JP5892447B2 - Method for forming bulk III-nitride material on metal nitride growth template layer and structure formed by the method - Google Patents

Description

  [001] Embodiments of the present invention generally relate to methods of depositing III-nitride material on a substrate and structures formed by such methods. More particularly, embodiments of the present invention relate to methods for depositing a group III nitride material on a substrate that includes a growth template layer that includes a metal nitride material, and structures formed by such methods.

  [002] Chemical vapor deposition (CVD) is a chemical process used to deposit solid materials on a substrate and is commonly used in the manufacture of semiconductor devices. In a chemical vapor deposition process, a substrate is exposed to one or more reagent gases that react, decompose, or react to result in depositing solid material on the surface of the substrate. And both disassembly.

  [003] One particular type of CVD process is referred to in the art as vapor phase epitaxy (VPE). In VPE processing, a substrate is exposed to one or more reagent gases in a reaction chamber that reacts, decomposes, or results in epitaxial deposition of solid material on the surface of the substrate, or Perform both reaction and decomposition. VPE processing is often used to deposit III-V semiconductor materials. If one of the reagent gases in the VPE process includes a halide gas, this process may be referred to as a halide vapor phase epitaxy (HVPE) process.

  [004] Forming a Group III nitride semiconductor material such as gallium nitride (GaN) using a VPE process that decomposes an organometallic (MO) precursor material in a reaction chamber to form a Group III nitride semiconductor material Is known in the art. Such a process is often referred to as a metal organic chemical vapor deposition (MOVPE) process and is sometimes characterized as a metal organic chemical vapor deposition (MOVCVD) process. Such MOVPE processes are typically performed using several successive predeposition processes prior to depositing the desired bulk III-nitride semiconductor material. These successive predeposition processes include high temperature hydrogen baking of the growth substrate (eg, sapphire substrate), nitridation of the growth substrate, and formation of a nucleation layer of group III nitride material on the growth substrate at a relatively low temperature. , Annealing of the nucleation layer at a relatively higher temperature, coalescence of the nucleation layer, and finally growth of a bulk III-nitride material layer on the nucleation layer.

[005] HVPE processing is also used to form III-nitride semiconductor materials such as gallium nitride (GaN). In such a process, a gas phase reaction between gallium monochloride (GaCl) and ammonia (NH ₃ ) is performed in the reaction chamber at a high temperature of about 500 ° C. to about 1,000 ° C., resulting in GaN on the substrate. Can be obtained. NH ₃ may be supplied from a standard NH ₃ gas source. In some methods, GaCl gas is supplied by passing hydrogen chloride (HCl) gas (which can be supplied from a standard HCl gas source) over heated liquid gallium (Ga) to produce a reaction chamber. In situ, GaCl is formed in situ. The liquid gallium can be heated to a temperature of about 750 ° C to about 850 ° C. GaCl and NH ₃ can be directed (eg, above the surface) to the surface of a heated substrate, such as a wafer of semiconductor material. US Pat. No. 6,179,913 issued January 30, 2001 by Solomon et al. Discloses a gas injection system for use in such a system and method.

  [006] With respect to the MOVPE process used to form the bulk III-nitride semiconductor material, several consecutive pre-deposition processes referred to above may be difficult to perform in an HVPE deposition reactor. .

  [007] This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description of some exemplary embodiments of the invention. Explained. This summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. Absent.

  [008] As discussed above, some used to form a nucleation layer of III-nitride material on a growth substrate before depositing a bulk III-nitride semiconductor material on the nucleation layer It may be difficult to perform a continuous pre-deposition process in an HVPE deposition reactor. As a result, known HVPE methods used to deposit bulk III-nitride semiconductor materials use a MOCVD process and are ex situ on a substrate (ie, performed separately in a separate chamber). In general, a growth substrate comprising a nucleation layer of deposited metal nitride material has been utilized. In that case, the desired bulk III-nitride material is deposited on the growth substrate in a separate HVPE process performed in a separate chamber.

  [009] In some embodiments, the present invention includes a method of depositing a bulk III-nitride semiconductor material on a growth substrate. A metal nitride nucleation template layer is formed on the substrate to form a growth substrate, and a bulk III-nitride semiconductor material is deposited on the growth substrate using a halide vapor phase epitaxy (HVPE) process. . Depositing a bulk III-nitride semiconductor material on the growth substrate includes substeps of decomposing at least one of the metal trichloride and metal tetrachloride to form a metal chloride III precursor gas; And a sub-step of reacting the metal chloride group III precursor gas with the group V precursor gas to form a bulk group III nitride semiconductor material on the growth substrate.

  [010] In at least some embodiments, the present invention provides a bulk III-nitride material on a growth substrate using an HPVE process without forming a nucleation template layer ex-situ using an MOCVD process. A method of depositing.

[011] In some embodiments, the present invention includes a method of depositing a bulk III-nitride semiconductor material on a growth substrate. A metal nitride nucleation template layer is formed on the substrate using a non-metal organic chemical vapor deposition (MOCVD) process in a first chamber to form a growth substrate, and a bulk III-nitride semiconductor material is formed. And deposited on the growth substrate using a halide vapor phase epitaxy (HVPE) process in a second chamber. Depositing the bulk III-nitride semiconductor material on the growth substrate includes substeps of flowing NH ₃ and at least one of metal trichloride and metal tetrachloride toward the second chamber. Can do.

[012] In a further embodiment of the method of depositing a bulk III-nitride semiconductor material on a growth substrate, the metal nitride nucleation template layer is formed using a metal organic chemical vapor deposition (MOCVD) process in the chamber. Formed above to form a growth substrate, a bulk III-nitride semiconductor material is deposited on the growth substrate using a halide vapor phase epitaxy (HVPE) process in the same chamber. Depositing the bulk III-nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process comprises NH ₃ and at least one of metal trichloride and metal tetrachloride. Can be included to flow toward the same chamber.

[013] In a further embodiment of the method of depositing a bulk III-nitride semiconductor material on a growth substrate, a metal nitride nucleation template layer is formed on the substrate using a halide vapor phase epitaxy (HVPE) process in a chamber. Formed into a growth substrate, and a bulk III-nitride semiconductor material is deposited on the growth substrate using a halide vapor phase epitaxy (HVPE) process in the same chamber. Depositing the bulk III-nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process comprises NH ₃ and at least one of metal trichloride and metal tetrachloride. Can be included to flow toward the same chamber.

  [014] Further embodiments of the present invention include structures comprising bulk III-nitride semiconductor materials formed using the methods disclosed herein.

  [015] The invention may be more fully understood by reference to the following detailed description of exemplary embodiments of the invention shown in the accompanying drawings.

FIG. 2 is a simplified cross-sectional view of a substrate that can be used with embodiments of the method of the present invention. FIG. 2 is a simplified cross-sectional view of a growth substrate that can be used by embodiments of the method of the present invention and that can be formed by depositing a nucleation template layer on the substrate of FIG. FIG. 3 is a simplified cross-sectional view of a structure including a bulk III-nitride semiconductor material deposited over the nucleation template layer of the growth substrate of FIG. 2 according to an embodiment of the method of the present invention. 1 is a cross-sectional view schematically illustrating an exemplary embodiment of an HVPE deposition system that includes a reaction chamber and at least one gas injector and that can be used by embodiments of the method of the present invention. 4B is a schematic cross-sectional view of the reaction chamber shown in FIG. 4A taken along line 4B-4B shown in FIG. 4A. 4B is a schematic diagram illustrating an embodiment of a thermal kinetic gas injector that can be used in the deposition system of FIG. 4A. FIG. FIG. 4B is a schematic diagram illustrating another exemplary embodiment of a gas injector that can be used in the deposition system of FIG. 4A. FIG. 7 is an enlarged partial cutaway view of the gas injection device of FIG. 6. 4 schematically represents a deposition process that can be used to deposit bulk III-nitride semiconductor material over a growth substrate, according to embodiments of the invention and using the HVPE deposition system shown in FIGS. 4A and 4B. It is a graph.

  [025] The figures presented herein are not intended to be actual drawings of any particular component, apparatus or system, and are used to describe embodiments of the present invention. It's just an idealized expression.

  [026] Although several references are cited herein, regardless of how any of the cited references are characterized herein, the subject claims It is not recognized as prior art in this specification.

  [027] As used herein, the term "III-V semiconductor material" refers to one or more elements (B, Al, Ga, In, and Ti) from group IIIA of the periodic table, And any semiconductor material composed at least primarily of one or more elements (N, P, As, Sb, and Bi) from Group VA of the periodic table. For example, group III-V semiconductor materials include, but are not limited to, GaN, GaP, GaAs, InN, InP, InAs, AlN, AlP, AlAs, InGaN, InGaP, InGaNP, and the like.

  [028] As used herein, the term "Group III nitride semiconductor material" refers to one or more elements from Group IIIA of the periodic table (B, Al, Ga, In, and Ti), As well as any III-V semiconductor material composed at least primarily of nitrogen. For example, group III nitride semiconductor materials include GaN, InN, AlN, InGaN, GaAlN, GaAlN, InAlN, and the like.

[029] As used herein, the term "metal nitride" means a compound of metal and nitrogen. Metal nitride materials are aluminum nitride (AlN), gallium nitride (GaN), aluminum gallium nitride (Al _x Ga _1-x N), titanium nitride (TiN), hafnium nitride (Hf), chromium nitride (CrN), nitride Including but not limited to tungsten (WN) and tantalum nitride (TaN).

  [030] As used herein, the terms "chemical vapor deposition" and "CVD" are synonymous and are used to deposit solid material (s) on a substrate in a reaction chamber Any process that is performed, including, in this reaction chamber, the substrate is exposed to one or more reagent gases, resulting in the deposition of solid material (s) on the surface of the substrate, This reagent gas reacts and decomposes, or both reaction and decomposition occur.

