FR2968831A1 - METHODS OF FORMING NITRIDE III MASSIVE MATERIALS ON METAL NITRIDE GROWTH MATRIX LAYERS AND STRUCTURES FORMED THEREFROM - Google Patents

Abstract

Massive semiconductor materials of nitride III are deposited using a HVPE process that uses a metal trichloride precursor on a metal nitride matrix layer of a growth substrate. Deposition of the solid nitride III semiconductor material can be achieved without ex situ formation of the matrix layer using a MOCVD method. In some embodiments, a nucleation matrix layer is formed ex situ using a non-MOCVD method prior to deposition of the solid nitride III semiconductor material on the matrix layer using a HVPE method. In other embodiments, a nucleation matrix layer is formed in situ using a MOCVD method prior to deposition of the solid nitride III semiconductor material on the matrix layer using a HVPE method. In other embodiments, a nucleation matrix layer is formed in situ using a HVPE process prior to deposition of the solid III nitride semiconductor material on the matrix layer using a HVPE method.

Description

METHODS OF FORMING NITRIDE III MASSIVE MATERIALS ON METAL NITRIDE GROWTH MATRIX LAYERS AND STRUCTURES FORMED THEREFROM DOMAIN METHODS As a general rule, the embodiments of the invention relate to methods of depositing nitride III materials on substrates, and structures formed by these methods. More particularly, the embodiments of the invention relate to methods of depositing nitride III materials on substrates that include a growth matrix layer comprising a metal nitride material, and structures formed by these methods.

BACKGROUND Chemical vapor deposition (CVD) is a chemical process that is used to deposit solid materials on substrates, and is commonly used in the manufacture of semiconductor devices. In chemical vapor deposition processes, a substrate is exposed to one or more reactive gases, which react, decompose, or react and decompose both in such a manner that it results in the deposition of a solid material on the substrate. surface of the substrate. One particular type of CVD process is named in the vapor phase epitaxy (VPE) art. In VPE processes, a substrate is exposed to one or more reactive vapors in a reaction chamber, which react, decompose, or react and decompose both in such a manner that this results in the epitaxial deposition of a solid material on the reaction chamber. surface of the substrate. VPE processes are often used to deposit III-V type semiconductor materials. When one of the reactive vapors in a VPE process comprises a halide vapor, the process may be termed hydrogenated vapor phase epitaxy (HVPE). According to the art, it is known to form nitride III semiconductor materials such as gallium nitride (GaN) using VPE processes in which organometallic precursor materials (OM) are decomposed in a reaction chamber to form the semiconductor material of nitride III. Such methods are often referred to as organometallic vapor phase epitaxy (MOVPE) processes, and may also be characterized as organometallic chemical vapor deposition (MOCVD) processes. Such MOVPE processes are usually performed using several sequential pre-deposition processes prior to deposition of the desired solid III nitride semiconductor material.

These sequential pre-deposition processes may include high temperature hydrogen cooking of the growth substrate (e.g. sapphire substrate), growth substrate nitriding, formation of a nucleation layer of a material nitride III at relatively low temperatures on the growth substrate, annealing of the nucleation layer at relatively high temperatures, coalescence of the nucleation layer, and finally growth of the layer of nitride material III on the layer. nucleation. HVPE processes are also used to form nitride III semiconductor materials such as gallium nitride (GaN). In such processes, the epitaxial growth of GaN on a substrate may be due to a vapor phase reaction between gallium monochloride (GaCl) and ammonia (NH3) which is carried out in a reaction chamber at high temperatures included between about 500 ° C and about 1000 ° C. NH3 can be provided by a standard source of gaseous NH3. In some processes, GaCl vapor is supplied by passing gaseous hydrogen chloride (HC1) (which may be supplied by a standard source of gaseous HCl) over heated liquid gallium (Ga) to form GaCl in situ. in the reaction chamber. The liquid gallium can be heated to a temperature of from about 750 ° C to about 850 ° C. GaCl and NH3 may be directed to (for example, on) a surface of a heated substrate, such as a slice of semiconductor material. U.S. Patent No. 6,179,913, issued January 30, 2001 to Solomon et al., Discloses a gas injection system for use in such systems and methods. The various sequential pre-deposition processes mentioned above with respect to the MOVPE processes used to form solid III nitride semiconductor materials can be difficult to achieve in a HVPE deposition reactor.

BRIEF SUMMARY This summary serves to introduce a selection of concepts of a simplified form, these concepts being further described in the following detailed description of some exemplary embodiments of the present invention. This summary is not intended to identify the key characteristics or essential characteristics of the subject claimed, nor is it intended to be used to limit the scope of the subject claimed. As previously mentioned, the various sequential pre-deposition methods used to form a nitride III material nucleation layer on the growth substrate prior to the deposition of the solid nitride III semiconductor material on the nucleation layer may be difficult to achieve in a HVPE storage reactor. Accordingly, the known HVPE methods used to deposit solid III nitride semiconductor material generally employ a growth substrate which comprises a nucleation layer of an ex situ metal nitride material (i.e., in a process separate deposition process performed in a separate chamber) on a substrate using a MOCVD method. The desired solid nitride III material is then deposited on the growth substrate in a separate HVPE process made in a separate chamber. In some embodiments, the present invention includes methods of depositing solid III nitride semiconductor materials on growth substrates. A metal nitride nucleation matrix layer is formed on a substrate to form a growth substrate, and the solid nitride III semiconductor material is deposited on the growth substrate using a halide vapor phase epitaxy (HVPE) process. ). The deposition of the solid III nitride semiconductor material on the growth substrate may include decomposing a metal trichloride and / or metal tetrachloride to form a Group III metal chloride precursor gas and the reaction of the gas. Group III metal chloride precursor with a Group V precursor gas to form a solid III nitride semiconductor material on the growth substrate. In at least some embodiments, the present invention provides methods of depositing nitride III bulk material onto growth substrates using HVPE methods without ex situ formation of the nucleation matrix layers using MOCVD methods. In some embodiments, the present invention provides methods of depositing a solid III nitride semiconductor material on a growth substrate. A metal nitride nucleation matrix layer is formed on a substrate using a non-organometallic chemical vapor deposition (MOCVD) process in a first chamber to form the growth substrate, and the solid semiconductor material of nitride III is deposited on the growth substrate using a halide vapor phase epitaxy (HVPE) process in a second chamber. The deposition of the solid nitride III semiconductor material on the growth substrate may comprise the flow of NH 3 and a metal trichloride and / or metal tetrachloride to the second chamber. In other embodiments of methods for depositing a solid III nitride semiconductor material on a substrate, a metal nitride nucleation matrix layer is formed on a substrate using a CVD method. organometallic (MOCVD) materials in a chamber to form the growth substrate, and the solid nitride III semiconductor material is deposited on the growth substrate using a halide vapor phase epitaxy (HVPE) process in the same chamber. The deposition of the solid III nitride semiconductor material on the growth substrate using the halide vapor phase epitaxy (HVPE) method may include the flow of NH 3 and a metal trichloride and / or a tetrachloride of metal to this same room.

In still other embodiments of methods of depositing a solid III nitride semiconductor material on a growth substrate, a metal nitride nucleation matrix layer is formed on a substrate using a phase epitaxy method. halide vapor (HVPE) in a chamber to form the growth substrate, and the solid nitride III semiconductor material is deposited on the growth substrate using a halide vapor phase epitaxy (HVPE) process in the same chamber . The deposition of the solid III nitride semiconductor material on the growth substrate using the halide vapor phase epitaxy (HVPE) method may include the flow of NH 3 and a metal trichloride and / or a tetrachloride of metal to this same room. Other embodiments of the invention include structures comprising the solid nitride III semiconductor material which are formed using the methods described herein. BRIEF DESCRIPTION OF THE DRAWINGS The present invention may be better understood by reference to the detailed description Following are examples of embodiments of the present invention, which are illustrated in the accompanying figures, in which: FIG. 1 is a simplified cross-sectional view of a substrate that may be used in accordance with embodiments of the methods of the invention; invention; FIG. 2 is a simplified cross-sectional view of a growth substrate that may be used in accordance with the embodiments of the methods of the invention, and which may be formed by deposition of a nucleation matrix layer on the substrate of Figure 1; Fig. 3 is a simplified cross-sectional view of a structure which comprises a solid nitride III semiconductor material deposited on the matrix layer 20 of nucleation of the growth substrate of Fig. 2 according to the embodiments of the methods of the invention; FIG. 4A is a cross-sectional view schematically illustrating an exemplary embodiment of a HVPE deposition system which comprises a reaction chamber and at least one gas injector, and which can be used in the embodiments of the methods of the invention. invention; Fig. 4B is a schematic cross-sectional view of the reaction chamber shown in Fig. 4A taken along section line 4B-4B shown thereon; Figure 5 schematically illustrates an embodiment of a thermalization gas injector that can be used in the deposition system of Figure 4A; Figure 6 schematically illustrates another exemplary embodiment of a gas injector which may be used in the deposition system of Figure 4A; Fig. 7 is an enlarged partial perspective sectional view of a portion of the gas injector of Fig. 6; and Fig. 8 is a graph schematically showing a deposition method that can be used to deposit solid III nitride semiconductor material on a growth substrate according to the embodiments of the invention and using a HVPE deposition system such as that illustrated in Figures 4A and 4B.

DETAILED DESCRIPTION OF THE EMBODIMENTS OF THE INVENTION The illustrations presented here are not the actual views of a particular component, device, or system, but are merely idealized representations that are used to describe the embodiments of the present invention.

A number of references are cited here, but none of the cited references, regardless of how they are characterized here, is accepted as prior art in relation to the invention of the subject claimed herein.

