METAL BASED NANOWIRE TUNNEL JUNCTIONS
20170323788 · 2017-11-09
Inventors
- Zetian Mi (Verdun, CA)
- Sharif Sadaf (Hamilton, CA)
- Yong-Ho Ra (Montreal, CA)
- Thomas SZKOPEK (Outremont, CA)
Cpc classification
H01L31/109
ELECTRICITY
B82Y20/00
PERFORMING OPERATIONS; TRANSPORTING
H01L33/04
ELECTRICITY
H01L33/16
ELECTRICITY
H01L33/10
ELECTRICITY
H01L33/08
ELECTRICITY
H01L29/20
ELECTRICITY
H01L29/0676
ELECTRICITY
H01L33/06
ELECTRICITY
Y10S977/762
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
H01L21/02
ELECTRICITY
H01L27/15
ELECTRICITY
Abstract
Semiconductor light emitting diodes (LEDs) formed as (Al)GaN-based nanowire structures have a first semiconductor layer, a second semiconductor layer, and a thin metallic layer fabricated therebetween. The structures, operating in the deep ultraviolet (UV) spectral range, exhibit high photoluminescence efficiency at room temperature. The structures may be formed of an epitaxial metal tunnel junction operating as a reflector that enhances carrier transport to and from the semiconductor alloy layers, capable of producing external quantum efficiencies at least one order of magnitude higher than convention devices.
Claims
1. A semiconductor emitter comprising: a tunnel junction comprising a metallic layer disposed between a first semiconductor alloy and a second semiconductor alloy; wherein the metallic layer also acts as a reflector within the semiconductor emitter.
2. The semiconductor emitter according to claim 1, wherein the semiconductor emitter is a nanowire and the tunnel junction is part of the nanowire.
3. A semiconductor device comprising a tunnel junction comprising a first semiconductor alloy of a first composition, and a layer of a metal of a second composition.
4. The semiconductor device according to claim 3, wherein the layer of the metal enhances carrier transport to and from at least one of the first semiconductor alloy and the second semiconductor alloy.
5. The semiconductor device according to claim 3, wherein the layer of the metal forms at least one of a quasi-ohmic contact and an ohmic contact with at least one of the first semiconductor alloy and the second semiconductor alloy.
6. The semiconductor device according to claim 5, wherein the layer of metal is positioned in the semiconductor device to form semiconductor/metal/semiconductor epitaxial layers exhibiting quasi-ohmic or ohmic contact characteristics and the layer of metal being positioned to enable efficient inter-band conduction from a first p-type semiconductor alloy to a second n-type semiconductor alloy, through the layer of metal.
7. The semiconductor device according to claim 6, wherein the layer of metal is an Al layer interconnect, the first p-type semiconductor alloy is a p.sup.++-GaN alloy, the second n-type semiconductor alloy is a n.sup.++-GaN alloy, and the semiconductor/metal/semiconductor epitaxial layers are n++-GaN/Al/p++-GaN epitaxial layers.
8. The semiconductor device according to claim 3, wherein the first semiconductor alloy is n.sup.++-GaN; the second semiconductor alloy is p.sup.++-GaN; and the layer of the metal is a metallic layer comprising Al.
9. The semiconductor device according to claim 3, wherein the layer of metal is a metallic layer configured to provide an optical reflector for photons emitted from the semiconductor device.
10. The semiconductor device according to claim 3, wherein the semiconductor device is a nanowire or a plurality of nanowires.
11. A semiconductor device comprising: a plurality of semiconductor layers, each semiconductor layer of the plurality of semiconductor layers having a composition; and a plurality of metallic layers, each metallic layer of the plurality of metallic layers comprising a metal and disposed between a pair of semiconductor layers of the plurality of semiconductor layers.
12. The semiconductor device according to claim 11, wherein a metallic layer of the plurality of layers in combination with its associated pair of semiconductor layers of the plurality of semiconductor layers comprises a tunnel junction.
