Method for fabricating embedded nanostructures with arbitrary shape

Abstract

A layered heterostructure, comprising alternating layers of different semiconductors, wherein one of the atom species of one of the semiconductors has a faster diffusion rate along an oxidizing interface than an atom species of the other semiconductor at an oxidizing temperature, can be used to fabricate embedded nanostructures with arbitrary shape. The result of the oxidation will be an embedded nanostructure comprising the semiconductor having slower diffusing atom species surrounded by the semiconductor having the higher diffusing atom species. The method enables the fabrication of low- and multi-dimensional quantum-scale embedded nanostructures, such as quantum dots (QDs), toroids, and ellipsoids.

Claims

1. A method for fabricating embedded nanostructures, comprising: providing a layered heterostructure, comprising alternating layers of at least two different semiconductors, wherein an atom species of one of the semiconductors has a faster diffusion rate along an oxidizing interface than a slower diffusing atom species of the other semiconductor at an oxidizing temperature; patterning the layered heterostructure to form a patterned heterostructure; removing portions of the patterned heterostructure to form a vertical heterostructure of arbitrary cross section; and oxidizing the vertical heterostructure at the oxidizing temperature to form embedded nanostructures having an arbitrary shape of the semiconductor having the slower diffusing atom species surrounded by the semiconductor having the faster diffusing atom species.

2. The method of claim 1, wherein the layered heterostructure comprises Si/SiGe.

3. The method of claim 2, wherein the layered heterostructure comprises at least one Si layer between SiGe layers.

4. The method of claim 2, wherein the embedded nanostructure comprises a embedded Si nanostructure surrounded by a SiGe.

5. The method of claim 4, wherein the embedded nanostructure comprises a Ge-rich cladding surrounding the embedded Si nanostructure.

6. The method of claim 4, further comprising implanting the surrounding SiGe with Si ions to amorphize the SiGe.

7. The method of claim 1, wherein the oxidizing comprises exposing the vertical pillars to O.sub.2 at an oxidizing temperature greater than 800° C.

8. The method of claim 1, further comprising annealing the embedded nanostructures at an annealing temperature to at least partially remove the surrounding semiconductor.

9. The method of claim 8, wherein the annealing comprises exposing the embedded nanostructures to O.sub.2 at an annealing temperature of greater than 500° C. and less than 800° C.

10. The method of claim 1, wherein the embedded nanostructure comprises an L, toroid, dot, or ellipsoid.

11. The method of claim 1, wherein the embedded nanostructure has a cross-sectional dimension of less than 10 nm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The detailed description will refer to the following drawings, wherein like elements are referred to by like numbers.

(2) FIG. 1A is a schematic illustration of three diffusion processes responsible for embedded nanostructure formation during Si/SiGe fin oxidation: 1) conventional interdiffusion between Si and Ge, 2) Ge rejection into SiGe from an oxidizing interface, and 3) rapid oxidation-assisted Ge diffusion along the oxidizing interface. FIG. 1B is a schematic illustration the combination of these three processes in the formation of an embedded nanowire, with a higher Ge concentration shown as the unhatched boundary between the SiGe and SiO.sub.2 regions. FIG. 1C is a cross-sectional scanning transmission electron microscopy (STEM) image of a 5.5 nm diameter Si nanowire (dark) embedded in single crystal SiGe (light) formed by the combination of these three processes during a 45-minute oxidation in dry O.sub.2 at 900° C.

(3) FIG. 2 is a schematic illustration of a method for fabricating Si or SiGe quantum dots in an array of vertical pillars or posts.

(4) FIG. 3 shows STEM images of the evolution of a 75 nm pillar during oxidation in O.sub.2 at 900° C.

(5) FIG. 4A is a STEM image of a 75 nm pillar after a 35-minute oxidation.

(6) FIG. 4B is a high-resolution STEM image of the top embedded Si quantum dot.

(7) FIG. 5A is a STEM image of the embedded Si dot. FIG. 5B is a greyscale intensity plot of the Si dot. FIG. 5C is a greyscale intensity plot across the center of the Si dot.

(8) FIG. 6A is a high angle annular dark field (HAADF) image of the Si dot.

(9) FIG. 6B shows Si and Ge energy dispersive X-ray spectroscopy (EDS) scans across the center of the dot.

