P-type conductive ultrawide bandgap semiconductor, method for manufacturing the same, and method for using the same

Abstract

This specification discloses an ultrawide bandgap semiconductor having p-type conductivity, a method for manufacturing the same, and a method for using the same. For example, this specification discloses a composition comprising an ultrawide bandgap oxide semiconductor having p-type conductivity, wherein Li x Ga y O z The present invention discloses compositions containing the following elements, wherein the atomic ratio of Li to Ga (e.g., x:y) is 0.0001 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.0001 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0. In some examples, the atomic ratio of Li to Ga (e.g., x:y) is 0.01 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.00625 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims priority to U.S. Provisional Application No. 63 / 531,083, filed 7 August 2023, the entire contents of which are incorporated herein by reference.

[0002] Description of government aid This invention was made with government support under grant / contract number FA9950-23-1-0142 from the United States Air Force Office of Scientific Research. The United States Government reserves certain rights in this invention. [Background technology]

[0003] There is a need for ultrawide bandgap semiconductors with improved p-type conductivity. The compositions, methods, and devices disclosed herein address these and other requirements. [Overview of the Initiative]

[0004] In accordance with the purpose of the compositions, methods, and devices disclosed, embodied, and broadly described herein, the subject matter of this disclosure is p-type conductive ultrawide bandgap semiconductors, methods for manufacturing the same, and methods for using the same.

[0005] For example, this specification provides for a composition comprising an ultrawide bandgap oxide semiconductor having p-type conductivity, Li x Ga y O z Includes, A composition is disclosed in which the atomic ratio of Li to Ga (e.g., x:y) is 0.0001 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.0001 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

[0006] In some examples, the atomic ratio of Li to Ga (e.g., x:y) is 0.01 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.00625 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

[0007] Also, in this specification, a composition comprising a p-type conductive ultra-wide bandgap oxide semiconductor, Li x Ga y O z containing, discloses a composition in which the atomic ratio of Li to Ga (e.g., x:y) is 0.01 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.00625 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

[0008] In some examples, the atomic ratio of Li, Ga, and O (e.g., x:y:z) is 1:5:8.

[0009] In some examples, the composition contains β-Li x Ga y O z including.

[0010] In some examples, the composition contains LiGa5O8.

[0011] In some examples, the composition contains Li-rich LiGa5O8.

[0012] In some examples, the composition contains Li-poor LiGa5O8.

[0013] In some examples, the composition contains O-poor LiGa5O8.

[0014] In some examples, the composition contains O-rich LiGa5O8.

[0015] In some examples, the composition further contains a dopant such as a p-type dopant.

[0016] In some examples, the composition contains virtually no dopants.

[0017] In some examples, the composition has a carrier concentration (e.g., hole concentration) of 1 × 10¹⁶ per cubic centimeter. 14 ~1 × 10 21 cm -3 In some examples, the composition has a carrier concentration (e.g., hole concentration) of 1 × 10⁻⁶. 14 ~1 5×10 19 cm -3 For example, 1 × 10 17 ~5×10 18 cm -3 That is the case.

[0018] In some examples, the composition has a mobility of 0.01 to 100 cm, such as hole mobility. 2 / Vs. In some examples, the composition has mobilities such as hole mobility of 0.1 to 10 cm. 2 / Vs, for example, 0.35~2cm 2 / Vs is the case.

[0019] In some examples, the composition exhibits high P-type conductivity.

[0020] Furthermore, this specification also discloses devices comprising any of the compositions disclosed herein. In some examples, the device further comprises a substrate, and the composition is deposited on the substrate as a layer.

[0021] In some examples, the substrates include LiGa5O8, freestanding GaN, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, AlN, AlGaN, diamond, or combinations thereof.

[0022] In some examples, the layers have a surface roughness RMS value of 20 nm or less. In some examples, the layers have a surface roughness RMS value of 15 nm or less, 10 nm or less, 5 nm or less, 2.5 nm or less, 1.75 nm or less, or 1.5 nm or less.

[0023] In some examples, the layers have an average thickness of 10–2000 nm. In other examples, the layers have an average thickness of 25 nm–1000 nm, for example, 50–100 nm.

[0024] In some examples, the device includes vertical PN diodes, MOSFET devices such as power MOSFETs or trench MOSFETs, MESFET devices, MODFET devices, current-aperture vertical electronic transistor (CAVET) devices, or combinations thereof. In some examples, the device includes vertical PN diodes, MOSFET devices such as power MOSFETs or trench MOSFETs, current-aperture vertical electronic transistor (CAVET) devices, or combinations thereof. In some examples, the device includes vertical power devices. In some examples, the device includes optical devices, electronic devices, optoelectronic devices, or combinations thereof. In some examples, the device includes diodes. In some examples, the device includes n-Ga2O3 / p-Li x Ga y O z This includes heterojunctions (e.g., n-Ga2O3 / p-LiGa5O8). In some examples, the device is n-GaN / p-Li x Ga y O z n-AlN / p-Li x Ga y O z n-diamond / p-Li x Ga y O z , or a combination thereof.

[0025] Furthermore, this specification also discloses methods for using any of the compositions disclosed herein.

[0026] Furthermore, this specification also discloses a method for producing any of the compositions disclosed herein, comprising contacting a gallium-containing precursor and a lithium-containing precursor at a predetermined temperature in the presence of oxygen or an oxygen-containing precursor to react the gallium-containing precursor, the lithium-containing precursor, and oxygen or an oxygen-containing precursor to form a composition.