13. The semiconductor device according to claim 11, wherein a portion of the semiconductor device is configured to be optically pumped; and/or a semiconductor layer of the plurality of semiconductor layers further comprises a quantum structure.
14. A semiconductor device comprising: a substrate; a metallic layer disposed on a surface of the substrate; a plurality of nanowires grown at locations on the substrate, the locations defined by openings within the metallic layer, wherein the metallic layer acts an optical reflector for the semiconductor device.
15. The semiconductor device according to claim 14, wherein the semiconductor device is an optical emitter, a photodetector, or a solar cell.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The figures described below depict various aspects of the system and methods disclosed herein. It should be understood that each figure depicts an example of aspects of the present systems and methods.
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DETAILED DESCRIPTION
[0034] The present techniques relate to nanowire devices and more particularly to the use of an epitaxial metal layer as a tunnel junction discretely, as a combined tunnel junction and optical emitter reflective facet, and the basis of metal and semiconductor nanowire heterojunctions for multi-functional nanoscale electronic and photonic devices.
[0035] The ensuing description provides example embodiment(s) only, and is not intended to limit the scope, applicability or configuration of the disclosure. Rather, the ensuing description of the embodiment(s) will provide those skilled in the art with an enabling description for implementing an exemplary embodiment. It is being understood that various changes may be made in the function and arrangement of elements without departing from the spirit and scope as set forth in the appended claims.
[0036] A “solid state light source” (SSLS) as used herein refers to, but is not limited to, a type of lighting that uses semiconductor electroluminescent light emitting structures such as semiconductor junctions, p-n junctions, p-i-n junctions, quantum structures, quantum dots. Such structures can comprise single or multiple quantum structures and junctions to generate single or multiple wavelengths and combinations thereof. Such SSLS may include, but are not limited to, semiconductor light-emitting diodes (LEDs), semiconductor nanowire LEDs and nanowire electrochemical SSLS devices. Such devices exploit the recombination of electrons and holes within the device or within/upon the surface of the device thereby releasing energy in the form of photons.
[0037] A “diode” as used herein refers to, but is not limited to, a two-terminal electronic device, component, or region of a semiconductor device that has asymmetric conductance such that it has low resistance to current in one direction, and high resistance in the other.
[0038] A “light emitting diode” (LED) as used herein refers to, but is not limited to, a particular type of light emitting diode comprising a p-n junction or p-i-n junction which emits light when activated by an external electrical source providing electrical current through the terminals or contacts of the device.
[0039] A “semiconductor” as used herein refers to, but is not limited to, a material having an electrical conductivity value falling between that of a conductor and an insulator wherein the material may be an elemental materials or a compound material. A semiconductor may include, but not be limited to, an element, a binary alloy, a tertiary alloy, and a quaternary alloy. Structures formed from a semiconductor or semiconductors may comprise a single semiconductor material, two or more semiconductor materials, a semiconductor alloy of a single composition, a semiconductor alloy of two or more discrete compositions, and a semiconductor alloy graded from a first semiconductor alloy to a second semiconductor alloy. A semiconductor may be undoped (intrinsic), p-type doped, n-typed doped, graded in doping from a first doping level of one type to second doping level of the same type, or grading in doping from a first doping level of one type to a second doping level of a different type. Semiconductors may include, but are not limited to, III-V semiconductors, such as those between aluminum (Al), gallium (Ga), and indium (In) with nitrogen (N), phosphorous (P), arsenic (As) and tin (Sb), including for example GaN, GaP, GaAs, InP, InAs, AlN and AlAs; II-VI semiconductors; I-VII semiconductors; IV-VI semiconductors; IV-VI semiconductors; V-VI semiconductors; II-V semiconductors; and I-III-VI2 semiconductors; oxides; layered semiconductors; magnetic semiconductors; organic semiconductors; some group IV and VI elements and alloys such as silicon (Si), germanium (Ge), silicon germanium (SiGe) and silicon carbide (SiC); and charge-transfer complexes, either organic or inorganic.
