited either ex situ in an ion-beam coater or in situ from an effusion cell in the MBE chamber. Subsequently, the substrates were annealed in the MBE chamber to 780 C for 15 min, which induced the formation of Ni islands, followed by the growth of GaN. The selfinduced GaN NWs were grown on bare Si(1 1 1) and Si(0 0 1) substrates without any buffer layers. Immediately before insertion into the MBE system, the Si substrates were cleaned by the Radio Corporation of America (RCA) procedure, and before GaN growth, the substrates were annealed at 950 C for 15 min. The morphology of the samples was investigated by scanning electron microscopy (SEM). Selected samples were prepared for the analysis by cross-sectional transmission electron microscopy (XTEM) by the standard procedure involving mechanical thinning and ion milling, and other NWs were simply harvested and transferred to TEM grids. An aberration-corrected scanning transmission electron microscope (STEM) was used for high-angle annular dark eld (HAADF) imaging and electron energy loss spectroscopy (EELS). X-ray diffraction (XRD) measurements were performed with a four-circle triple-axis diffractometer equipped with a CuK 1 source in the focus of a multilayer X-ray mirror and a Ge(0 2 2) hybrid monochromator. For photoluminescence (PL) measurements, samples were put into a microscope cryostat and excited by the 325-nm line of a HeCd laser. The laser beam was focused by a 15 objecFig. 1. SEM images of GaN NWs grown at 730 C in the self-induced approach on (a) Si(1 1 1) and (b) Si(0 0 1), as well as (c) in the collector-induced approach on sapphire. Top-to-bottom rows correspond to cross section, birds eye, and plan views, respectively.

tive to a micrometer-sized spot. The PL signal was collected by the same objective, selected by a 0.8-m monochromator, and measured by a cooled Si charge-coupled-device detector. III. GROWTH AND MORPHOLOGY Typical SEM images of both collector-induced and selfinduced GaN NWs grown at 730 C are depicted in Fig. 1. All the three samples were covered by NWs that were oriented perpendicular with respect to the substrate and whose number density was very high. The general morphology was very similar, but the Ni-induced NWs were signicantly longer than the self-induced ones. The top-view images indicate for all the three samples that a signicant number of neighboring NWs coalesced. A detailed analysis of the NW morphology yielded the following values: the self-induced NWs both on Si(1 1 1) and Si(0 0 1) were 380 90 nm long and 45 30 nm thick, and the number density was 0.8 and 0.9 1 010 cm2 on Si(1 1 1) and Si(0 0 1), respectively. Thus, the effect of the substrate orientation on the morphology of the self-induced NWs is negligible. In contrast, the length of the collector-induced NWs was 880 140 nm, their diameter was 35 20 nm, and their number density was 1.1 1010 cm2 . Dedicated growth experiments indicated that the collector-induced NWs were longer because the incorporation efciency for diffusing Ga at the NW tip is higher than for the self-induced NWs [29]. It is well known that the growth of the self-induced GaN NWs depends sensitively on the V/III ratio, and that they form only under N-rich conditions [2]. We restrict the detailed description of the morphology to the growth conditions under which clearly well separated NWs form. Very generally, when the Ga ux is increased, the NWs become thicker, a compact layer grows between the NWs, and eventually NWs do not form at all [30].

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Fig. 2. SEM images of (a) GaN layer grown under N-excess on bare sapphire, (b) GaN layer grown under excess Ga on Ni-covered sapphire, and GaN NWs grown under excess N on (c) and (d) Si(1 1 1) and Si(0 0 1) covered by Ni, respectively. Top and bottom rows correspond to cross section and birds eye views, respectively.