  [031] As used herein, the terms "vapor phase epitaxy" and "VPE" are synonymous and mean any CVD process in which a substrate is exposed to one or more reagent gases; This reagent gas reacts, decomposes, or both reacts and decomposes so as to result in an epitaxial deposition of the solid material (s) on the surface of the substrate.

  [032] As used herein, the terms "halide vapor phase epitaxy" and "HVPE" are synonymous and any at least one reagent gas used in the VPE process includes any halide gas. Means VPE processing.

  [033] As used herein, the term "organometallic" refers to any compound comprising an organic species comprising at least one metal element and at least one carbon-based ligand. Means and includes. Organometallics are often referred to in the art as “organometallic compounds” and such terms are synonymous for the purposes of this disclosure. Organometals include trimethylgallium (TMG), triethylgallium (TEG), trimethylaluminum (TMA), triethylaluminum (TEA), tetrakisdiethylaminotitanium (TDEAT), and tetrakis (dimethylamido) titanium (TDMAT). It is not limited to.

  [034] As used herein, the terms "organometallic vapor phase epitaxy" and "MOVPE" are synonymous and any at least one reagent gas used in a VPE process includes an organometallic gas. Means VPE processing.

  [035] As used herein, the terms "non-organometallic chemical vapor deposition process" and "non-MOCVD process" are synonymous and mean and include any deposition process that is not a MOCVD process.

  [036] As used herein, the terms "non-organometallic vapor phase epitaxy process" and "non-MOVPE process" are synonymous and mean and include any deposition process that is not a MOVPE process.

  [037] As used herein, the term "gas" refers to gas (a fluid that does not have an independent shape or volume) and gas (a diffused liquid or suspended solid). The terms “gas” and “gas” are used interchangeably herein.

[038] FIGS. 1-3 illustrate the deposition of a bulk III-nitride semiconductor material on a growth substrate according to an embodiment of the present invention. Referring to FIG. 1, a substrate 10 is prepared. The substrate 10 may be a substantially flat disk-shaped main body, a substantially circular rectangle, or the like. The substrate 10 may include what is referred to in the art as a “die” or “wafer”. The substrate 10 may be at least substantially composed of a homogeneous material 12. The material 12 may be, for example, a ceramic such as an oxide (for example, silicon dioxide (SiO ₂ ) or aluminum oxide (Al ₂ O ₃ ) (for example, sapphire which is α-Al ₂ O ₃ )), or nitride ( For example, silicon nitride (Si ₃ N ₄ ) or boron nitride (BN)) can be included. As a further example, the material 12 can include a semiconductor material such as, for example, silicon (Si), germanium (Ge), a III-V semiconductor material. In some embodiments, the material 12 of the substrate 10 may consist at least substantially of the single crystal material 12. Further, in such embodiments, the single crystal can have a selected crystallographic orientation such that the exposed major surface 14 of material 12 exhibits a selected crystallographic face of the single crystal of material 12. Will be included. As a non-limiting example, the substrate 10 may be selected to include a sapphire substrate. Such a sapphire substrate is commercially available.

Referring to FIG. 2, a growth substrate 20 can be formed by forming (eg, depositing) a metal nitride nucleation template layer 18 on the exposed major surface 14. According to embodiments of the method of the present invention, the metal nitride nucleation template layer 18 can be formed on the substrate in a number of different ways, as will be described in further detail below. By way of example and not limitation, the exposed major surface 14 is such that the metal nitride nucleation template layer 18 has an average thickness T ₁ of about 2 nanometers (2 nm) to about 5 microns (5 μm). A template layer 18 can be deposited thereon.

  [040] Using this metal nitride nucleation template layer 18, bulk III-V semiconductor material is deposited over the substrate 10 while maintaining the desired defect density in the deposited bulk III-V semiconductor material. It can be deposited to the desired average total thickness. The difference between the crystal lattice structure of the material 12 of the substrate 10 and the crystal lattice structure of the bulk III-V semiconductor material that will be deposited over the substrate 10 (this difference is often referred to in the art as “crystal lattice mismatch”). The crystal structure of the bulk III-V semiconductor material is relatively high and undesired density when the bulk III-V semiconductor material is deposited directly on the exposed major surface 14 of the substrate 10. It may contain defects such as dislocations. Accordingly, a metal nitride nucleation template layer 18 is provided on the substrate 10 and the bulk III-V semiconductor material is a metal nitride nucleation template layer 18 between the substrate 10 and the bulk III-V semiconductor material. And a composition selected to have a relatively low crystal lattice mismatch with each of the substrate 10 and each of the bulk III-V semiconductor materials to be deposited over the substrate 10 as compared to the crystal lattice mismatch of It can have a fine structure. In other words, a nucleation template layer can be used to buffer crystal lattice mismatch between the substrate 10 and the bulk III-V semiconductor material that is to be deposited over the substrate 10, such nuclei. The generated template layer 18 is also referred to in the art as a “buffer” layer. Further, a nucleation template layer can be used as a seed layer for nucleation of bulk III-V semiconductor material, and such nucleation template layer 18 is also referred to in the art as a “seed” layer.

  [041] Referring to FIG. 3, after forming the growth substrate 20, a HVPE process is used to nucleate bulk III-V semiconductor material 22 on the exposed major surface 19 of the metal nitride nucleation template layer 18. And can be deposited. Although a discontinuous boundary is visible between the metal nitride nucleation template layer 18 and the bulk III-V semiconductor material 22 in the simplified drawing of FIG. 3, the metal nitride nucleation template layer 18 and the bulk III- The group V semiconductor material 22 may have at least substantially the same composition in some embodiments, and any gap between the metal nitride nucleation template layer 18 and the bulk III-V semiconductor material 22. Note that it may be difficult or impossible to visualize or otherwise identify continuous boundaries.

[042] By way of example and not limitation, bulk III-V semiconductor material 22 may be applied to growth substrate 20 over at least about 5 microns (5 μm), at least about 7 microns (7 μm), at least about 10 microns (10 μm), It can be deposited to an average total thickness T ₂ of at least about 20 microns (20 μm), or even at least about 30 microns (30 μm). Due to the presence of the metal nitride nucleation template layer 18 fabricated according to embodiments of the present invention, the dislocation density in the bulk III-V semiconductor material 22 at the exposed main surface 23 of the bulk III-V semiconductor material 22 is 1 Bulk III-V semiconductor material 22 can be deposited to such an average total thickness T ₂ while maintaining a density of about 5 × 10 ⁸ or less per square centimeter.

  [043] FIGS. 4A and 4B are simplified diagrams that schematically illustrate embodiments of an HVPE deposition system 100 that can be used in embodiments of the method of the present invention, as described herein. is there. By way of non-limiting example, the deposition system 100 is described in US Patent Application Publication No. 2009 / 0223442A1, published on September 10, 2009 by Arena et al., US patent filed on March 3, 2009 by Arena et al. The deposition system described in any of provisional application 61 / 157,112 and US patent application Ser. No. 12 / 894,724 filed Sep. 30, 2010 by Bertran may be provided. The deposition system 100 shown in FIGS. 4A and 4B includes a reaction chamber 102 and one or more gas injectors (as described in more detail below).

  [044] In the following description of the deposition system 100, and more specifically the reaction chamber 102 of the deposition system 100, the terms "longitudinal" and "transverse" are the reactions seen from the perspective of FIGS. 4A and 4B. Used to refer to the direction with respect to the chamber 102, the longitudinal direction is the vertical direction from the viewpoint of FIG. 4A and the direction extending into the plane of FIG. 4B, and the transverse or lateral direction is the direction of FIGS. This is a direction extending horizontally as seen from each viewpoint. The transverse direction is also referred to as the direction extending “cross the reactor”.

  [045] The deposition system 100 includes a reaction chamber 102 and one or more workpiece substrates 106 (which are initially shown in the figure) that it is desired to deposit or otherwise provide material within the deposition system 100. A substrate support structure 104 (eg, a support platform) configured to support a substrate 10 shown in FIG. 1 or a growth substrate 20 shown in FIG. By way of non-limiting example, the reaction chamber 102 can have a height of about 2 inches, a width of about 12 inches, and a length of about 20 inches, and the substrate support structure 104 can be a single 8 inch processed substrate. 106, one 6-inch processed substrate 106, three 4-inch processed substrates 106, or eight 2-inch processed substrates 106. The deposition system 100 further includes a heating element 108 (FIG. 4B), which is selectively used to heat the deposition system 100, thereby increasing the average temperature in the reaction chamber 102 to a desired temperature increase during the deposition process. Can be controlled within the range. The heating element 108 can include, for example, a resistance heating element or a radiant heating element.

  [046] As shown in FIG. 4B, the substrate support structure 104 may be attached to a spindle 110, such that the spindle 110 rotates the spindle 110 and thus the substrate support structure 104 in the reaction chamber 102. It can be coupled (eg, directly structurally coupled, magnetically coupled, etc.) to a drive device 112 such as a configured electric motor.

  [047] In some embodiments, one or more of the reaction chamber 102, the substrate support structure 104, the spindle 110, and any other components in the reaction chamber 102 are made of a heat resistant ceramic material, For example, at least ceramic oxide (eg, silica (quartz), alumina, zirconia, etc.), carbide (eg, silicon carbide, boron carbide, etc.), or nitride (eg, silicon nitride, boron nitride, etc.) It can be configured substantially.

  [048] The deposition system 100 further includes a gas flow system that is used to inject one or more gases into the reaction chamber 102 and exhaust the gases from the reaction chamber 102. Referring to FIG. 4A, the deposition system 100 can include three gas inlet conduits 114A, 114B, 114C that carry gases from respective gas sources 128A, 128B, 128C. An apparatus 117A that can optionally include one or more of a valve, a back pressure regulator, and a mass flow controller to selectively control the flow of gas through each of the gas inlet conduits 114A, 114B, 114C. 117B, 117C can be used.