[0040] A “metal” as used herein refers to, but is not limited to, a material (an element, compound, or alloy) that have good electrical and thermal conductivity as a result of readily losing outer shell electrons which generally provides a free flowing electron cloud. This may include, but not be limited to, gold, chromium, aluminum, silver, platinum, nickel, copper, rhodium, palladium, tungsten, palladium, and combinations of such materials
[0041] A “transparent electrode” or “transparent contact” as used herein refers to, but is not limited to, a material having electrical conductivity and optical transparency over a predetermined wavelength range. Such transparent electrodes may include, but are not limited to, indium tin oxide (ITO, or tin-doped indium oxide) which is a solid solution of indium (III) oxide (In.sub.2O.sub.3) and tin (IV) oxide (SnO); carbon nanotube conductive coatings; graphene films; thin metal films or hybrid material alternatives, such as silver nanowires covered with graphene; inherently conductive polymers (ICPs) and conducting polymers, such as polyaniline and poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS); and amorphous transparent conducting oxides including, for example, aluminum, gallium or indium-doped zinc oxide (AZO, GZO or IZO).
[0042] A “quantum structure” as used herein refers to, but is not limited, to a semiconductor structure having physical dimensions in one or more axes that are small enough that the properties of electrons and/or holes are governed by quantum mechanical and/or quantum electrical properties. This may include, but not be limited to, a quantum dot which is a nanocrystal of a semiconductor material small enough that its excitons are confined in all three spatial dimensions, a quantum well wherein the excitons are confined in one dimension such that they may move in a planar layer, and a quantum wire wherein the excitons are confined in two dimensions. A “quantum structure” may include, but not be limited to, a discrete quantum structure such as a colloidal quantum dot, a discrete quantum wire such as a nanotube, a quantum structure within a semiconductor structure such as a quantum dot within a nanowire, a quantum structure within another quantum structure such as a quantum dot within a quantum well or quantum dot within another quantum dot.
[0043] A “substrate” as used herein refers to, but is not limited to, a surface upon which semiconductor structures, such as nanowires for example, may be grown. This may include, but not be limited, silicon, silica-on-silicon, silica, silica-on-polymer, glass, a metal, a ceramic, a polymer, or a combination thereof. The substrate may be flat and smooth, profiled, curved, concave, convex, patterned, etc.
[0044] A “nanostructure” as used herein refers to, but is not limited to, a structure having one or more dimensions at the nanometer level, which is typically between the lower and upper dimensions of 0.1 nm and 100 nm. Such structures, may include, nanotextured surfaces having one dimension on the nanoscale, nanotubes having two dimensions on the nanoscale, and nanoparticles having three dimensions on the nanoscale. Nanotextured surfaces may include, but not be limited, nano-grooves, nano-channels, and nano-ridges. Nanotubes may include structures having geometries resembling, but not be limited to, tubes, solid rods, whiskers, and rhomboids with square, rectangular, circular, elliptical, and polygonal cross-sections perpendicular to an axis of the nanotube. Nanoparticles may include structures having geometries representing, but not limited to, spheres, pyramids, and cubes. The cross-sectional geometry of nanotubes and nanoparticles may not be constant such that a nanostructure may taper in one or two dimensions.
[0045] A “nanowire” as used herein refers to, but is not limited to, a structure within the category of nanotubes by virtue of being nanoscale on two dimensions and solid cross-sectionally formed from one or more materials.
Metal Based Tunnel Junctions
[0046] The inventors have established a novel metal based tunnel junction for integration with semiconductor nanowires in order to address limitations within the prior art. For example, the inventors have established novel aluminum (Al) tunnel junctions that overcomes some of the critical issues related to conventional GaN-based tunnel junction designs, including stress relaxation, wide depletion region, and light absorption, and holds promise for realizing low resistivity, high brightness III-nitride nanowire LEDs in the visible and deep ultraviolet spectral range. Moreover, the demonstration of monolithic integration of metal and semiconductor nanowire heterojunctions provides a seamless platform for realizing a broad range of multi-functional nanoscale electronic and photonic devices.
