- Nano Express
- Open Access
Investigating the Composition and Conductance Distributions on Highly GeSi Mixed Quantum Dots and Inside Oxidation Problem
© Ye et al. 2015
Received: 9 October 2015
Accepted: 1 December 2015
Published: 9 December 2015
With the help of a nanoscale trench, the composition and conductance distributions of single GeSi quantum dots (QDs) are obtained by conductive atomic force microscopy combined with selective chemical etching. However, the obtained composition and current distributions are unwonted and inconsistent on the QDs grown at 680 °C. With a series of confirmatory experiments, it is suggested that a thick oxide layer is formed and remains on the QDs’ surface after etching. Though this selective chemical etching has already been widely applied to investigate the composition distribution of GeSi nanostructures, the oxidation problem has not been concerned yet. Our results indicate that the oxidation problem could not be ignored on highly GeSi mixed QDs. After removing the oxide layer, the composition and conductance distributions as well as their correlation are obtained. The results suggest that QDs’ current distribution is mainly determined by the topographic shape, while the absolute current values are influenced by the Ge/Si contents.
Self-assembled GeSi quantum dots (QDs) have received great interests for their promising applications in optoelectronics and quantum information technology due to their unique properties and compatibility with the Si technology [1–4]. In the past years, the composition distributions of GeSi QDs have been greatly concerned as it determines the QDs’ electronic structure together with their size and shape. Many methods have been applied to get the composition distributions of GeSi QDs , including anomalous X-ray scattering [6–8], cross-sectional transmission electron microscopy (TEM) [9–11], Raman spectroscopy , and atomic force microscopy (AFM) combined with selective chemical etching [11, 13–19]. Among these methods, AFM combined with selective etching in a NHH solution (28 % NH4OH:31 % H2O2 = 1:1), which can selectively remove GeSi alloys with the etching rate approximately exponential with the Ge content [20, 21], has been particularly applied due to its simplicity and effectiveness. Recently, three-dimensional (3D) composition profiles of GeSi QDs have been achieved by AFM imaging, the same QDs after NHH etching .
On the other hand, the QDs’ electrical properties have also attracted a large number of researches since they are essentially important for the practical applications. To get the QDs’ electrical properties, measurement on single QDs is particularly important as it can exclude the averaging effect. Therefore in recent years, scanning probe microscopy (SPM)-based techniques have been attempted to investigate the electrical properties on single QDs [23–32]. Among these techniques, conductive atomic force microscopy (CAFM) is mostly often applied. The conductive properties of individual InAs, InGaAs, and GeSi QDs have already been achieved by CAFM [27–32]. However, the combined studies on the QDs’ composition distribution and their electrical properties are still lacking, and thus the correlations between these two characteristics are not clear yet.
In this paper, with the help of a nanoscale trench, the 3D composition and conductance distributions are simultaneously measured on same single GeSi QDs by combining CAFM measurement with NHH etching. The results present that the highly GeSi mixed QDs (grown at 680 °C) exhibit extremely poor conductance after 2-min NHH etching, which can be recovered after the subsequent NHH etching processes. With further confirmatory experiments, it is predicted that a thick oxide layer is formed and remains on these QDs’ surface after NHH etching. This oxidation problem has never been mentioned in previous experiments with similar etching method, probably due to the following: conductive properties were not concerned in those cases or the dealt QDs were not highly GeSi mixed. Therefore, our experimental findings should be useful to make clear the NHH etching process of highly GeSi mixed QDs, as well as to get the exact composition and conductive properties of those kinds of QDs.
The GeSi QDs studied here were grown on a p-type Si(001) wafer (1 ~ 10 Ω cm) by solid source molecular beam epitaxy. The Si substrates were chemically cleaned using the Shiraki method, and the protective oxide layer was removed by heating the substrate at 1000 °C for 10 min inside the growth chamber. The substrate temperature was then lowered to 640 °C, and a 64-nm Si buffer layer was deposited at a growth rate of 0.08 nm/s, followed by a 12 ML Ge layer deposition at the temperature of 680 °C with a growth rate of 0.01 nm/s. The selective chemical etching was performed by dipping the sample in a fresh NHH solution and rinsing in flowing deionized water. Before each NHH etching process, the sample was dipped in a 10 % HF solution for 30 s to remove the native oxide layer and the same as the original sample.