As used herein, the term "III-V semiconductor material" means and includes any semiconductor material that is at least predominantly composed of one or more elements of Group IIIA of the periodic table (B, Al, Ga, In and Ti) and one or more elements of group VA of the periodic table (N, P, As, Sb and Bi). For example, type III-V semiconductor materials include, without limitation, GaN, GaP, GaAs, InN, InP, InAs, AlN, AlP, AlAs, InGaN, InGaP, InGaNP, etc.

As used herein, the term "III nitride semiconductor material" means and includes any type III-V semiconductor material that is at least predominantly composed of one or more elements of Group IIIA of the periodic table (B, Al, Ga, In and Ti) and nitrogen. For example, III nitride semiconductor materials include GaN, InN, AlN, InGaN, GaAlN, InAlN, etc. As used herein, the term "metal nitride" means a compound of metal and nitrogen. The metal nitride materials include, but are not limited to, aluminum nitride (A1N), gallium nitride (GaN), gallium aluminum nitride (Al, Gal_XN), titanium nitride (TiN), nitride of hafnium (HfN), chromium nitride (CrN), tungsten nitride (WN) and tantalum nitride (TaN). As used herein, the terms " chemical vapor deposition " and " CVD " are synonymous and mean and include any method used to deposit one or more solid materials on a substrate in a reaction chamber in which the substrate is exposed to one or more reactive gases, which react, decompose, or react and decompose in such a manner that this results in the deposition of the solid material (s) on a surface of the substrate.

As used herein, the terms "vapor phase epitaxy" and "VPE" are synonymous and mean and include any CVD process in which the substrate is exposed to one or more reactive gases, which react, decompose, or react and decompose at both in such a way that this results in the epitaxial deposition of the solid material (s) on a surface of the substrate. As used herein, the terms "halide vapor phase epitaxy" and "HVPE" are synonymous and mean and include any VPE process in which at least one reactive gas used in the VPE process comprises a halide vapor. As used herein, the term "organometallic" means and includes any compound comprising at least one metal element and an organic chemical species comprising at least one carbon-based ligand. Organometallics are sometimes called "metallorganic" and these terms are synonymous for the purposes of this description. Organometallics include, but are not limited to, trimethylgallium (TMG), triethylgallium (TEG), trimethylaluminum (TMA), triethylaluminum (TEA), tetrakisdiethylaminotitanium (TDEAT), and tetrakis (dimethylamido) titanium (TDEAT).

As used herein, the terms "organometallic vapor phase epitaxy" and "MOVPE" are synonymous and mean and include any VPE process in which at least one reactive vapor used in the VPE process comprises an organometallic vapor.

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

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

As used herein, the term "gas" includes gases (fluids that have neither independent form nor volume) and vapors (gases that include a diffused liquid or a solid material suspended therein) and "gas" And "steam" are synonymous here. Figures 1 to 3 illustrate the deposition of a solid semiconductor material of nitride III on a growth substrate according to the embodiments of the invention. Referring to Figure 1, a substrate (10) is provided. In general, the substrate (10) may be a flat, discoidal body, and may generally be circular, rectangular, etc. The substrate (10) may comprise what is known in the art as the "matrix" or "slice". The substrate (10) may be at least largely composed of a homogeneous material (12). The material (12) may comprise, 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 a nitride (for example silicon nitride (Si3N4) or boron nitride (BN)). As other examples, the material {12) may comprise a semiconductor material such as silicon (Si), germanium (Ge), a III-V semiconductor material, etc. In some embodiments, the material (12) of the substrate (10) may be composed at least substantially of a single crystal of the material (12). Further, in such embodiments, the single crystal may have a selected crystallographic orientation, so that an exposed major surface (14) of the material (12) comprises a selected crystallographic plane of the single crystal of the material (12). In a non-limiting example, the substrate (10) may be selected to include a sapphire substrate. Such sapphire substrates are commercially available. Referring to FIG. 2, a metal nitride nucleation matrix layer (18) may be formed (eg deposited) on the exposed major surface (14) to form a growth substrate (20). According to the embodiments of the methods of the invention, the metal nitride nucleation matrix layer (18) can be formed on the substrate in a number of different ways, which are described in more detail below. By way of example and without limitation, the metal nitride nucleation matrix layer (18) may be deposited on the exposed main surface (14) so that the matrix layer (18) has an average thickness T1 of about two nanometers (2 nm) and about five micrometers (5 μm). The metal nitride nucleation matrix layer (18) is used to facilitate the deposition of a solid III-V type semiconductor material on the substrate (10) with a desired average total thickness while maintaining the defect densities in the substrate. solid type III-V semiconductor material at the desired concentrations. Due to the differences between the structures of the crystal lattice of the material (12) of the substrate (10) and the solid III-V type semiconductor material to be deposited on the substrate (10) (these differences are often named in the art "Crystalline lattice inconsistency"), the crystalline structure of the solid III-V semiconductor material may include undesired, relatively large concentrations of defects such as dislocations if the solid III-V type semiconductor material is to be directly deposited on the exposed main surface (14) of the substrate (10). Therefore, a metal nitride nucleation matrix layer (18) is provided between the substrate (10) and the III-V type solid semiconductor material which may have a composition and / or microstructure chosen so that the matrix layer of metal nitride nucleation (18) has a relatively lower crystal lattice inconsistency with the substrate (10) and the solid III-V type semiconductor material to deposit thereon with respect to the crystal lattice inconsistency between the substrate (10) and the solid III-V type semiconductor material. In other words, the nucleation matrix layer can be used to minimize the incoherence of the crystal lattice between the substrate (10) and the solid III-V type semiconductor material to be deposited on it, and such matrix nucleation layers ( 18) are also named in the art "buffer" layers. Further, the nucleation matrix layer may be used as a seed layer to nucleate the growth of the solid III-V type semiconductor material thereon, and such nucleation matrix layers (18) are also referred to in the layer art of germination ". Referring to Fig. 3, after formation of the growth substrate (20), the solid III-V type semiconductor material (22) can be nucleated and deposited on an exposed main surface (19) of the nucleation matrix layer of metal nitride (18) using a HVPE process. Although a discrete bond is visible between the metal nitride nucleation matrix layer (18) and the solid III-V type semiconductor material (22) in the simplified drawing of Figure 3, it should be noted that the matrix layer metal nitride nucleation (18) and the solid III-V semiconductor material may, in some embodiments, be at least substantially the same composition, and it may be difficult or impossible to visualize or identifying any discrete bond between the metal nitride nucleation matrix layer (18) and the solid III-V semiconductor material (22). By way of example and without limitation, the III-V type solid semiconductor material (22) can be deposited on the growth substrate (20) with a mean total thickness T2 of at least about five micrometers (5} gym) at least about seven microns (7 μm), at least about ten microns (10 μm), at least about twenty microns (20 μm), or even at least about thirty microns (30 μm). The presence of the metal nitride nucleation matrix layer (18) prepared according to the embodiments of the present invention can facilitate the deposition of the solid III-V type semiconductor material (22) with this average total thickness T2, while maintaining the dislocation densities in the III-V solid semiconductor material (22) on the exposed major surface (23) of the III-V solid semiconductor material (22) at concentrations of about 5 x 108 per square centimeter or less. Figs. 4A and 4B are schematic illustrations schematically illustrating an embodiment of a HVPE deposition system (100) that may be used in the embodiments of the methods of the invention, as described herein. In non-limiting examples, the deposition system (100) may include a deposition system as described in US Patent Application Publication No. US 2009/0223442 A1 published on September 10, 2009 in the name of Arena et al. , US Patent Application Serial No. 61 / 157,112 filed March 3, 2009 in the name of Arena et al., and US Patent Application Serial No. 12 / 894,724 filed September 30, 2010 in the name of from Bertran. The deposition system (100) illustrated in Figures 4A and 4B includes a reaction chamber (102) and one or more gas injectors (as described in more detail below).

In the following description of the deposition system (100) and, more particularly, the reaction chamber (102) of the deposition system (100), the terms "longitudinal" and "transverse" are used to indicate the directions relating to the chamber. reaction (102) according to Figures 4A and 4B, the longitudinal direction being the vertical direction with respect to Figure 4A and the direction extending in the plane of Figure 4B, and the transverse or lateral directions being those s' extending horizontally with respect to each of FIGS. 4A and 4B. The transverse directions are also called directions extending "from one side to the other of the reactor". The deposition system (100) comprises the reaction chamber (102), a substrate support structure (104) (for example a susceptor) configured to support one or more work substrates (106) (which may initially comprise a substrate ( 10) as illustrated in Figure 1 or a growth substrate (20) as shown in Figure 2) on which it is desired to deposit or otherwise provide a material of the deposition system (100). By way of nonlimiting example, the reaction chamber (102) may have a height of about two inches, a width of about twelve inches, and a length of about twenty inches, and the support structure of the substrate (104 ) may be configured to support an eight inch working substrate (106), a six inch working substrate (106), a three inch four working substrate (106) or an eight inch working substrate (106) two. The deposition system (100) further comprises heating elements (108) (Fig. 4B), which can be used to selectively heat the deposition system (100), so that an average temperature in the reaction chamber ( 102) can be controlled in a desirable high temperature range during the deposition process. The heating elements (108) may include, for example, resistive heating elements or radiant heating elements. As illustrated in FIG. 4B, the support structure of the substrate (104) can be mounted on an axis (110), which can be coupled (for example, directly structurally coupled, magnetically coupled, etc.) to a device drive (112) such as an electric motor which is configured to cause rotation of the axis (110) and, therefore, of the support structure of the substrate (104) in the reaction chamber (102).