(10) FIG. 7 shows a method to fabricate novel 3D quantum structures. Vertical pillars can be patterned with arbitrary cross-sections, such as a square (as shown), L, ring, circle, or oval. Subsequent thermal oxidation forms an embedded L, toroid, dot, or ellipsoid, respectively.

(11) FIG. 8 is schematic illustration of Si ion implantation to amorphize SiGe.

(12) FIG. 9 is a schematic illustration of a SiGe quantum dot transistor.

(13) FIG. 10 is a schematic illustration of a Si quantum dot-based optical source.

DETAILED DESCRIPTION OF THE INVENTION

(14) The present invention is directed to a novel method for fabricating low- and multi-dimensional quantum-scale embedded nanostructures, such as quantum dots (QDs), toroids, and ellipsoids, from semiconductor layered heterostructures. In general, the method can be used with any layered heterostructure, comprising alternating layers of different semiconductors, wherein one of the atom species of one of the semiconductors has a faster diffusion rate along an oxidizing interface than an atom species of the other semiconductor at an oxidizing temperature. The result of the oxidation will be an embedded nanostructure comprising the semiconductor having the slower diffusing atom species surrounded by the semiconductor having the higher diffusing atom species. For example, the method can be used with GaAs/AlGaAs layered heterostructures to form GaAs nanostructures embedded in AlGaAs, InAs/AlInAs layered heterostructures to form InAs nanostructures embedded in AlInAs, and Si/SiGe layered heterostructures to form Si nanostructures embedded in SiGe.

(15) As an example, the invention enables the controlled and scalable fabrication of on-chip Si/SiGe quantum-scale structures below 10 nm. These embedded nanostructures can exhibit unique and useful new properties. For example, the indirect bandgap of Si limits its usefulness as an optoelectronic material. However, at small enough sizes (e.g. <2.5 nm), Si nanowires have been theoretically predicted to transition from an indirect to a direct bandgap. See M. O. Baykan et al., J. Appl. Phys. 108(9), 1 (2010). Direct bandgap Si/SiGe quantum-scale structures may enable a host of integrated all Si(Ge)-based photonics, including on-chip optical sources for interconnects, which is a highly sought-after goal that could eliminate the current need for integrating III-V and Si(Ge) materials and devices. The fabrication of novel embedded nanostructures using the method of the present invention enables a wide range of unique morphologies for these and other future applications.

(16) There are three distinct diffusion-related processes hypothesized to be involved in the evolution of these oxidizing Si/SiGe nanostructures, illustrated in FIG. 1A. Process 1 indicates the interdiffusion of Si and Ge in bulk diffusion couples. This interdiffusion process is well understood. See R. Kube et al., Mater. Sci. Semiconduct. Process. 11(5), 378 (2008); R. Kube et al., J. Appl. Phys. 107, 1 (2010); G. L. McVay and A. R. DuCharme, J. Appl. Phys. 44, 1409 (1973); and M. Gavelle et al., J. Appl. Phys. 104, (2008). This interdiffusion controls the upper limit of the oxidation temperature, as excessive interdiffusion is undesirable and will lead to a non-abrupt interface between the Si and SiGe layers. Process 2 indicates the pile-up/snow plow effect of Ge during the oxidation of SiGe. This process is also well-studied, although questions on the exact mechanism remain. See E. Long et al., J. Vac. Sci. Technol. B, (2012); M. Tanaka et al., (2008); and S. Margalit et al., J. Cryst. Growth, 17, 288 (1972). Since the oxidation potential of Si is greater than Ge, the Si is selectively oxidized and the Ge is rejected back into the SiGe, producing a Ge-rich layer in the SiGe at the oxidizing SiGe/SiO.sub.2 interface. The steady-state Ge concentration in this Ge rich layer is highly dependent on temperature and does not depend on the initial Ge concentration of the SiGe. Process 3 is an enhanced vertical Ge diffusion process along the oxidizing Si/SiO.sub.2 interface. This diffusion is estimated to be at least two orders of magnitude faster than Ge diffusing through bulk crystalline Si. The mechanism or details of the formation of the initial SiGe layer along the oxidizing Si/SiO.sub.2 interface is unknown. See W. M. Brewer et al., Nano Lett. 17(4), 2159 (2017).