[049] In some embodiments, at least one of the gas sources 128A, 128B includes a metal trichloride such as GaCl ₃ , InCl ₃ , described in US Patent Application Publication No. 2009 / 0223442A1, Alternatively, an external source of AlCl ₃ can be provided. GaCl ₃ , InCl ₃ , and AlCl ₃ can each exist in the form of a dimer such as, for example, Ga ₂ Cl ₆ , In ₂ Cl ₆ , and Al ₂ Cl ₆ . Thus, at least one of the gas sources 128A, 128 can include a dimer such as Ga ₂ Cl ₆ , In ₂ Cl _6, or Al ₂ Cl ₆ . As a non-limiting example, one or more of the gas sources 128A, 128B can provide a mass flow of GaCl ₃ gas as a group IIIA precursor component. The gas source 128C can comprise an external source of a Group VA precursor, such as ammonia (NH ₃ ).

[050] Gas sources 128A, is one or more of GaCl ₃ sources of 128B, or in embodiments comprising GaCl ₃ source, the GaCl ₃ source, to a temperature of at least 120 ° C. (e.g., about 130 ° C.) A maintained liquid GaCl ₃ storage vessel may be included and physical means for promoting the evaporation rate of the liquid GaCl ₃ may be included. Such physical means include, for example, an apparatus configured to agitate liquid GaCl ₃ , an apparatus configured to spray liquid GaCl ₃ , and configured to rapidly flow a carrier gas over liquid GaCl _3. A device configured to bubble carrier gas through liquid GaCl ₃ , a device configured to disperse liquid GaCl ₃ with ultrasound, such as a piezoelectric device, and the like. As a non-limiting example, a carrier gas such as He, N ₂ , H ₂ , or Ar, or a mixture thereof (eg, a mixture of N ₂ and H ₂ ) and liquid GaCl ₃ are maintained at a temperature of at least 120 ° C. However, it can be bubbled through liquid GaCl ₃ so that the source gas can contain one or more carrier gases.

[051] Gas injection apparatus 150A, one or flux of GaCl ₃ gas into more of 150B, in some embodiments of the present invention can be controlled. For example, in embodiments where the carrier gas is bubbled through the liquid GaCl _3, gas source 128A, 128B, the flux of GaCl ₃ from 128C, for example, the temperature of GaCl _3, GaCl ₃ above the pressure, and GaCl ₃ Depends on one or more factors including the flow rate of the carrier gas being bubbled through. By any of these parameters, it is possible to control the mass flux GaCl ₃ as a rule, in some embodiments, the mass flux of GaCl _3, using the mass flow controller, It may be controlled by changing the flow rate of the carrier gas.

[052] In some embodiments, the temperature of the gas inlet conduits 114A, 114B can be controlled between the gas sources 128A, 128B and the gas injectors 150A, 150B. The temperature of the gas inlet conduits 114A, 114B and the associated mass flow sensors, controllers, etc., can be controlled by a respective gas source 128A, 128B to prevent condensation of gas (eg, GaCl ₃ gas) in the gas inlet conduits 114A, 114B. May gradually increase from a first temperature (eg, about 120 ° C. or higher) to a second temperature (eg, about 160 ° C. or lower) of the gas injectors 150A, 150B. Optionally, the length of the gas inlet conduits 114A, 114B between the respective gas sources 128A, 128B and the gas injectors 150A, 150B is about 90 centimeters (about 3 feet) or less, about 60 centimeters (about 2 centimeters). Feet) or less, or even about 30 centimeters (about 1 foot) or less. The pressure of the source gas can be controlled using one or more pressure control systems.

  [053] Each of the two gas inlet conduits 114A, 114B can optionally extend to the respective gas injector of the two gas injectors 150A, 150B, as will be described in detail below.

  [054] In further embodiments, the deposition system 100 can include less than two (ie, one) gas inlet conduits and respective gas injectors, or the deposition system 100 can include more than two. Gas inlet conduits (eg, three, four, five, etc.) and respective gas injectors can be included.

  [055] In the embodiment of FIGS. 4A and 4B, the gas injectors 150A, 150B are all located outside the reaction chamber. However, in other embodiments, the gas injectors 150A, 150B may all be disposed within the reaction chamber 102, or at least a portion of the gas injectors 150A, 150B may be at least partially at the reaction chamber 102. Can extend through.

  [056] The deposition system 100 may further include three gas ports 116A, 116B, 116C that provide fluid communication between the exterior and interior of the reaction chamber 102. Each of the gas ports 116A, 116B, 116C passes through one or more of the sidewalls, ceiling, or floor of the reaction chamber 102 and is within the respective gas injectors and reaction chambers 102 of the gas injectors 150A, 150B. Fluid communication may be provided between the respective gas distribution conduits 118A, 118B, 118C.

  [057] The gas distribution conduits 118A, 118B, 118C in the reaction chamber 102 may be used to carry gas to a desired location in the enclosure. The gas distribution conduits 118A, 118B, 118C are positioned and configured to inject gas into the interior of the reaction chamber 102 in a selected direction with respect to the work substrate 106 conveyed on the substrate support structure 104. sell. Gases carried by gas distribution conduits 118A, 118B, 118C, such as precursor gas and carrier gas, can flow through reaction chamber 102 in a longitudinal direction (vertical direction from the perspective of FIG. 4A) from which reaction It can be injected in a direction that extends longitudinally in the chamber 102 toward the work substrate 106 and is oriented at least substantially parallel to the exposed major surface of the upper portion of the work substrate 106. The gas distribution conduits 118A, 118B, 118C can be supported and held in place within the reaction chamber 102 using a conduit support fixture.

  [058] The specific layout and configuration of the gas distribution conduits 118A, 118B, 118C is merely one of many layouts and configurations that may be used in embodiments of the present invention, and further implementation of the reaction chamber 102. The configuration can have various configurations and layouts of gas distribution conduits within the reaction chamber 102.

  [059] The gas distribution conduits 118A, 118B, 118C may be actively heated, passively heated, or both passively and actively heated. For example, a heat generating element (not shown) can be placed adjacent to at least a portion of the gas distribution conduits 118A, 118B, 118C. In some embodiments, gas distribution conduits 118A, 118B, 118C are heated by heating element 108 (FIG. 4B). Optionally, a passive heat transfer structure (eg, a structure containing a material that acts like a black body) is placed adjacent to or in close proximity to at least a portion of the gas distribution conduits 118A, 118B, 118C in the reaction chamber 102. Thus, heat transfer to the gas distribution conduits 118A, 118B, 118C can be improved.

  [060] Passive heat transfer structures (eg, structures including materials that behave similarly to black bodies) are disclosed, for example, in US Patent Application Publication No. 2009 / 0214785A1 published by Arena et al. On Aug. 27, 2009. Can be provided in the reaction chamber 102. For example, a heat transfer plate 124 (represented by a dashed line in FIGS. 4A and 4B) may be a processed substrate 106 in which the heat transfer plate 124 is supported by the substrate support structure 104 and the substrate support structure 104 across the reaction chamber 102. It can be arranged in the reaction chamber 102 so as to extend upward. The heat transfer plate 124 absorbs radiation from a heating element (such as the heating element 108) and re-radiates the absorbed heat to the process gas, thereby thermally moving the process gas flowing near the heat transfer plate 124. Can help.

[061] Such a passive heat transfer structure can improve heat transfer within the reaction chamber 102, and can improve temperature uniformity and homeostasis within the reaction chamber 102. The passive heat transfer structure may include a material with a high emissivity value (close to 1) that can withstand the high temperature, corrosive environment that may be encountered in the deposition system 100 (black body material). Such materials can include, for example, aluminum nitride (AlN), silicon carbide (SiC), and boron carbide (B ₄ C), which are 0.98, 0.92, and 0. 0, respectively. It has an emissivity value of 92.

  [062] Gaseous by-products, carrier gas, and any excess precursor gas may be exhausted from reaction chamber 102 through chamber outlet 126.

  [063] As previously mentioned, one or more of the gas injectors 150A, 150B of the deposition system 100 of FIGS. 4A and 4B may be further described below with reference to FIGS. It may be an injection device or may include such a gas injection device.

[064] In some embodiments, the gas injectors 150A, 150B comprise the gas injectors disclosed in WO 2010 / 101715A1 published by Arena et al. On September 10, 2010. Can do. For example, FIG. 5 is a perspective view of a thermal kinetic gas injector 160 that can be used for one or both of the gas injectors 150A, 150B shown in FIG. 4A. As shown in FIG. 6, the gas injector 160 includes a conduit 162 that includes an inlet portion 164, a coiled central portion 166, and an outlet portion 168. A source gas (eg, GaCl ₃ ), a carrier gas (eg, H ₂ , N _2, etc.), or a mixture of source gas and carrier gas can be supplied to the inlet portion 164. These one or more gases exit from the inlet portion 164, through the coiled central portion 166, and out of the outlet portion 168 into the reaction chamber 102 (FIG. 4A). At least the coiled central portion 166 of the conduit 162 can be heated, as will be discussed in further detail below. By coiling the conduit 162, the length of the physical space occupied by the conduit 162 is significantly shorter than the actual length of the flow path through the conduit 162. In other words, the length of the conduit 162 may be longer than the shortest distance between the inlet portion 164 and the outlet portion 168. The conduit 162 can have other configurations. For example, the conduit 162 can have a serpentine configuration including a plurality of generally parallel straight sections connected together between ends by curved sections extending at an angle of 180 °.

  [065] The conduit 162 may be configured to heat the gas flowing through the conduit 162 for a desired time (ie, residence time), which is the cross-sectional area of the flow path within the conduit 162, the conduit 162. Can be a function of the flow rate of the source gas through the pipe 162 and the overall length of the conduit 162. As discussed in further detail below, the conduit 162 may be shaped and configured to be located proximate to one or more active or passive heating elements.

  [066] As shown in FIG. 5, at least a coiled central portion 166 of the conduit 162 may be included in the outer housing 170. The outer housing 170 can also serve as an additional gas conduction conduit for a gas, such as a purge gas. For example, as shown in FIG. 5, the outer housing 170 can include a housing inlet 172 and a housing outlet 174. Purge gas may flow through the outer housing 170 from the housing inlet 172 to the housing outlet 174. As the purge gas passes through the outer housing 170, it can be heated by the thermal kinetic gas injector 160.