In some embodiments, one or more of the reaction chamber (102), substrate support structure (104), axis (110), and any other component in the reaction chamber (102) may be at least generally comprised of a refractory ceramic material such as a ceramic oxide (for example silica (quartz), alumina, zirconia, etc.), a carbide (for example silicon carbide, boron carbide, etc.) or a nitride (for example silicon nitride, boron nitride, etc.).

The deposition system (100) further includes a gas flow system used to inject one or more gases into the reaction chamber (102) and to eject the gases out of the reaction chamber (102). Referring to FIG. 4A, the deposition system (100) may include three gas supply lines (114A, 114B, 114C) which carry the gases from the respective gas sources (128A, 128B, 128C). Optionally, devices (117A, 117B, 117C), which may include one or more of the valves, backpressure regulators, and mass flow controllers, may be used to selectively control the flow of gas through the fuel lines. gas inlet (114A, 114B, 114C) respectively. In some embodiments, at least one of the gas sources (128A, 128B) may comprise an external source of a metal trichloride such as GaC13, InC13 or A1C13r as described in US Patent Application Publication No. US 2009/0223442 Al. GaC13, InCl3 and AlCl3 may exist in the form of a dimer such as, for example Ga2C16, In2Cl6 and Al2C16 respectively. Accordingly, at least one of the gas sources (128A, 128B) may comprise a dimer such as Ga2C16, In2Cl6 or Al2C16. As a non-limiting example, one or more gas sources (128A, 128B) may provide a mass flow of GaCl 3 vapor as a Group IIIA precursor component. The gas source (128C) may comprise an external source of a VA group precursor, such as ammonia (NH3) In embodiments in which one or more of the gas sources (128A, 128B) are or comprise a source of GaC13r the GaC13 source comprises a reservoir of liquid GaC13 maintained at a temperature of at least 120 ° C (eg, about 130 ° C) and may include physical means to improve the rate of evaporation of GaC13 liquid. Such physical means may include, for example, a device configured to stir liquid GaC13, a device configured to spray liquid GaC13, a device configured to rapidly circulate a carrier gas over liquid GaC13, a device configured to bubble a liquid carrier gas in liquid GaC13, a device, such as a piezoelectric device, configured to ultrasonically disperse liquid GaC13, and the like. As a nonlimiting example, a carrier gas, such as He, N2, H2 or Ar, or a mixture thereof (for example a mixture of N2 and H2) can be bubbled in the liquid GaC13, while the GaCl3 liquid is maintained at a temperature of at least 120 ° C, so that the source gas may comprise one or more carrier gases. The circulation of GaCl 3 vapor in one or more gas injectors (150A, 150B) can be controlled in some embodiments of the invention. For example, in embodiments in which a carrier gas is bubbled in liquid GaCl3, the circulation of GaCl3 from the gas source (128A, 128B, 128C) depends on one or more factors, including for example the temperature of GaC13, the pressure above the GaCl3 and the circulation of the carrier gas which bubbles in GaC13. While the mass flow rate of GaC13 can be, in principle, controlled by any of these parameters, in some embodiments, the mass flow rate of GaC13 can be controlled by varying the flow of the carrier gas using a regulator of mass flow. In some embodiments, the temperatures of the gas supply lines (114A, 114B) can be controlled between the gas sources (128A, 128B) and the gas injectors (150A, 150B). The temperatures of the gas supply lines (114A, 114B) and the associated sensors, mass flow controllers and the like can gradually increase from a first temperature (e.g., about 120 ° C or more) to the output of the sources. respective gases (128A, 128B) to a second temperature (e.g., about 160 ° C or less) at the gas injectors (150A, 150B) to prevent condensation of gases (e.g. of GaCl3) in the gas supply lines (114A, 114B) and the like. Optionally, the length of the gas supply lines (114A, 114B) between the respective gas sources (128A, 128B) and the gas injectors (150A, 150B) may be about three feet or less, about two feet or less, or even about one foot or less. Source gas pressure can be controlled using one or more pressure control systems. Each of the two gas supply lines (114A, 114B) may optionally extend to one of two respective gas injectors (150A, 150B), which are described in more detail below.

In other embodiments, the deposition system (100) may comprise less than two (e.g. gas delivery lines and respective gas injectors, or the deposition system (100) may comprise more than two (for example, three, four, five, etc.) gas supply lines and respective gas injectors. In the embodiment of Figures 4A and 4B, the gas injectors (150A, 150B) are entirely located outside the reaction chamber (102).

However, in other embodiments, the gas injectors (150A, 150B) may be fully located within the reaction chamber (102) or at least a portion of the gas injectors (150A, 150B) may be at least partially extend in the reaction chamber (102). The deposition system (100) may further include three vents (116A, 116B, 116C) that provide fluid communication between the exterior and interior of the reaction chamber (102). Each vent (116A, 116B, 116C) may provide fluid communication through a wall, ceiling and / or bottom of the reaction chamber (102) between one of the gas injectors (150A, 150B) respective ones and one of the respective gas dispersion lines (118A, 118B, 118C) in the reaction chamber (102). The gas dispersion lines (118A, 118B, 118C) in the reaction chamber (102) may be used to transport the gases to the desired sites in the enclosure. The gas dispersion conduits (118A, 118B, 118C) may be located and configured to inject gases into the reaction chamber (102) in selected directions relative to the work substrates (106) carried by the structure supporting the substrate (104). The gases transported by the gas dispersion conduits (118A, 118B, 118C), such as the precursor gases and the carrier gases, can flow in the longitudinal direction through the reaction chamber (102) (vertical direction with respect to FIG. 4A) and can be injected in directions extending to the working substrates (106) longitudinally into the reaction chamber (102), the directions being oriented at least generally parallel to the upper exposed major surfaces of the substrates to be worked. (106). Gas dispersion lines (118A, 118B, 118C) may be supported and held in place in the reaction chamber (102) using conduit supports. The particular arrangement and configuration of the gas dispersion lines (118A, 118B, 118C) is simply one or more of the many arrangements and configurations that can be used in the embodiments of the invention, and other modes of The reaction chambers (102) may have different configurations and arrangements of the gas dispersion lines in the reaction chamber (102). The gas dispersion lines (118A, 118B, 118C) can be actively heated, passively heated or passively and actively heated. For example, the heat generating elements (not shown) may be positioned adjacent to at least a portion of the gas dispersion lines (118A, 118B, 118C). In some embodiments, the gas dispersion lines (118A, 118B, 118C) are heated by the heating elements (108) (Figure 4B). Optionally, passive heat transfer structures (e.g., structures comprising materials that behave similarly to a blackbody) may be located adjacent to or near at least a portion of the gas dispersion lines (118A). , 118B, 118C) in the reaction chamber (102) to improve heat transfer to gas dispersion lines (118A, 118B, 118C). Passive heat transfer structures (e.g., structures comprising materials that behave similarly to a blackbody) may be present in the reaction chamber (102) as described, for example, in US Patent Application Publication No. US 2009/0214785 Al, which was published on August 27, 2009 in the name of Arena et al. For example, a heat transfer plate (124) (shown in Figs. 4A and 4B by a dotted line) can be placed in the reaction chamber (102) so that the heat transfer plate (124) extends through the reaction chamber (102) on the support structure of the substrate (104) and the substrates to be worked (106) supported by the support structure of the substrate (104). The heat transfer plate (124) can facilitate in a thermalization process the flow of gases in the vicinity of the heat transfer plate (124) by absorbing radiation from the heating elements (such as the heating elements (108)) and again irradiating the heat absorbed in the process gases. Such a passive heat transfer structure can enhance heat transfer within the reaction chamber (102), and can improve the homogeneity and consistency of the temperature in the reaction chamber (102). Passive heat transfer structures may include materials having high emissivity values (close to unity) (blackbody materials) that are also capable of withstanding a high temperature, corrosive environments that may be encountered in the deposit system (100). These materials may comprise, for example, aluminum nitride (AlN), silicon carbide (SiC) and boron carbide (B4C) which have emissivity values of 0.98, 0.92 and 0.92, respectively. The gaseous byproducts, carrier gases, and any excess precursor gas may be discharged from the reaction chamber (102) through an outlet of the chamber (126). As mentioned previously, one or more gas injectors (150A, 150B) of the deposition system (100) of FIGS. 4A and 4B may be or comprise a gas injector as described in more detail below with reference to FIGS. In some embodiments, the gas injectors (150A, 150B) may comprise gas injectors such as those described in International Application WO 2010/101715 A1, published on September 10, 2010 in the name of Arena et al. For example, Fig. 5 is a perspective view of a thermalization gas injector (160), which may be used for one or both of the gas injectors (150A, 150B) shown in Fig. 4A. As illustrated in Figure 6, the gas injector (160) includes a conduit (162) that includes an inlet portion (164), a helical core portion (166), and an outlet portion (168). A source gas (e.g. GaC13), a carrier gas (e.g., H2, N2, etc.) or a mixture of a source gas and a carrier gas may be supplied to the inlet portion (164). The gas or gases flow from the inlet portion (164) through the helical core portion (166) to the outlet portion (168) and the reaction chamber (102) (Fig. 4A). At least the helical core portion (166) of the conduit (162) may be heated as described in more detail below. By cooling the line (162), a length of the physical space occupied by the line (162) is significantly less than the actual length of the flow path through the line (162). In other words, a length of the pipe (162) may be longer than the shortest distance between the inlet portion (164) and the outlet portion (168). The conduit (162) may have other configurations. For example, the conduit (162) may have a serpentine configuration that includes a plurality of generally parallel linear sections connected together end-to-end by curved sections that extend at an angle of 180 °. The conduit (162) may be configured to heat the gas flowing in the conduit (162) for a desirable time (for example a residence time), which may depend on the cross-sectional area of the circulation circuit in the conduit (162), the flow of the source gas in the line (162) and the overall length of the line (162). The conduit (162) may be shaped and configured to be located close to one or more active or passive heating elements, as described in more detail below. As illustrated in Figure 5, at least the helical central portion (166) of the conduit (162) may be contained in an outer housing (170). The outer casing (170) may also serve as an additional gas conduit for gases such as purge gases. For example, as shown in Figure 5, the outer housing (170) may include a housing inlet (172) and a housing outlet (174). The purge gas may be forced to flow into the outer housing (170) from the housing inlet (172) to the housing outlet (174). The purge gas may be heated by the thermalization gas injector (160) as it passes through the outer casing (170). The conduit (162) and the outer housing (170) may include a refractory material that is stable and inert at the elevated temperatures to which it is subjected during use. For example, the conduit (162) and the outer housing (170) may be at least substantially comprised of quartz. The thermalization gas injector (160) can be heated using active heat generating elements close to (for example adjacent) the outer casing (170) and / or the helical central portion (166) of the duct (172). ). Active heating elements include radiation emitting elements such as infrared lamps, inductive heating elements, electric heating elements such as resistive heating elements and the like. The thermalization gas injector (160) may also include passive heaters that do not generate heat themselves, but are used to redistribute, reflect, or otherwise affect heat transfer in and around the fuel injector. thermalization gas (160). For example, as illustrated in Figure 5, the thermalization gas injector (160) may include an active heating element (180), which may include a resistance heated heater that at least partially surrounds the exterior of the housing external (170). Accordingly, the gases flowing through the conduit (162) and / or the outer housing (170) can be heated by the active heating element (180). As illustrated in Figure 5, an optional heating element (182), which may be active or passive, may be placed in the outer housing (170). The heating element (182) may have an elongate cylindrical shape, and the helical core portion (166) of the conduit (162) may meander around the heating element (182) as shown in FIG. For example and without limitation, the heating element (182) may include a rod comprising 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) can improve the efficiency with which the gases in the helical central portion (166) of the coil (162) and the gases in the outer casing (170) are heated by the active heating element (180). In embodiments of the invention wherein the source gas supplied to the thermalization gas injector (160) by one of the gas sources (128A, 128B) comprises a metal trichloride such as GaCl3 and a H2 hydrogen carrier gas, metal trichloride and hydrogen gas can decompose to form a metal monochloride vapor such as GaCl and HCl vapor, which vapor can exit through the exit portion ( 168) of the line (162) and go to the reaction chamber (102).