[0027] In some cases, the gallium-containing precursor includes an organometallic Ga-containing precursor. In some cases, the gallium-containing precursor includes Ga(acac)3([CH3COCH=C(O-)CH3]3Ga).

[0028] In some cases, the lithium-containing precursor includes an organometallic Li-containing precursor. In some cases, the lithium-containing precursor includes lithium acetoacetate (C4H5LiO3).

[0029] In some examples, the gallium-containing precursor and / or lithium-containing precursor independently contain fluids.

[0030] In some cases, gallium-containing precursors and / or lithium-containing precursors are supplied independently with a carrier gas. In some cases, the carrier gas includes argon, helium, N2, or a combination thereof. In some cases, the carrier gas includes argon.

[0031] In some examples, the temperature is between 300°C and 1200°C. In some examples, the temperature is between 800°C and 1000°C, for example, 800°C to 950°C, or 850°C to 950°C. In some examples, the temperature is 900°C.

[0032] In some examples, this method includes metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), hydride vapor deposition (HVPE), pulsed laser deposition (PLD), low-pressure chemical vapor deposition (LPCVD), mist CVD, or a combination thereof. In some examples, this method includes mist CVD.

[0033] In some examples, the method involves depositing a composition onto a substrate. In some examples, the substrate includes LiGa5O8, freestanding GaN, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, AlN, AlGaN, diamond, or a combination thereof. In some examples, the substrate includes LiGa5O8, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, or a combination thereof.

[0034] Further advantages of the disclosed compositions, devices, and methods will be partially described below and partially apparent from the specification. The advantages of the disclosed compositions, devices, and methods are realized and achieved by the elements and combinations specifically pointed out in the appended claims. It should be understood that both the above summary and the following detailed description are merely illustrative and explanatory and do not limit the claimed disclosed devices and methods.

[0035] Details of one or more embodiments of the present invention are described in the accompanying drawings and the following description. Other characteristics, purposes, and advantages of the present invention will become apparent from the description and drawings, as well as from the claims.

[0036] The accompanying drawings, which are incorporated herein by reference and constitute part of this specification, illustrate several aspects of this disclosure and, together with the description, serve to illustrate the principles of this disclosure. [Brief explanation of the drawing]

[0037] [Figure 1A] This is a planar SEM image of a LiGa5O8 sample grown on GaN on a sapphire template at a growth temperature (TG) of 800°C. [Figure 1B] This is a planar SEM image of a LiGa5O8 sample grown on GaN on a sapphire template at a growth temperature (TG) of 850°C. [Figure 1C] This is a planar SEM image of a LiGa5O8 sample grown on GaN on a sapphire template at a growth temperature (TG) of 900°C. [Figure 1D] This is a planar SEM image of a LiGa5O8 sample grown on GaN on a sapphire template at a growth temperature (TG) of 950°C. [Figure 2A] This is a 5 μm × 5 μm AFM image of a LiGa5O8 sample grown on GaN on a sapphire template at a growth temperature (TG) of 800°C. [Figure 2B] This is a 5 μm × 5 μm AFM image of a LiGa5O8 sample grown on GaN on a sapphire template at a growth temperature (TG) of 850°C. [Figure 2C] This is a 5 μm × 5 μm AFM image of a LiGa5O8 sample grown on GaN on a sapphire template at a growth temperature (TG) of 900°C. [Figure 2D] This is a 5 μm × 5 μm AFM image of a LiGa5O8 sample grown on GaN on a sapphire template at a growth temperature (TG) of 950°C. [Figure 3A] This is a cross-sectional TEM image of a LiGa5O8 sample grown on GaN on a sapphire template at 900°C. The interface is indicated by a red dashed line. [Figure 3B] This is an atomic-resolution HAADF STEM image of a LiGa5O8 sample grown on GaN on a sapphire template at 900°C. The interface is indicated by a red dashed line. [Figure 4] This is the result of an XRD 2θ-ω scan of a LiGa5O8 sample grown on a GaN-on-sapphire substrate at a temperature of 900°C. The peak corresponding to LiGa5O8 is indicated by a red arrow. [Figure 5A] This is a planar SEM image of a LiGa5O8 sample grown on an on-axis c-sapphire substrate at 850°C. [Figure 5B] This is a planar SEM image of a LiGa5O8 sample grown on a 6° off-cut c-sapphire substrate at 850°C. [Figure 5C]This is a 5 μm × 5 μm AFM image of a LiGa5O8 sample grown on an on-axis c-sapphire substrate at 850°C. [Figure 5D] This is a 5 μm × 5 μm AFM image of a LiGa5O8 sample grown on a 6° off-cut c-sapphire substrate at 850°C. [Figure 6A] This is a cross-sectional TEM image of a LiGa5O8 sample grown on an on-axis c-sapphire substrate at 850°C. The interface is indicated by a red dashed line. [Figure 6B] This is an atomic-resolution HAADF STEM image of a LiGa5O8 sample grown on an on-axis c-sapphire substrate at 850°C. The interface is indicated by a red dashed line. [Figure 7A] This is an XPS spectrum near the Li 1s peak obtained from a Li-rich LiGa5O8 film grown on GaN on a sapphire template at 900°C. [Figure 7B] This is an XPS spectrum near the Ga 3s peak obtained from a Li-rich LiGa5O8 film grown on GaN on a sapphire template at 900°C. [Figure 7C] This is an XPS spectrum near the O 1s peak obtained from a Li-rich LiGa5O8 film grown on GaN on a sapphire template at 900°C. [Figure 7D] This is an XPS spectrum near the Li 1s peak obtained from a Li-poor LiGa5O8 film grown on GaN on a sapphire template at 900°C. [Figure 7E] This is an XPS spectrum near the Ga 3s peak obtained from a Li-poor LiGa5O8 film grown on GaN on a sapphire template at 900°C. [Figure 7F] This is an XPS spectrum near the O 1s peak obtained from a Li-poor LiGa5O8 film grown on GaN on a sapphire template at 900°C. [Figure 8A] This is an example of a vertical PN diode design structure based on an n-Ga2O3 drift layer, an n+-Ga2O3 substrate, and a p-LiGa5O8 layer. [Figure 8B] This is an example of a design structure for a LiGa5O8-Ga2O3 MOSFET. [Figure 8C] This is an example of a design structure for a LiGa5O8-Ga2O3 trench type MOSFET. [Figure 8D] This is an example of a design structure for a LiGa5O8-Ga2O3 current-aperture vertical electron transistor (CAVET). [Figure 9] (010) This is a cross-sectional STEM image showing a LiGa5O8 sample grown on a Fe-doped β-Ga2O3 substrate. A is a low-magnification image. B is a high-magnification image. The interface is shown by a gray dashed line, and the crystal zone axis is shown in the figure. The inset in C shows