(17) It is not well understood how each of these three diffusion processes contribute to the accumulation of Ge along the sides of the nanostructure. However, the interaction between these three combined processes in the oxidation of a Si/SiGe fin structure has been shown to form longitudinal strained Si single crystal nanowires encapsulated in SiGe with a rounded cross-section down to 2 nm. See W. M. Brewer et al., Nano Lett. 17(4), 2159 (2017). FIG. 1B is a schematic illustrating the combination of these three processes in the formation of a nanowire, with a higher Ge concentration shown as the unhatched boundary between the SiGe and SiO.sub.2 regions. FIG. 1C shows a cross-sectional scanning transmission electron microscopy (STEM) image of a 5.5 nm diameter Si nanowire (dark) embedded in single crystal SiGe (light) formed by the combination of these three processes after a 45-minute oxidation in dry O.sub.2 at 900° C.

(18) These diffusion processes have competing activation energies, suggesting that the size and shape of the embedded nanostructures can be controlled by tuning the oxidation time and temperature and by the starting geometry. See P.-E. Hellberg et al., J. Appl. Phys. 82, 5779 (1997). If these processes can be predictably controlled, scalable, sub-10 nm nanostructure formation is possible. In particular, the enhanced Ge diffusion process can be exploited to create completely novel multi-dimensional quantum structures not easily realized or even possible using current top-down or bottom-up approaches. For example, quantum dots can have excellent optical quality and may allow for electron charging down to the single electron level. Finally, selective amorphization of the SiGe alloy surrounding the embedded Si nanostructure, via ion implantation, can provide a route to electronic confinement.

(19) By creating a patterned, starting heterostructure with layers of differing composition, it is possible to shrink and embed the layer comprising the slower diffusing species, creating an embedded nanostructure with the shape and size determined by the starting layered structure shape and the thermal oxidation condition. In FIG. 2 is shown an exemplary method to fabricate OD structures (e.g., Si/SiGe quantum dots) in vertical pillars, or posts, enabled by the enhanced diffusion process. The process begins with depositing a layered Si/SiGe epitaxial heterostructure 11, comprising alternating layers of Si 12 and SiGe 13, on a substrate 14. In this example, the substrate 14 is Si. The layered heterostructure 11 can be patterned using e-beam lithography to define circular features. Next, an array 10 of vertical pillars 15 can be created in the patterned Si/SiGe heterostructure using reactive ion etching. The pillars 15 are preferably long enough to allow uninhibited Ge diffusion down the sidewalls and strong enough to maintain structural integrity during the subsequent processing steps. The pillars 15 can then be annealed under a high temperature oxidizing condition using rapid thermal oxidation (RTO) to form embedded Si dots 16. Finally, the SiGe sidewalls can be removed via a low temperature oxidizing anneal to form an array 17 of Si (or SiGe) quantum dots 18 in the oxidized pillars 19. The size of the quantum dots 18 can be controlled by the starting pillar 15 diameter and the annealing times and temperatures.

(20) The structural evolution of embedded nanostructures can be examined using cross-sectional high angle annular dark field scanning transmission electron microscopy (HAADF-STEM). In FIG. 3 are shown cross-sectional STEM images of 75 nm pillars oxidized at 900° C. in dry O.sub.2 for a range of times. The images clearly show the enhanced vertical diffusion of Ge along the Si/SiO.sub.2 interface, resulting in an embedded Si dot. FIGS. 4A and 4B are STEM images of a Si dot fully encapsulated by single crystal SiGe after 35-minute oxidation at 900° C. in 02. The embedded Si dot is less than 10 nm in diameter. FIG. 5A is a STEM image of the embedded Si dot (shown as the darker circular region). FIG. 5B is a greyscale intensity plot of the Si dot. FIG. 5C is a greyscale intensity plot across the center of the Si dot. The HAADF-STEM micrographs can be used to estimate the Ge concentration through Z-contrast analysis. See T. Grieb et al., Ultramicroscopy 184, 29 (2018). FIG. 6A is a HAADF image of the dot. FIG. 6B shows Si and Ge energy dispersive X-ray spectroscopy (EDS) scans across the center of the dot. The images indicate a Si-rich dot surrounded by a Ge-rich halo, or sphere. The Ge-rich sphere will have a larger Ge concentration than the surrounding SiGe, and therefore a smaller bandgap than both the surrounding single crystal SiGe and the embedded Si-rich dot. Therefore, the Ge-rich shell can be electronically and optically confined which can be useful for some applications.

