High quality ammonothermal group III metal nitride crystals having a pattern of locally-approximately-linear arrays of threading dislocations, methods of manufacturing high quality ammonothermal group III metal nitride crystals, and methods of using such crystals are disclosed. The crystals are useful for seed bulk crystal growth and as substrates for light emitting diodes, laser diodes, transistors, photodetectors, solar cells, and for photoelectrochemical water splitting for hydrogen generation devices.

Embodiments of the present disclosure include techniques related to techniques for processing materials for manufacture of group-III metal nitride and gallium based substrates. More specifically, embodiments of the disclosure include techniques for growing large area substrates using a combination of processing techniques. Merely by way of example, the disclosure can be applied to growing crystals of GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, and others for manufacture of bulk or patterned substrates. Such bulk or patterned substrates can be used for a variety of applications including optoelectronic and electronic devices, lasers, light emitting diodes, solar cells, photo electrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, and transistors, and others.

Embodiments of the present disclosure include techniques related to techniques for processing materials for manufacture of group-III metal nitride and gallium based substrates. More specifically, embodiments of the disclosure include techniques for growing large area substrates using a combination of processing techniques. Merely by way of example, the disclosure can be applied to growing crystals of GaN, AlN, InN, InGaN, AlGaN, and AlInGaN, and others for manufacture of bulk or patterned substrates. Such bulk or patterned substrates can be used for a variety of applications including optoelectronic and electronic devices, lasers, light emitting diodes, solar cells, photo electrochemical water splitting and hydrogen generation, photodetectors, integrated circuits, and transistors, and others.

An object is to provide a nonpolar or semipolar GaN substrate having improved size and crystal quality. A self-standing GaN substrate has an angle between the normal of the principal surface and an m-axis of 0 degrees or more and 20 degrees or less, wherein: the size of the projected image in a c-axis direction when the principal surface is vertically projected on an M-plane is 10 mm or more; and when an a-axis length is measured on an intersection line between the principal surface and an A-plane, a low distortion section with a section length of 6 mm or more and with an a-axis length variation within the section of 10.0×10.sup.−5 Å or less is observed.

A process of preparing polycrystalline group III nitride chunks comprising the steps of (a) placing a group III metal inside a source chamber; (b) flowing a halogen-containing gas over the group III metal to form a group III metal halide; (c) contacting the group III metal halide with a nitrogen-containing gas in a deposition chamber containing a foil, the foil comprising at least one of Mo, W, Ta, Pd, Pt, Ir, or Re; (d) forming a polycrystalline group III nitride layer on the foil within the deposition chamber; (e) removing the polycrystalline group III nitride layer from the foil; and (f) comminuting the polycrystalline group III nitride layer to form the polycrystalline group III nitride chunks, wherein the removing and the comminuting are performed in any order or simultaneously.

An object is to provide a nonpolar or semipolar GaN substrate having improved size and crystal quality. A self-standing GaN substrate has an angle between the normal of the principal surface and an m-axis of 0 degrees or more and 20 degrees or less, wherein: the size of the projected image in a c-axis direction when the principal surface is vertically projected on an M-plane is 10 mm or more; and when an a-axis length is measured on an intersection line between the principal surface and an A-plane, a low distortion section with a section length of 6 mm or more and with an a-axis length variation within the section of 10.0×10 .sup.−5 Å or less is observed.

A method for growing a crystalline composition, the first crystalline composition may include gallium and nitrogen. The crystalline composition may have an infrared absorption peak at about 3175 cm.sup.−1, with an absorbance per unit thickness of greater than about 0.01 cm.sup.−1. In one embodiment, the composition ay have an amount of oxygen present in a concentration of less than about 3×10.sup.18 per cubic centimeter, and may be free of two-dimensional planar boundary defects in a determined volume of the first crystalline composition.

A new GaN single crystal is provided. A GaN single crystal according to the present embodiment comprises a gallium polar surface which is a main surface on one side and a nitrogen polar surface which is a main surface on the opposite side, wherein on the gallium polar surface is found at least one square area, an outer periphery of which is constituted by four sides each with a length of 2 mm or more, and, when the at least one square are is divided into a plurality of sub-areas each of which is a square of 100 μm×100 μm, pit-free areas account for 80% or more of the sub-areas.

Various articles and devices can be manufactured to take advantage of a what is believed to be a novel thermodynamic cycle in which spontaneity is due to an intrinsic entropy equilibration. The novel thermodynamic cycle exploits the quantum phase transition between quantum thermalization and quantum localization. Preferred devices include a phonovoltaic cell, a rectifier and a conductor for use in an integrated circuit.

A conductive C-plane GaN substrate has a resistivity of 210.sup.2 .Math.cm or less or an n-type carrier concentration of 110.sup.18 cm.sup.3 or more at room temperature. At least one virtual line segment with a length of 40 mm can be drawn at least on one main surface of the substrate. The line segment satisfies at least one of the following conditions (A1) and (B1): (A1) when an XRC of (004) reflection is measured at 1 mm intervals on the line segment, a maximum value of XRC-FWHMs across all measurement points is less than 30 arcsec; and (B1) when an XRC of the (004) reflection is measured at 1 mm intervals on the line segment, a difference between maximum and minimum values of XRC peak angles across all the measurement points is less than 0.2.