In other embodiments, the gas injectors (150A, 150B) may comprise the gas injectors disclosed in US Patent Application Serial No. 12 / 894,724. For example, the gas injectors (150A, 150B ) may comprise a reservoir configured to contain a liquid metal or other element, such as, for example, liquid gallium (Ga), liquid aluminum (Al) or liquid indium (In) or an organometallic substance such as trimethylgallium (TMG), triethylgallium (TEG), trimethylaluminum (TMA), triethylaluminum (TEA), tetrakisdiethylaminotitanium (TDEAT) and tetrakis (dimethylamido) titanium (TDMAT). In other embodiments of the invention, the reservoir may be configured to contain a solid reagent for reaction with a source gas (or a decomposition or reaction product of a source gas). For example, the reservoir may be configured to contain a solid volume of one or more materials such as for example solid silicon (Si) or solid magnesium (Mg). Fig. 6 is a perspective view of a gas injector (200) that may be used for one or both gas injectors (150A, 150B) shown in Fig. 4A. As illustrated in Figure 6, the gas injector (200) includes an inlet (202), an outlet (204), a thermalization pipe (206) and a container (210). The container (210) is configured to contain a liquid reagent. For example, a liquid metal, such as liquid gallium, liquid indium, liquid aluminum, etc., or a liquid organometallic substance can be placed in the container (210). A source gas (for example GaC13), a carrier gas (for example H2, N2, etc.) or a mixture of a source gas and a carrier gas can be supplied to the inlet (202). The source gas (s) may flow from the inlet (202) into the thermalization pipe (206). The thermalization duct (206) may be configured to heat the gas flowing in the thermalization duct (206) for a desirable time (for example a residence time), which may depend on the cross-sectional area of the circulation circuit in the duct. of thermalization (206), the flow of the source gas in the thermalization pipe (206) and the overall length of the thermalization pipe (206). The thermalization pipe (206) can be shaped and configured to be located close to one or more active or passive heating elements, as described in more detail below.

In addition, the thermalization duct (206) may comprise one or more curved sections or loops so that the length of the physical space occupied by the thermalization duct (206) is significantly less than the actual length of the circulation circuit in the thermalization pipe (206). In other words, a length of the thermalization pipe (206) may be longer than the shortest distance between the inlet (202) and the liquid container (210). In some embodiments, the length of the thermalization conduit (206) may be at least about two times the shortest distance between the inlet (202) and the liquid container (210), at least about three times the the shortest distance between the inlet (202) and the liquid container (210), or even at least about four times the shortest distance between the inlet (202) and the liquid container (210). For example, the thermalization duct (206) may have a serpentine configuration, as illustrated in FIG. 6, which comprises a plurality of generally parallel linear sections connected together end-to-end by curved sections which extend through an angle of 180 °. The thermalization conduit (206) may comprise a tube which is at least largely made of a refractory material such as quartz for example.

In some embodiments, the gas may comprise a source gas that is at least partially decomposed in the thermalization conduit (206). For example, in embodiments in which the gas comprises a Gac13 source gas and a carrier gas comprising H2, the source gas can decompose to form gaseous GaCl and hydrogen chloride (HCl). The gases flow from the thermalization pipe (206) into the container (210). Figure 7 is an enlarged partial section of the container (210). As illustrated in FIG. 7, the container (210) comprises a bottom wall (212), an upper wall (214) and at least one side wall (216). In the embodiment of Figures 6 and 7, the reservoir has a generally cylindrical shape so that the bottom wall (212) and the top wall (214) each have a circular shape and are each at least flat overall. , and so that the side wall (216) is at least cylindrical (for example tubular) in the assembly. In other embodiments of the invention, the reservoir may be configured according to other geometric configurations. The bottom wall (212), the top wall (214) and at least one of the side walls (216) together define a hollow body, the interior of which defines a reservoir for containing a liquid reagent such as liquid gallium or organometallic substance. The interior space in the hollow container (210) can be partially filled with a liquid reagent. For example, the container (210) can be filled with a liquid reagent to the level indicated by the dotted line (220) in Figure 7, so that a gap or gap (222) is present over the liquid reagent in the container (210). The gases flowing out of the thermalization conduit (206) may be injected into the space (222) above the liquid reagent in the container (210). In a non-limiting example, gases flowing out of the thermalization conduit (206) may flow through the bottom wall (212) into a tube (224). In some embodiments, the tube (224) may include a constituent portion of the thermalization conduit (206) that extends into the container (210). The tube (224) may extend into the liquid reagent placed in the liquid container at the space (222) above the liquid reagent. The tube (224) may comprise a bend of 90 ° so that an end portion of the tube (224) extends horizontally above the liquid reagent. As illustrated in FIG. 7, an opening may be present in the cylindrical side wall of the tube (224) on one of its sides facing the surface of the liquid reagent, so that the gases flowing in the tube (224) exiting the tube (224) through the opening (226). The gases exiting through the opening (226) may be directed out of the opening in a direction toward the surface of the liquid reagent to promote a reaction between one or more components of the gases and the liquid reagent. For example, in embodiments in which the source gas comprises GaC13 transported in a carrier gas such as H2, and the source gas has decomposed to comprise GaCl gas and a chlorinated species such as for example chloride of hydrogen (HC1) in the thermalization conduit (206), the liquid reagent in the liquid container may comprise liquid gallium, which may react with the chlorine gas (eg HCl) generated in the thermalization line ( 206) to form additional gaseous GaCl. The gases in the space (222) above the liquid reagent in the container (210) can flow out of the container through a vent (228). For example, the vent (228) may be located in the top wall (214) of the container above the portion of the tube (224) extending horizontally. The vent (228) may lead to an outlet pipe (230), the end of which may delimit the outlet (204) of the gas injector (200). In other embodiments, the gases flowing out of the thermalization conduit (206) can be injected into the liquid reagent into the container (210), so that the gases rise up as bubbles in the liquid reagent until at the space (222) above the liquid reagent. The various components of the container (210) may be at least in the assembly made of a refractory material such as quartz for example.

GaCl may be a desired precursor gas for GaN formation. Therefore, converting the chlorinated species to excess such as, for example, gaseous hydrogen chloride (HC1) from thermal decomposition of GaC13 and H2 (in systems that utilize a source gas comprising GaC13 and of H2) to additional GaCl, the deleterious effects of the excess chlorinated species on the deposited GaN material can be avoided since the amount of the chlorinated species that enters the reaction chamber (102) can be reduced. These adverse effects may include, for example, incorporation of chlorine atoms into the crystal lattice of gallium nitride and cracking or delamination of the deposited GaN film. The introduction of excess hydrogen chloride (HCl) into the reaction chamber can cause the action of hydrogen chloride as a chemical striker on the GaN in the reaction chamber, thereby reducing the rate of growth or preventing even the growth of GaN. In addition, by reacting the excess chlorine species with the liquid gallium to form additional GaCl, the efficiency of the deposition system (100) can be improved. The HVPE deposition system (100) described above with reference to FIGS. 4A and 4B may be used to deposit the solid nitride III semiconductor material (22) on a growth substrate (20) according to the embodiments of the invention. the invention, as previously described with reference to FIG. 3. FIG. 8 is a graph showing schematically a non-limiting example of a HVPE deposition process that can be used to deposit the solid semiconductor material of nitride III (22) on a growth substrate (20) using the deposition system (100) of Figs. 4A and 4B. The deposition process illustrated in FIG. 8 is exemplified, and other HVPE deposition methods can also be used to deposit solid III nitride semiconductor material on a growth substrate (20) (FIG. 3).