In contrast to the numerous studies on self-induced NWs, there are only very few reports on the growth of Ni-induced NWs by MBE [14], [29]. The sample shown in Fig. 1(c) was grown under N-rich conditions and the assistance of Ni. Under the same conditions but without Ni, a rough compact layer forms on the bare sapphire substrate, and NWs do not appear [see Fig. 2(a)]. The importance of the V/III ratio for the Ni-induced NWs can be seen in Fig. 2(b). In this case, Ni was deposited on the sapphire substrate, but GaN was grown under Ga-rich conditions. The result was a smooth thin lm without any NWs. Hence, on bare sapphire substrates, GaN NWs form under the explored growth conditions only in the presence of Ni and if N is supplied in excess. However, it should be noted that NWs may also form without Ni on sapphire, if initially an AlN or low-temperature GaN buffer layer is grown [1], [18]. Since the presence of Ni can induce the formation of GaN NWs on sapphire substrates, the question arises whether Ni has any effect, if deposited on Si substrates. The samples whose SEM images are depicted in Fig. 2(c) and (d) were grown in the same way as those in Fig. 1(a) and (b) but with Ni on the substrates. The general morphology was very similar to that of the Ni-free samples, but on Si(1 1 1), there were some areas with a lower density of NWs that were in addition tilted [see Fig. 2(c)]. On Si(0 0 1), Ni does not seem to have any effect on the NW formation [see Fig. 2(d)]. The Si(1 1 1) sample was also characterized by XTEM, and the resulting micrographs are presented in Fig. 3. Elongated islands were found that locally prevented the growth of NWs. The composition of these islands was analyzed by energy-dispersive X-ray spectroscopy (EDXS), and the result was that they consist of NiSi [see Fig. 3(b) and (c)]. The formation of Ni2 Si starts already at around 200 C [31]; therefore, the silicidation of the Ni islands is not so surprising. Hence, the role of Ni is remarkably different on sapphire and on Si(1 1 1). While on sapphire Ni induces the growth of the NWs, on Si(1 1 1), Ni locally reacts with the Si substrate and prevents NW growth. For the experiments presented earlier, the substrate temperature of 730 C was chosen because at this temperature, the decomposition of GaN can be neglected, which is benecial for studies aimed at the investigation of growth mechanisms [29].

Fig. 3. (a) XTEM images along [110]S i of GaN NWs grown on Ni-covered Si(1 1 1) revealing the formation of NiSi islands, which hinder NW growth. (b) Ni (yellow) and (c) Si (orange) distribution in the island found by EDXS.

Fig. 4. SEM images of GaN NWs grown at 780 C (a) and (b) self-induced on Si(1 1 1) and on Si(0 0 1), respectively, and (c) Ni-induced on sapphire. Top and bottom rows correspond to cross section and plan views, respectively.

However, the material quality of semiconductors in general is often improved by an increase in growth temperature. SEM images of samples that were grown at 780 C are shown in Fig. 4. In comparison to the experiments at 730 C, the NWs on all the three substrates were more homogeneous in length and slightly shorter and thinner. In detail, the self-induced NWs were on average 20 nm shorter than for growth at 730 C and 15100 nm (average 45 nm) thick, and their number density was 1.8 1010 cm2 . The average length of the Ni-induced NWs was 70 nm smaller than at 730 C, their diameter was 1560 nm (average 27 nm), and their number density was 2.5 1010 cm2 . The increase in number density on all the three samples grown at higher temperature is due to the reduced coalescence [32], and the absolute value is of the same order of magnitude as given in [3]. These data show that the growth temperature can

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Fig. 5. RHEED patterns along the [1120] direction of GaN NWs grown at 730 C in the self-induced approach on (a) Si(1 1 1) and (b) Si(0 0 1), as well as (c) in the collector-induced approach on sapphire.