(21) The enhanced Ge diffusion process enables a new method to create totally novel nano- and quantum-scale structures not achievable or previously demonstrated by other methods. FIG. 7 illustrates vertical Si/SiGe nanostructures with different and arbitrarily defined cross-sectional shapes. First, vertical 1-D Si/SiGe pillars 15 can be created by e-beam lithography and plasma etching of the patterned heterostructure, resulting in defined cross-sectional shapes, including square (as shown), ‘L’, ring, circle, or oval. These nanopillars 15 can then be thermally oxidized to drive the enhanced Ge diffusion process, resulting in encapsulated Si Ls 21, toroids 22, dots 23, or ellipsoids 24 surrounded by a SiGe alloy 25. These on-chip structures may exhibit novel shape-dependent physical properties, such as optical polarization.

(22) The encapsulated nanostructures most easily created by this method are composed of a wider bandgap material (Si) surrounded by a narrower bandgap material (SiGe), which can present a challenge for use in applications requiring quantum or optical confinement. The bandgap can be modified by the selective amorphization of the surrounding single crystal SiGe using ion beam irradiation while leaving the Si crystalline, as shown in FIG. 8. Selective amorphization of SiGe in a Si/SiGe planar superlattice by Si ion irradiation has previously been demonstrated. See M. Vos et al., Appl. Phys. Lett. 58(9), 951 (1991). The SiGe alloy can be implanted with Si ions at doses that exceed the threshold damage density (TDD) for amorphization of SiGe but are below the TDD for Si. In particular, the dose can be below the threshold for forming stable extended defects in Si, and the sample can be annealed (up to 350° C.) to repair most of the Frenkel pair damage in the Si nanostructures without recrystallizing the amorphous SiGe. See Y. Tong et al., Thin Solid Films 291, 464 (1996). As amorphous Si.sub.0.6Ge.sub.0.4 has a significantly larger bandgap (˜1.5 eV) compared to Si (1.1 eV), this enables confinement of the inner Si nanostructure by a wider bandgap amorphous outer SiGe material. Selective amorphization can thus serve as a method to engineer the Si/SiGe band structures to suit the desired application.

(23) The method enables novel microelectronics applications. FIG. 9 is a schematic illustration of a SiGe quantum dot single transistor 30, comprising an embedded SiGe quantum dot 31 for trapping an electron under a gate. See M. H. M. Van Weert et al., Appl. Phys. Lett. 96, 233122 (2010), which is incorporated herein by reference. A gate dielectric 32 and gate metal 33 can be deposited on the walls of the pillar 34 after formation of the SiGe quantum dot 31. The transistor can further comprise a source 35 and a drain 36. The method enables a surround-gated vertical nanowire quantum dot. Different quantum dot charge states can be accessed by tuning the gate voltage.

(24) The method also enables novel optical applications. FIG. 10 is a schematic illustration of a Si quantum dot-based optical source 40. The optical source 40 comprises an embedded direct gap Si quantum dot 41. The pillars 42 can be surrounded by insulating SiO.sub.2 43. Light can be extracted though an optically transparent, electrically conducting, top indium tin oxide (ITO) layer 44 enabling a forward-biased diode. Quantum dots potentially are robust, have large absorption cross-sections, and emission wavelengths that can be tuned by size, and thus offer optical and chemical advantages compared to current state-of-the art organic molecules. Silicon is non-toxic and abundant, thereby eliminating many of the drawbacks commonly found for the direct bandgap materials. At small enough sizes (e.g. <2.5 nm), Si nanowires have been theoretically predicted to transition from an indirect to a direct bandgap. See M. O. Baykan et al., J. Appl. Phys. 108(9), 1 (2010); and K. Dohnalova et al., Light: Science and Applications 2, e47 (2013). Therefore, direct bandgap Si/SiGe quantum-scale structures may enable a host of integrated all Si(Ge)-based photonics, including on-chip optical sources for interconnects, that could eliminate the current need for integrating III-V and Si(Ge) materials and devices.

(25) The present invention has been described as a method for fabricating embedded nanostructures with arbitrary shape. It will be understood that the above description is merely illustrative of the applications of the principles of the present invention, the scope of which is to be determined by the claims viewed in light of the specification. Other variants and modifications of the invention will be apparent to those of skill in the art.