Epitaxial hexagonal materials on IBAD-textured substrates
09735318 · 2017-08-15
Assignee
Inventors
Cpc classification
H10K59/00
ELECTRICITY
H01L27/15
ELECTRICITY
H01L33/16
ELECTRICITY
H01L21/02483
ELECTRICITY
International classification
H01L21/02
ELECTRICITY
Abstract
A multilayer structure including a hexagonal epitaxial layer, such as GaN or other group III-nitride (III-N) semiconductors, a <111> oriented textured layer, and a non-single crystal substrate, and methods for making the same. The textured layer has a crystalline alignment preferably formed by the ion-beam assisted deposition (IBAD) texturing process and can be biaxially aligned. The in-plane crystalline texture of the textured layer is sufficiently low to allow growth of high quality hexagonal material, but can still be significantly greater than the required in-plane crystalline texture of the hexagonal material. The IBAD process enables low-cost, large-area, flexible metal foil substrates to be used as potential alternatives to single-crystal sapphire and silicon for manufacture of electronic devices, enabling scaled-up roll-to-roll, sheet-to-sheet, or similar fabrication processes to be used. The user is able to choose a substrate for its mechanical and thermal properties, such as how well its coefficient of thermal expansion matches that of the hexagonal epitaxial layer, while choosing a textured layer that more closely lattice matches that layer.
Claims
1. A multilayer structure comprising: an epitaxial hexagonal crystal layer; a layer of a cubic material having a <111> out of plane orientation and having an in-plane crystalline texture with a full width half maximum (FWHM) less than or equal to approximately 12°; and a non-single crystal substrate.
2. The structure of claim 1 wherein the epitaxial hexagonal crystal layer comprises a group III-nitride semiconductor.
3. The structure of claim 2 wherein the epitaxial hexagonal crystal layer comprises GaN.
4. The structure of claim 1 wherein the epitaxial hexagonal crystal layer serves a template layer for a light-emitting diode (LED).
5. The structure of claim 1 wherein the layer of cubic material has been textured by ion beam-assisted deposition (IBAD).
6. The structure of claim 1 wherein a property of the substrate is selected from the group consisting of amorphous, polycrystalline, flexible, ductile, metallic, ceramic, glass, plastic, and polymer.
7. The structure of claim 1 wherein the epitaxial hexagonal crystal layer was grown using metal-organic chemical vapor deposition (MOCVD), reactive sputtering, reactive evaporation or molecular beam epitaxy (MBE).
8. The structure of claim 1 wherein the coefficients of thermal expansion of the substrate and the epitaxial hexagonal crystal layer are within approximately 12%.
9. The structure of claim 8 wherein the coefficients of thermal expansion of the substrate and the epitaxial hexagonal crystal layer are within approximately 5%.
10. The structure of claim 1 wherein the epitaxial hexagonal crystal layer comprises GaN and the substrate comprises molybdenum, tungsten, tantalum, alloys thereof, Mo—Cu, or TZM.
11. The structure of claim 1 wherein the layer of cubic material has an in-plane crystalline texture having a FWHM of less than or equal to approximately 8°.
12. The structure of claim 11 wherein the layer of cubic material has an in-plane crystalline texture having a FWHM of less or equal to than approximately 5°.
13. The structure of claim 1 wherein the layer of cubic material is selected from the group consisting of MgO, CeO.sub.2, a bixbyite structure, Sc.sub.2O.sub.3, Y.sub.2O.sub.3, Al.sub.2O.sub.3, a fluorite structure, TiN, a rock salt structure, CaF.sub.2, cubic ZrO.sub.2, HfO.sub.2, ScO.sub.x, and Mn.sub.2O.sub.3.
14. The structure of claim 1 comprising a base layer disposed between the substrate and the layer of cubic material.
15. The structure of claim 14 wherein the base layer comprises amorphous Al.sub.2O.sub.3, Y.sub.2O.sub.3, or SiO.sub.2.
16. The structure of claim 1 comprising one or more epitaxial buffer layers disposed between the layer of cubic material and the epitaxial hexagonal crystal layer.
17. The structure of claim 16 wherein the epitaxial buffer layers each have a lattice parameter that successively provides a transition from the lattice parameter of the cubic material to the lattice parameter of the epitaxial hexagonal crystal.
18. The structure of claim 17 wherein the epitaxial hexagonal crystal layer comprises GaN and the epitaxial buffer layers comprise a layer of Sc.sub.2O.sub.3, a layer of Zr, and a layer of AlN.