The topography and current measurements were carried out with a commercial AFM equipment (Multi-Mode V, Bruker) at room temperature. The topographic images of GeSi QDs were obtained by AFM in tapping mode, while their conductive properties were measured by CAFM in contact mode. Pt-coated Si tips were used in CAFM measurements, and the bias voltage was applied to the substrate while the tip was grounded. To reduce the influence of local anode oxidation, the current images were measured at negative sample biases and all experiments were performed in a flowing nitrogen atmosphere. To realize the measurements on the same QDs before and after etching, a nanoscale trench with more than 20 nm in depth was made by the AFM tip during scanning, as introduced in our previous work . As the bottom of the trench reaches the pure Si buffer layer, it can hardly be etched in NHH solution since the etching rate decreases to be smaller than 0.01 nm/min for pure Si [20, 21] and hence can act as a better height benchmark than the wetting layer (WL).
Results and Discussion
Similar unwonted result is obtained on QDs. The topography images of same QDs before and after the same etching processes as above are presented in Fig. 1e–h, respectively. The height profiles of the same QD along the same line are given in Fig. 1j, which are aligned by considering the etched height of the WL in each etching process. It can be seen that, after the initial 2-min NHH etching, only a thin layer on the QD’s top center is removed. To the contrary, a large amount of the QD is etched away after the subsequent 5-min NHH etching. By subtracting the height line after etching from that before etching, the etched height and hence the etching rate are obtained. Previous studies found that the NHH etching rate (r) increased with the Ge content (x) exponentially [20, 21], which could be written as follows: r = ae bx (with a = (7.3 ± 0.4) × 10−4 nm/min and b = 14.4 ± 0.1) . Using this equation, the etching rate can be converted to the Ge content. The composition profiles along the marked line are plotted in Fig. 1k. It can be observed that the Ge content on the QD’s top layer (before NHH etching) is about 45 %, but it increases to about 55 % at underneath region of the QD (2-min NHH-etched surface). These results suggest that Ge is not enriched in QDs’ top layer but in the beneath region instead, which again violates the common sense as reported in previous literatures [6–19].
Based on the above results, it can be demonstrated that a thick oxide layer is formed and remains on highly GeSi mixed QDs after NHH etching. Particularly, the above phenomena can only be observed on highly GeSi mixed QDs (e.g., grown at 680 °C). Similar measurements have been performed on both GeSi QDs grown at 570 °C and 640 °C which contain higher Ge contents. Normal composition distribution and conductive behaviors are measured, where the conductance monotonically decreases with the etching time (decreased Ge content), indicating the oxide layer formed in those cases is much thinner. On the other hand, from the above result as shown in Fig. 2f, it can seen that the conductance of the WL is better than that of the QDs, suggesting that the oxide layer formed on the WL, which has higher Si content, is thinner than that on the QDs. Consistently, the oxide layer formed in the subsequent 5-min NHH etching which is done with a pretreatment of HF dipping is much thinner than in the former 2-min etching, as the current can be detected again after this etching process. These results suggest that the oxide layer thickness decreases with the Ge content decreasing. Therefore, the formed oxide layer thickness is obviously related to the Ge content, and it is large for highly GeSi mixed QDs. By either increasing or decreasing the Ge content, the thickness of the formed oxide layer by NHH etching decreases.