[0110] LiGa5O8 superimposed on the atomic model in D, demonstrating the structural agreement of

[0110] LiGa5O8. [Figure 10] (010) This is the result of an XRD 2θ-ω scan of a LiGa5O8 sample grown on an Fe-doped β-Ga2O3 substrate. The LiGa5O8 peak is indicated by the black arrow. [Figure 11A] This is the XPS spectrum of the Li 1s peak obtained from a LiGa5O8 sample grown on a (010)Fe-doped β-Ga2O3 substrate. [Figure 11B] This is the XPS spectrum of the Ga 3s peak obtained from a LiGa5O8 sample grown on a (010)Fe-doped β-Ga2O3 substrate. [Figure 11C] This is the XPS spectrum of the O1s peak obtained from a LiGa5O8 sample grown on a (010)Fe-doped β-Ga2O3 substrate. The black circles indicate the original data points. The solid curves show the peaks fitted assuming a Voigt shape and Shirley background. The background is shown by the gray dashed line. [Figure 12] This is the bandgap energy of a LiGa5O8 sample grown on a (010)Fe-doped β-Ga2O3 substrate, determined by the energy difference between the O 1s core level peak and the rise of the energy loss spectrum. An enlarged view of the spectrum in the enclosed region is shown in the inset. [Figure 13]These are the spectra of the Li 1s and Ga 3s core levels and the valence band. A is from a 50 nm thick LiGa5O8 sample grown on a (010)Fe-doped β-Ga2O3 substrate. B is from the (010)Fe-doped β-Ga2O3 substrate. C is from the LiGa5O8 / β-Ga2O3 interface sample. The original data is shown by black circles. The solid curves are peaks fitted assuming a Voigt shape and Shirley background. The background is shown by a gray dashed line. [Figure 14] This is the experimentally measured valence band alignment at the LiGa5O8 / β-Ga2O3 heterointerface. [Figure 15] A is a planar SEM image of a LiGa5O8 film grown on a (010)Fe-doped β-Ga2O3 substrate. B is a 2μm × 2μm AFM image. [Figure 16] A shows the results of an XRD 2θ-ω scan of a LiGa5O8 sample grown to a thickness of approximately 400 nm on a (010)Fe-doped β-Ga2O3 substrate. The peaks corresponding to β-Ga2O3 and LiGa5O8 are indicated by black arrows. B is the (44-0) peak of the rocking curve scan. [Modes for carrying out the invention]

[0038] The compositions, methods, and devices described herein may be more readily understood by referring to the following detailed descriptions of specific aspects of the disclosed subject matter and the examples contained herein.

[0039] Before disclosing and describing the compositions, methods, and devices of the present invention, it should be understood that the embodiments described below are not limited to specific synthesis methods or specific reagents, and therefore may vary considerably. It should also be understood that the terms used herein are intended solely to describe specific embodiments and are not intended to limit them.

[0040] Furthermore, various publications are referenced throughout this specification. The disclosures of those publications as a whole are incorporated herein by reference to more completely explain the current art to which the subject matter of this disclosure pertains. The disclosed references are also incorporated herein by reference individually and specifically with respect to the material contained therein, as considered in the sentences on which the references are based.

[0041] In this specification and the subsequent claims, several terms are referenced and defined as follows:

[0042] Throughout this description and the claims, the word “comprise” and other forms thereof, such as “comprising” and “comprises,” mean “including but not limited to,” and are not intended to exclude, for example, other appendages, components, integers, or steps.

[0043] As used herein and in the appended claims, the singular forms "a," "an," and "the" include multiple references unless the context clearly indicates otherwise. Thus, for example, a reference to "composition" includes mixtures of two or more such compositions; a reference to "agent" includes mixtures of two or more such agents; a reference to "component" includes mixtures of two or more such components, and so on.

[0044] "Optional" or "optional" means that the event or situation described thereafter may or may not occur, and that the description includes both instances in which the event or situation occurs and instances in which it does not occur.