be varied both for the collector- and the self-induced GaN NWs without a signicant effect on the overall morphology. IV. MICROSTRUCTURE The crystal structure of the NWs can be determined already in the MBE chamber with reection high-energy electron diffraction (RHEED). Typical images are presented in Fig. 5. In all the three cases, spot patterns were observed that are characteristic for transmission through 3-D GaN crystals in the wurtzite (WZ) structure along the [11-20] direction. The collector-induced and self-induced NWs have in common that they grow in the Cdirection. For collector-induced growth on sapphire, the spots were positioned on a rectangular lattice, which indicates wellaligned growth perpendicular to the substrate. The in-plane orientation was [11-20]GaN [10-10]sapphire . The self-induced NWs on Si(1 1 1) exhibited a diffraction pattern in which the reections appeared as broken rings. This observation implies a slight spread in orientation of the GaN crystal with respect to the substrate, i.e., a misalignment of the NWs. These NWs exhibited the in-plane relation [11-20]GaN [1-10]Si . On Si(0 0 1), the broken rings were even more pronounced. Moreover, there were additional spots that belong to the diffraction pattern for transmission in the [10-10]GaN azimuth. Thus, the GaN NWs exhibited on Si(0 0 1) several in-plane orientations with respect to the substrate. The results presented here have also been conrmed by selected area electron diffraction and are consistent with those of other groups [5], [22], [33]. In addition, the polarity of the NWs was determined by convergent beam electron diffraction. Both the collector-induced NWs grown on sapphire and the self-induced NWs on Si(1 1 1) are Ga-polar [27]. Complementary to the electron diffraction experiments, the samples were characterized by XRD. Symmetric /2 scans of the (0 0 0 2)GaN reection were used to determine the alignment of the NWs with the substrate normal and are presented in Fig. 6. The C-direction of GaN is oriented perpendicular to the substrates, as deduced from the RHEED data. However, for the self-induced NWs on Si(1 1 1) and Si(0 0 1), there are additional GaN reections in scans over a wider angular range indicating that growth also took place in different crystallographic directions. Since there was no such evidence in RHEED, these peaks are most likely due to parasitic planar growth between the NWs. The X-ray pole gures depicted in Fig. 7 reveal the symmetry of the GaN NW crystals with respect to the substrates. While for growth on Si(1 1 1) and sapphire, the symmetry is sixfold [34]; it is 12-fold for the Si(0 0 1) sample. The latter result implies that GaN NWs align on Si(0 0 1) along two equivalent azimuthal directions [22]. In addition, the angular spread of tilt of the NWs was determined from scans (see insets to Fig. 6), and

Fig. 6. XRD /2 scans across the (0 0 0 2)G a N reection of the NW sample grown on (a) Si(1 1 1), (b) Si(0 0 1), and (c) Ni-covered sapphire. Insets are the corresponding scans across the (0 0 0 2)G a N reection used to extract the NW tilt presented in Table I.

their range of twist from the pole gures and additional scans across the asymmetric (1014)GaN reection (not shown). The full-widths at half-maximum (FWHMs) of the respective peaks are presented in Table I. Both tilt and twist are quite substantial on all the samples, but signicantly more pronounced for the self-induced NWs, and in particular, for growth on Si(0 0 1).

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TABLE I ANGULAR SPREAD OF TILT AND TWIST (FWHM OF SUITABLE X-RAY DIFFRACTION REFLECTIONS) FOR GAN NWS GROWN IN THE SELF-INDUCED APPROACH ON SI(1 1 1) AS WELL AS ON SI(0 0 1) AND IN THE NI-INDUCED APPROACH ON SAPPHIRE

Fig. 8. Plan-view SEM images of GaN NWs grown (a) and (b) at 730 C, and (c) and (d) at 780 C on (a) and (c) Si(1 1 1), and (b) and (d) Ni-covered sapphire, respectively.

Fig. 7 X-ray (1014)G a N pole gures of the NW samples grown at 780 C (a) and (b) in the self-induced approach on Si(1 1 1) and Si(0 0 1), respectively, and (c) in the collector-induced approach on Ni-covered sapphire. The two NW orientations separated by 30 are revealed in (b).