[0047] Accordingly, the inventors have established a monolithically integrated metal/semiconductor nanowire tunnel junction LED, wherein the tunnel junction consists of n.sup.++-GaN/Al/p.sup.++-GaN as described and depicted in respect of
Metal Based Tunnel Junction LED Structures and Reference LED
[0048] The inventors have implemented two metal based tunnel junction InGaN/GaN nanowires according to embodiments of the invention within the results described below together with a reference nanowire LED structure. These being:
[0049] LED-A 21: depicted in first schematic 200A in
[0050] LED-B 22: depicted in second schematic 200B in
[0051] LED-C 23: depicted in third schematic 200C in
[0052] The tunnel junction of LED-A 24 includes n.sup.++-GaN(7 nm)/Al(2 nm)/p.sup.++-GaN(10 nm). The tunnel junction of LED-B 22 is identical to that of LED-A 21 but without the incorporation of the Al layer thereby yielding a tunnel junction design of n.sup.++-GaN(7 nm)/p.sup.++-GaN(10 nm) 25. In each design the active regions of each LED includes ten self-organized InGaN(3 nm)/GaN(3 nm) quantum dots 26. Each quantum dot layer is modulation doped p-type to enhance the hole injection and transport in the device active region as reported within the prior art by the inventors.
Nanowire Growth
[0053] In order to examine the intrinsic properties of the tunnel junction dot-in-a-wire LEDs, no AlGaN electron blocking layers were incorporated. All the LED structures were grown by plasma-assisted MBE on n-Si(111) substrates under nitrogen-rich conditions without using any external metal catalyst as reported by the inventors within the prior art. Prior to the growth, native oxide on the Si substrate was removed by hydrofluoric acid (10%), and further in situ desorbed at ˜770° C. The N.sub.2 flow rate was kept at 1.0 standard cubic centimeter per minute (sccm) with a forward plasma power of ˜350 W during the growth. The substrate temperature was ˜780° C. for n-GaN and 750° C. for p-GaN segments. Doping concentration and degeneracy in the tunnel junction were controlled by the Si (n-doping) and Mg (p-doping) effusion cell temperatures. The Al layer was grown at ˜450° C. and was subsequently capped with a thin layer of Ga. In this process, the nitrogen plasma was turned off to avoid the formation of AlN. The substrate temperature was then increased to 650° C. for the growth of p.sup.++-GaN(10 nm). Such optimum growth conditions were obtained based on extensive studies of the LED performance by varying the Al thickness (1 nm≦t.sub.al≦6 nm) and growth temperature (300° C.≦T.sub.Growth≦650° C.) and by changing the Si and Mg-doping concentrations. It was observed that a high quality pure Al metal layer could be grown in situ on GaN nanowires without any metal agglomeration and void formation. Moreover, detailed structural characterization, described below, further confirmed that defect-free nanowires could be grown directly on an epitaxial Al layer.
[0054] The three nanowire LED structures exhibited nearly identical photoluminescence (PL) characteristics. Shown in
Nanowire LED Structure Characterization
[0055] Scanning transmission electron microscopy (STEM) and high resolution transmission electron microscopy (HR-TEM) studies were further performed to characterize the tunnel junction thickness and composition. The nanowires were first dispersed on a Cu grid. A JEOL JEM-2100F equipped with a field emission gun with an accelerating voltage of 200 kV was used to obtain bright-field TEM images. For STEM and high angle annular dark field (HAADF) imaging, the same equipment with a cold field emission emitter operated at 200 kV and with an electron beam diameter of approximately 0.1 nm was used. Illustrated in
Nanowire LED Processing
[0056] Subsequent to the growth of the nanowire arrays with or without Al -based tunnel junctions or tunnel junctions at all the arrays were processed to form LEDs. This processing 40 begins, as depicted in
Nanowire LED Characterization
[0057] Current-voltage characteristics of the nanowire LEDs were measured under continuous wave biasing conditions at room temperature. During the measurements, a negative bias was applied on the top surface for n-GaN up LEDs (LED-A and LED-B). As such, for each of LED-A and LED-B these were forward biased and the tunnel junction was reverse biased. Conversely, a positive bias was applied on the top surface for p-GaN up device (LED-C, without the use of tunnel junction).