Referring to Fig. 8, the deposition method of the example is shown by plotting the temperature T in the reaction chamber (102) as a function of time t. As illustrated in the graph, the deposition process comprises ten (10) steps, which are sequentially named Si to 510. The parameters of a non-limiting example of the deposition process for each of the ten steps Si to no are illustrated in the table. 1 below.

TABLE 1 Step Description Temp. Time Pressure Source Source Group Gas III group V purge If Load 350 ° C --- Atm --- S2 Stabilization 400 ° C 30 s 200 Torr --- --- N2 10 slm S3 Heating --- 4.5 min 200 Torr --- NH3 1 slm N2 15 slm H2 2 slm S4 Stabilization 1025 ° C 30 s 200 Torr --- NH3 N2 23 slm 18 sin 'H2 16 slm S5 1st deposit 1025 ° C 5.0 min 200 Torr N2 2 , 5 slm NH3 N2 23 slm H2 0.8 slm 18 slm H2 5 slm GaC13 51 sccm S6 2nd deposit 1025 ° C 20.0 min 200 Torr N2 2.5 slm NH3 N2 23 slm H2 1.2 slm 18 slm H2 5 slm GaC13 80 sccm S7 Annealing 1025 ° C 10.0 min 200 Torr --- NH3 N2 23 slm 14 slm H2 5 slm S8 Cooling --- 4.5 min 200 Torr --- NH3 N2 23 slm 14 slm H2 12 slm S9 Purge 400 ° C 5.0 min Atm --- --- N2 16 slm S10 Unload 350 ° C --- Atm --- --- N2 10 slm As shown in Figure 8 and Table 1, Step S1 is a loading step during which the substrates to be worked (106) are loaded onto the support structure of the substrate (104). After loading the substrates to be worked (106) onto the support structure of the substrate (104), the reaction chamber (102) is heated to a temperature T1 of 350 ° C at atmospheric pressure while circulating a purge gas comprising N2 in the reaction chamber (102) at a flow rate of 10 standard liters per minute (slm). As illustrated in FIG. 8, the stabilization step S2 begins at the time t1 and is prolonged for a duration of 30 seconds. During the stabilization step S2, the reaction chamber (102) is heated to a temperature T2 of 400 ° C at a pressure of 200 Torr while flowing a purge gas into the reaction chamber (102). The purge gas comprises N2 at a rate of 15 slm and H2 at a rate of 2 slm. The heating step S3 begins at time t2 and continues for a period of 4.5 minutes. During the heating step S3, the reaction chamber (102) is stably and continuously heated at a substantially constant heating rate of a temperature T2 at a temperature T3 of 1025 ° C. The pressure in the reaction chamber (102) is maintained at 200 Torr during the heating step S3. During the heating step S3, a group V source gas comprising NH3 flows in the reaction chamber (102) at a flow rate of 1 slm, and a purge gas comprising N2 at a flow rate of 23 slm and the H2 at a flow rate of 16 slm passes into the reaction chamber (102). Stabilization step S4 begins at time t3 and continues for a period of 30 seconds. During the stabilization step S4, the reaction chamber (102) is maintained at the temperature T3 of 1025 ° C and at a pressure of 200 Torr. During the stabilization step S4, a group V source gas comprising NH3 flows into the reaction chamber (102) at a flow rate of 18 slm, and a purge gas comprising N2 at a flow rate of 23 slm and the H2 at a flow rate of 5 slm passes into the reaction chamber (102).

The deposition step S5 starts at time t4 and continues for a period of 5.0 minutes. During the deposition step S5, the reaction chamber (102) is maintained at the temperature T3 of 1025 ° C. and at a pressure of 200 Torr. During the deposition step S5, a group III source gas comprising GaCl 3 circulates in the reaction chamber at a flow rate of 51 standard cubic centimeters per minute (sccm) with a carrier gas comprising N 2 at a flow rate of 2.5 slm. and H2 at a flow rate of 0.8 slm A Group V source gas comprising NH3 flows through the reaction chamber (102) at a rate of 18 slm. A purge gas comprising N 2 at a rate of 23 slm and H 2 at a rate of 5 slm also flows into the reaction chamber (102).

The second deposit step S6 begins at time t5 and continues for a period of 20.0 minutes. During the second deposition step S6, the reaction chamber (102) is maintained at the temperature T3 of 1025 ° C. and at a pressure of 200 Torr. During the second deposition step S6, the flow of the group III source gas comprising GaCl 3 is increased to 80 sccm, the GaCl 3 being transported by the carrier gas comprising N 2 at a flow rate of 2.5 μm and the H2 at a flow rate of 1.2 slm and a group V source gas comprising NH3 circulates in the reaction chamber (102) at a flow rate of 18 slm. A purge gas comprising N2 at a flow rate of 23 slm and H2 at a flow rate of 5 slm also flows into the reaction chamber (102) during the second deposition step S6. During the deposition step S5 and / or the second deposition step S6, the solid nitride III semiconductor material (22) can be deposited on the growth substrate (20) in the HVPE process at a speed of minus ten micrometers (10 pm) per hour or even at a speed of at least about twenty micrometers (20 pm) per hour. The deposition rates can be significantly higher than the deposition rates that can be obtained using the MOCVD methods for the deposition of solid nitride III semiconductor materials. The annealing step S7 begins at time t6 and continues for a period of 20.0 minutes. During the annealing step S7, the reaction chamber (102) is maintained at the temperature T3 of 1025 ° C. and at a pressure of 200 Torr. During the annealing step S7, a group V source gas comprising NH3 flows in the reaction chamber (102) at a flow rate of 14 slm, and a purge gas comprising N2 at a flow rate of 23 slm and the H2 at a flow rate of 5 slm passes into the reaction chamber (102). The cooling step S8 begins at time t7 and continues for a period of 4.5 minutes.

During the cooling step S8, the reaction chamber (102) is stably cooled and continuous at a substantially constant cooling rate from the temperature T3 to the temperature T2 of 400 ° C. The pressure in the reaction chamber (102) is maintained at 200 Torr during the cooling step S8. During the cooling step S8, a group V source gas comprising NH3 flows in the reaction chamber (102) at a flow rate of 14 slm, and a purge gas comprising N2 at a flow rate of 23 slm and the H2 at a rate of 12 slm passes into the reaction chamber (102). The purge step S9 begins at time t8 and continues for a period of 5.0 minutes. During the purge step S9, the reaction chamber (102) is maintained at the temperature T2 of 400 ° C while the pressure in the reaction chamber (102) is reduced to 200 Torr at atmospheric pressure. During the purge step S9, a purge gas comprising N2 at a rate of 16 slm passes into the reaction chamber (102). The discharge step S10 begins at time t9 and continues until the substrates to be worked (106) are discharged from the reaction chamber (102). During the unloading step S10, the reaction chamber (102) is reduced to, and maintained at, the temperature T1 of 350 ° C, and the pressure is maintained at atmospheric pressure, while a purge gas comprising N2 at a flow rate of 10 slm passes into the reaction chamber (102). Referring again to FIGS. 1 to 3, as previously mentioned, according to the embodiments of the methods of the invention, the solid semiconductor material of nitride III (22) can be deposited on the growth substrate (20) in using a HVPE process (as described below) without ex situ formation (for example using another deposition system and / or in another reaction chamber) of the metal nitride nucleation matrix layer (18) on the substrate (10) using a MOCVD method. In some embodiments, the metal nitride nucleation matrix layer (18) (Figure 2) is formed on the substrate (100) using a non-MOCVD process in a first reaction chamber to form the growth substrate (20). and the solid nitride III semiconductor material (22) is deposited on the growth substrate (20) using a HVPE process such as that described above in a second reaction chamber which is different from the first reaction chamber. For example, the metal nitride nucleation matrix layer (18) (Figure 2) may comprise aluminum nitride (AlN) and / or titanium nitride (TiN), and may be formed on the substrate (100) using a plasma-activated physical deposition method (PEPVD) or a plasma-activated chemical deposition method (PECVD). By way of example and without limitation, the metal nitride nucleation matrix layer (18) may comprise aluminum nitride (AIN) and may be prepared using the systems and methods of physical vapor deposition activated by plasma (PEPVD) described in U.S. Patent No. 6,784,085, issued August 31, 2004 to Cuomo et al. For example, the substrate (100) and a Group III metal target can be loaded into a spray deposition chamber (separate from the reaction chamber (102) of the HVPE deposition system (100)). A highly energetic plasma activated environment can be generated in the spray deposition chamber using a suitable bottom gas such as argon. A source gas containing separate nitrogen can be introduced into the chamber. In addition, or alternatively, the gas used to generate the plasma may be used as the reactive source gas, in which case the bottom gas may provide the nitrogen species. The Group III metal target is pulverized to produce a group III metal source vapor. The Group III metal source vapor is combined with the nitrogen-containing gas, which is characterized as comprising one or more species such as diatomic nitrogen, atomic nitrogen, nitrogen ions, and nitrogen. partially ionized nitrogen, as well as nitrogen-containing compounds such as ammonia. Accordingly, reactive vapors comprising Group III metal components and nitrogen are produced in the reaction chamber, and are deposited on and over the exposed major surface (14) of the substrate (10). The reactive vapor is deposited on the substrate (100) to produce the metal nitride nucleation matrix layer (18) of Figure 2. In some embodiments, the metal nitride nucleation matrix layer (18) thus deposited may be subjected to one or more thermal processes to improve the crystalline quality of the metal nitride nucleation matrix layer (18) thus deposited. For example, the metal nitride material thus deposited may be a polycrystalline and / or amorphous material, and may be subjected to one or more thermal processes to improve the crystallinity of the metal nitride nucleation matrix layer (18). In some embodiments, the thermal process (s) may include a rapid thermal annealing (RTA) method. The thermal process (s) may be carried out, for example, in an oven, a rapid thermal annealing chamber and / or a vapor deposition reactor. By way of example and without limitation, the thermal process (s) may comprise subjecting the metal nitride nucleation matrix layer (18) thus deposited at a temperature or temperatures above about 600 ° C., greater than about 800 ° C. C, or even above about 1000 ° C. The thermal process (es) for the treatment of the metal nitride nucleation matrix layer (18) thus deposited can be carried out under a controlled gaseous atmosphere. For example, the gaseous atmosphere may comprise ammonia, nitrogen, hydrogen and / or argon. The metal nitride nucleation matrix layer (18) may be optionally doped with one or more dopant elements using known doping methods. For example, gases containing a doping element can be introduced into the reaction chamber under controlled conditions. In another non-limiting example, the metal nitride nucleation matrix layer (18) may comprise titanium nitride (TiN) and may be prepared using plasma activated chemical vapor deposition systems and methods (PECVD ) described in US Patent No. 5,610,106, published March 11, 1997 in the name of Foster et al. For example, the substrate (10) can be loaded into a chemical vapor deposition chamber (separated from the reaction chamber (102) of the HVPE deposition system (100)). A radiofrequency (RF) generating electrode / shower head may be present in the CVD chamber, and reactive gases may be pumped into the chamber, through the electrode / shower head, and to the substrate (10). ). The reactive gases include titanium tetrachloride (TiCl4), ammonia (NH3) and a diluent. The diluent may include hydrogen, helium, argon and / or nitrogen. The substrate (10) can be spaced about 0.25 to 3 inches from the electrode / shower head, so that the active ions reach the substrate (10). Plasma is generated from the reactive gases using the RF generating electrode / shower head when the reactant gases pass into the electrode / shower head. The reactive ions of the plasma reach the substrate (10). The pressure in the CVD chamber can be maintained between about 0.5 Torr and about 20 Torr (e.g. about 5 Torr). The substrate (10) may be maintained at a temperature of about 400 ° C to about 500 ° C (eg, about 450 ° C) during the deposition process. The substrate (10) may be heated by heating a support structure on which the substrate (10) rests during the deposition process. In addition, the support structure on which the substrate (10) rests can rotate at about 100 rpm or more during the deposition process.