The combination of top-view SEM images with the crystallographic information known from XRD allows determining the orientation of the NW sidewall facets. SEM images that are

representative for the self-induced NWs on Si(1 1 1) and the collector-induced NWs on sapphire are depicted in Fig. 8. In all cases, the NWs exhibit clearly developed facets, and the NW cross sections are hexagonal, although the facets are not always even in size. The facet orientation of the self-induced NWs is both for growth at 730 C and 780 C M-plane [see Fig. 8(a) and (c)], which is in agreement with other reports [34], [35]. On Si(0 0 1), the cross sections of the NWs are also hexagonal, but some of them are rotated by 30 (not shown). This behavior is consistent with the XRD data that indicated two types of epitaxial orientation. Since the two different alignments to the substrate cannot be distinguished in SEM, the occurrence of A-plane facets for the self-induced NWs grown on Si(0 0 1) cannot be rigorously excluded, but it seems extremely unlikely. Interestingly, the facet orientation of the Ni-induced NWs on sapphire is different for the two growth temperatures [see Fig. 8(b) and (d)]. For growth at 780 C, only M-plane facets were found [see Fig. 8(d)], i.e., the same orientation as for the self-induced NWs. However, among the Ni-induced NWs grown at 730 C, some NWs exhibited both M- and A-plane facets. The diameter of the NW shown in Fig. 8(b) varies with height, and three distinct concentric hexagons can be seen. The top two hexagons form M-plane facets like the other NWs described so far. However, the lowest part of the NW is conned by A-plane facets. In other words, the orientation of the hexagonal cross section changes along the length of the NW. The same effect is also visible in Fig. 9, where dispersed Ni-induced NWs are displayed that were also grown at 730 C but for a longer time. The two magnied images clearly reveal that there is a transition of the facet orientation near both NW ends. Also, the main image shows that the diameter of the middle segment is

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Fig. 9. SEM images of harvested GaN NWs grown at 730 C revealing a transition in their facet planes. Enlarged views in (a) correspond to area near to (b) the NW foot and (c) the NW tip.

Fig. 11. HR-XTEM images of the tip of GaN NWs grown (a) at 730 C selfinduced on Si(1 1 1), and (b) at 780 C Ni-induced on sapphire. In (a), the NW tip is smooth, while in (b), the Ni-particle is clearly observed.

Fig. 10. HR-XTEM images of the interface area of the substrate and GaN NWs grown at 730 C (a) and (b) self-induced on Si(1 1 1) and on Si(0 0 1), respectively, and (c) Ni-induced on sapphire. In (a) and (b), a partially amorphous IL layer formed, while in (c), the interface remained sharp.

larger than that of the ends. Thus, the change in facet orientation seems to be related to growth on the NW sidewalls. Similar behavior has been reported for the Au-induced growth of GaAs NWs by gas-source MBE [36]. There are two possible reasons for the facet transition along the Ni-induced GaN NWs: rst, these NWs contain a high number of basal-plane stacking faults (SFs), as will be shown in the following. The incorporation rate of diffusing atoms might be increased at the termination points of these SFs on the sidewall facets. Second, Ni atoms might diffuse from the collector at the NW tip to the sidewall facets and favor energetically the formation of a different facet orientation. In fact, the second effect has been observed when Ni-induced GaN NWs were doped with transition metals at a high concentration [37]. High-resolution XTEM (HR-XTEM) images of the interface between NW and substrate are depicted in Fig. 10 for the three different types of NWs. The self-induced GaN NWs grown on Si(1 1 1) are separated from the substrate by an interfacial layer (IL) that is about 2 nm thin and mostly or even completely amorphous [see Fig. 10(a)]. The interface to the Si(0 0 1) substrate looks very similar, although in this case a fairly large tilt of 2 is observed between NW and substrate [see Fig. 10(b)]. This IL is

