The potential advantages of GaN-based devices for, for example among other but not limited to, power switching and light emitting diode (LED) and laser applications have been known for some time, and in recent times there has been a resurgence of interest in using alternative substrates to sapphire and silicon carbide (SiC) as a result of the potential to produce these devices at significantly reduced cost on large area Si substrates. Silicon provides good thermal conductivity for power devices, however, the differences in lattice constant and coefficient of thermal expansion (CTE) between GaN and Si gives rise to a high density of threading dislocations (TDs) and tensile stress in the film which is relaxed via the formation of channeling cracks. The film cracking problem has been ameliorated through the use of various transitions layers such as AlN and SiN interlayers, AlN/GaN superlattices and compositionally graded AlxGa1-xN layers. The transition layer introduces compressive stress into the structure which partially off-sets the tensile CTE stress and induces the bending of edge-type TDs which reduces TD density. While this approach has been very successful at eliminating cracking in GaN layers up to a few microns in thickness, the growth of thicker (>5 μm) layers which are required to achieve high breakdown voltages (>1000V) and also for flexibility remains a challenge, particularly over large substrate areas.
A further understanding of the various exemplary embodiments may be realized by reference to the figures which are described in remaining portions of the specification. In the figures, like reference numerals may be used throughout several drawings to refer to similar components.
The drawings and description, in general, disclose systems and methods for gallium nitride growth on silicon. As a result of the crystalline symmetry, GaN epitaxy is typically carried out on (111) Si substrates. However, the use of large area, low cost (001) Si offers the intriguing potential to seamlessly integrate Si electronics and processing technology with GaN-based devices. For example, high performance DC power converters can be realized by combining high voltage AlGaN/GaN power switches with lower voltage Si power MOSFETs and integrated optoelectronic devices, structures, systems, etc. including but not limited to LED and/or laser based devices with silicon electronics can be realized. A structure of this type has been demonstrated on (001) Si using a wafer bonding approach, however, this involved multiple bonding and etch-back steps which pose difficulties in scale-up to large areas. The direct epitaxial growth of GaN on (001) Si is therefore highly desirable but poses significant challenges to heteroepitaxy. The (001) Si surface has fourfold symmetry as compared to the sixfold symmetry of the (0001) plane of wurtzite GaN. It has been demonstrated that (0001) AlN grows on (001) Si with two preferred rotational alignments 100, 102 (See
In addition to growth on (001) Si, there is also the need for vertical GaN-on-Si structures in which the Si substrate plays a functional role in the device. This requires either direct epitaxial growth of GaN on Si or the development of highly conductive buffer layer strategies that introduce minimal series resistance. The direct growth of GaN on Si at high temperatures is challenging due to the formation of a Ga—Si liquid alloy which generates surface pits via melt-back etching of the Si at elevated temperatures. As a result, AlN is widely employed as an initial nucleation layer for GaN growth on Si, however, the high resistivity of AlN is problematic for the realization of vertical devices structures. Conductive nucleation and transition layers are therefore required that enable the growth of high quality GaN epilayers without the introduction of undesired high resistivity layers. In addition, being able to have heteroepitaxial GaN-based devices with Si-based devices and integrated circuits including but not limited to complementary metal oxide semiconductor (CMOS) devices, circuits, integrated circuits is of great value.
An embodiment of the present invention comprises an InGaN-GaN light emitting diode (LED) on CMOS-compatible (001) Si substrates. The present invention involves the materials growth and processing technologies to enable the fabrication of high crystalline quality, crack-free GaN epilayers on (001) Si substrates with conductive buffer layers that enable realization of true vertical GaN-on-Si devices. This is accomplished in a multi-stage approach that addresses the key challenges of stress mediation and TD reduction in GaN on Si epitaxy along with development of novel methods to integrate device layers on (001)Si. As an example, the nitride-based materials growth can be carried out in a group III-nitride MOCVD reactor that, for example, incorporates an in-situ wafer curvature measurement system for real time monitoring of film stress and growth rate. The use of graphene formed on (001) Si can be used as a template layer for GaN epitaxy. Graphene templates can be fabricated using two different processes. The first process utilizes a highly-scalable metal-mediated synthesis method for direct formation of GaN on graphene. The second process uses a method for transfer of CVD grown graphene from copper growth substrates to (001) Si. Conductive, strain mitigating buffer layer utilizing Si-doped GaN and AlGaN transition layers which significantly reduce TD density and provide thick crack-free epilayers can be used as part of the present invention. GaN epilayers with suitable material quality can be produced on the graphene/(001)Si substrates to fabricate p-GaN/InGaN/n-GaN epilayers and devices such as LEDs and transistors.