  [067] Conduit 162 and outer housing 170 may include a refractory material that is stable and inert at the elevated temperatures to which they are exposed during use. For example, the conduit 162 and the outer housing 170 may be formed from quartz and at least substantially composed of quartz.

  [068] Thermal motion using an active heat generating element disposed proximate to (eg, adjacent to) one or more of the outer housing 170 and the coiled central portion 166 of the conduit 172 The gas injector 160 can be heated. The active heating element includes, for example, a heat radiation element such as a heating lamp, an inductive heating element, an electrical heating element such as a resistive heating element. Also, the thermal kinetic gas injector 160 does not generate heat itself, but redistributes, reflects, or otherwise transfers heat transfer within and around the thermal kinetic gas injector 160. Passive heating elements used to influence can be included. For example, as shown in FIG. 5, the thermal kinetic gas injector 160 may include an active heating element 180, which is a resistive heating clamp shell heater that at least partially surrounds the exterior of the outer housing 170. (Clamp-shell heater). Accordingly, the gas flowing through the conduit 162 and / or the outer housing 170 can be heated by the active heating element 180. As shown in FIG. 5, an optional heating element 182, which can be active or passive, can be disposed in the outer housing 170. As shown in FIG. 5, the heating element 182 can have an elongated cylindrical shape, and a central portion 166 around which the coil 162 is wound can be coiled around the heating element 182. By way of example and not limitation, the heating element 182 may comprise a rod that includes a black body material that is used to redistribute the heat generated by the active heating element 180. The presence of the heating element 182 may improve the efficiency with which the gas within the central portion 166 wound by the coil 162 and the gas within the outer housing 170 are heated by the active heating element 180.

[069] Gas sources 128A, in an embodiment of the present invention the raw material gas supplied to the thermalized gas injection device 160 comprises a metal trichloride and hydrogen H ₂ carrier gas, such as GaCl ₃ by one of 128B , Metal trichloride and hydrogen gas can be decomposed to form metal monochloride gases, such as GaCl and HCl gases, which are emitted from an outlet portion 168 of conduit 162 and into reaction chamber 102. Can be passed.

  [070] In a further embodiment, gas injectors 150A, 150B may comprise a gas injector disclosed in US Provisional Application No. 12 / 894,724. For example, the gas injection devices 150A and 150B include, for example, a liquid metal such as liquid gallium (Ga), liquid aluminum (Al), or liquid indium (In), or other elements, trimethyl gallium (TMG), triethyl gallium ( A storage container configured to hold organometallic materials such as TEG), trimethylaluminum (TMA), triethylaluminum (TEA), tetrakisdiethylaminotitanium (TDEAT), tetrakis (dimethylamido) titanium (TDMAT), etc. can be provided. . In further embodiments, the storage container may be configured to hold a solid reagent for reacting with the source gas (or decomposition or reaction product of the source gas). For example, the storage container may be configured to hold a solid volume of one or more materials such as, for example, solid silicon (Si) or solid magnesium (Mg).

[071] FIG. 6 is a perspective view of the gas injector 200, which can be used for one or both of the gas injectors 150A, 150B shown in FIG. 4A. As shown in FIG. 6, the gas injection device 200 includes an inlet 202, an outlet 204, a thermal kinetic conduit 206, and a container 210. Container 210 is configured to hold a liquid reagent therein. For example, a liquid metal such as liquid gallium, liquid indium, and liquid aluminum, or a liquid organometallic material can be placed in the container 210. Source gas (eg, GaCl ₃ ), carrier gas (eg, H ₂ , N _2, etc.), or a mixture of source gas and carrier gas can be supplied to the inlet 202. These one or more gases may flow from the inlet 202 into the thermal kinetic conduit 206. The thermal kinetic conduit 206 may be configured to heat the gas flowing through the thermal kinetic conduit 206 for a desired time (i.e., residence time), this time being the flow break in the thermal kinetic conduit 206. It can be a function of the area, the flow rate of the feed gas through the thermal kinetic conduit 206, and the overall length of the thermal kinetic conduit 206. Thermal kinetic conduit 206 may be shaped and configured to be located proximate to one or more active or passive heating elements, as discussed in more detail below.

  [072] Further, the thermal kinetic conduit 206 has a physical space length occupied by the thermal kinetic conduit 206 that is substantially shorter than the actual length of the flow path through the thermal kinetic conduit 206. As such, one or more curved sections or turns may be included. In other words, the length of the thermal kinetic conduit 206 may be longer than the shortest distance between the inlet 202 and the liquid container 210. In some embodiments, the length of the thermal kinetic conduit 206 is at least about twice the shortest distance between the inlet 202 and the liquid container 210 and at least about the shortest distance between the inlet 202 and the liquid container 210. It may be three times, or even at least about four times the shortest distance between the inlet 202 and the liquid container 210. For example, as shown in FIG. 6, the thermal kinetic conduit 206 can have a serpentine configuration, which is a plurality of approximate connections connected together between ends by a curved section extending at an angle of 180 °. Includes parallel straight sections.

  [073] Thermal kinetic conduit 206 may comprise a tube at least substantially composed of a refractory material such as, for example, quartz.

[074] In some embodiments, the gas can include a feed gas that decomposes at least partially within the thermal kinetic conduit 206. For example, in embodiments where the gas includes a GaCl ₃ source gas and a carrier gas containing H ₂ , the source gas can be decomposed to form gaseous GaCl and hydrogen chloride (HCl).

  [075] Each gas flows from the thermal kinetic conduit 206 into the vessel 210. FIG. 7 is an enlarged partial cutaway view of the container 210. As shown in FIG. 7, the container 210 includes a bottom wall 212, a top wall 214, and at least one side wall 216. In the embodiment of FIGS. 6 and 7, the storage container has a generally cylindrical shape, whereby each of the bottom wall 212 and the top wall 214 has a circular shape and is at least substantially planar, The sidewall 216 has at least a substantially cylindrical shape (eg, a tube shape). In further embodiments of the present invention, the storage container may be configured with alternative geometric configurations. The bottom wall 212, the top wall 214, and the at least one side wall 216 together define a hollow body, and the interior of the hollow body defines a storage container for holding a liquid reagent such as liquid gallium or an organometallic material. .

  [076] The internal space within the hollow container 210 may be partially filled with a liquid reagent. For example, the container 210 may be filled with liquid reagent to the level indicated by the dashed line 220 in FIG. 7 so that a gap or space 222 exists above the liquid reagent in the container 210. Gas exiting the thermal kinetic conduit 206 can be injected into the space 222 above the liquid reagent in the container 210. As a non-limiting example, gas exiting the thermal kinetic conduit 206 can flow through the bottom wall 212 and into the tube 224. In some embodiments, the tube 224 can constitute an integral part of the thermal kinetic conduit 206 that extends into the vessel 210. The tube 224 can extend through the liquid reagent disposed in the liquid container to the space 222 above the liquid reagent. The tube 224 can have a 90 degree bend so that the end of the tube 224 extends horizontally over the liquid reagent.

[077] As shown in FIG. 7, an opening through the cylindrical side wall of tube 224 is provided on the side facing the surface of the liquid reagent so that the gas flowing through tube 224 exits tube 224 through opening 226. . The gas exiting the opening 226 exits the opening and is directed toward the surface of the liquid reagent, which can facilitate the reaction between the gas reagent or components and the liquid reagent. For example, the source gas contains GaCl ₃ that is carried in a carrier gas such as H ₂ , the source gas is decomposed in the thermal kinetic conduit 206, and gaseous GaCl and chlorine such as, for example, hydrogen chloride (HCl) In embodiments that include chemical species, the liquid reagent in the liquid container can include liquid gallium, which reacts with chlorinated gas (eg, HCl) generated in the thermal kinetic conduit 206. Further gaseous GaCl can be formed. Gas in the space 222 above the liquid reagent in the container 210 can flow out of the container through the outlet port 228. For example, the outlet port 228 can be located on the top wall 214 of the container above the horizontally extending portion of the tube 224. The outlet port 228 can lead to the outlet conduit 230, and the end of the outlet conduit 230 can define the outlet 204 of the gas injector 200.

  [078] In a further embodiment, gas exiting the thermal kinetic conduit 206 can be injected into the liquid reagent in the container 210, thereby allowing the gas to pass through the liquid reagent in the space 222 above the liquid reagent. Can be foamed.

  [079] The various components of the container 210 may be at least substantially composed of a refractory material such as quartz, for example.

[080] GaCl can be a desirable precursor gas for forming GaN. Thus, for example, to convert the excess chlorinating species, such as the additional GaCl (GaCl ₃ and in a system using raw material gas containing _{H 2)} GaCl ₃ and hydrogen chloride gas caused by thermal decomposition of _{H 2} (HCl) This can reduce the amount of chlorinated species entering the reaction chamber 102, thereby avoiding the deleterious effects of excess chlorinated species on the deposited GaN material. Such detrimental effects can include, for example, the incorporation of chlorine atoms into the gallium nitride crystal lattice, and cracks or delamination of the deposited GaN film. By introducing excess hydrogen chloride gas (HCl) into the reaction chamber, hydrogen chloride acts as an etchant for GaN in the reaction chamber, thereby reducing the growth rate of GaN or even inhibiting growth. Sometimes. Furthermore, the efficiency of the deposition apparatus 100 can be improved by reacting excess chlorinated species with liquid gallium to form additional GaCl.

  [081] The HVPE film deposition apparatus 100 described above with reference to FIGS. 4A and 4B, as described above with reference to FIG. 3, has a bulk III group over the growth substrate 20 according to an embodiment of the present invention. It can be used to deposit nitride semiconductor material 22. FIG. 8 illustrates a non-limiting example of an HVPE deposition process that can be used to deposit a bulk III-nitride semiconductor material 22 over the growth substrate 20 using the deposition apparatus 100 of FIGS. 4A and 4B. Is a graph schematically representing The deposition process shown in FIG. 8 is provided as an example, and other HVPE deposition processes can be used to deposit the bulk III-nitride semiconductor material 22 over the growth substrate 20 (FIG. 3).