common for self-induced NWs grown on bare Si substrates and consists of SiN [38]. In the initial phase of GaN NW growth, there is a competition between the nucleation of GaN and the nitridation of the Si substrate [39]. It should be noted that the formation of the IL can be avoided, if rst a planar AlN buffer is grown because Al binds more strongly to Si. In contrast, the interface between the collector-induced GaN NWs and the sapphire substrate is sharp, and there is no IL [see Fig. 10(c)]. Nevertheless, this NW is also slightly tilted with respect to the substrate (cf. Table I). Obviously, an amorphous IL is a decisive factor for both the out-of-plane and in-plane epitaxial alignment between NWs and substrate. If a sufciently thick amorphous IL formed, any epitaxial orientation between NW and substrate would be impossible. At the same time, it has been proposed that the self-induced NWs grow perpendicular to the substrate as long as the substrate surface is smooth [19], which leads to the out-of-plane epitaxial alignment observed by RHEED and XRD. However, the degree of alignment is still expected to be reduced on top of the amorphous IL. Thus, the FWHM of the XRD peaks is larger for the self-induced GaN NWs (cf. Table I). The XRD pole gures clearly demonstrate that there is also an in-plane alignment between the self-induced NWs and the Si substrates, and without such an alignment, it would be impossible to see in Fig. 10 the atomic structure of both the GaN and the Si lattices. While a smooth amorphous IL might enable the out-of-plane epitaxial alignment of the NWs, the in-plane orientation of such NWs is expected to be random. In order to resolve this discrepancy, it has been argued that the SiN IL may not prevent the in-plane epitaxial alignment as long as it is very thin and not entirely amorphous [38]. Indeed, on some HRTEM images, a certain level of crystallinity is preserved across the IL [38]. In thicker regions, this alignment is expected to be lost. However, it should be noted that Furtmayr et al. observed that the out-ofplane alignment was improved for longer substrate nitridation durations prior to GaN growth, and they attributed this trend to a higher homogeneity of the SiN layer [35]. The last surface boundary conning the NWs that needs to be discussed is the NW tip. As can be seen in the micrograph in Fig. 11(a), the tip of the self-induced NWs is a at and smooth

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Fig. 13. XTEM images of harvested GaN NWs grown (a) in the self-induced approach on Si(1 1 1), and (b) and (c) in the collector-induced approach on Ni-covered sapphire. The samples were grown at 730 C in (a) and (b), and at 780 C in (c).

Fig. 12. (a) HAADF STEM image of a GaN NW tip grown at 730 C in the collector-induced approach, and (b) quantied compositional EELS line scan across the Ni-based particle along the line indicated perpendicular to the NW-particle interface in (a).

GaN C-plane facet. In particular, there is no indication of any droplet or particle. In contrast, the Ni-induced NWs end at the tip in a particle of different crystal structure [cf. Fig. 11(b)], consistent with the collector-induced growth mechanism. A more detailed analysis of HRTEM images indicated that the collector exhibits a cubic crystal structure with a lattice spacing of 0.21 0.01 nm [33], [40]. These results are consistent with NiO, Ni3 Ga, and a range of NiGa solid solutions. The in situ characterization of Ni-induced NW growth by RHEED and lineof-sight quadrupole mass spectrometry also supports the latter two compositions [15]. In order to elucidate the chemical composition of the collector remaining at the end of each NW, EELS analysis of the N, O, Ni, and Ga distribution within the collector was carried out. These data were quantied as discussed in [41]. The analysis conrmed the presence of Ga within the Ni collector, whereas the N signal rapidly falls to the noise level [see Fig. 12(b)]. In the same region, the O content was detected at the background level, whereas it increases together with the Ga signal, as the Ni signal decreases outside of the collector. This result indicates the presence of an oxide shell around the collector containing both Ni and Ga. The formation of such an oxide shell is most likely due to postgrowth exposure to the ambient atmosphere. The defect structure of the MBE-grown GaN NWs was also investigated by XTEM. Micrographs of self-induced NWs grown on Si(1 1 1) and collector-induced NWs grown at two different temperatures are shown in Fig. 13. The self-induced NWs are basically perfect WZ crystals and contain almost no extended defects [see Fig. 13(a)]. This result is in accord with many other TEM studies of this type of NW [38]. However, it should be pointed out that the coalescence of neighboring, slightly tilted NWs may induce the formation of a local network of boundary