19. The structure of claim 1 wherein the FWHM of the in-plane crystalline texture of the layer of cubic material is greater than an FWHM of an in-plane crystalline texture of the epitaxial hexagonal crystal layer.
20. The structure of claim 1 used as a component of an electronic or optoelectronic device.
21. The structure of claim 20 wherein the electronic or optoelectronic device is selected from the group consisting of LED, MOSFET, MESFET, HEMT, Heterojunction FET, heterojunction bipolar transistor (HBT), thin-film transistor, sensor, memristor, laser diode (LD), SAW device, spintronic device, photodetector, and photovoltaic (PV) diode.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings, which are incorporated into and form a part of the specification, illustrate the practice of embodiments of the present invention and, together with the description, serve to explain the principles of the invention. The drawings are only for the purpose of illustrating certain embodiments of the invention and are not to be construed as limiting the invention. In the drawings:
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DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION
(32) The present invention is related to an approach to scale up GaN production using ion-beam crystal alignment for epitaxial films. The process is sometimes called ion-beam assisted deposition (IBAD), but it really refers to texturing of films with IBAD. IBAD texturing can occur at different time scales or thicknesses of films, but preferably occurs right at initial film nucleation and coalescence, which is known as ion-texturing at nucleation (ITaN). It typically occurs in the first 5-10 nm of deposit and has been demonstrated to be extremely fast, can occur in less than 1 second of deposition time. IBAD texturing can be performed on a large-area substrate that is typically a flexible metal foil. IBAD texture formation can alternatively be performed on flexible glass, ceramic, plastic or polymer. The process is easily scalable to long lengths with flexible substrates that can be put onto a spool suitable for roll-to-roll processing. The substrate itself can be polycrystalline but is preferably chosen for its mechanical as well thermal properties. Thus the material and the thickness of the foil are preferably optimized for the final application. Thin foils are preferably flexible and ductile. Additionally, since MOCVD growth (when utilized) is performed at high temperature, the material preferably has a good match to the coefficient of thermal expansion (CTE) of the thick GaN layers that will subsequently be deposited. For GaN molybdenum or tungsten or alloys thereof are preferably used. By eliminating the need for lattice matching in the substrate a greater variety of substrates may be chosen.
(33) Embodiments of the present invention are based on a novel GaN growth process which, compared to existing methods reported for GaN growth, comprises the use of non-single crystal substrates such as polycrystalline commercial metal foils or amorphous glass, upon which epitaxial GaN films are deposited directly and can be used for various applications including electronics, optics and optoelectronics, etc. In some embodiments, several different uniform films of thicknesses in the range of tens of nm are preferably evaporated or sputtered onto biaxially textured layers that are generated by an IBAD process. Amorphous wafers (amorphous materials such as glass, or a single-crystal wafer coated by a vacuum deposited amorphous thin film) or polycrystalline metal substrates, for example, can be used as flat substrates. For metal substrates it is preferable to utilize materials having a coefficient of thermal expansion closely matching that of GaN, for example elements such as molybdenum, tungsten, tantalum and alloys thereof.
(34) The process of putting GaN on metal typically comprises three steps: 1) SDP, 2) IBAD+buffer layers, and 3) MOCVD GaN. The first step is solution deposition planarization (SDP). It is essentially chemical solution deposition (CSD) that has been optimized to smooth, or level, the surface by multiple coatings. In practice an initial root mean square (RMS) roughness of 20-100 nm on 5×5 μm scale can be reduced to about 0.5 nm after 10-30 coatings. A schematic and results of the SDP process are shown in
(35) In past decades a number of ITaN materials have been explored, but most work was focused on MgO. IBAD-MgO produces <100> out of plane orientation and that is suitable for depositing cubic materials on top with the same orientation. However, for deposition of hexagonally symmetric materials, such as wurtzite GaN, it can produce two epitaxial domains that are 30° rotated with respect to one another. In order to go from a cubic material to a hexagonal structure one would need a <111> orientation, as shown in
(36) The IBAD layer can in principle be chosen to lattice match the functional epitaxial layer, e.g. GaN. In order to come closer to the GaN lattice an epitaxial buffer layer can be deposited that transitions from the 3.826 Å lattice parameter of CeO.sub.2 to 3.189 Å of GaN. Many materials with intermediate lattice parameters can be used. In one embodiment, Sc.sub.2O.sub.3 and Zr are used as two intermediate layers that will transition to AlN. A sputtered AlN surface is then used as a seed layer for GaN growth. That complete structure, called the IBAD template, can then be used as a template for epitaxial GaN growth. MOCVD GaN is grown directly on AlN or on GaN deposited by physical vapor deposition (PVD) on the IBAD template.