[0045] A range may be expressed herein as "approximately" from one particular value and / or "approximately" to another particular value. "Approximately" means within 5% of a value, for example, within 4, 3, 2, or 1% of the value. Where such a range is expressed, another aspect includes from one particular value and / or to another particular value. Similarly, where a value is expressed as an approximation using the preceding "approximately," it will be understood that the particular value forms another aspect. It will be further understood that each endpoint of a range is significant in relation to and independently of the other endpoints.

[0046] In this specification, values ​​may be expressed as "mean" values. "Mean" generally refers to the statistical mean.

[0047] "Effectively" means within 5%, for example, within 4%, 3%, 2%, or 1%.

[0048] "Exemplary" means "an example of," and is not intended to indicate a preferred or ideal embodiment. "Such as" is used for explanatory purposes, not in a restrictive sense.

[0049] Throughout this specification, it should be understood that the identifiers “First” and “Second” are used simply to facilitate the distinction between the various components and steps of the disclosed subject matter. The identifiers “First” and “Second” are not intended to indicate any particular order, quantity, priority, or importance of the components or steps to which these terms are applied.

[0050] In this specification and the concluding claims, any reference to parts by weight of a particular element or component in a composition indicates a weight relationship between the element or component in the composition or article in which the parts by weight are expressed and any other element or component. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight of component Y, X and Y are present in a weight ratio of 2:5, and in such a ratio whether or not further components are present in the compound.

[0051] The weight percentage (W%) of a component is based on the total weight of the preparation or composition containing that component, unless otherwise specified.

[0052] As used herein, the term “or any combination thereof” refers to all permutations and combinations of the listed items preceding that term. For example, “A, B, C, or any combination thereof” is intended to include A, B, C, AB, AC, BC, or ABC, and, where the order is important in a particular context, at least one of BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this embodiment, combinations containing repetitions of one or more items or terms, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, etc. A person skilled in the art will understand that, typically, there is no limit to the number of items or terms in any combination unless otherwise evident from the context.

[0053] This specification discloses an ultrawide bandgap semiconductor having p-type conductivity, a method for manufacturing the same, and a method for using the same.

[0054] For example, this specification provides a composition comprising an ultrawide bandgap oxide semiconductor having p-type conductivity, wherein Li x Ga y O z The present invention discloses a composition containing the following, wherein the atomic ratio of Li to Ga (e.g., x:y) is 0.0001 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.0001 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

[0055] In some examples, the composition, β-Li x Ga y O z Includes.

[0056] For example, the atomic ratio of Li to Ga (e.g., x:y) is 0.0001 or greater (e.g., 0.0005 or greater, 0.001 or greater, 0.005 or greater, 0.01 or greater, 0.02 or greater, 0.03 or greater, 0.04 or greater, 0.05 or greater, 0.06 or greater, 0.07 or greater, 0.08 or greater, 0.09 or greater, 0.1 or greater, 0.15 or greater, 0.2 or greater, 0.25 or greater, 0.3 or greater, 0.35 or greater, 0.45 or greater, 0.5 or greater, 0.55 or greater, 0.6 or greater, 0.65 or greater, 0.7 or greater, 0.75 or greater, 0.8 or greater, 0.85 or greater, or 0.9 or greater). In some examples, the atomic ratio of Li to Ga (e.g., x:y) is less than or equal to 1.0 (e.g., less than or equal to 0.95, less than or equal to 0.9, less than or equal to 0.85, less than or equal to 0.8, less than or equal to 0.75, less than or equal to 0.7, less than or equal to 0.65, less than or equal to 0.6, less than or equal to 0.55, less than or equal to 0.5, less than or equal to 0.45, less than or equal to 0.4, less than or equal to 0.35, less than or equal to 0.3, less than or equal to 0.2, less than or equal to 0.15, or less than or equal to 0.1, less than or equal to 0.09, less than or equal to 0.08, less than or equal to 0.07, less than or equal to 0.06, less than or equal to 0.05, less than or equal to 0.04, less than or equal to 0.03, less than or equal to 0.02, less than or equal to 0.01, less than or equal to 0.005, or less than or equal to 0.001). The atomic ratio of Li to Ga (e.g., x:y) can be in the range from any of the minimum values ​​above to any of the maximum values ​​above. For example, the atomic ratio of Li to Ga (e.g., x:y) is 0.0001~1.0 (e.g., 0.0001~0.5, 0.5~1, 0.0001~0.2, 0.2~0.4, 0.4~0.6, 0.6~0.8, 0.8~1.0, 0.0001~0.8, 0.0001~0.6, 0.0001~0.4, 0.0001~0.1, 0.0005~1.0, 0.001~1.0, 0. The atomic ratios can be 0.05-1.0, 0.01-1.0, 0.01-0.5, 0.5-1, 0.01-0.2, 0.01-0.8, 0.01-0.6, 0.01-0.4, 0.01-0.1, 0.05-1.0, 0.1-1.0, 0.4-1.0, 0.6-1.0, 0.0005-0.95, 0.1-0.9, 0.2-0.8, 0.2-0.5, or 0.2-0.3). In some examples, the atomic ratio of Li to Ga is 0.01 or greater. In some examples, the atomic ratio of Li to Ga is 0.01-1.0. In some examples, the atomic ratio of Li to Ga is 0.1-0.3.In some examples, the atomic ratio of Li to Ga is 0.2-0.3. In other examples, the atomic ratio of Li to Ga is 0.2.