[082] Referring to FIG. 8, an exemplary deposition process is represented by plotting the temperature T in the reaction chamber 102 as a function of time t. As shown in the graph, the deposition process includes 10 stages, and the 10 stages are sequentially labeled from S1 to S10. Non-limiting process parameters for the deposition process are provided in Table 1 below over each of the 10 stages of S1-S10.

[083] As shown in FIG. 8 and Table 1, step S1 is a loading step of placing the processed substrate 106 on the substrate support structure 104. After placing the processed substrate 106 on the substrate support structure 104, the reaction chamber 102 is heated to a temperature of 350 ° C. at atmospheric pressure while a purge gas containing N ₂ is supplied to the reaction chamber 102 at a flow rate of 10 standard liters per minute (slm). heated to a T _1.

[084] As shown in FIG. 8, the stabilization operation S2 begins at time t _1, lasts for 30 seconds. During the stabilization phase S2, while flowing a purge gas into the reaction chamber 102, the reaction chamber 102 is heated to a temperature _{T 2} of the 400 ° C. at a pressure of 200 Torr. The purge gas includes N _{2 with} a flow rate of 15 slm and H ₂ with a flow rate of ₂ slm.

[085] lamp operation S3 begins at time _{t 2,} lasts for 4.5 minutes. The ramp step S3, the reaction chamber 102 is steadily continuously heated at a substantially constant ramp to a temperature T ₃ from the temperature T ₂ 1025 ° C.. The pressure in the reaction chamber 102 is maintained at 200 Torr during the ramp phase S3. During the ramp stage S3, a group V source gas containing NH ₃ is flowed into the reaction chamber 102 at a flow rate of ₁ slm, and a purge gas containing N _{2 at} a flow rate of 23 slm and H ₂ at a flow rate of 16 slm is passed through the reaction chamber 102.

[086] stabilization operation S4 begins at time t _3, lasting for 30 seconds. In stabilization phase S4, the reaction chamber 102 is maintained at a temperature _{T 3} and a pressure of 200Torr of 1025 ° C.. During the stabilization step S4, a group V source gas containing NH ₃ is passed through the reaction chamber 102 at a flow rate of 18 slm, and a purge gas containing N _{2 at} a flow rate of 23 slm and H ₂ at a flow rate of 5 slm is passed through the reaction chamber 102.

[087] The first deposition step S5, the start at time _{t 4,} persists for 5.0 minutes. During the deposition phase S5, the reaction chamber 102 is maintained at a temperature T _{3 of} 1025 ° C. and a pressure of 200 Torr. During the deposition step S5, a group III source gas containing GaCl ₃ is reacted at a flow rate of 51 standard cubic centimeters per minute (sccm) with a carrier gas containing N _{2 at} a flow rate of 2.5 slm and H ₂ at a flow rate of 0.8 slm. Flow into chamber. A group V source gas containing NH ₃ is flowed into the reaction chamber 102 at a flow rate of 18 slm. A purge gas containing N _{2 at} a flow rate of 23 slm and H ₂ at a flow rate of 5 slm is also passed through the reaction chamber 102.

[088] The second deposition step S6 starts at time _{t 5,} last for 20.0 minutes. The reaction chamber 102 is in the second deposition step S6, is maintained at a temperature _{T 3} and a pressure of 200Torr of 1025 ° C.. The flow rate of the GaCl ₃ Group III source gas is increased to 80 sccm during the deposition step S6, and the GaCl ₃ is carried by a carrier gas containing N _{2 with} a flow rate of 2.5 slm and H ₂ with a flow rate of 1.2 slm. A group V source gas containing NH ₃ is flowed into the reaction chamber 102 at a flow rate of 18 slm. A purge gas containing N _{2 with} a flow rate of 23 slm and H ₂ with a flow rate of 5 slm is also flowed into the reaction chamber 102 during the second deposition step S6.

  [089] During at least one period of the first deposition stage S5 and the second deposition stage S6, in the HVPE process, the bulk III-nitride semiconductor material 22 is fed at a rate of at least about 10 microns (10 μm) per hour, or even Can be deposited over the growth substrate 20 at a rate of at least about 20 microns (20 μm) per hour. Such a deposition rate can be significantly higher than the deposition rate that can be deposited using a MOCVD process to deposit a bulk III-nitride semiconductor material.

[090] annealing step S7, it starts the time _{t 6,} persist for 20.0 minutes. Among annealing step S7, the reaction chamber 102 is maintained at a temperature _{T 3} and a pressure of 200Torr of 1025 ° C.. During the annealing step S7, a group V source gas containing NH ₃ is flowed into the reaction chamber 102 at a flow rate of 14 slm, and a purge gas containing N _{2 at} a flow rate of 23 slm and H ₂ at a flow rate of 5 slm is passed through the reaction chamber 102.

[091] Lamp step S8, starts at time _{t 7,} persists for 4.5 minutes. Among lamp step S8, the reaction chamber 102 is substantially steady continuously cooled at a constant ramp rate from temperature T ₃ to a temperature T ₂ of the 400 ° C.. The pressure in the reaction chamber 102 is maintained at 200 Torr during the ramp phase S8. During the ramp stage S8, a group V source gas containing NH ₃ is passed through the reaction chamber 102 at a flow rate of 14 slm, and a purge gas containing N _{2 at} a flow rate of 23 slm and H ₂ at a flow rate of 12 slm is passed through the reaction chamber 102.

[092] Purge step S9 begins at time _{t 8,} persists for 5.0 minutes. During the purge phase S9, the reaction chamber 102 is maintained at a temperature T _{2 of} 400 ° C., while the pressure in the reaction chamber 102 is reduced from 200 Torr to atmospheric pressure. During the purge step S9, a purge gas containing N ₂ at a flow rate of 16 slm is passed through the reaction chamber 102.

[093] At time _{t 9,} begins unloading step S10, the processing substrate 106 is maintained until removed from the reaction chamber 102. During the unloading phase S10, the reaction chamber 102 is lowered to a temperature T _{1 of} 350 ° C. and maintained at that temperature, the pressure is maintained at atmospheric pressure, while a purge gas containing N ₂ at a flow rate of 10 slm is supplied to the reaction chamber 102. Pass through.

  [094] Referring again to FIGS. 1-3, as previously mentioned, according to an embodiment of the method of the present invention, the metal nitride nucleation template layer 18 is exposed on the substrate 10 using an MOCVD process. Bulk III-nitridation on growth substrate 20 using HPVE processes (such as those described above) without forming in situ (eg, using a separate deposition apparatus and / or in a separate reaction chamber) The physical semiconductor material 22 can be deposited.

  [095] In some embodiments, a non-MOCVD process is used in the first reaction chamber to form the metal nitride nucleation template layer 18 (FIG. 2) on the substrate 100 to form the growth substrate 20. The bulk III nitride semiconductor material 22 is then deposited on the growth substrate 20 using a HVPE process, such as the process described above, in a second reaction chamber that is different from the first reaction chamber. For example, the metal nitride nucleation template layer 18 (FIG. 2) includes at least one of aluminum nitride (AlN) and titanium nitride (TiN), and may be a plasma physical deposition process (PEPVD) or a plasma chemical deposition process (PECVD). ) Can be formed on the substrate 100.

  [096] By way of example and not limitation, the metal nitride nucleation template layer 18 comprises aluminum nitride (AlN), a plasma physical vapor deposition (PEPVD) system, and Cuomo et al. And may be made using the method disclosed in US Pat. No. 6,784,085 issued by. For example, the substrate 100 and the group III metal target can be loaded into a sputter deposition chamber (separate from the reaction chamber 102 of the HVPE deposition apparatus 100). Using a suitable background gas such as argon, a high energy plasma assisted environment can be created in the sputter deposition chamber. Another nitrogen-containing source gas can be directed into the chamber. Additionally or alternatively, the gas utilized to generate the plasma can be used as the reactive source gas, in which case the background gas can supply nitrogen species. The group III metal target is sputtered to generate a group III metal source gas. The Group III metal source gas is a nitrogen-containing gas characterized by containing one or more of diatomic nitrogen, nitrogen atoms, nitrogen ions, and partially ionized nitrogen, and nitrogen-containing compounds such as ammonia, and Join. As a result, reactive gas species including Group III metal and nitrogen components are generated in the reaction chamber and deposited on and over the exposed major surface 14 of the substrate 10. As-deposited reactive gas species are deposited on the substrate 100 to produce the metal nitride nucleation template layer 18 of FIG. In some embodiments, the as-deposited metal nitride nucleation template layer 18 can be subjected to one or more heat treatments to improve the crystal quality of the as-deposited metal nitride nucleation template layer 18. For example, as-deposited metal nitride material can be polycrystalline and / or amorphous and can be subjected to one or more heat treatments to form the metal nitride nucleation template layer 18. Crystallinity can be improved. In some embodiments, the one or more heat treatments can include a rapid thermal annealing (RTA) process. The one or more heat treatments may be performed, for example, in one or more of a furnace, a rapid thermal annealing chamber, and a chemical vapor deposition reactor. By way of example and not limitation, the one or more thermal treatments may cause the as-deposited metal nitride nucleation template layer 18 to be higher than approximately 600 ° C, greater than approximately 800 ° C, or even greater than approximately 1000 ° C. Can also be exposed to elevated temperature (s). One or more heat treatments for treating the metal nitride nucleation template layer 18 immediately after deposition may be performed in a controlled gas atmosphere. For example, the gaseous atmosphere can include one or more of ammonia, nitrogen, hydrogen, and argon.

  [097] The metal nitride nucleation template layer 18 may optionally be doped with one or more dopant elements using known doping methods. For example, the dopant-containing gas can be introduced into the reaction chamber in a controlled manner.