The concentration of the reactive gases in the CVD chamber can be controlled by the flow rate. In general, titanium tetrachloride can be introduced at a flow rate of about 1 sccm to about 40 sccm (for example at about 10 sccm). The TiC14 partial pressure must be low enough to form the TiN. If the TiCl4 partial pressure becomes too high, TiN may not form. When the total pressure is 5 Torr, the TiC14 partial pressure may be less than 0.02 Torr (e.g., about 0.01 Torr to about 0.001 Torr). At lower pressures (e.g., about 0.0001 Torr), the reaction rate may be significantly reduced and the recovery step may be unacceptable. When the total pressure increases above 5 Torr, the partial pressure of TiCl4 can be increased accordingly. In general, the molar ratio of NH3 to TiCl4 may be from about 2: 1 (NH3 to TiCl4) to about 100: 1 (NH3 to TiCl4) (eg, about 10: 1). According to these embodiments of the method of forming the metal nitride nucleation matrix layer (18), the metal nitride nucleation matrix layer (18) can be formed to have an average thickness T1 of about twenty-five nanometers (25 nm) or less, or even about ten nanometers (10 nm) or less, and the solid nitride III semiconductor material (22) can be deposited on and over the matrix layer of metal nitride nucleation (18) at an average thickness T2 of at least about two micrometers (2 μm), at least about five microns (5 μm), or even about ten micrometers (10 μm) or more. Samples were prepared by forming an AIIN nucleation matrix layer on a sapphire substrate using a PEPVD deposition method described in US Pat. No. 6,784,085 and then depositing solid GaN on the nucleation matrix layer. of AIN using a metal trichloride source gas in a HVPE deposition process as described above. In a first sample, the exposed main surface (19) (FIG. 2) of the AIN nucleation matrix layer is a 0.5 ° cut with respect to the AIN crystalline structure plane A, and the layer AIN nucleation matrix has an average thickness of about ten nanometers (10 nm). In a second sample, the exposed main surface (19) (Figure 2) of the AIN nucleation matrix layer is a 0.25 ° cut from the AIN crystal structure plane A, and the layer AIN nucleation matrix has an average thickness of about twenty-five nanometers (25 nm). The crystalline quality of the resulting bulk GaN material is measured using X-ray diffractometry (XRD), and it is observed that the crystalline quality is substantially equivalent to the reported crystalline grades of massive GaN formed using standard MOCVD techniques. In addition, the surface roughness of the exposed major surface (23) of the bulk GaN material is measured after deposition of the solid GaN material on the AlN matrix nucleation layers of the growth substrates. It is observed that the exposed main surface of the massive GaN material deposited on top of the first sample (0.5 ° slice with respect to the A-plane of a 10 nm AIN nucleation matrix layer) is smoother than the exposed main surface of solid GaN material deposited over the second sample (0.25 ° to A-plane cut of 25 nm AIN nucleation matrix layer). In particular, the first sample shows a root mean square (RMS) roughness of about 0.92 nm, while the second sample shows an RMS surface roughness of about 10.58 nm. Referring again to FIGS. 1 to 3, in other embodiments, the metal nitride nucleation matrix layer (18) (FIG. 2) is formed on the substrate (100) using a method MOCVD in situ in the same reaction chamber (102) (Figs. 4A and 4B) as used for the subsequent deposition of solid III nitride semiconductor material (22) thereon in a HVPE process. For example, the metal nitride nucleation matrix layer (18) (Figure 2) may comprise gallium nitride (GaN), aluminum nitride (AlN), aluminum gallium nitride (Al, Gal_XN) and / or titanium nitride (TiN). Therefore, in some embodiments, the deposition system (100) previously described with reference to Figs. 4A and 4B may be capable of, and configured to perform, a MOCVD process and a HVPE process. Referring to FIG. 4A, by way of example and without limitation, one of the gas sources (128A, 128B) may comprise an organometallic precursor source such as trimethylgallium (TMG), triethylgallium (TEG), trimethylaluminum (TMA), triethylaluminum (TEA), tetrakisdiethylaminotitanium (TDEAT) and / or tetrakis (dimethylamido) titanium (TDEAT). In these embodiments, it may not be necessary to use a thermalization gas injector (150A, 150C) in conjunction with the source of an organometallic precursor, although the organometallic precursor can be transported into the reaction chamber. using a carrier gas. For example, a carrier gas may be bubbled through a heated organometallic precursor reservoir to form an organometallic vapor, which may then flow into the reaction chamber (102). The organometallic vapor (102) can decompose in the reaction chamber (102) resulting in the deposition of the metal nitride nucleation matrix layer (18) on the substrates to be worked (106) (eg substrates (100) illustrated on Figure 1). MOCVD methods that can be used to form the metal nitride nucleation matrix layer (18) in situ in the same reaction chamber (102) as used for the deposition of solid III nitride semiconductor material in a HVPE process using a deposit system as described herein are described for example in US Patent Application Publication No. 2009/0184398 A1 published July 23, 2009 in the name of Choi. In some embodiments, the metal nitride nucleation matrix layer (18) may be formed to have an average thickness T1 of between about one half nanometer (0.5 nm) and about two micrometers (2 μm) and the material Solid III nitride semiconductor (22) may be formed to have an average thickness T2 of at least about two micrometers (2 μm), at least about five micrometers (5 μm), at least about seven micrometers (7 μm). } gym), at least about ten micrometers (10 μm), at least about twenty micrometers (20 μm) or at least about thirty micrometers (30 μm). In addition, an exposed major surface (23) of the solid nitride III semiconductor material (22) may have a mean square surface roughness of about two nanometers (2.0 nm) or less (e.g., about 0.112 nm) in some embodiments. Referring again to FIGS. 1 to 3, in other embodiments, the metal nitride nucleation matrix layer (18) (FIG. 2) is formed on the substrate (100) using an in situ HVPE process. in the same reaction chamber (102) (Figs. 4A and 4B) as used for depositing solid III nitride semiconductor material (22) thereon in a HVPE process as described herein. For example, the metal nitride nucleation matrix layer (18) (FIG. 2) may comprise aluminum nitride (A1N) and / or titanium nitride (TiN) and may be formed using the methods described in FIG. U.S. Patent No. 6,221,174 published April 24, 2001 in the name of Chen et al. and in international application WO 2010/101715 A1 published on September 10, 2010 in the name of Arena et al. Referring to FIG. 4A, the gas source (128A) can be used for the formation of the metal nitride nucleation matrix layer (18) (FIG. 2) in a HVPE process, and the source gas (128B). can be used for the formation of the solid III nitride semiconductor material (22) in a subsequent HVPE process. In a non-limiting example, the metal nitride nucleation matrix layer (18) (Figure 2) may comprise aluminum nitride (A1N), and the gas source (128A) may comprise a source of AlCl3 gas. The source of AlCl3 gas may comprise a liquid AlCl3 reservoir maintained at a temperature of at least 190 ° C (e.g., about 195 ° C) and at a pressure of about 2.5 atmospheres, and may optionally include physical means for improving the evaporation rate of the liquid AlCl 3. Such physical means may include, for example, a device configured to agitate liquid AlC13, a device configured to spray liquid AlC13, a device configured to circulate a carrier gas rapidly over liquid AlC13, a device configured to bubbling a carrier gas into the liquid AlCl3, a device, such as a piezoelectric device, configured to ultrasonically disperse the liquid AlC13, and the like. In a nonlimiting example, a carrier gas, such as He, N 2, H 2 or Ar, or a mixture thereof (for example a mixture of N 2 and H 2) can be bubbled into the liquid AlCl 3 while the Liquid AlCl 3 is maintained at a temperature of at least 195 ° C, so that the source gas may comprise one or more carrier gases. Optionally, AlC13 and a carrier gas comprising H2 can be fed to the thermalization injector (150A), the AlCl3 being able to decompose and form AlCl and HCl. HCl can react with the liquid aluminum contained in the thermalization injector (150A) to form more AIC1. The gases can then be directed into the reaction chamber (102) where the AlCi can react with the NH3 fed by the gas source (128C) to form AIN on and over the substrate. In another nonlimiting example, the metal nitride nucleation matrix layer (18) (FIG. 2) may comprise titanium nitride (TiN) and the gas source (128A) may comprise a source of TiC14 gas. The source of TiC14 gas may comprise a liquid TiC14 reservoir maintained at a temperature of at least 80 ° C, and may optionally include physical means for improving the evaporation rate of liquid TiC14 as described above.