dislocations and very few I1-type SFs [42]. In marked contrast, there are many dark stripes across the Ni-induced NWs depicted in Fig. 13(b). High-resolution images reveal that these contrasts are basal-plane SFs of the I1 type. There are no other extended defects in the collector-induced NWs. The SFs are randomly distributed along the entire length of the NWs, and their density is 106 cm1 . In fact, these NWs contain many more SFs than found in planar GaN grown on sapphire by MBE. The NWs described so far were grown at 730 C. Fig. 13(c) shows a micrograph of Ni-induced NWs grown at 780 C. There are still fairly many SFs in these NWs, but their density is lower than in the 730- C NWs. Hence, the increase in growth temperature did indeed lead to better crystal quality. The main difference in microstructure between the selfinduced and collector-induced NWs is that while the latter contain a high number of SFs, the former are virtually free of any extended defects. The occurrence of SFs and polytypism is actually a fairly common phenomenon for collector-induced NWs in general [43], which makes the very high crystal quality of the self-induced GaN NWs grown by MBE even more remarkable. Moreover, the self-induced and collector-induced GaN NWs discussed here were grown in the same MBE chamber under the same growth conditions. The only difference was the choice of substrate. However, NW growth takes place at the tip, and any effect of the substrate should quickly wash out. In contrast, the SFs were found along the entire length of the Ni-induced NWs. Therefore, the direct comparison suggests that the occurrence of the SFs is related to the collector. In fact, there are several ways how the presence of the Ni collector may induce SF formation: rst, the collector is actually solid during growth and its crystal structure is partly cubic, as described earlier. Thus, for any GaN nucleus that grows at the interface between the WZ GaN NW and the cubic Ni collector, it might be favorable to adopt the cubic bonding conguration. Second, some Ni from the collectors might be incorporated into the GaN NWs. Impurities are known to stabilize the zinc-blende (ZB) phase in GaN [44], and high doping with Mg induces SFs in self-induced GaN NWs [45]. In a similar way, Ni contamination may also cause SFs. Third, materials that are ZB in bulk often grow as collector-induced NWs in the WZ structure. As an explanation, it has been proposed that the nucleation at the triple-phase line among vapor, collector,

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and NW may shift the formation energies for WZ and ZB [46]. Hence, for the collector-induced GaN NWs, an equivalent phenomenon might favor ZB instead of WZ nucleation. Fourth, the presence of the collector on top of the GaN growth front might inhibit diffusion. Hence, adatoms might be trapped in ZB sites [47]. The detailed elucidation of why the SFs appear in the Ni-induced GaN NWs would be very challenging. In any case, the inferior crystal quality of these NWs compared to the self-induced ones is very likely related to the collector-induced growth mechanism. V. OPTICAL PROPERTIES In order to assess the suitability of GaN NWs for optoelectronic applications, it is very important to investigate their optical properties. Typically, material quality depends sensitively on the growth temperature. The PL spectra of both self-induced and collector-induced NWs grown at 730 C, 755 C, and 780 C are presented in Fig. 14. For the self-induced NWs grown both on Si(1 1 1) and Si(0 0 1), there are three pronounced emission bands at 3.472, 3.45, and 3.413.425 eV. The rst one corresponds to the donor-bound exciton (D0 ,XA ), and its energy position conrms that these NWs are unstrained [18], [48]. The second one is characteristic for this type of NW. Its origin is still under discussion and will be addressed in more detail in the following. The emission around 3.42 eV is due to SFs that are caused by the coalescence of close-standing NWs [42]. Except for growth at the lowest temperature, there is no yellow luminescence, which indicates a very low density of the related point defects. As expected, the (D0 ,XA ) emission becomes brighter and sharper with increasing growth temperature and dominates the spectra of the 780- C samples, while the relative contribution of the two other bands decreases. The narrowest FWHM of 3.1 meV was obtained for growth at 780 C on Si(1 1 1). Experiments in a different growth chamber, where higher growth temperatures were possible, showed that similar samples grown at around 820 C did not exhibit any signicant emission besides the donor-bound exciton, and the FWHM was 1.6 meV [49]. The line at 3.45 eV is a characteristic feature in the luminescence of self-induced GaN NWs [18], [50][53]. Various mechanisms have been proposed to explain this band, but none of them explains all experimental observations. Most likely, this luminescence is not related to the incorporation of an impurity, as GaN layers and collector-induced NWs grown in the same MBE do not show this band (cf. Fig. 15). While in ensemble measurements commonly one broad peak or a peak doublet with an energetic separation of 67 meV is observed, experiments with single NWs indicate that this band is actually a convolution of numerous sharp peaks [50]. Calleja et al. deduced an excitonic nature of the 3.45-eV band due to the evolution of its peak energy with excitation density as well as with temperature [18]. Its lifetime and decay characteristics are in addition similar to the excitonic near-band-edge decay. Furtmayr et al. observed different thermal quenching behaviors for the (D0 ,XA ) line and the 3.45-eV band [51]. Furthermore, Mg-doping affects both transitions differently. As possible origin, excitonic recombination involving Ga vacancies due to the N-rich growth conditions