The origin why the formed oxide layer thickness varies with Ge content is not clear yet, and only a rough assumption is supposed as follows. As stated in previous literatures [20, 21, 34], Ge can be removed in aqueous H2O2 solutions since it is oxidized by the latter and its oxide is water soluble, while Si can be removed by NH4OH solution but the etching rate decreases with the addition of H2O2. When NHH solution etches GeSi alloys with high Ge contents, the formed oxide is mainly Ge oxide which can be dissolved in water, so no or little oxide layer would remain on the QDs’ surface. Contrary to the Ge oxide, Si oxide is much stable and dissolved slowly in NHH solution. But the fast passivation of Si by the Si oxide would stop the etching procedure. Thus, etching of GeSi QDs with high Si contents would also result in a thin Si oxide layer on the QDs’ surface and hence the current is still detectable. On the contrary, when NHH etches highly GeSi mixed QDs (medium Ge content of 40–60 %), the presence of Ge or the GeSi mixing can significantly enhance the oxidation of Si without passivation. In previous researches dealing with thermal oxidation of GeSi alloys [35, 36], it was indeed found that Ge could act as a catalyst during oxidation of Si, which was interpreted by the reduced binding energy of Si atoms at the interface due to alloying with Ge . While the oxidation of Si is enhanced by alloying with Ge, the passivation of Si by the Si oxide is reduced by the presence of Ge contrary. Therefore, the stopping of Si oxidation is impeded; as a result, a thick Si oxide layer is formed on highly GeSi mixed surface.
On the other hand, from the current profiles as shown in Fig. 5j, similar ring-shaped distributions are observed for all dome-shaped QDs, except some QDs present asymmetric distributions corresponding to their asymmetric topographic shape. The ring-shaped feature is not very obvious for the QDs before NHH etching, which is most probably due to the saturation effect of the current at the QDs’ edges. After NHH etching, the composition distribution of QDs greatly changes, but the ring-shaped current distribution as well as dome-shaped topography remains, except the dome height and current values greatly decrease with the decreasing of Ge content. The origin of the ring-shaped current distribution has been interpreted in our previous paper  as follows: a large number of Si atoms in the substrate were incorporated into the Ge QDs at the high deposition temperature, forming roughly uniform GeSi alloys in the QDs with high Si concentration, resulting in large dot resistance. As the dot resistance is proportional to the current path length, i.e., dot height, it has a smaller value at its side region than at its center. Furthermore, the contact area between the tip and dot surface is also larger at the periphery, forming ring-shaped current distribution. Since the dome-shaped QDs with different GeSi compositions (after different etching processes) exhibit similar ring-shaped current distribution, it can de declared that the QDs’ current distribution is mainly determined by its topography, while the current values are greatly influenced by the Ge content, similar to the conclusion obtained on GeSi quantum rings [33, 37].
In conclusion, the conductive properties and the composition distributions are obtained simultaneously on same single QDs by CAFM measurements combined with NHH etching with a nanoscale trench. In particular, it should be noticed that, for highly GeSi mixed QDs grown at 680 °C, the NHH etching would form a thick oxide layer on the QDs’ surface, resulting in poorer conductance even more than the WL. This finding should be useful for similar etching experiments, as it has never been concerned previously. By adding a HF dipping after each NHH etching, the exact composition and current distributions as well as their correlation are obtained. The results suggested that the ring-shaped current distribution is determined by its topography while the composition distribution mainly influences the current values.