In a nonlimiting example, a carrier gas, such as He, N2, H2 or Ar, or a mixture thereof (for example a mixture of N2 and H2) can be bubbled in the liquid TiC14 while the TiC14 The liquid is maintained at a temperature of at least 137 ° C, so that the source gas can comprise one or more carrier gases. The TiC14 vapor can then be directed into the reaction chamber (102) where the TiC14 can react with the NH3 fed by the gas source (128C) to form TiN on and over the substrate.

Further details regarding the process parameters for TiN formation in such a process are described in the aforementioned US Patent No. 6,221,174. After forming the metal nitride nucleation matrix layer (18) in the reaction chamber (102) using a HVPE method as described above, the solid nitride III semiconductor material (22) can be formed in the same reaction chamber (102) using a HVPE method as previously described with reference to Figures 3 and 8.

The solid nitride III semiconductor material (22) can be deposited on the growth substrate (20) after formation of the metal nitride nucleation matrix layer (18) without removing the growth substrate (20) from the reaction chamber (102) after formation of the metal nitride nucleation matrix layer (18) and prior to deposition of the solid nitride III semiconductor material (22) on the growth substrate (20). Embodiments of the methods of the present invention may allow the preparation of solid III nitride semiconductor materials without requiring the ex situ formation of a metal nitride nucleation matrix layer using a MOCVD method. Therefore, at least some embodiments of the methods of the invention may be more cost-effective in forming solid nitride III semiconductor materials than previously known methods.

Other examples of non-limiting embodiments of the invention are described below. Embodiment 1: A method of depositing a solid III nitride semiconductor material on a growth substrate, comprising: forming a metal nitride nucleation matrix layer on a substrate to form the growth substrate; and depositing the solid III nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) method, depositing the solid III nitride semiconductor material on the growth substrate comprising: a metal trichloride and / or metal tetrachloride to form a Group III metal chloride precursor gas, and reacting the Group III metal chloride precursor gas with a Group V precursor gas to form the solid semiconductor material of nitride III on the growth substrate.

Embodiment 2: The method of Embodiment 1, wherein forming the metal nitride nucleation matrix layer on the substrate comprises using an organometallic non-chemical vapor phase (MOCVD) method to form the metal nitride nucleation matrix layer. Embodiment 3: The method according to embodiment 1, wherein forming the metal nitride nucleation matrix layer on the substrate comprises using a plasma-enhanced chemical vapor deposition (PECVD) method to form the metal nitride nucleation matrix layer. Embodiment 4: The method according to Embodiment 3, wherein the use of the Plasma Activated Chemical Vapor Deposition (PECVD) method to form the metal nitride nucleation matrix layer comprises: a metal nitride material on the substrate; and subjecting the deposited metal nitride material to one or more thermal processes to improve the crystallinity of the deposited metal nitride material. Embodiment 5: A method according to embodiment 4, wherein subjecting the deposited metal nitride material to one or more thermal processes to improve the crystallinity of the deposited metal nitride material comprises subjecting the metal nitride material deposited to a rapid thermal annealing process.

Embodiment 6: A method according to embodiment 1, wherein forming the metal nitride nucleation matrix layer on the substrate comprises using a halide vapor phase epitaxy (HVPE) method for forming the metal nitride nucleation matrix layer. Embodiment 7: A method according to embodiment 6, wherein the use of a halide vapor phase epitaxy (HVPE) method to form the metal nitride nucleation matrix layer comprises: GaC13 decomposition , InCl3, AlCl3 and / or TiCl4 to form a group III trichloride, dichloride and / or monochloride precursor gas; and reacting the group III precursor gas with an NH 3 precursor gas to form the metal nitride nucleation matrix layer on the substrate. Embodiment 8: A method according to any one of embodiments 1 to 7, further comprising: forming the metal nitride nucleation matrix layer in a first chamber; and depositing the solid III nitride semiconductor material on the growth substrate in a different second chamber. Embodiment 9: A method according to any one of embodiments 1 to 7, further comprising: forming the metal nitride nucleation matrix layer in a chamber and depositing the solid nitride III semiconductor material on the growth substrate in the chamber in which the metal nitride nucleation matrix layer is formed. Embodiment 10: A method of depositing a solid III nitride semiconductor material on a growth substrate, comprising: forming a metal nitride nucleation matrix layer on a substrate using a chemical phase deposition method non-organometallic vapor (MOCVD) in a first chamber to form the growth substrate; and depositing the solid III nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process in a second chamber, depositing the solid III nitride semiconductor material on the growth substrate comprising : Circulation of NH3 and metal trichloride and / or metal tetrachloride to the second chamber. Embodiment 11: The method of Embodiment 10, further comprising selecting the substrate to include a sapphire substrate.

Embodiment 12: A method according to Embodiment 10 or Embodiment 11, further comprising selecting the metal nitride nucleation matrix layer to include aluminum nitride and / or titanium nitride .

Embodiment 13: A method according to any one of embodiments 10 to 12, wherein the formation of the metal nitride nucleation matrix layer on the substrate using the non-organometallic chemical vapor deposition method ( MOCVD) comprises forming the metal nitride nucleation matrix layer on the substrate using a plasma activated deposition method.

Embodiment 14: A method according to any one of embodiments 10 to 13, wherein the solid nitride III semiconductor material on the growth substrate comprises deposition of GaN, InN, AlN, InGaN, GaAlN, GaAlN and / or or InAlN on the growth substrate. Embodiment 15: A method according to any one of embodiments 10 to 14, wherein depositing solid III nitride semiconductor material on the growth substrate comprises depositing solid III nitride semiconductor material on the growth substrate. at a rate of at least about ten micrometers (10 pm) per hour. Embodiment 16: The method according to Embodiment 15, wherein depositing solid III nitride semiconductor material on the growth substrate at a rate of at least about ten microns (10 μm) per hour comprises deposition of the material. Solid III nitride semiconductor on the growth substrate at a rate of at least about twenty microns (20 μm) per hour. Embodiment 17: A method according to any of embodiments 10 to 16, wherein the solid III nitride semiconductor material on the growth substrate comprises depositing a layer of solid III nitride semiconductor material having a thickness of average of at least about two micrometers on the growth substrate. Embodiment 18: A method according to any one of embodiments 10 to 17, wherein the formation of the metal nitride nucleation matrix layer on the substrate further comprises forming the nitride nucleation matrix layer. metal having an average thickness of about fifty nanometers (50 nm) or less. Embodiment 19: A method according to embodiment 18, wherein forming the metal nitride nucleation matrix layer having an average thickness of about fifty nanometers (50 nm) or less comprises forming the matrix layer of metal nitride nucleation having an average thickness of about ten nanometers (10 nm) or less. Embodiment 20: Process according to any one of embodiments 10 to 19, wherein the circulation of NH3 and a metal trichloride and / or metal tetrachloride to the second chamber comprises the circulation of GaC13 , InC13, A1C13 and / or TiCl4 to the second chamber.

Embodiment 21: The process according to embodiment 20, wherein the circulation of NH 3 and a metal trichloride and / or metal tetrachloride to the second chamber further comprises the circulation of a metal trichloride. and / or metal tetrachloride to the second chamber at a rate of about 100 sccm or less. Embodiment 22: A method according to embodiment 21, wherein the circulation of a metal trichloride and / or metal tetrachloride to the second chamber at a flow rate of about 100 sccm or less comprises the circulation of metal trichloride and / or metal tetrachloride to the second chamber at a flow rate of about 80 sccm or less. Embodiment 23: A method according to any one of embodiments 20 to 22, further comprising selecting a metal trichloride and / or metal tetrachloride so as to comprise GaCl 3. Embodiment 24: Method according to any one of Embodiments 10 to 23, in the deposition of the solid nitride III semiconductor material provides an exposed main surface of the deposited solid nitride III semiconductor material having an average rms surface roughness. about ten nanometers (10 nm) or less.

Embodiment 25: A method according to any one of embodiments 10 to 24, in the deposition of the solid nitride III semiconductor material provides an exposed main surface of deposited solid nitride III semiconductor material having an average dislocation density of about 5 to 9 x 108 per square centimeter or less. Embodiment 26: A method of depositing a solid III nitride semiconductor material on a growth substrate, comprising: forming a metal nitride nucleation matrix layer on a substrate using a chemical phase deposition method organometallic vapor (MOCVD) in a chamber to form the growth substrate; and depositing solid III nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process in that same chamber; depositing solid III nitride semiconductor material on the growth substrate using the halide vapor phase epitaxy (HVPE) process which comprises circulating NH 3 and a metal trichloride and / or metal tetrachloride to that same room. Embodiment 27: The method of Embodiment 26, further comprising selecting the substrate to include a sapphire substrate. Embodiment 28: A method according to Embodiment 26 or Embodiment 27, further comprising selecting the metal nitride nucleation matrix layer so as to include gallium nitride, aluminum nitride, aluminum gallium nitride, hafnium nitride, chromium nitride, tungsten nitride and / or titanium nitride. Embodiment 29: A method according to any one of embodiments 26 to 28, wherein the solid nitride III semiconductor material on the growth substrate comprises deposition of GaN, InN, AlN, InGaN, GaAlN, GaAlN and / or or InAlN on the growth substrate.