Synthesis of high conductivity graphene as a growth template for GaN-based vertical devices on Si(001). The development of a high quality growth template for gallium nitride epitaxial layers on silicon (001) has been a goal of many research efforts for more than a decade, however it has been met with limited success. However the use of a relatively unique material—graphene—as a novel template for GaN epitaxy on arbitrary substrates provides the possibilities of achieving the growth of GaN-based materials on (001)Si substrates. Graphene templates offer several advantages for group III-nitride epitaxy. The hexagonal atomic arrangement of carbon atoms in graphene is crystallographically compatible with the wurtzite phase of GaN. Furthermore, several methods exist to either transfer or directly fabricate graphene on a variety of substrates such as Si and glass. However, there are significant challenges associated with GaN epitaxy on graphene. The surface energy of graphene is significantly different than that of sapphire, SiC, Si or other common substrates used for GaN growth. This results in differences in the wetting behavior of AlN and GaN on graphene which impact film nucleation and growth. In addition, the graphene surface often contains wrinkles, grain boundaries and other defects which impact the growth process.
Wafer scale graphene can be implemented using a variety of synthesis techniques, such as, but not limited to: silicon sublimation from SiC (epitaxial graphene), catalytic chemical vapor deposition (CVD), and non-catalytic CVD. Synthesis from SiC, while highly scalable, does not provide a route to a high quality template for GaN synthesis on Si(001). On the other hand, CVD of graphene works on a variety of metal substrates, including nickel, iridium, ruthenium, platinum, and copper, but the required layer transfer is non-ideal for high-performance epitaxial template applications due to microcracking, interfacial contamination between graphene and the overlaying epitaxial layer, and the generation of unintentionally doped regions of graphene from the metal etchant. As a result, the synthesis of graphene films without a metallic catalyst can be an excellent route for the development of a high quality growth template.
In addition the use of epitaxial graphene which offers a higher quality template than CVD grapheme can also be used with the present invention. Embodiments of the present invention can transfer epitaxial graphene to (001)Si.
As an example of an implementation of the present invention, graphene was used as a template layer for the growth of GaN and GaN/InGaN MQW and LED device structures on (001)Si substrates. The substrates were prepared with CVD graphene transferred onto oxidized (001)Si substrates. A further embodiment of the present invention can utilize a two-step AlN buffer layer growth process to enable growth of c-axis oriented GaN grains on the CVD graphene. Using such embodiments, InGaN MQW and LED structures were fabricated on the CVD graphene substrates.
As part of one example embodiment of the present invention, large scale epitaxial graphene on (0001) oriented, semi-insulating 6H-SiC through combination of sublimation and hydrogen intercalation leading to carrier mobilities as high as 3000 cm2/V·sec at 1013 cm−2 can be produced. Hydrogen intercalation is a key step in maintaining high carrier mobility for epitaxial graphene because it eliminates the interface layer between graphene and SiC, and therefore reduces a major source of scattering. The presence of step bunching in the SiC substrate is linked to degraded performance, which can be ameliorated to improve performance in graphene materials. Various embodiments of the invention enable direct synthesis of graphene on silicon. This should not be viewed as limiting in any way or form for the present invention,
Some embodiments of the present invention use a unique method of graphene synthesis that utilizes the dissolution of amorphous carbon in a thin nickel film, followed by quenching to form a high quality graphene layer directly on Si(001) without the typical intermetallic reactions that can occur when utilizing silicon substrates for graphene synthesis.