This work was supported by the National Natural Science Foundation of China (No. 11274072) and Major State Basic Research Project of China (No. 2011CB925601).
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- Kiravittaya S, Rastelli A, Schmidt OG (2009) Advanced quantum dot configurations. Rep Prog Phys 72:046502View ArticleGoogle Scholar
- Bimberg D, Pohl UW (2011) Quantum dots: promises and accomplishments. Mater Today 14:388–97View ArticleGoogle Scholar
- Barbagiovanni EG, Lockwood DJ, Simpson PJ, Goncharova LV (2014) Quantum confinement in Si and Ge nanostructures: theory and experiment. Appl Phys Rev 1:011302View ArticleGoogle Scholar
- Lozovoy KA, Voytsekhovskiy AV, Kokhanenko AP, Satdarov VG, Pchelyakov OP, Nikiforov AI (2014) Heterostructures with self-organized quantum dots of Ge on Si for optoelectronic devices. Opto − Electron Rev 22:171–7Google Scholar
- Biasiol G, Heun S (2011) Compositional mapping of semiconductor quantum dots and rings. Phys Rep 500:117–73View ArticleGoogle Scholar
- Schülli TU, Vastola G, Richard MI, Malachias A, Renaud G, Uhlík F, Montalenti F, Chen G, Miglio L, Schäffler F, Bauer G (2009) Enhanced relaxation and intermixing in Ge islands grown on pit-patterned Si(001) substrates. Phys Rev Lett 102:025502View ArticleGoogle Scholar
- Mocuta C, Stangl J, Mundboth K, Metzger TH, Bauer G, Vartanyants IA, Schmidbauer M, Boeck T (2008) Beyond the ensemble average: X-ray microdiffraction analysis of single SiGe islands. Phys Rev B 77:245425View ArticleGoogle Scholar
- Malachias A, Kycia S, Medeiros-Ribeiro G, Magalhães-Paniago R, Kamins TI, Williams RS (2003) 3D composition of epitaxial nanocrystals by anomalous X-ray diffraction: observation of a Si-rich core in Ge domes on Si(100). Phys Rev Lett 91:176101View ArticleGoogle Scholar
- Floyd M, Zhang Y, Driver KP, Drucker J, Crozier PA, Smith DJ (2003) Nanometer-scale composition measurements of Ge/Si(100) islands. Appl Phys Lett 82:1473–5View ArticleGoogle Scholar
- Lee SW, Chang HT, Chang JK, Cheng SL (2001) Formation mechanism of self-assembled Ge/Si/Ge composite islands. J Electrochem Soc 158:H1113–6View ArticleGoogle Scholar
- Bollani M, Chrastina D, Montuori V, Terziotti D, Bonera E, Vanacore GM, Tagliaferri A, Sordan R, Spinella C, Nicotra G (2012) Homogeneity of Ge-rich nanostructures as characterized by chemical etching and transmission electron microscopy. Nanotechnology 23:045302View ArticleGoogle Scholar
- Ogawa Y, Toizumi T, Minami F, Baranov AV (2011) Nanometer-scale mapping of the strain and Ge content of Ge/Si quantum dots using enhanced Raman scattering by the tip of an atomic force microscope. Phys Rev B 83:081302View ArticleGoogle Scholar
- Denker U, Stoffel M, Schmidt OG (2003) Probing the lateral composition profile of self-assembled islands. Phys Rev Lett 90:196102View ArticleGoogle Scholar
- Zhong Z, Katsaros G, Stoffel M, Costantini G, Kern K, Schmidt OG, Jin-Phillipp NY, Bauer G (2005) Periodic pillar structures by Si etching of multilayer GeSi/Si islands. Appl Phys Lett 87:263102View ArticleGoogle Scholar
- Katsaros G, Costantini G, Stoffel M, Esteban R, Bittner AM, Rastelli A, Denker U, Schmidt OG, Kern K (2005) Kinetic origin of island intermixing during the growth of Ge on Si(001). Phys Rev B 72:195320View ArticleGoogle Scholar
- Stoffel M, Malachias A, Rastelli A, Metzger TH, Schmidt OG (2009) Composition and strain in SiGe/Si(001) “nanorings” revealed by combined x-ray and selective wet chemical etching methods. Appl Phys Lett 94:253114View ArticleGoogle Scholar
- Lee SW, Chen LJ, Chen PS, Tsai MJ, Liu CW, Chien TY, Chia CT (2003) Self-assembled nanorings in Si-capped Ge quantum dots on (001)Si. Appl Phys Lett 83:5283–5View ArticleGoogle Scholar
- Alonso MI, de la Calle M, Ossó JO, Garriga M, Goñi AR (2005) Strain and composition profiles of self-assembled Ge/Si(001) islands. J Appl Phys 98:033530View ArticleGoogle Scholar