Embodiment 30: A method according to any one of embodiments 26 to 29, wherein depositing solid III nitride semiconductor material on the growth substrate comprises depositing solid III nitride semiconductor material on the growth substrate. at a rate of at least about ten micrometers (10 pm) per hour. Embodiment 31: The method according to Embodiment 30, wherein depositing solid III nitride semiconductor material on the growth substrate at a rate of at least about ten microns (10 μm) per hour comprises deposition of the material. Solid III nitride semiconductor on the growth substrate at a rate of at least about twenty microns (20 μm) per hour.

Embodiment 32: A method according to any one of embodiments 26 to 31, wherein depositing solid III nitride semiconductor material on the growth substrate comprises depositing a solid nitride III semiconductor layer having a average thickness of at least about two micrometers (2} gym) on the growth substrate. Embodiment 33: A method according to any one of embodiments 26 to 32, wherein forming the metal nitride nucleation matrix layer on the substrate further comprises forming the nitride nucleation matrix layer. metal having an average thickness of from about half a nanometer (0.5 nm) to about two micrometers (2.0 μm). Embodiment 34: Process according to any one of Embodiments 26 to 33, wherein the circulation of NH 3 and a metal trichloride and / or metal tetrachloride to this same chamber comprises the circulation of GaCl 3 , InCl3, AlCl3 and / or TiCl4 to this same chamber. Embodiment 35: Process according to embodiment 34, wherein the circulation of GaC13, InCl3, AlCl3 and / or TiCl4 to this same chamber further comprises the circulation of GaC13, InCl3, AlCl3 and / or TiCl4 to this same chamber at a flow rate of about 100 sccm or less. Embodiment 36: The method according to embodiment 35, wherein the circulation of GaC13, InC13, AlC13 and / or TiC14 to that same chamber at a flow rate of about 100 sccm or less comprises the circulation of GaC13, InC13r A1C13 and or TiC14 to the same chamber at a flow rate of about 80 sccm or less.

Embodiment 37: A method according to any one of embodiments 26 to 36, further comprising selecting a metal trichloride and / or metal tetrachloride so as to comprise GaC13.

Embodiment 38 method according to any one of the embodiments 26 to 37, in the deposition of the solid nitride III semiconductor material gives an exposed main surface of deposited solid nitride III semiconductor material having a mean square surface roughness of about two nanometers (2.0 nm) or less. Embodiment 39: A method according to any one of Embodiments 26 to 38, in the deposition of the solid nitride III semiconductor material provides an exposed major surface of deposited solid nitride III semiconductor material having an average dislocation density of about 5 x 108 per square centimeter or less. Embodiment 40: A method of depositing a solid III nitride semiconductor material on a growth substrate, comprising: forming a metal nitride nucleation matrix layer on a substrate using a vapor deposition method halide (HVPE) in a chamber to form the growth substrate; and depositing the solid III nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) process in the same chamber, depositing the solid III nitride semiconductor material on the growth substrate using the halide vapor phase epitaxy (HVPE) process which comprises circulating NH 3 and a metal trichloride and / or metal tetrachloride to the same chamber.

Embodiment 41: The method of Embodiment 40, further comprising selecting the substrate to include a sapphire substrate. Embodiment 42: A method according to Embodiment 40 or Embodiment 41, further comprising selecting the metal nitride nucleation matrix layer to include aluminum nitride and / or titanium nitride . Embodiment 43: A method according to any one of embodiments 40 to 42, wherein the deposition of the solid nitride III semiconductor material on the growth substrate comprises deposition of GaN, InN, AlN, InGaN, GaAlN, GaAlN and / or InAlN on the growth substrate.

Embodiment 44: A method according to any one of Embodiments 40 to 43, wherein depositing solid III nitride semiconductor material on the growth substrate comprises depositing solid III nitride semiconductor material on the growth substrate. at a rate of at least about ten micrometers (10 pm) per hour. Embodiment 45: The method according to Embodiment 44, wherein depositing solid III nitride semiconductor material on the growth substrate at a rate of at least about 10 micrometers (10Hg) per hour comprises depositing the solid III nitride semiconductor material on the growth substrate at a rate of at least about twenty micrometers (20} gpm) per hour.

Embodiment 46: A method according to any of embodiments 40 to 45, wherein the deposition of the solid nitride III semiconductor material on the growth substrate comprises depositing a layer of solid semiconductor material of nitride III having an average thickness of at least about two micrometers (2 μm) on the growth substrate. Embodiment 47: A method according to any one of embodiments 40 to 46, wherein the formation of the metal nitride nucleation matrix layer on the substrate further comprises forming the nitride nucleation matrix layer. metal having an average thickness of about fifty nanometers (50 nm) or less. Embodiment 48: Process according to embodiment 47, wherein the circulation of NH 3 and a metal trichloride and / or metal tetrachloride to this same chamber further comprises the circulation of a metal trichloride and / or a metal tetrachloride to the same chamber at a flow rate of about 100 sccm or less. Embodiment 49: The method according to embodiment 48, wherein the circulation of a metal trichloride and / or metal tetrachloride to that same chamber at a flow rate of about 100 sccm or less comprises the circulation of metal trichloride and / or metal tetrachloride to the same chamber at a flow rate of about 80 sccm or less.

Embodiment 50: A method according to any one of embodiments 40 to 49, further comprising selecting a metal trichloride and / or metal tetrachloride to comprise GaC13, InCl3r AlC13 and / or or TiC14.

Embodiment 51: A method according to any of embodiments 40 to 50, wherein the deposition of the solid nitride III semiconductor material provides an exposed major surface of deposited solid nitride III semiconductor material having an average RMS surface roughness about ten nanometers (10.0 nm) or less. Embodiment 52: A method according to any one of embodiments 40 to 51, wherein the deposition of the solid nitride III semiconductor material provides an exposed major surface of the deposited solid nitride III semiconductor material having an average dislocation density d about 5 x 108 per square centimeter or less.

Embodiment 53: A method according to any one of embodiments 40 to 52, wherein deposition of the solid nitride III semiconductor material on the growth substrate using the halide vapor phase epitaxy (HVPE) method in the same chamber comprises depositing the solid III nitride semiconductor material on the growth substrate without removing the growth substrate from the same after formation of the metal nitride nucleation matrix layer on the substrate to form the substrate growth and before the deposition of the solid III nitride semiconductor material on the growth substrate. Embodiment 54: A structure comprising a solid nitride III semiconductor material, the structure being prepared according to a method according to any one of Embodiments 1 to 53.

Claims (10)

REVENDICATIONS1. A method of depositing a solid III nitride semiconductor material on a growth substrate, comprising: forming a metal nitride nucleation matrix layer on a substrate to form the growth substrate; and depositing the solid III nitride semiconductor material on the growth substrate using a halide vapor phase epitaxy (HVPE) method, depositing the solid III nitride semiconductor material on the growth substrate comprising: decomposing a metal trichloride and / or a metal tetrachloride to form a Group III metal chloride precursor gas, and reacting the Group III metal chloride precursor gas with a Group V precursor gas to Forming the solid III nitride semiconductor material on the growth substrate. The method of claim 1, wherein forming the metal nitride nucleation matrix layer on the substrate comprises using a non-organometallic chemical vapor deposition (MOCVD) process to form the layer. metal nitride nucleation matrix. 30 The method of claim 1, wherein forming the metal nitride nucleation matrix layer on the substrate comprises using a plasma-enhanced chemical vapor deposition (PECVD) process to form the matrix layer. metal nitride nucleation. The method of claim 3, wherein using a plasma-enhanced chemical vapor deposition (PECVD) method to form the metal nitride nucleation matrix layer comprises: depositing a nitride material metal on the substrate; and subjecting the deposited metal nitride material to one or more thermal processes to improve the crystallinity of the deposited metal nitride material. The method of claim 4, wherein subjecting the deposited metal nitride material to one or more thermal processes to improve the crystallinity of the deposited metal nitride material comprises subjecting the deposited metal nitride material to a method of rapid thermal annealing. The method of claim 1, wherein forming the metal nitride nucleation matrix layer on the substrate comprises using a halide vapor phase epitaxy (HVPE) process to form the matrix layer of nucleation of metal nitride. The method of claim 6, wherein using a halide vapor phase epitaxy (HVPE) process to form the metal nitride nucleation matrix layer comprises: decomposing GaC13, InC13, AlC13 and and / or TiCl4 to form a group III trichloride, dichloride and / or monochloride precursor gas, and reacting the group III precursor gas with an NH 3 precursor gas to form the metal nitride nucleation matrix layer on the substrate. The method of any one of claims 1 to 7, further comprising: forming the metal nitride nucleation matrix layer in a first chamber; and depositing the solid III nitride semiconductor material on the growth substrate in a different second chamber. 15 The method of any one of claims 1 to 7, further comprising: forming the metal nitride nucleation matrix layer in a chamber; and depositing the solid nitride III semiconductor material on the growth substrate in the chamber in which the metal nitride nucleation matrix layer is formed. 10. A structure comprising a solid nitride III semiconductor material, the structure being prepared according to a method according to any one of claims 1 to 9.