(37) In one embodiment a substrate comprises a metal foil, preferably having a CTE matched to the desired functional semiconductor material. Deposited on the substrate is a base layer to enable IBAD. This layer can also be used to planarize the substrate and act as a diffusion barrier. Next is deposited an IBAD textured layer, then one or more intermediate buffer layer(s). The final layer is a hexagonal material, preferably a semiconductor material such as III-N or ZnO. The substrate is preferably chosen to match the functional layer or semiconductor layer coefficient of thermal expansion as closely as possible. The IBAD layer is preferably chosen to match the lattice constant of the semiconductor layer as closely as possible. This enables the decoupling of matching the two properties in selecting the substrate. In a conventional single-crystal substrate one has to use the materials that have a good enough lattice match and cannot independently adjust other properties.
(38) For substrates used for IBAD texturing, a substrate with desired mechanical properties, such as flexibility and thermal properties such as CTE (coefficient of thermal expansion) can be selected, and then the IBAD layer with the desired lattice constant can be chosen independently. Furthermore, a large area substrate, not one that is limited to single-crystal boule sizes, can be used, enabling production to be scaled to extremely large areas, and enabling production of integrated devices over those large areas via printing, for example. Roll-to-roll (R2R) is a method to scale production to very large areas (in small volumes), but it can also be scaled up sheet-to-sheet (S2S). Also, the substrate and IBAD layer can have different orientations, lattice mismatches, etc., greatly increasing the versatility of the present invention.
(39) One embodiment of the present invention comprises a single-crystal-like hexagonal-structure material, epitaxially deposited on an ion-beam-assist deposit (IBAD) textured layer. Epitaxial intermediate buffer layers between the IBAD layer and the hexagonal-structure material may optionally be deposited. The hexagonal-structure material optionally comprises graphene, MoS.sub.2, WS.sub.2, or another two dimensional material, or GaN, AlN, InGaN, or another III-N material. The IBAD layer material preferably comprises a cubic structure in the (111) orientation giving a 3-fold symmetry for alignment of the hexagonal materials on top, such as fluorite or bixbyite structure materials.
(40) Another embodiment of the present invention is ion-beam alignment of a film of a bixbyite-structure material, i.e. structure of (Mn—Fe).sub.2O.sub.3, such as Sc.sub.2O.sub.3 or Y.sub.2O.sub.3, on top with a (111) orientation out of plane and in-plane orientation, preferably with in-plane orientation better than 15°, and more preferably with in-plane orientation better than 10°.
(41) Embodiments of the present invention comprise a CTE-matched metal substrate for IBAD obtained by alloying the metal to get perfect matching to the semiconductor, such as in the Mo—Cu alloy system.
(42) Embodiments of the present invention comprise base (or planarization) layers for IBAD flourites or bixbyites that include amorphous-Al.sub.2O.sub.3, Y.sub.2O.sub.3, SiO.sub.x; these layers can be deposited by chemical solution deposition in manner that produces planarization (e.g. SDP).
(43) Embodiments of the present invention comprise integration of active devices fabricated using epitaxial III-N materials on IBAD substrates, such as metal foils with a textured layer. Devices are printed using several different possible printing technologies, e.g. screen printing or inkjet printing, patterned and contacts and passive devices are preferably printed on top afterwards. A display can be manufactured using this printing of LED devices on IBAD substrates. Power devices integrated with LEDs can provide constant power, switching, or dimming control of LED devices, or different colors and different color temperatures.
(44) Embodiments of the present invention are novel methods for GaN growth on non-single-crystal substrates with the use of an IBAD template (4-fold symmetric and 3-fold symmetric IBAD) that can be applied to almost any substrate that can sustain the GaN growth temperature, in the case of MOCVD above 1000° C., such as metals, ceramics or glass (quartz). Other methods for deposition of GaN-based devices are reactive evaporation (esp. MBE) and reactive sputtering. The latter methods utilize a lower temperature during deposition and growth and hence are more amenable to non-standard substrates that are not single-crystal wafers, such as plastics and glass. Matching the coefficient of thermal expansion (CTE) enables metals to be used ideally as substrates for GaN growth. These metals include, for example, molybdenum, tantalum, tungsten and alloys of these elements with other elements, such as TZM, an alloy of molybdenum and small amounts of titanium and zirconium, or molybdenum-copper alloys. These alloys exhibit a high thermal conductivity which is useful for devices requiring conductive cooling such as GaN power electronics.