[098] As another non-limiting example, the metal nitride nucleation template layer 18 can include titanium nitride (TiN), a plasma enhanced chemical vapor deposition (PECVD) system, and March 11, 1997. Can be made using the method disclosed in US Pat. No. 5,610,106 issued to Foster et al. For example, the substrate 10 can be loaded into a chemical vapor deposition chamber (separate from the reaction chamber 102 of the HVPE deposition apparatus 100). A showerhead / electrode that generates radio frequency (RF) can be provided in the CVD chamber, and a reactive gas can be pumped into the chamber through the showerhead / electrode toward the substrate 10. The reactive gas includes titanium tetrachloride (TiCl ₄ ), ammonia (NH ₃ ), and a diluent gas. The diluent gas can include one or more of hydrogen, helium, argon, and nitrogen.

  [099] The substrate 10 can be positioned about 0.25 to 3 inches away from the showerhead / electrode so that the active ions strike the substrate 10. The plasma is generated from the reactive gas using a showerhead / electrode that generates RF as the reactive gas passes through the showerhead / electrode. Plasma reactive ions strike the substrate 10.

  [0100] The pressure in the CVD chamber may be maintained between about 0.5 Torr and about 20 Torr (eg, about 5 Torr). The substrate 10 can be maintained at a temperature of about 400 ° C. to about 500 ° C. (eg, 450 ° C.) during the deposition process. The substrate 10 can be heated by heating the support structure on which the substrate 10 rests during the deposition process. Furthermore, the support structure on which the substrate 10 rests can rotate about 100 revolutions per minute (rpm) or more during the deposition process.

[0101] The concentration of the reactive gas in the CVD chamber can be controlled by the flow rate. In general, titanium tetrachloride can be introduced at a flow rate between about 1 sccm and about 40 sccm (eg, about 10 sccm). The partial pressure of TiCl ₄ should be low enough to form TiN. If the partial pressure of TiCl ₄ becomes too high, TiN may not be formed. When the total pressure is 5 Torr, the TiCl ₄ partial pressure may be less than 0.02 Torr (eg, about 0.01 Torr to about 0.001 Torr). At lower pressures (ie, about 0.0001 Torr), the reaction rate can be significantly reduced and step coverage can be unacceptable. As the total pressure increases above 5 Torr, the TiCl ₄ partial pressure can be increased accordingly. In general, the molecular ratio of NH ₃ for TiCl ₄ is from about 2: 1 (NH ₃ vs. TiCl ₄₎ from about 100: 1 (NH ₃ vs. TiCl ₄₎ (e.g., about 10: 1) may be used.

[0102] In accordance with such embodiments of the method of forming the metal nitride nucleation template layer 18, the metal nitride nucleation template layer 18 may be about 25 nanometers or less (25 nm), or even about 10 nanometers or less (10 nm). It can be formed to have an average thickness T ₁ of, bulk III-nitride semiconductor material 22, on the metal nitride nucleation template layer 18, and the layer 18 one side, at least about 2 microns (2 μm), at least about 5 microns (5 μm), or even an average thickness T ₂ of about 10 microns or more (10 μm).

  [0103] A PEPVD deposition process disclosed in US Pat. No. 6,784,085 is used to form an AlN nucleation template layer on a sapphire substrate, followed by an HVPE deposition process, such as the process described above. Samples were prepared by depositing bulk GaN over the AlN nucleation template layer using a metal trichloride source gas. In the first sample, the exposed main surface 19 (FIG. 2) of the AlN nucleation template layer is cut off by 0.5 ° with respect to the A-plane of the AlN crystal structure, and the AlN nucleation template layer is about 10 nanometers. It had an average thickness of meters (10 nm). In the second sample, the exposed major surface 19 (FIG. 2) of the AlN nucleation template layer is cut off 0.25 ° with respect to the M-plane of the AlN crystal structure, and the AlN nucleation template layer is about 25 nanometers. It had an average thickness of meters (25 nm).

  [0104] The crystal quality of the resulting bulk GaN material was measured using X-ray diffraction (XRD) analysis, and the crystal quality was reported for bulk GaN formed using conventional MOCVD techniques. It was found to be substantially equivalent to the crystal quality. Furthermore, the surface roughness of the exposed main surface 23 of the bulk GaN material was measured after depositing the bulk GaN material over the AlN nucleation template layer of the growth substrate. The exposed main surface of the bulk GaN material deposited on one surface of the first sample (10 nm AlN nucleation template layer that is 0.5 ° off-cut with respect to the A plane) becomes the second sample (on the M plane). A 25 nm AlN nucleation template layer that is 0.25 ° offcut relative to the exposed main surface of the bulk GaN material deposited on one side was observed. In particular, the first sample exhibited a root mean square (RMS) surface roughness of about 9.72 nm, and the second sample exhibited an RMS surface roughness of about 10.58 nm.

[0105] Referring again to FIGS. 1-3, in a further embodiment, the metal nitride nucleation template layer 18 (FIG. 2) is subsequently bulk bulk III nitride semiconductor material by HVPE treatment over the layer 18. Formed on the substrate 100 using an MOCVD process in situ within the same reaction chamber 102 (FIGS. 4A and 4B) used to deposit 22. For example, the metal nitride nucleation template layer 18 (FIG. 2) is made of gallium nitride (GaN), aluminum nitride (AlN), aluminum gallium nitride (Al _x Ga _1-x N), and titanium nitride (TiN). At least one can be included.

  [0106] Thus, in some embodiments, the deposition system 100 described above with reference to FIGS. 4A and 4B can and is configured to perform each of a MOCVD process and an HVPE process. sell. Referring to FIG. 4A, by way of example and not limitation, one of the gas sources 128A, 128B includes, for example, trimethyl gallium (TMG), triethyl gallium (TEG), trimethyl aluminum (TMA), triethyl aluminum (TEA). ), Tetrakisdiethylaminotitanium (TDEAT), and tetrakis (dimethylamido) titanium (TDMAT). In such an embodiment, a carrier gas can be used to carry the organometallic precursor into the reaction chamber, but it is necessary to utilize thermal kinetic gas injectors 150A, 150C in conjunction with the organometallic precursor source. There may be no. For example, a carrier gas can be bubbled through a heated reservoir of liquid organometallic precursor to form an organometallic gas, which can then flow into the reaction chamber 102. . The organometallic gas 102 decomposes within the reaction chamber 102, and as a result, a metal nitride nucleation template layer 18 can be deposited on the processing substrate 106 (eg, the substrate 100 shown in FIG. 1). Using the deposition system described herein, the metal nitride nucleation template layer 18 is formed in situ in the same reaction chamber 102 used to deposit bulk III nitride semiconductor material in an HVPE process. A MOCVD method that can be used to do so is disclosed, for example, in US Patent Application Publication No. 2009 / 0184398A1, published July 23, 2009, under the name of Choi.

[0107] In such an embodiment, the metal nitride nucleation template layer 18 has an average thickness T ₁ of about one-half nanometer (0.5 nm) to about 2 microns (2 μm). The bulk III-nitride semiconductor material 22 can be formed at least about 2 microns (2 μm), at least about 5 microns (5 μm), at least about 7 microns (7 μm), at least about 10 microns (10 μm), at least about 20 microns. (20 μm), or even having an average thickness T ₂ of at least about 30 microns (30 μm). Further, the exposed major surface 23 of the deposited bulk III-nitride semiconductor material 22 is, in some embodiments, a root mean square surface of about 2 nanometers (2.0 nm) or less (eg, about 0.112 nm). Can have roughness.

  [0108] Referring again to FIGS. 1-3, in a further embodiment, the metal nitride nucleation template layer 18 (FIG. 2) is subsequently bulk III treated with the HVPE process described herein over the layer 18. Formed on the substrate 100 using an HVPE process in situ within the same reaction chamber 102 (FIGS. 4A and 4B) used to deposit the group nitride semiconductor material 22. For example, the metal nitride nucleation template layer 18 (FIG. 2) includes at least one of aluminum nitride (AlN) and titanium nitride (TiN), and is published in the United States on 24 April 2001 by Chen et al. It may be formed using the method disclosed in Patent No. 6,221,174 and International Publication No. 2010/101715 A1 published on Sep. 10, 2010 in the name of Arena et al.

  [0109] Referring to FIG. 4A, source gas 128A can be used in forming metal nitride nucleation template layer 18 (FIG. 2) in the HVPE process, and source gas 128B is followed by bulk III-nitridation in the HVPE process. It can be used in the formation of the physical semiconductor material 22.

[0110] As a non-limiting example, the metal nitride nucleation template layer 18 (FIG. 2) can include aluminum nitride (AlN), and the gas source 128A can include a gas source of AlCl _3. . Gas source AlCl ₃ is at least 190 ° C. (e.g., about 195 ° C.) may comprise temperature, and the reservoir of liquid AlCl ₃ which was maintained at a pressure of about 2.5 atm, optionally liquid AlCl ₃ Physical means for improving the evaporation rate may be included. Such physical means include, for example, an apparatus configured to stir liquid AlCl ₃ , an apparatus configured to spray liquid AlCl ₃ , and configured to quickly flow a carrier gas over liquid AlCl _3. apparatus, an apparatus configured bubbling carrier gas through the liquid AlCl _3, and so forth apparatus such configured piezoelectric device to disperse liquid AlCl ₃ with ultrasound. As a non-limiting example, a carrier gas such as He, N ₂ , H ₂ or Ar, or mixtures thereof (eg, a mixture of N ₂ and H ₂ ) while maintaining liquid AlCl ₃ at a temperature of at least 195 ° C. Can be bubbled through liquid AlCl ₃ , whereby the source gas can contain one or more carrier gases. Optionally, a carrier gas comprising AlCl ₃ and H ₂ can be supplied to the thermal kinetic implanter 150A, where AlCl ₃ can be decomposed to form AlCl and HCl. HCl can react with liquid aluminum held in thermal kinetic injector 150A to form additional AlCl. The gas is then directed into the reaction chamber 102 where AlCl can react with NH ₃ supplied from the gas source 128C to form AlN on and over the substrate.