[0057] In some examples, the atomic ratio of Li to O (e.g., x:z) is 0.0001 or greater (e.g., 0.0005 or greater, 0.001 or greater, 0.005 or greater, 0.01 or greater, 0.02 or greater, 0.03 or greater, 0.04 or greater, 0.05 or greater, 0.06 or greater, 0.07 or greater, 0.08 or greater, 0.09 or greater, 0.1 or greater, 0.15 or greater, 0.2 or greater, 0.25 or greater, 0.3 or greater, 0.35 or greater, 0.4 or greater, or 0.45 or greater). In some examples, the atomic ratio of Li to O (e.g., x:z) is less than or equal to 0.5 (e.g., less than or equal to 0.45, less than or equal to 0.4, less than or equal to 0.35, less than or equal to 0.3, less than or equal to 0.25, less than or equal to 0.2, less than or equal to 0.15, less than or equal to 0.1, less than or equal to 0.09, less than or equal to 0.08, less than or equal to 0.07, less than or equal to 0.06, less than or equal to 0.05, less than or equal to 0.04, less than or equal to 0.03, less than or equal to 0.02, less than or equal to 0.01, less than or equal to 0.005, or less than or equal to 0.001). The atomic ratio of Li to O (e.g., x:z) can be in the range from any of the minimum values ​​above to any of the maximum values ​​above. For example, the atomic ratio of Li to O (e.g., x:z) is 0.0001~0.5 (e.g., 0.0001~0.25, 0.25~0.5, 0.0001~0.1, 0.1~0.2, 0.2~0.3, 0.3~0.4, 0.4~0.5, 0.0001~0.4, 0.0001~0.3, 0.0001~0.2, 0.0001~0.1, 0.0001~0.05, 0.00625~0.2) 5, 0.00625~0.1, 0.00625~0.4, 0.00625~0.3, 0.00625~0.2, 0.00625~0.1, 0.00625~0.05, 0.00625~0.5, 0.01~0.5, 0.05~0.5, 0.1~0.5, 0.2~0.5, 0.3~0.5, 0.01~0.45, 0.05~0.4, or 0.05~0.2). In some examples, the atomic ratio of Li to O (e.g., x:z) is greater than or equal to 0.00625. In some examples, the atomic ratio of Li to O (e.g., x:z) is between 0.00625 and 0.5. In some examples, the atomic ratio of Li to O (e.g., x:z) is 0.05 to 0.2. In some examples, the atomic ratio of Li to O (e.g., x:z) is 0.125 to 0.25. In some examples, the atomic ratio of Li to O (e.g., x:z) is 0.125.

[0058] In some examples, the atomic ratio of Ga to O (e.g., y:z) is 0.5 or greater (e.g., 0.525 or greater, 0.55 or greater, 0.575 or greater, 0.6 or greater, 0.625 or greater, 0.65 or greater, 0.675 or greater, 0.7 or greater, 0.725 or greater, 0.75 or greater, 0.775 or greater, 0.8 or greater, 0.825 or greater, 0.85 or greater, 0.875 or greater, 0.9 or greater, 0.925 or greater, or 0.95 or greater). In some examples, the atomic ratio of Ga to O (e.g., y:z) is less than or equal to 1.0 (e.g., less than or equal to 0.975, less than or equal to 0.95, less than or equal to 0.925, less than or equal to 0.9, less than or equal to 0.875, less than or equal to 0.85, less than or equal to 0.825, less than or equal to 0.8, less than or equal to 0.775, less than or equal to 0.75, less than or equal to 0.725, less than or equal to 0.7, less than or equal to 0.675, less than or equal to 0.625, less than or equal to 0.6, less than or equal to 0.575, or less than or equal to 0.55). The atomic ratio of Ga to O (e.g., x:z) can be in the range from any of the minimum values ​​above to any of the maximum values ​​above. For example, the atomic ratio of Ga to O (e.g., y:z) can be 0.5 to 1.0 (e.g., 0.5 to 0.75, 0.75 to 1.0, 0.5 to 0.6, 0.6 to 0.7, 0.7 to 0.8, 0.8 to 0.9, 0.9 to 1.0, 0.5 to 0.9, 0.5 to 0.8, 0.5 to 0.7, 0.6 to 1.0, 0.7 to 1.0, 0.8 to 1.0, 0.6 to 0.9, or 0.625 to 0.8). In some examples, the atomic ratio of Ga to O (e.g., y:z) is 0.625 to 0.8. In some examples, the atomic ratio of Ga to O (e.g., y:z) is 0.65 to 0.75. In some examples, the atomic ratio of Ga to O (e.g., y:z) is 0.625.

[0059] In some examples, composition Li x Ga y O z It contains such that the atomic ratio of Li to Ga (e.g., x:y) is 0.01 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.00625 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

[0060] In some examples, the atomic ratios of Li, Ga, and O (e.g., x:y:z) can be 1:5:8.

[0061] In some examples, the composition contains LiGa5O8.

[0062] In some examples, the composition includes Li-rich LiGa5O8.

[0063] In some examples, the composition contains Li-poor LiGa5O8.

[0064] In some examples, the composition contains 0-pure LiGa5O8.

[0065] In some examples, the composition includes O-rich LiGa5O8.

[0066] In some examples, the composition further includes dopants such as p-type dopants.

[0067] In some examples, the composition is substantially dopant-free.