In addition to the direct growth of graphene on Si(001), functionalization schemes that include nitrogen doping and ammonia treatments to enhance the interaction between GaN and graphene as a means to promote a low resistance interface for device operation can also be used. The functionalization process will yield nitrogen terminated surface, ideal for subsequent synthesis of GaN epitaxial layers. In addition to functionalizing the graphene for GaN synthesis, GaN, in some embodiments of the present invention, nucleate preferentially at multilayer graphene ridges on non-functionalized graphene. Therefore the nucleation and growth characteristics of GaN films on non-functionalized graphene with variations in step-edge and defect density can also be employed. GaN can be nucleated preferentially on step-edges and defects in the graphene layer.
Growth of GaN epitaxy on graphene/(001)Si substrates: GaN epitaxy on graphene/(001)Si includes having a working understanding of how AlN and GaN nucleate on graphene layers. GaN can also nucleate on graphene layers deposited on sapphire substrates. It was reported that GaN preferentially nucleated at multi-layer graphene ridges. Step-edge and defect density in graphene on the nucleation of AlN and GaN can be used. By varying the density of step-edges and defects in graphene the density of AlN and GaN nuclei formed at these defects can be tailored. The effect of the graphene thickness (i.e. the number of graphene layers) on AlN and GaN nucleation can be used to implement the optimal graphene buffer layer conditions for subsequent AlN and GaN growth on Si(001). The differences between the two graphene deposition methods (transfer of CVD graphene and direct graphene deposition using a Ni layer) on GaN nucleation can be optimized and exploited in embodiments of the present invention. The effect of graphene thickness, step-edge, and defect density can also be used to determine the optimal graphene growth conditions for the nucleation of c-axis oriented, wurtzite GaN nuclei. After these conditions have been obtained, growth of coalesced GaN films on graphene layers can be performed such that the graphene buffer layer is used to affect the stress state of the GaN film.
The GaN layers can be grown by metalorganic chemical vapor deposition (MOCVD) in a system that, for example, but not limited to, incorporates a laser reflectance tool for real-time measurements of wafer curvature during growth. Such a system can be used to carry out detailed studies of stress evolution during GaN growth on (111) Si. In-situ wafer curvature measurements are an essential tool in the development of GaN-on-Si epitaxy. An example MOCVD reactor 300, shown schematically in
where hf and hs are the film and substrate thickness, respectively and Ms is the substrate biaxial modulus. An example of the data obtained from the MOSS system during MOCVD growth of Al0.44Ga0.56N/AlN/SiC structure is shown in the plot 400 of
This approach can be used to study and set the parameters of GaN epitaxy on Si substrates using a variety of interlayer and transition layer approaches. The stress-thickness data shown in the plot 500 of
Compositionally graded AlxGa1-xN layers have successfully been employed between the AlN nucleation layer and the GaN epilayer to modify stress, film cracking and dislocation density in GaN on Si epitaxy. The plot 600 of
Development of conductive, strain-mitigating buffer layers for GaN-on-Si: The implementation of a conductive buffer layer methodology for GaN on (001)Si can be employed in the present invention. As mentioned previously, the direct growth of GaN on Si at high temperatures is challenging due to the formation of a Ga—Si liquid alloy which generates surface pits via melt-back etching of the Si at elevated temperatures. As a result, AlN is widely employed as an initial nucleation layer for GaN growth on Si, however, the high resistivity of AlN is problematic for the realization of a number of types of structures and devices including but not limited to vertical devices structures. In some embodiments, conductive nucleation and transition layers are used that enable the growth of high quality GaN epilayers without the introduction of undesired high resistivity layers. A similar problem is encountered in the heteroepitaxial growth of GaN on SiC where AlN is commonly employed to improve wetting and act as a nucleation layer. In this case, however, it has proven feasible to utilize heavily n-type doped AlxGa1-xN layers fabricated with low Al fractions (x<0.1) along with compositional grading of the layers to form low resistivity buffer layers that have enabled the realization of vertical GaN-on-SiC