[0111] As another non-limiting example, the metal nitride nucleation template layer 18 (FIG. 2) can include titanium nitride (TiN), and the gas source 128A includes a TiCl ₄ gas source. Can do. The TiCl ₄ gas source can include a liquid TiCl ₄ storage vessel maintained at a temperature of at least 80 ° C., and optionally physical to enhance the evaporation rate of the liquid TiCl ₄ , such as the means discussed above. Means may be included. As a non-limiting example, a carrier gas such as He, N ₂ , H ₂ or Ar, or mixtures thereof (eg, a mixture of N ₂ and H ₂ ) while maintaining liquid TiCl ₄ at a temperature of at least 137 ° C. Is bubbled through liquid TiCl ₄ so that the source gas may contain one or more carrier gases. TiCl ₄ gas is then directed into reaction chamber 102 where TiCl ₄ can react with NH ₃ supplied from gas source 128C to form TiN on and over the substrate. . Further details relating to the process parameters for forming TiN in such processes can be found in the aforementioned US Pat. No. 6,221,174.

  [0112] After forming the metal nitride nucleation template layer 18 in the reaction chamber 102 using HVPE processing as discussed above, as previously described with reference to FIGS. Bulk III-nitride semiconductor material 22 can be formed in the same reaction chamber 102 by HVPE processing. The bulk III nitride semiconductor material 22 is removed from the reaction chamber 102 after forming the metal nitride nucleation template layer 18 and before depositing the bulk III nitride semiconductor material 22 on the growth substrate 20. Without removal, it can be deposited on the growth substrate 20 after forming the metal nitride nucleation template layer 18.

  [0113] The method embodiments of the present invention allow bulk III-nitride semiconductor materials to be fabricated without the need to form metal nitride nucleation template layers ex situ using MOCVD processes. . Thus, at least some embodiments of the method of the present invention may be more cost effective than methods already known for forming bulk III-nitride semiconductor materials.

  [0114] Further non-limiting exemplary embodiments of the invention are described below.

  [0115] Embodiment 1: A method of depositing a bulk III-nitride semiconductor material on a growth substrate, forming a growth substrate by forming a metal nitride nucleation template layer on the substrate, and a halide Depositing a bulk III-nitride semiconductor material on the growth substrate using a vapor phase epitaxy (HVPE) process, and depositing the bulk III-nitride semiconductor material on the growth substrate. A substep of decomposing at least one of chloride and metal tetrachloride to form a metal chloride group III precursor gas, and reacting the metal chloride group III precursor gas with a group V precursor gas; Forming a bulk III-nitride semiconductor material on the growth substrate.

  [0116] Embodiment 2: The step of forming a metal nitride nucleation template layer on a substrate comprises forming a metal nitride nucleation template layer using a non-organometallic chemical vapor deposition (MOCVD) process. The method of embodiment 1, comprising:

  [0117] Embodiment 3: Forming a metal nitride nucleation template layer on a substrate includes forming a metal nitride nucleation template layer using a plasma enhanced chemical vapor deposition (PECVD) process. The method of embodiment 1.

  [0118] Embodiment 4: Forming a metal nitride nucleation template layer using a plasma enhanced chemical vapor deposition (PECVD) process is deposited with a sub-step of depositing a metal nitride material on a substrate. The method of embodiment 3, comprising the step of subjecting the metal nitride material to one or more heat treatments to improve the crystallinity of the deposited metal nitride material.

  [0119] Embodiment 5: Exposing the deposited metal nitride material to one or more heat treatments to improve the crystallinity of the deposited metal nitride material rapidly causes the deposited metal nitride material to rapidly Embodiment 5. The method of embodiment 4 comprising the substep of subjecting to a thermal annealing treatment.

  [0120] Embodiment 6: The step of forming a metal nitride nucleation template layer on a substrate includes the sub-step of forming a metal nitride nucleation template layer using a halide vapor phase epitaxy (HVPE) process. The method of embodiment 1.

[0121] Embodiment 7: forming a halide vapor phase epitaxy (HVPE) metal nitride nucleation template layer using the _{process, GaCl 3, InCl 3, AlCl} 3, and at least one of TiCl ₄ A sub-step of cracking one to form at least one of a trichloride, dichloride, and monochloride group III precursor gas, and reacting the group III precursor gas with an NH ₃ precursor gas. And forming a metal nitride nucleation template layer on the substrate.

  [0122] Embodiment 8: Forming a metal nitride nucleation template layer in a first chamber; Sub-step of depositing a bulk III-nitride semiconductor material on a growth substrate in a second different chamber; The method of any one of embodiments 1-7, further comprising:

  [0123] Embodiment 9: Forming a metal nitride nucleation template layer in a chamber and depositing a bulk III-nitride semiconductor material on a growth substrate in the chamber in which the metal nitride nucleation template layer is formed The method of any one of embodiments 1-7, further comprising:

[0124] Embodiment 10: A method of depositing a bulk III-nitride semiconductor material on a growth substrate, using a non-metal organic chemical vapor deposition (MOCVD) process in a first chamber on the substrate. Forming a growth substrate by forming a metal nitride nucleation template layer; and using a halide vapor phase epitaxy (HVPE) process in a second chamber to form a bulk III-nitride semiconductor material on the growth substrate. and depositing, towards the step of depositing a bulk III-nitride semiconductor material on the growth substrate is at least one of NH _3, and metal trichloride and the metal tetrachloride to the second chamber A method comprising a flow sub-step.

  [0125] Embodiment 11: The method of embodiment 10, further comprising selecting the substrate to include a sapphire substrate.

  [0126] Embodiment 12: The method of embodiment 10 or embodiment 11, further comprising selecting the metal nitride nucleation template layer to include at least one of aluminum nitride and titanium nitride.

  [0127] Embodiment 13: Forming a metal nitride nucleation template layer on a substrate using a non-organometallic chemical vapor deposition (MOCVD) process is performed on the substrate using a plasma deposition process. The method of any one of embodiments 10-12, comprising the substep of forming a metal nitride nucleation template layer.

  [0128] Embodiment 14: Depositing a bulk III-nitride semiconductor material on the growth substrate deposits at least one of GaN, InN, AlN, InGaN, GaAlN, GaAlN, and InAlN on the growth substrate. Embodiment 14. The method of any one of embodiments 10-13, comprising the step of:

  [0129] Embodiment 15: Sub-depositing a bulk III-nitride semiconductor material on a growth substrate deposits a bulk III-nitride semiconductor material on the growth substrate at a rate of at least about 10 microns (10 μm) per hour. The method of any one of embodiments 10-14, comprising a step.

  [0130] Embodiment 16: Depositing a bulk III-nitride semiconductor material on the growth substrate at a rate of at least about 10 microns (10 μm) per hour comprises at least about a bulk III-nitride semiconductor material on the growth substrate per hour. Embodiment 16. The method of embodiment 15 comprising the substep of depositing at a rate of 20 microns (20 μm).

  [0131] Embodiment 17: Depositing a bulk III-nitride semiconductor material on the growth substrate comprises depositing a layer of bulk III-nitride semiconductor material on the growth substrate having an average thickness of at least about 2 microns. Embodiment 17. The method according to any one of embodiments 10-16, comprising a sub-step of depositing.

  [0132] Embodiment 18: Forming a metal nitride nucleation template layer such that forming a metal nitride nucleation template layer on a substrate has an average thickness of about 50 nanometers (50 nm) or less. Embodiment 18. The method of any one of embodiments 10 through 17, further comprising:

  [0133] Embodiment 19: The step of forming the metal nitride nucleation template layer to have an average thickness of about 50 nanometers (50 nm) or less comprises an average of about 10 nanometers or less (10 nm) 19. The method of embodiment 18 comprising the substep of forming the metal nitride nucleation template layer to have a thickness.

[0134] Embodiment 20: NH _3, as well as metal third step of passing at least one towards the second chamber of the chlorides and metal tetrachloride _{is, GaCl 3, InCl 3, AlCl} 3, and TiCl ₄ Embodiment 20. The method of any one of embodiments 10-19, comprising the sub-step of flowing at least one of the flow toward the second chamber.

[0135] Embodiment 21: NH _3, and flowing the at least one towards the second chamber of the metal trichloride and the metal tetrachloride is selected from metal trichloride and the metal tetrachloride 21. The method of embodiment 20, further comprising a sub-step of flowing at least one toward the second chamber at a flow rate of about 100 sccm or less.

  [0136] Embodiment 22: flowing at least one of metal trichloride and metal tetrachloride toward the second chamber at a flow rate of about 100 sccm or less comprises the steps of metal trichloride and metal tetrachloride. 22. The method of embodiment 21, comprising the sub-step of flowing at least one of them towards the second chamber at a flow rate of about 80 sccm or less.

[0137] Embodiment 23: a metal trichloride to include GaCl ₃ and further comprising the step of selecting at least one of the metal tetrachloride, according to any one of embodiments 20-22 method .

  [0138] Embodiment 24: The step of depositing a bulk III-nitride semiconductor material results in the deposition of a bulk III-nitride semiconductor material having a root mean square surface roughness of about 10 nanometers (10 nm) or less. Embodiment 24. The method of any one of embodiments 10-23, wherein an exposed major surface is obtained.

[0139] Embodiment 25: The step of depositing a bulk III-nitride semiconductor material results in the deposition of a bulk III-nitride semiconductor material having an average dislocation density of less than or equal to about 5-9 x 10 ⁸ per square centimeter. Embodiment 25. The method of any one of embodiments 10-24, wherein an exposed major surface is obtained.