[0068] In some examples, the composition is 1 cubic centimeter (cm). -3 The carrier concentration (e.g., hole concentration) per unit is 1 × 10⁻⁶ 14 (For example, 5 x 10) 14 cm -3 The above is 1 x 10 15 cm -3 The above 5 x 10 15 cm -3 The above is 1 x 10 16 cm -3 The above 5 x 10 16 cm -3 The above is 1 x 10 17 cm -3 The above 5 x 10 17 cm -3 The above is 1 x 10 18 cm -3 The above 5 x 10 18 cm -3 The above is 1 x 10 19 cm -3 The above 5 x 10 19 cm -3 The above is 1 x 1020 cm -3 or more, or 5×10 20 cm -3 or more). In some examples, the composition has a carrier concentration (e.g., hole concentration) of 1×10 21 cm -3 or less (e.g., 5×10 20 cm -3 or less, 1×10 20 cm -3 or less, 5×10 19 cm -3 or less, 1×10 19 cm -3 or less, 5×10 18 cm -3 or less, 1×10 18 cm -3 or less, 5×10 17 cm -3 or less, 1×10 17 cm -3 or less, 5×10 16 cm -3 or less, 1×10 15 cm -3 or less, 5×10 15 cm -3 or less, 1×10 15 cm -3 or less, or 5×10 14 cm -3 or less). The carrier concentration (e.g., hole concentration) can range from any of the above minimum values to any of the above maximum values. For example, the composition can have a carrier concentration (e.g., hole concentration) per cubic centimeter of 1×10 14 ~1×10 21 cm -3 (e.g., 1×10 14 ~1×10 17 cm -3 , 1×10 17 ~5×10 19 cm -3 , 5×10 19 ~1×10 21 cm -3 , 1×10 14 ~1×10 15 cm -3 , 1×10 15 cm -3 ~1×1016 , 1 x 10 16 ~1 × 10 17 cm -3 , 1 x 10 17 ~1 × 10 18 cm -3 , 1 x 10 18 ~1 × 10 19 cm -3 , 1 x 10 19 ~1 × 10 20 cm -3 , 1 x 10 20 ~1 × 10 21 cm -3 , 1 x 10 14 ~5×10 19 cm -3 , 1 x 10 14 ~1 × 10 18 cm -3 , 1 x 10 15 ~1 × 10 21 cm -3 , 1 x 10 15 ~5×10 19 cm -3 , 1 x 10 18 ~5×10 19 cm -3 , 1 x 10 15 ~1 × 10 18 cm -3 , or 1 × 10 17 ~5×10 18 cm -3 ) can be made. In some examples, the composition has a carrier concentration (e.g., hole concentration) of 5 × 10 19 cm -3 The following applies: In some examples, the composition has a carrier concentration (e.g., hole concentration) of 1 × 10¹⁶ per cubic centimeter. 14 ~5×10 19 cm -3 In some cases, the dopant concentration is 1 × 10⁻⁶. 17 ~5×10 18 cm -3 That is the case.

[0069] In some examples, the composition has a mobility of 0.01 cm, such as hole mobility. 2 / Vs or greater (for example, 0.05cm) 2 / Vs or more, 0.1cm 2 / Vs or more, 0.25cm 2 / Vs or more, 0.5cm 2 / Vs or more, 0.75cm 2 / Vs or more, 1cm 2 / Vs or more, 1.5cm 2 / Vs or more, 2cm 2 / Vs or more, 2.5cm 2 / Vs or more, 3cm 2 / Vs or more, 3.5cm 2 / Vs or more, 4cm 2 / Vs or more, 4.5cm 2 / Vs or more, 5cm 2 / Vs or more, 5.5cm 2 / Vs or more, 6cm 2 / Vs or more, 6.5cm 2 / Vs or more, 7cm 2 / Vs or more, 7.5cm 2 / Vs or more, 8cm 2 / Vs or more, 8.5cm 2 / Vs or more, 9cm 2 / Vs or more, 10cm 2 / Vs or more, 15cm 2 / Vs or more, 20cm 2 / Vs or more, 25cm 2 / Vs or more, 30cm 2 / Vs or more, 40cm 2 / Vs or more, 50cm 2 / Vs or higher, or 75cm 2 (Vs or greater). In some examples, the composition has a mobility such as hole mobility of 100 cm². 2 / Vs or less (for example, 90cm) 2 / Vs or less, 80cm 2 / Vs or less, 70cm 2 / Vs or less, 60cm 2 / Vs or less, 50cm 2 / Vs or less, 40cm 2 / Vs or less, 30cm 2 / Vs or less, 25cm 2 / Vs or less, 20cm 2 / Vs or less, 15cm 2 / Vs or less, 10cm 2 / Vs or less, 9.5cm2 / Vs or less, 9cm 2 / Vs or less, 8.5cm 2 / Vs or less, 8cm 2 / Vs or less, 7.5cm 2 / Vs or less, 7cm 2 / Vs or less, 6.5cm 2 / Vs or less, 6cm 2 / Vs or less, 5.5cm 2 / Vs or less, 5cm 2 / Vs or less, 4.5cm 2 / Vs or less, 4cm 2 / Vs or less, 3.5cm 2 / Vs or less, 3cm 2 / Vs or less, 2.5cm 2 / Vs or less, 2cm 2 / Vs or less, 1.5cm 2 / Vs or less, 1cm 2 / Vs or less, 0.75cm 2 / Vs or less, or 0.5cm 2 The value is less than or equal to / Vs. The mobility of the composition (e.g., hole mobility) can be within the range of any of the above minimum values ​​to any of the above maximum values. For example, the composition may have a mobility such as hole mobility of 0.01 to 100 cm. 2 / Vs (for example, 0.01~50cm) 2 / Vs, 50~100cm 2 / Vs, 0.01~20cm 2 / Vs, 20-40cm 2 / Vs, 40-60cm 2 / Vs, 60-80cm 2 / Vs, 80~100cm 2 / Vs, 0.01~75cm 2 / Vs, 0.01~25cm 2 / Vs, 0.1~100cm 2 / Vs, 10~100cm 2 / Vs, 25~100cm 2 / Vs, 75~100cm 2 / Vs, 0.05~75cm 2 / Vs, 0.1~10cm 2 / Vs, 0.1~5cm 2 / Vs, 5~10cm 2 / Vs, 0.1~4cm 2 / Vs, 4~7cm 2 / Vs, 7-10cm 2 / Vs, 0.1~8cm 2 / Vs, 0.1~6cm 2 / Vs, 0.1~3cm 2 / Vs, 0.1~1cm 2 / Vs, 1-10cm 2 / Vs, 2-10cm 2 / Vs, 4~10cm 2 / Vs, 6-10cm 2 / Vs, 8-10cm 2 / Vs, 1.5~9.5cm 2 / Vs, or 0.35~2cm 2 It can be expressed as / Vs).