[0058] Now referring to
[0061] These issues can be potentially addressed by developing highly uniform nanowire arrays using the technique of selective area growth. Taking these factors into account, we estimated that the specific resistivity for the Al tunnel junction is in the range of 1×10.sup.−3Ω.Math.cm.sup.2, or smaller. Specific resistivity values in the range of 10.sup.−4Ω.Math.cm.sup.2 to 10.sup.−2Ω.Math.cm.sup.2 have been previously reported in GaN-based planar tunnel junction devices as evidenced from Table 1 below. Given the identical design, growth and fabrication processes for the three LEDs within the work by the inventors, the significantly reduced turn-on voltage and resistance of LED-A provides unambiguous evidence that the n.sup.++-GaN/Al/p.sup.++-GaN can serve as a low resistivity tunnel junction.
TABLE-US-00001 TABLE 1 Summary of Specific Resistance Values of Prior Art Tunnel Junction Devices versus Embodiment of the Invention Tunnel Junction (TJ) Device Ref. Material (Ω .Math. cm.sup.2) (Ω .Math. cm.sup.2) Structure Method 1 InGaN/GaN 5 × 10.sup.−4 2 × 10.sup.−2 Planar, TJ LED PA-MBE 2 GdN/GaN 1.3 × 10.sup.−3 N/A Planar, TJ p-n device PA-MBE 3 p.sup.++-GaN/n.sup.++-GaN 22.5 × 10.sup.−2 N/A Planar TJ device PA-MBE 4 InGaN/GaN 6.05 × 10.sup.−3 2.38 × 10.sup.−2 Planar TJ LED MOCVD 5 AlGaN/InGaN 1.95 × 10.sup.−3 1.97 × 10.sup.−2 Planar TJ LED MOCVD 6 InGaN/GaN 5 × 10.sup.−4 0.3 × 10.sup.−2 Planar, cascaded TJ PA-MBE 7 p.sup.++-GaN/n.sup.++-GaN N/A 3.7 × 10.sup.−4 Planar, TJ LED Ammonia MBE 8 InGaN/GaN N/A 3 × 10.sup.−2 Nanowire, TJ LED PA-MBE 9 Al/GaN ~10.sup.−3 0.4 × 10.sup.−2 Nanowire, TJ LED PA-MBE 10 InGaN/GaN ~10.sup.−4 N/A Planar, TJ device PA-MBE 1: APL, 105, 141104, 2014 2: Nano Lett, 13, 2570-2575, 2013 3: Nano Lett, 13, 2570-2575, 2013 4: IEEE EDL, 36, 4, 2015 5: IEEE JOE, 51, 8, 2015 6: APEX, 8, 082103, 2015 7: APL, 107, 051107, 2015 8: Nano Lett., 15, 10, 6696, 2015 9: Inventors, this work 10: APL, 99, 233504, 2011
[0062] The Al tunnel junction LED also showed significantly improved light intensity compared to the conventional nanowire device (LED-C) and n.sup.++-GaN/p.sup.++-GaN tunnel junction device (LED-B) as depicted in
[0063] Shown in
[0064] Shown in
[0065] The high-luminescene efficiency is directly related to the significantly reduced defect densities in AlGaN nanowires and the formation of an Al-rich AlGaN shell structure that minimizes nonradiative surface recombination.
[0066] Electroluminescence (EL) spectra of LED-B and LED-C are also shown in
[0067]
[0068] Significantly, defect-related emission in the UV or visible spectral range that was commonly observed in conventional AlGaN quantum wells is absent in the presented AlGaN nanowires, shown in the inset of
[0069] Output power of nanowire LEDs was measured directly on wafer without any packaging.