(45) Embodiment substrates for growth of epitaxial films of group-III nitride formed by ion-beam textured layers with epitaxial overlayers comprise IBAD biaxially textured layers comprising IBAD-MgO, TiN, or other rock-salt structured materials, previously known to be amenable to ion-beam biaxial texturing, but also IBAD-CeO.sub.2 (cerium dioxide) or other fluorite structure materials such as CaF.sub.2, cubic ZrO.sub.2, or HfO.sub.2, which form a (111) orientation during IBAD. Other materials include IBAD-ScO.sub.x (with the Sc.sub.2O.sub.3 structure) and other oxides or nitrides in the bixbyite structure, such as Y.sub.2O.sub.3 or Mn.sub.2O.sub.3, bixbyite being a vacancy ordered derivative of the fluorite structure; epitaxial overlayers (buffer layers) lattice matched for growth of GaN or other group III nitride compounds, such as AlN or other nitrides, or elemental metal layers such as Zr or Hf, or oxides such as cubic Al.sub.2O.sub.3. A single-crystal-like cubic film with a (111) orientation on an arbitrary surface can be manufactured for growth of epitaxial III-N, or other hexagonal structure semiconductor or semi-metal such as InP (111), transition metal dichalogenides, and Indium Gallium Zinc Oxide (IGZO), layers using ion beam textured layers. These same textured layers can be obtained by other means besides IBAD such as inclined substrate evaporation or inclined sputtering. III-N layers can be grown by MOCVD, MBE, reactive evaporation, reactive sputtering, or other methods. A metal substrate may be used to produce III-N layers on a flexible metal foil or other metal substrate by use of an ion beam textured layer; metal substrates include materials such as molybdenum, tantalum, tungsten and alloy of these elements with other elements. III-N layers may be grown on a glass substrate with an intermediate ion beam assisted deposition (IBAD) textured layer. An electronic or optoelectronic device can be manufactured that comprises the epitaxial III-N material on an IBAD template substrate; such a device includes MOSFET's, MESFETs, HEMTs, Heterojunction FETs, heterojunction bipolar transistors (HBTs), thin-film transistors, sensors, memristors, light emitting diodes (LEDs), laser diodes (LD), SAW devices, spintronic devices, photodetectors, photovoltaic (PV) diodes. Furthermore these devices can be used in products such as LED-based displays, LED-based lighting products, PV cells and modules.
(46) Some embodiments of the present invention are a process for making an aligned layer on top of a metal to manufacture an LED; an LED structure made on top of an ion-aligned layer; a metal/amorphous planarizing layer/(111) textured layer/hexagonal semiconductor layer structure; IBAD texturing of Bixbyite materials; base layers deposited on a flexible substrate for IBAD layers, such as amorphous Al.sub.2O.sub.3, Y.sub.2O.sub.3, or SiO.sub.2; a GaN PVD layer used as a nucleation layer for MOCVD GaN; and a metal alloy substrate to match the CTE of GaN very closely, such as Mo—Cu alloy.
(47) The IBAD texture has been improved in embodiments of the present invention to below 10°, and the use of additional buffer layers and a high temperature MOCVD process for GaN growth produces GaN of much higher quality, <1° in-plane FWHM (as opposed to >10°) and less than 0.5° out-of-plane (as opposed to <1.5°) that enables the manufacture of high quality devices. The way that epitaxial GaN grows in embodiments of the present process is fundamentally different from epitaxial growth of Si and other semiconductors. This means that active devices such as a light-emitting diode (LED) consisting of III-N materials (such as InGaN) fabricated on a (111) ion-beam-assist deposit (IBAD) textured layer can be fabricated.
Example 1
(48) To demonstrate the applicability of IBAD templates for epitaxial growth of GaN and related group III nitride materials, MOCVD growth of GaN, also known as MOVPE (metal-organic vapor phase epitaxy), was performed. Samples were briefly heated to 800-1000° C. in flowing H.sub.2 prior to growth. The GaN nucleation layer was grown using trimethylgallium (TMGa) and ammonia (NH.sub.3) using H.sub.2 and N.sub.2 push flows at a substrate temperature of 530° C. After the growth of the GaN NL, the TMGa was turned off and the wafers were ramped in temperature to 1050° C. over 8 minutes. At 1050° C. the TMGa was turned on for 1 hour resulting in ≦2 μm of GaN film. After growth the wafers were cooled in the NH.sub.3, H.sub.2, and N.sub.2 flows and removed from the growth reactor.