Fig. 14. Low-temperature (10 K) PL spectra of GaN NWs grown at 730 C, 755 C, and 780 C (a) and (b) in the self-induced approach on Si(1 1 1) and Si(0 0 1), respectively, and (c) in the collector-induced approach on Ni-covered sapphire.

was discussed. Corfdir et al. suggested that this band represents the two-electron satellite (TES) from the (D0 ,XA ) transition [52]. The unusual strong intensity of this band compared to the (D0 ,XA ) transition is explained by a core-shell model, which implies that the (D0 ,XA ) transition stems from the inner part of the NWs, whereas the TES contributions mainly come from the region close to the NW surface. Robins et al. tentatively assigned the band to the presence of inversion domain boundaries [53]. Brandt et al. observed in excitation-dependent measurements that the (D0 ,XA ) transition saturates much faster than the 3.45-eV band [50]. In the same study, the long-time evolution of single-NW spectra indicated that the 3.45-eV band is caused by the abundant presence of surface defects. The spectra of the collector-induced NWs contain also the (D0 ,XA ) peak at 3.472 eV, and in addition, a pronounced peak

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Fig. 15. Low-temperature (10 K) PL spectra of GaN NWs grown at 780 C in the self-induced approach on Si(1 1 1) (dashdot line) and Si(0 0 1) (dash line) and in the collector-induced approach on Ni-covered sapphire (dot line). As a comparison, the spectrum of a GaN layer grown under optimized conditions in the same MBE chamber (solid line) is also reported in the gure.

Fig. 16. Low-temperature (10 K) PL spectra after background subtraction of a single NW taken (a) one month after and (b) right after its dispersion on the Si(1 1 1) carrier. The symbols represent the data, and the solid lines represent the Gaussian ts to determine the spectral position and linewidth of the individual transitions.

at 3.413.43 eV, as well as a very broad emission band at lower energies. Most notably, none of the spectra is dominated by the donor-bound exciton transition, which is unlike the case of planer GaN grown on sapphire (cf. Fig. 15). Nevertheless, compared to the other emission bands, this peak is brightest for the highest growth temperature. Also, the position of the (D0 ,XA ) peak indicates again that the GaN NWs are free of strain. The emission at around 3.42 eV is most likely caused by SFs [27]. This assignment is consistent with the nding for the self-induced NWs and the TEM analysis. The very broad features below 3.4 eV that are present in particular for the lower growth temperatures are difcult to identify, but could be related to the donoracceptor-pair transition and its replica. Finally, yellow luminescence is observed only for the sample grown at the lowest temperature, as it is the case for the self-induced NWs. The experiments discussed earlier show that the best optical material quality was observed for the highest investigated growth temperature. In order to directly compare the results for the self-induced and collector-induced NWs, the corresponding spectra are depicted in one diagram in Fig. 15. As a reference, the spectrum of a GaN lm grown under optimized conditions on sapphire in the same MBE chamber is also included. There are three different emission bands in the NW spectra: the (D0 ,XA ) peak at 3.472 eV, the peak at 3.45 eV that is characteristic for the self-induced NWs and whose origin has not been claried yet, and features in the range 3.413.43 eV that are most likely due to stacking faults. Most interesting are the differences in the PL intensities. While the emission of the self-induced NWs is clearly brighter than that of the reference layer, the luminescence of the collector-induced NWs is weaker. Moreover, in direct comparison, the maximum (integrated) intensity is 25 (6) times higher for the self-induced NWs than for the collector-induced NWs. There are several factors that might affect the luminescence of these NWs. First, the morphology is very similar, i.e., they ex-