devices including LEDs and p-i-n diodes. The extension of this approach to Si substrates is more complicated given the problem of melt-back etching and the need to utilize the AlGaN both as a nucleation layer and as a strain mediating layer to reduce film cracking. However, H-termination of the Si surface, achieved through the use of high H2 partial pressures at the start of growth, can successfully suppress Ga—Si liquid alloy formation. Therefore some embodiments of the present invention utilize an AlGaN strain-mitigating layer in order to build in compressive stress from the epitaxial mismatch between GaN and AlN within the epilayer structure to offset the CTE mismatch between GaN and Si. However, compressive stress induces the bending of TDs which relaxes the compressive stress and can even generate additional tensile stress. Consequently, it is beneficial to achieve the lowest possible TD density at the start of growth in order to retain the maximum compressive stress within the layer structure. Intentional Si doping can also induce the inclination of TDs even in films that grow under a tensile stress. Therefore the use of heavy Si doping in the initial AlGaN transition layer which grows under a tensile stress as a route to promote the bending and annihilation of TDs as well as to obtain a conductive buffer layer structure can be employed. Once the film stress has transitioned from tensile to compressive as shown in
A secondary layer structure that utilizes Si-doped GaN to lower the TD density and AlGaN interlayers to induce compressive stress can also be used. Previous studies have presented a stress-mitigating layer structure for GaN growth on Si(111) which utilized a Si-doped GaN layer followed by a thin AlN interlayer. TD densities on the order of ˜108 cm−2 and no channeling cracks were observed in final GaN films up to 1 μm thick when using this layer structure. The Si-doped GaN layer causes inclination of TDs at early stages of the growth process, resulting in annihilation of neighboring dislocations and a reduction in the TD density. The thin AlN layer then induces a compressive stress in the GaN film, with minimal relaxation during growth due to the reduced TD density in the film. A similar modified approach for GaN grown on graphene can be used in order to obtain low dislocation density, crack free GaN. In some embodiments of the invention, heavily-doped AlGaN layers are utilized to induce compressive stress in the GaN film, instead of the previously used AlN layers, in order to obtain a conductive layer structure to mitigate stress in the GaN film.
Development of GaN-based LED device structures on Si(001): As another example, an InGaN-GaN LED on CMOS-compatible Si(001) can be generated. For example using GaN films on Si(001) with acceptable dislocation density, the growth of AlGaN/GaN heterostructures can be performed. Both N-type and p-type doped GaN films can be fabricated. Si-doping from a SiH4 source is used in some embodiments to form n-type device layers. Biscyclopentadienyl magnesium (Cp2Mg) can also be used as the Mg source for p-type doping of GaN layers for doping and InGaN growth, p-GaN/InGaN/n-GaN device layers can be grown on (001)Si. Low resistance metal contacts can be deposited on the p-type and n-type GaN layers.
Development of GaN-based power device structures and devices on Si(001): As yet another example, GaN-based power transistors and diodes on CMOS-compatible Si(001) can be obtained. For example using GaN films on Si(001) with acceptable dislocation density, the growth of GaN/InGaN/GaN heterostructures and quantum wells can be performed. N-type and p-type doped GaN films can be fabricated. Si-doping from a SiH4 source can be utilized to form n-type device layers. Biscyclopentadienyl magnesium (Cp2Mg) as well as carbon precursors can also be used as the Mg source for p-type doping of GaN layers for doping and growth, device layers can be grown on (001)Si. Low resistance metal contacts can be deposited on the p-type and n-type GaN layers.
Although MOCVD growth was discussed herein, other growth methods including, but not limited to, molecular beam epitaxy (MBE), gas source MBE (GSMBE), plasma assisted MBE (PAMBE), chemical beam epitaxy (CBE), atomic layer epitaxy (ALE), atomic layer deposition (ALD), hydride vapor phase epitaxy (HVPE), sputtering, pulsed laser deposition (PLD), electron beam evaporation, thermal evaporation and deposition, other chemical vapor deposition (CVD) and physical vapor deposition (PVD) methods, approaches, techniques, etc., other methods approaches, techniques, etc. known, etc. can be used to with and/or as part of embodiments of the present invention.