[0070] In some examples, the composition has a mobility of 0.1 cm, such as hole mobility. 2 The value is greater than or equal to / Vs. In some examples, the composition has a mobility such as hole mobility of 10 cm 2 The value is less than or equal to / Vs. In some examples, the composition has a mobility of 0.1 to 10 cm, such as hole mobility. 2 The value is / Vs. In some examples, the composition has mobilities such as hole mobility of 0.35-2 cm. 2 / Vs is the case.

[0071] In some examples, the composition exhibits high p-type conductivity.

[0072] This specification also discloses devices comprising any of the compositions disclosed herein.

[0073] In some examples, the device further comprises a substrate, and the composition is deposited on the substrate as a layer. The substrate may include any suitable substrate. For example, the substrate may include LiGa5O8, freestanding GaN, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, AlN, AlGaN, diamond, or a combination thereof. In some examples, the substrate may include LiGa5O8, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, or a combination thereof.

[0074] In some examples, the layer has a surface roughness RMS value of 20 nm or less (e.g., 19 nm or less, 18 nm or less, 17 nm or less, 16 nm or less, 15 nm or less, 14.5 nm or less, 14 nm or less, 13.5 nm or less, 13 nm or less, 12.5 nm or less, 12 nm or less, 11.5 nm or less, 11 nm or less, 10.5 nm or less, 10 nm or less, 9.5 nm or less, 9 nm or less, 8.5 nm or less, 8 nm or less, 7.5 nm or less, 7 nm or less, 6.5 nm or less, 6 nm or less, 5.5 nm or less, 5 nm or less, 4.5 nm or less, 4 nm or less, 3.5 nm or less, 3 nm or less, 2.5 nm or less, 2 nm or less, 1.75 nm or less, 1.5 nm or less, 1.25 nm or less, 1 nm or less, 0.75 nm or less, or 0.5 nm or less). In some examples, the layer has a surface roughness RMS value of 15 nm or less. In some cases, the layer has a surface roughness RMS value of 10 nm or less. In some cases, the layer has a surface roughness with an RMS value of 5 nm or less. In some cases, the layer has a surface roughness RMS value of 2.5 nm or less. In some cases, the layer has a surface roughness RMS value of 1.75 nm or less, and in some cases, the layer has a surface roughness RMS value of 1.5 nm or less.