- Wu CC, Hull R (2006) Composition and stress fields in undulated Si0.7Ge0.3/Si(100) thin films. J Appl Phys 100:083510View ArticleGoogle Scholar
- Katsaros G, Rastelli A, Stoffel M, Isella G, von Känel H, Bittner AM, Tersoff J, Denker U, Schmidt OG, Costantini G, Kern K (2006) Investigating the lateral motion of SiGe islands by selective chemical etching. Surf Sci 600:2608–13View ArticleGoogle Scholar
- Stoffel M, Malachias A, Merdzhanova T, Cavallo F, Isella G, Chrastina D, von Känel H, Rastelli A, Schmidt OG (2008) SiGe wet chemical etchants with high compositional selectivity and low strain sensitivity. Semicond Sci Technol 23:085021View ArticleGoogle Scholar
- Rastelli A, Stoffel M, Malachias A, Merdzhanova T, Katsaros G, Kern K, Metzger TH, Schmidt OG (2008) Three-dimensional composition profiles of single quantum dots determined by scanning-probe-microscopy-based nanotomography. Nano Lett 8:1404–9View ArticleGoogle Scholar
- Oliver RA (2008) Advances in AFM for the electrical characterization of semiconductors. Rep Prog Phys 71:076501View ArticleGoogle Scholar
- Ishii M, Dhesi SS, Hamilton B (2009) Confinement, overflow, and emission of holes on SiGe surface with Ge dots: heterogeneous hole redistribution and its application to virtual dot manipulation. Appl Phys Lett 95:093101View ArticleGoogle Scholar
- Shusterman S, Raizman A, Sher A, Paltiel Y, Schwarzman A, Lepkifker E, Rosenwaks Y (2007) Nanoscale mapping of strain and composition in quantum dots using Kelvin probe force microscopy. Nano Lett 7:2089–93View ArticleGoogle Scholar
- Wong KM, Chim WK, Huang JQ, Zhu L (2008) Scanning capacitance microscopy detection of charge trapping in freestanding germanium nanodots and the passivation of hole trap sites. J Appl Phys 103:054505View ArticleGoogle Scholar
- Tanaka I, Kamiya I, Sakaki H, Qureshi N, Allen SJ Jr, Petroff PM (1999) Imaging and probing electronic properties of self-assembled InAs quantum dots by atomic force microscopy with conductive tip. Appl Phys Lett 74:844–6View ArticleGoogle Scholar
- Okada Y, Miyagi M, Akahane K, Iuchi Y, Kawabe M (2001) Self-organized InGaAs quantum dots on GaAs (311)B studied by conductive atomic force microscope tip. J Appl Phys 90:192–6View ArticleGoogle Scholar
- Smaali K, Hdiy AE, Molinari M, Troyon M (2010) Band-gap determination of the native oxide capping quantum dots by use of different kinds of conductive AFM probes: example of InAs/GaAs quantum dots. IEEE Trans Electron Devices 57:1455–9View ArticleGoogle Scholar
- Tanaka I, Tada Y, Nakatani S, Uno K, Kamiya I, Sakaki H (2010) Resonant tunneling of electrons through single self-assembled InAs quantum dot studied by conductive atomic force microscopy. Phys E 42:2606–9View ArticleGoogle Scholar
- Xue F, Qin J, Cui J, Fan YL, Jiang ZM, Yang XJ (2005) Studying the lateral composition in Ge quantum dots on Si(001) by conductive atomic force microscopy. Surf Sci 592:65–71View ArticleGoogle Scholar
- Wu R, Zhang SL, Lin JH, Jiang ZM, Yang XJ (2011) Bias-dependent conductive characteristics of individual GeSi quantum dots studied by conductive atomic force microscopy. Nanotechnology 22:095708View ArticleGoogle Scholar
- Lv Y, Cui J, Jiang ZM, Yang XJ (2013) Composition and conductance distributions of single GeSi quantum rings studied by conductive atomic force microscopy combined with selective chemical etching. Nanotechnology 24:065732Google Scholar
- Johnson FS, Miles DS, Grider DT, Wortman JJ (1992) Selective chemical etching of polycrystalline SiGe alloys with respect to Si and SiO2. J Electron Mater 21:805–10View ArticleGoogle Scholar
- Hoiland OW, White CW, Fathy D (1987) Novel oxidation process in Ge+ -implanted Si and its effect on oxidation kinetics. Appl Phys Lett 51:520–2View ArticleGoogle Scholar
- LeGoues FK, Rosenberg R, Nguyen T, Himpsei F, Meyerson BS (1989) Oxidation studies of SiGe. J Appl Phys 65:1724–8View ArticleGoogle Scholar
- Zhang SL, Lv Y, Jiang ZM, Yang XJ (2011) Electrical properties of individual self-assembled GeSi quantum rings. J Appl Phys 110:094313View ArticleGoogle Scholar