The present invention can allow for thinned downed/etched back power MOSFET structures essentially of any type including those discussed above and then growing a GaN epilayer on, for example, the etched back/thinned down (001) Si which is also written as (100) orientation Si to create and fabricate a Si power FET structure with, for example, a GaN epitaxial drift region. Such structures can then have an appropriate mechanical and electrical support structure or structures to enable the device to be completed and, for example, packaged. Band gap offsets also referred to as band offsets (i.e., conduction band and/or valance band offsets) can be used to support current transport; if desired additional steps and/or layers can be employed including, but not limited to, hetero-interfaces, superlattice(s), heavily doped layers, tunneling layers, tunnel junctions, etc., other processing steps and techniques, or combinations of these, etc. In addition, other methods including but not limited to wafer bonding, other types of bonding, attaching, epitaxial growth, regrowth, selective growth, diffusion blocking layers, chemical mechanical polishing (CMP), surfactants, templates, patterning, crystal orientation, layers, etc. can also be used. The present invention can use but is not limited to using chemical vapor deposition (CVD), metalorganic CVD (MOCVD), organometallic vapor phase epitaxy (OMVPE), atomic layer epitaxy (ALE), atomic layer deposition (ALD), migration-enhanced epitaxy (MEE), selective area growth, selective area epitaxy, molecular beam epitaxy (MBE), gas source molecular beam epitaxy (GSMBE), chemical beam epitaxy (CBE), plasma enhanced CVD (PECVD), plasma enhanced MBE (PEMBE), liquid phase epitaxy (LPE), selective epitaxy growth (SEG), selective area etching (SAE), epitaxial lateral overgrowth (ELO), vapor phase epitaxy (VPE) including all types of VPE such as hydride vapor phase epitaxy (HVPE), physical vapor deposition (PVD), electron beam evaporation, sputtering, sol gel processes, ink jet, screen printing, chemical etching, dry etching including reactive ion etching (RIE) and deep RIE (DRIE), etc., combinations of these, etc. to create, fabricate, etc., implementations and embodiments of the present invention. The term “create” is used herein to refer generically to any method or technique for growing, forming, depositing, fabricating, evaporating, etc. layers and/or structures in the device, and should not be interpreted as being limited to any particular technique.
The present invention can also be used to realize micro LEDs (μLEDs) and nano LEDs (nLEDs) that, for example, but, not limited to, can be used in displays and lighting including in television displays, cellular phone displays, tablets, other personal digital assistants, other hand held devices, projection systems, wearables, watches, smart watches, etc. Embodiments of the present invention can be used to create self-assembly mLEDs and/or nLEDs that can be self-assembled and aligned including but not limited to self-aligned and permit any number of colors of display (i.e., red, green, blue; red, green, blue, amber, white with red, green, blue and one or more white with red, green, blue, etc., combinations of these, etc.) including in combination with other types and forms of emissive or down-converting/up-converting, etc. technologies, techniques, etc. including but not limited to quantum dots, quantum dot LEDs, organic light emitting diodes (OLEDs), phosphors, phosphor-coatings, etc., combinations of these, etc. In addition, the present invention can be used in mini or any other size displays or lighting including solid state lighting and general lighting. Such self-assembly could be accomplished, for example, but not limited to, by using the graphene template and related layers/materials to form specific micro or nano LED structures that each have, for example, but are not limited to, a different shape to fit into a display grid, matrix, arrangement, etc. A plot 800 in
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While illustrative embodiments have been described herein, it is to be understood that the concepts disclosed herein may be otherwise variously embodied and employed. The example embodiments disclosed herein illustrate certain features of the present invention and are not limiting in any way, form or function of the present invention. The present invention is, likewise, not limited in materials choices including semiconductor and substrate materials such as, but not limited to, silicon (Si), silicon carbide (SiC), silicon on insulator (SOI), other silicon combination and alloys such as silicon germanium (SiGe), etc., diamond, graphene, graphene oxide, gallium nitride (GaN) and GaN-based materials, aluminum nitride (AlN) and AlN-based materials, indium nitride (InN) and InN-based materials, gallium arsenide (GaAs) and GaAs-based materials, etc. The present invention can include any type of transistor or light emitting device (LED) including switching transistors, linear transistors and elements including, but not limited to, field effect transistors (FETs) of any type such as metal oxide semiconductor field effect transistors (MOSFETs) including either p-channel or n-channel MOSFETs of any type, junction field effect transistors (JFETs) of any type, metal emitter semiconductor field effect transistors, etc. again, either p-channel or n-channel or both, bipolar junction transistors (BJTs) again, either NPN or PNP or both, heterojunction bipolar transistors (HBTs) of any type, high electron mobility transistors (HEMTs) of any type, tunnel junction field-effect transistors (TFETs) of any type, unijunction transistors of any type, modulation doped field effect transistors (MODFETs) of any type, etc., again, in general, n-channel or p-channel or both, vacuum tubes including diodes, triodes, tetrodes, pentodes, etc. and any other type of switch, etc.