(49) For the templates for GaN growth, substrates were prepared separately prior to GaN growth. In one embodiment we utilized IBAD-textured MgO films. These films are oriented with the (100) axis out of the plane and form a square, 4-fold symmetric lattice on the surface. IBAD-MgO films were first deposited on amorphous Y.sub.2O.sub.3 surfaces, the base layer for IBAD texturing. For good texturing of MgO during the ion beam assisted deposition (IBAD) it is important to have a smooth surface, which was obtained by sequential chemical solution deposition of Y.sub.2O.sub.3 or Al.sub.2O.sub.3 using acetate precursors dissolved in methanol. This process is called solution deposition planarization or SDP, and can produce surfaces as smooth as 0.5 nm RMS roughness when starting with a 50 nm RMS roughness metal foil substrate. The substrate was then placed in the vacuum deposition system where MgO is deposited at a rate of about 3-5 Å/s and an Ar ion beam incident at 45° and with an ion energy of 700-1000 eV. Deposition typically takes about 10-30 seconds. Following IBAD a 50 nm thick film of homoepitaxial MgO was deposited in the vacuum chamber by evaporation at a substrate temperature of 400-700° C. During the IBAD process as well as homoepitaxial deposition, film growth was monitored by Reflection High Energy Electron Diffraction (RHEED) to verify the crystalline alignment of the film.
(50) In a second embodiment of the IBAD template, we utilized IBAD-textured CeO.sub.2 textured films. These IBAD films are oriented with the (111) axis out of the plane and form a 3-fold symmetric lattice on the surface, suitable for growth of hexagonal structure materials such as wurtzite GaN, hexagonally close packed (hcp) metals, or other 3-fold symmetric (111) buffer layers. IBAD-CeO.sub.x films were grown on amorphous Al.sub.2O.sub.3 surfaces, the base layer for IBAD CeO.sub.x. Other amorphous layers such as SiO.sub.x and Y.sub.2O.sub.3 are also suitable for IBAD-CeO.sub.x. Just as for MgO, to obtain the best texturing it is important to have a smooth surface, which was produced by sequential chemical solution deposition planarization (SDP) of Y.sub.2O.sub.3 or Al.sub.2O.sub.3. With multiple coatings surfaces as smooth as 0.5 nm RMS roughness when starting with a 50 nm RMS roughness metal foil substrate can be achieved. The substrate was then placed in the vacuum deposition system where CeO.sub.2 was deposited at a rate of about 3-5 Å/s by electron-beam evaporation and with an Ar ion beam incident at 45° and with an ion energy of 700-1000 eV. Deposition typically took about 10-30 seconds. Following IBAD a 50 nm thick film of homoepitaxial CeO.sub.2 was deposited in the vacuum chamber by evaporation. During the IBAD process as well as homoepitaxial deposition, film growth was monitored by Reflection High Energy Electron Diffraction (RHEED) to verify the crystalline alignment of the film.
(51) Several different epitaxial buffer layers were deposited on IBAD-textured substrates by evaporation in vacuum. Although growth of epitaxial GaN on CeO.sub.2 is challenging due to the large lattice mismatch of the two crystalline lattices (GaN has a 16.7% smaller lattice constant than CeO.sub.2 (111)), by providing suitable intermediate buffer layers one can transition or step-grade to a lattice match close to GaN. These intermediate buffer layers consisted of (111) metal oxides (such as ZrO.sub.2, Sc.sub.2O.sub.3, Y.sub.2O.sub.3), hexagonally close packed metals (such as Zr, Hf, Ti, Sc, etc.), and wurtzite or (111) metal nitrides (such as AlN, ZrN, TiN, etc.) During deposition of epitaxial buffer layers, film growth was also monitored by RHEED to verify the crystalline alignment.
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Example 2
(60) A thick layer of GaN was deposited on an IBAD template. Typically GaN is 4 to 6 micrometers in thickness, the top part of which is n-doped with Si, as can be seen in
(61) Performance of such an LED device was measured as compared to LEDs prepared on single-crystal sapphire, which is a standard substrate in industry. Results are shown in
(62) Although the invention has been described in detail with particular reference to the disclosed embodiments, other embodiments can achieve the same results. Variations and modifications of the present invention will be obvious to those skilled in the art and it is intended to cover all such modifications and equivalents. The entire disclosures of all patents and publications cited above are hereby incorporated by reference.