[0140] Embodiment 26: A method of depositing a bulk III-nitride semiconductor material on a growth substrate, wherein the metal nitride nuclei are deposited on the substrate using a metal organic chemical vapor deposition (MOCVD) process in a chamber Forming a production template layer to form a growth substrate and depositing a bulk III-nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process in the same chamber. Depositing a bulk III-nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process comprising NH ₃ and at least one of metal trichloride and metal tetrachloride Including a sub-step of flowing toward the same chamber.

  [0141] Embodiment 27: The method of embodiment 26, further comprising selecting the substrate to include a sapphire substrate.

  [0142] Embodiment 28: Selecting a metal nitride nucleation template layer to include at least one of gallium nitride, aluminum nitride, aluminum gallium nitride, hafnium nitride, chromium nitride, tungsten nitride, and titanium nitride The method of embodiment 26 or embodiment 27, further comprising:

  [0143] Embodiment 29: Depositing a bulk III-nitride semiconductor material on the growth substrate deposits at least one of GaN, InN, AlN, InGaN, GaAlN, GaAlN, and InAlN on the growth substrate. 29. The method according to any one of embodiments 26-28, comprising the substep of:

  [0144] Embodiment 30: A step of depositing a bulk III-nitride semiconductor material on a growth substrate deposits a bulk III-nitride semiconductor material on the growth substrate at a rate of at least about 10 microns (10 μm) per hour. 30. The method of any one of embodiments 26-29, comprising a step.

  [0145] Embodiment 31: Depositing a bulk III-nitride semiconductor material on the growth substrate at a rate of at least about 10 microns (10 μm) per hour on the growth substrate at a rate of at least about 20 microns (20 μm) per hour Embodiment 31. The method of embodiment 30 comprising the substep of depositing a bulk III nitride semiconductor material.

  [0146] Embodiment 32: Bulk III-nitride semiconductor material wherein depositing bulk III-nitride semiconductor material on the growth substrate has an average thickness of at least about 2 microns (2 μm) on the growth substrate 32. The method of any one of embodiments 26-31, comprising the sub-step of depositing a layer of:

  [0147] Embodiment 33: The step of forming a metal nitride nucleation template layer on a substrate comprises an average thickness of about one-half nanometer (0.5 nm) to about 2 microns (2.0 μm). 33. The method according to any one of embodiments 26-32, further comprising the substep of forming a metal nitride nucleation template layer having:

[0148] Embodiment 34: NH _3, and the step of flowing at least one towards the same chamber of the metal trichloride and the metal tetrachloride _{is, GaCl 3, InCl 3, AlCl} 3, and of TiCl ₄ 34. The method of any one of embodiments 26-33, comprising the substep of flowing at least one of the

[0149] Embodiment _{35: GaCl 3, InCl 3,} AlCl 3, and the step of flowing at least one towards the same chamber of the TiCl _{4 is, GaCl 3, InCl 3, AlCl} 3, and of the TiCl ₄ 35. The method of embodiment 34, further comprising the sub-step of flowing at least one toward the same chamber at a flow rate of about 100 seem or less.

[0150] Embodiment 36: flowing at least one of GaCl ₃ , InCl ₃ , AlCl ₃ , and TiCl ₄ toward the same chamber at a flow rate of about 100 sccm or less comprising GaCl ₃ , InCl ₃ , AlCl ₃ , 36. The method of embodiment 35, comprising the step of flowing at least one of TiCl ₄ and TiCl ₄ toward the same chamber at a flow rate of about 80 sccm or less.

[0151] Embodiment 37: a metal trichloride to include GaCl ₃ and further comprising the step of selecting at least one of the metal tetrachloride, according to any one of embodiments 26-36 method .

  [0152] Embodiment 38: Depositing bulk III-nitride semiconductor material by depositing bulk III-nitride semiconductor material, resulting in a root mean square surface roughness of about 2 nanometers (2.0 nm) or less 38. The method according to any one of embodiments 26-37, wherein an exposed major surface of the material is obtained.

[0153] Embodiment 39: Depositing a bulk III-nitride semiconductor material results in exposing a deposited bulk III-nitride semiconductor material having an average dislocation density of less than or equal to about 5 × 10 ⁸ per square centimeter 39. A method according to any one of embodiments 26-38, wherein a major surface is obtained.

[0154] Embodiment 40: A method of depositing a bulk III-nitride semiconductor material on a growth substrate, using a halide vapor phase epitaxy (HVPE) process in a chamber to produce metal nitride nuclei on the substrate Forming a template layer to form a growth substrate; and depositing a bulk III-nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process in the same chamber; Depositing a bulk III-nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process comprises NH ₃ and at least one of metal trichloride and metal tetrachloride. A method comprising the substep of flowing towards the same chamber.

  [0155] Embodiment 41: The method of embodiment 40, further comprising selecting the substrate to include a sapphire substrate.

  [0156] Embodiment 42: The method of embodiment 40 or embodiment 41, further comprising selecting the metal nitride nucleation template layer to include at least one of aluminum nitride and titanium nitride.

  [0157] Embodiment 43: Depositing a bulk III-nitride semiconductor material on the growth substrate deposits at least one of GaN, InN, AlN, InGaN, GaAlN, GaAlN, and InAlN on the growth substrate. 43. The method of any one of embodiments 40-42, comprising the substep of:

  [0158] Embodiment 44: A step of depositing a bulk III-nitride semiconductor material on a growth substrate depositing a bulk III-nitride semiconductor material on the growth substrate at a rate of at least about 10 microns (10 μm) per hour. 45. A method according to any one of embodiments 40-43, comprising steps.

  [0159] Embodiment 45: depositing a bulk III-nitride semiconductor material on the growth substrate at a rate of at least about 10 microns (10 μm) per hour on the growth substrate at a rate of at least about 20 microns (20 μm) per hour 45. The method of embodiment 44, comprising the substep of depositing a bulk III nitride semiconductor material.

  [0160] Embodiment 46: Bulk III-nitride semiconductor material wherein depositing bulk III-nitride semiconductor material on the growth substrate has an average thickness of at least about 2 microns (2 μm) on the growth substrate 46. The method according to any one of embodiments 40-45, comprising the substep of depositing a layer of:

  [0161] Embodiment 47: A step of forming a metal nitride nucleation template layer on a substrate forms a metal nitride nucleation template layer having an average thickness of about 50 nanometers (50 nm) or less. 47. The method according to any one of embodiments 40-46, further comprising a step.

[0162] Embodiment 48: NH _3, and the step of flowing at least one towards the same chamber of the metal trichloride and the metal tetrachloride is a metal trichloride in the following flow rate of about 100sccm and metal tetrachloride 48. The method of embodiment 47, further comprising the substep of flowing at least one of the objects towards the same chamber.

  [0163] Embodiment 49: flowing at least one of metal trichloride and metal tetrachloride toward the same chamber at a flow rate of about 100 sccm or less, wherein metal trichloride and metal at a flow rate of about 80 sccm or less 49. The method of embodiment 48, comprising the substep of flowing at least one of the tetrachlorides toward the same chamber.

[0164] Embodiment _{50: GaCl 3, InCl 3,} AlCl 3, and further the step of selecting at least one of a metal trichloride and the metal tetrachloride to include at least one of TiCl ₄ 50. The method of any one of embodiments 40-49, comprising.

  [0165] Embodiment 51: Depositing a bulk III-nitride semiconductor material with a step of depositing a bulk III-nitride semiconductor material resulting in a root mean square surface roughness of about 10 nanometers (10.0 nm) or less The method according to any one of embodiments 40-50, wherein an exposed major surface of the material is obtained.

[0166] Embodiment 52: Depositing a bulk III-nitride semiconductor material results in exposing the deposited bulk III-nitride semiconductor material having an average dislocation density of about 5 × 10 ⁸ or less per square centimeter 52. The method according to any one of embodiments 40-51, wherein a major surface is obtained.

  [0167] Embodiment 53: Depositing a bulk III-nitride semiconductor material on a growth substrate using a halide vapor phase epitaxy (HVPE) process in the same chamber comprises a metal nitride nucleation template on the substrate. After forming the layer and forming the growth substrate and before depositing the bulk III nitride semiconductor material on the growth substrate, the bulk III nitride on the growth substrate without removing the growth substrate from the same chamber 53. The method according to any one of embodiments 40-52, comprising the sub-step of depositing semiconductor material.

[54] Embodiment 54: A structure comprising a bulk III-nitride semiconductor material made by the method described in any one of embodiments 1-53.

Claims (5)

A method of depositing a bulk III-nitride semiconductor material on a growth substrate, comprising:
Forming a metal nitride nucleation template layer on a substrate to form the growth substrate;
Depositing the bulk III-nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process;
Depositing the bulk III-nitride semiconductor material on the growth substrate;
Substeps of decomposing at least one of metal trichloride and metal tetrachloride prior to introduction into the reaction chamber of the HVPE deposition system to form a metal chloride group III precursor gas;
The metal chloride group III precursor gas is introduced into the reaction chamber, the metal chloride group III precursor gas is reacted with the group V precursor gas in the reaction chamber, and the bulk on the growth substrate. A sub-step of forming a group III nitride semiconductor material;
Including
Forming the metal nitride nucleation template layer on the substrate comprises forming the metal nitride nucleation template layer using a plasma enhanced chemical vapor deposition (PECVD) process; Forming the metal nitride nucleation template layer using the plasma enhanced chemical vapor deposition (PECVD) process;
Depositing a metal nitride material on the substrate;
The method of claim 1, comprising: subjecting the deposited metal nitride material to one or more heat treatments to improve the crystallinity of the deposited metal nitride material.   A sub-step of subjecting the deposited metal nitride material to one or more heat treatments to improve the crystallinity of the deposited metal nitride material comprises rapid thermal annealing of the deposited metal nitride material The method of claim 2, comprising exposing to water. Forming the metal nitride nucleation template layer in a first chamber;
Depositing the bulk III-nitride semiconductor material on the growth substrate in a second different chamber. Forming the metal nitride nucleation template layer in a chamber;
Depositing the bulk III-nitride semiconductor material on the growth substrate in the chamber in which the metal nitride nucleation template layer is formed. the method of.

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