Integration and co-integration of radio frequency (RF), microwave, millimeter-wave (mm-wave), optical, opto-electronics, light emitting diodes (LEDs), solid state lasers, integrated circuits (ICs), application specific integrated circuits (ASICs), memory including but not limited to, FLASH, electrically erasable read only memory (EEPROM , E2PROM, etc.), programmable read only memory (PROM), random access memory (RAM), static random access memory (SRAM), high temperature electronics, etc. The present invention allows the integration of lateral and vertical devices including but not limited to GaN-related containing material (i.e., GaN, AlGaN, InGaN, InN, AlN, etc.) with Si-based power devices and ICs including but not limited to complementary metal oxide semiconductor (CMOS), SOI, n-channel MOS (NMOS), p-channel MOS (PMOS), doubly diffused MOS (DMOS), bipolar CMOS DMOS (BCD), etc.
The examples, illustrations, Figures and implementations contained within are not to be construed as limiting in any way or form.
The example embodiments disclosed herein illustrate certain features of the present invention and are not limiting in any way, form or function of present invention. The present invention is, likewise, not limited in materials choices including semiconductor materials such as, but not limited to, silicon (Si), silicon carbide (SiC), silicon on insulator (SOI), other silicon combination and alloys such as silicon germanium (SiGe), etc., diamond, graphene, graphene oxide, gallium nitride (GaN) and GaN-based materials, aluminum nitride (AlN) and AlN-based materials, indium nitride (InN) and InN-based materials, gallium arsenide (GaAs) and GaAs-based materials, diamond on Si, diamond on other substrates, etc.
The present invention can include many types of switching elements including, but not limited to, field effect transistors (FETs) such as metal oxide semiconductor field effect transistors (MOSFETs) including either p-channel or n-channel MOSFETs, junction field effect transistors (JFETs), metal emitter semiconductor field effect transistors (MESFETs), other double diffused MOSFETs and lateral diffused MOSFETs (LDMOS), etc. again, either p-channel or n-channel or both, high electron mobility transistors (HEMTs), tunnel junction field-effect transistors (TFETs), unijunction transistors, modulation doped field effect transistors (MODFETs), insulated gate bipolar transistor (IGBT), BCD devices including but not limited to transistors, other types of transistors, switches, structures, including but not limited to silicon controlled rectifiers, diodes, rectifiers, triacs, thyristors, etc. The present invention may also be applicable to certain types of hetero-interface or heterojunction bipolar transistors.
The following flow diagrams should not be viewed as limiting in any way or form, including, but not limited to, order of performance, exclusivity of steps, mandatory inclusion of steps, or details of performance of steps, etc.
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While detailed descriptions of one or more embodiments of the invention have been given above, various alternatives, modifications, and equivalents will be apparent to those skilled in the art without varying from the spirit of the invention. Therefore, the above description should not be taken as limiting the scope of the invention.
Filing Document | Filing Date | Country | Kind |
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PCT/US2015/062230 | 11/23/2015 | WO | 00 |
Number | Date | Country | |
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62083830 | Nov 2014 | US |