hibit the same type of sidewall facets, and the surface-to-volume ratios differ only by a factor of 1.7. Thus, differences in surface recombination or light-extraction efciency cannot explain the observed difference in PL intensity. Second, the main difference in microstructure is the abundance of SFs. However, these defects are radiative and can account for additional emission bands but not for the measured quenching. Third, the NWs are essentially strain free. Hence, the type of substrate is not expected to have any inuence on the PL intensities. Therefore, the most likely explanation for the reduced luminescence of the collector-induced NWs is that the collector material Ni is incorporated as an impurity that acts as a nonradiative recombination center. The precise nature of this center is unclear, and it could be located either in the bulk or at the surface of the NWs. The sharpest (D0 ,XA ) line of all the spectra presented earlier has a FWHM of 3.1 meV. Somewhat smaller values have been reported in the literature, but they all exceed 1 meV [20], [49], [54]. However, for GaN that is free of strain as in these NWs, actually much smaller linewidths would be expected [53]. In order to investigate this discrepancy, the PL of single, dispersed, self-induced NWs was measured [50]. In most cases, the spectra were broadened by interaction between the horizontally lying NW and the supporting substrate. However, in a few cases, extremely sharp peaks were resolved, as presented in Fig. 16. It is important to note that each NW emits its individual spectrum. The two depicted spectra stem from one and the same NW but were acquired with one month in between. We would like to point out three important observations. First, we measured excitonic transitions with linewidth below 300 eV, i.e., the resolution of the spectrometer. Second, there are pronounced emission lines in the energy range between the donor-bound exciton (D0 ,XA ) and the free exciton XA (3.4723.479 eV), where only extremely weak emission is known in GaN. Third, the spectra, and thus, the electronic properties of the singleGaN NW evolve with time. All of these results lead to the following conclusions: the PL spectrum of a single-GaN NW depends on the spatial distribution of donors in that NW. For

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donors close to the surface, the binding energy of the respective donor-bound exciton is reduced and depends on the distance to the surface, as theoretically predicted [55]. The average over the spectra of many NWs results in the measured ensemble linewidths greater than 1 meV. Our results can be explained by the tendency of impurities to segregate to the surface that is expected from theory [56], [57]. Although it is difcult to exclude other factors like surface oxidation, these observations suggest that the material quality in NWs is better than in the best planar layers. VI. CONCLUSION The growth of self-induced and collector-induced GaN NWs in the same MBE chamber under similar growth conditions allows investigating the effect of the collector on the material properties of the NWs. The structural and optical qualities of the self-induced NWs are clearly superior. Moreover, the material quality of the self-induced NWs is potentially better than that of planar GaN layers. Very importantly, these self-induced GaN NWs form on Si substrates that are available in large size at low cost. Hence, the growth of GaN in the form of NWs may be a path to overcome the lack of substrates suitable for this material. This lack presents a serious limitation for the material quality that can be achieved in planar GaN layers. Therefore, self-induced GaN NWs may allow the realization of the full potential of GaN for applications. ACKNOWLEDGMENT The authors would like to thank U. Jahn for critical reading of the manuscript. REFERENCES
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