[0070] Given the similar optical properties of both nanowire devices under optical pumping, the drastically improved output power for LED A is attributed to the significantly enhanced hole transport and injection into the device active region, due to the incorporation of Al tunnel junction, and the elimination of resistive and absorptive p-GaN contact layer.
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[0072] The efficiency droop can be minimized by incorporating an AlGaN electron blocking layer and by p-type modulation doping to enhance the hole injection and transport in the active region. The maximum wall-plug efficiency (WPE) was ˜0.3%.
[0073] It is observed that nearly dislocation-free Al-rich AlGaN nanowire heterostructures can be formed on an epitaxial Al tunnel junction, using the present techniques. The resulting core-shell nanowire arrays exhibit high luminescence efficiency of ˜80% in the UV-C band at room temperature.
[0074] Such p-(Al)GaN contact-free deep UV LEDs showed nearly one order of magnitude reduction in the device resistance and more than two orders of magnitude enhancement in the output power.
[0075] The device performance can be further improved by optimizing the tunnel junction and device active region, including the use of quantum dots or quantum disks and the incorporation of electron blocking layer.
[0076] It is further envisioned that the Al tunnel junction with optimized design can be exploited to significantly enhance the light reflection and extraction, which together with a precise control of the nanowire size and spacing can lead to deep UV LED devices with significantly improved performance.
[0077] The present techniques have been used to develop a low resistance Al tunnel junction integrated dot-in-a-wire LEDs, enabling p- contact free devices with significantly improved hole injection efficiency. Compared to prior art polarization engineered tunnel junctions, the novel and inventive Al tunnel junction completely eliminates the use of either a low band gap InGaN or a large bandgap Al(Ga)N layer in the tunnel junction design which has been shown in the prior art to result in undesired optical absorption and/or high voltage loss. Such an Al tunnel junction may also be implemented in either N-face or Ga-face III-nitride quantum well and nanowire LEDs.
[0078] The novel and inventive Al tunnel junction also offers promise for applications in the emerging non-polar and semi-polar GaN optoelectronic devices. Moreover, the seamless integration of defect-free nanowire structures with various metal layers offers a unique approach for achieving high performance nanoscale electronic and photonic devices which have hitherto not been previously possible.
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[0081] This concept is extended in
[0082] Whilst example embodiments have been presented with respect to Al and GaN, it will be evident to one of skill in the art that with other semiconductors that other metals may provide the same desired combination of quasi-ohmic contacts between the metal layer and the two semiconductor alloys either side of it forming the overall tunnel junction. In these embodiments, the metallic layer may directly or in combination with doping yield the appropriate energy level structure(s) to support carrier transport from one semiconductor to the metallic layer and therein the metallic layer to the second semiconductor. In this manner, the need for polarization engineering may be eliminated and/or reduced in order to provide a sufficiently narrow depletion region for efficient tunneling.
[0083] Whilst example embodiments have been described with respect to a metallic element for the metal layer within the tunnel junction, it would be evident to one of skill in the art that the metal may alternatively be an alloy or a combination of metals
[0084] The foregoing disclosure of the exemplary embodiments of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many variations and modifications of the embodiments described herein will be apparent to one of ordinary skill in the art in light of the above disclosure. The scope of the invention is to be defined only by the claims appended hereto, and by their equivalents.
[0085] Further, in describing representative embodiments of the present invention, the specification may have presented the method and/or process of the present invention as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. As one of ordinary skill in the art would appreciate, other sequences of steps may be possible. Therefore, the particular order of the steps set forth in the specification should not be construed as limitations on the claims. In addition, the claims directed to the method and/or process of the present invention should not be limited to the performance of their steps in the order written, and one skilled in the art can readily appreciate that the sequences may be varied and still remain within the spirit and scope of the present invention.