[0075] In some examples, the layers have an average thickness of 10 nanometers (nm) or more (for example, 15nm or more, 20nm or more, 25nm or more, 30nm or more, 35nm or more, 40nm or more, 45nm or more, 50nm or more, 55nm or more, 60nm or more, 65nm or more, 70nm or more, 75nm or more, 80nm or more, 85nm or more, 90nm or more, 95nm or more, 100nm or more, 125nm or more, 150nm or more, 175nm or more, 200nm or more, 225nm or more, 250nm or more, 275nm or more, 300nm or more, 325nm or more, 350nm or more, 375nm or more, 400nm or more, 425nm or more, 450 (1000nm or more, 475nm or more, 500nm or more, 525nm or more, 550nm or more, 575nm or more, 600nm or more, 625nm or more, 650nm or more, 675nm or more, 700nm or more, 725nm or more, 750nm or more, 775nm or more, 800nm ​​or more, 825nm or more, 850nm or more, 875nm or more, 900nm or more, 925nm or more, 950nm or more, 975nm or more, 1000nm or more, 1050nm or more, 1100nm or more, 1150nm or more, 1200nm or more, 1250nm or more, 1300nm or more, 1400nm or more, 1500nm or more, or 1750nm or more).In some examples, the layers have an average thickness of 2000nm or less (for example, 1900nm or less, 1800nm ​​or less, 1700nm or less, 1600nm or less, 1500nm or less, 1450nm or less, 1400nm or less, 1350nm or less, 1300nm or less, 1250nm or less, 1200nm or less, 1150nm or less, 1100nm or less, 1050nm or less, 1000nm or less, 975nm or less, 950nm or less, 925nm or less, 900nm or less, 875nm or less, 850nm or less, 825nm or less, 800nm ​​or less, 775nm or less, 750nm or less, 725nm or less, 700nm or less, 675nm or less, 650nm or less, 625nm or less, 6 The minimum and maximum wavelengths are 00nm or less, 575nm or less, 550nm or less, 525nm or less, 500nm or less, 475nm or less, 450nm or less, 425nm or less, 400nm or less, 375nm or less, 350nm or less, 325nm or less, 300nm or less, 275nm or less, 250nm or less, 225nm or less, 200nm or less, 175nm or less, 150nm or less, 125nm or less, 100nm or less, 95nm or less, 90nm or less, 85nm or less, 80nm or less, 75nm or less, 70nm or less, 65nm or less, 60nm or less, 55nm or less, 50nm or less, 45nm or less, 40nm or less, 35nm or less, 30nm or less, 25nm or less, or 20nm or less. The average thickness of the layer can be within the range of any of the minimum and maximum values ​​listed above. For example, the layers have an average thickness of 10-2000nm (e.g., 10-1000nm, 1000-2000nm, 10-500nm, 500-1000nm, 1000-1500nm, 1500-2000nm, 10-1750nm, 10-1500nm, 25-2000nm, 100-2000nm, 20-1750nm, 25-1000nm, 25-500nm, 500-1000nm, 25- The wavelengths can be 200nm, 200-400nm, 400-600nm, 600-800nm, 800-1000nm, 25-800nm, 25-600nm, 25-400nm, 25-100nm, 50-1000nm, 100-1000nm, 200-1000nm, 400-1000nm, 600-1000nm, 35-950nm, 50-900nm, or 50-100nm).In some examples, the layer has an average thickness of 25 nanometers (nm) or more. In some examples, the layer has an average thickness of 1000 nm or less. In some examples, the layer has an average thickness of 25 to 1000 nm. In some examples, the layer has an average thickness of 50 to 100 nm.

[0076] The device may include any suitable device. In some examples, the device includes vertical PN diodes, MOSFET devices such as power MOSFETs or trench MOSFETs, MESFET devices, MODFET devices, current-aperture vertical electronic transistor (CAVET) devices, or combinations thereof. In some examples, the device includes vertical PN diodes, MOSFET devices such as power MOSFETs or trench MOSFETs, current-aperture vertical electronic transistor (CAVET) devices, or combinations thereof. In some examples, the device includes vertical power devices. In some examples, the device includes optical devices, electronic devices, optoelectronic devices, or combinations thereof. In some examples, the device includes diodes. In some examples, the device includes n-Ga2O3 / p-Li x Ga y O z This includes heterojunctions (e.g., n-Ga2O3 / p-LiGa5O8). In some examples, the device is n-GaN / p-Li x Ga y O z n-AlN / p-Li x Ga y O z n-diamond / p-Li x Ga y O z , or a combination thereof.

[0077] Furthermore, this specification also discloses methods for using any of the compositions disclosed herein.

[0078] This specification also discloses methods for producing any of the compositions or devices disclosed herein. In some examples, the method involves reacting a gallium-containing precursor, a lithium-containing precursor, and oxygen or an oxygen-containing precursor to form a composition by contacting the gallium-containing precursor and the lithium-containing precursor at a predetermined temperature in the presence of oxygen or an oxygen-containing precursor.

[0079] In some examples, the gallium-containing precursor includes Ga(acac)3([CH3COCH=C(O-)CH3]3Ga), an organometallic Ga-containing precursor, or a combination thereof. In some examples, the gallium-containing precursor includes an organometallic Ga-containing precursor. In some examples, the gallium-containing precursor includes Ga(acac)3([CH3COCH=C(O-)CH3]3Ga).

[0080] In some examples, the lithium-containing precursor includes lithium acetoacetate (C4H5LiO3), an organometallic Li-containing precursor, or a combination thereof. In some examples, the lithium-containing precursor includes an organometallic Li-containing precursor. In some examples, the lithium-containing precursor includes lithium acetoacetate (C4H5LiO3).

[0081] In some examples, the gallium-containing precursor and / or lithium-containing precursor independently contain fluids.

[0082] In some cases, gallium-containing precursors and / or lithium-containing precursors are supplied independently with a carrier gas. In some cases, the carrier gas includes argon, helium, N2, or a combination thereof. In some cases, the carrier gas includes argon.

[0083] In some cases, the temperature is 300°C or higher (for example, 350°C or higher, 400°C or higher, 450°C or higher, 500°C or higher, 550°C or higher, 600°C or higher, 650°C or higher, 700°C or higher, 750°C or higher, 800°C or higher, 825°C or higher, 850°C or higher, 875°C or higher, 900°C or higher, 925°C or higher, 950°C or higher, 975°C or higher, 1000°C or higher, 1050°C or higher, or 1100°C or higher). In some examples, the temperature is 1200°C or less (e.g., 1150°C or less, 1100°C or less, 1050°C or less, 1000°C or less, 975°C or less, 950°C or less, 925°C or less, 900°C or less, 875°C or less, 850°C or less, 825°C or less, 800°C or less, 750°C or less, 700°C or less, 650°C or less, 600°C or less, 550°C or less, 500°C or less, 450°C or less, or 400°C or less). The temperature can be within the range of any of the minimum and maximum values ​​listed above. For example, the temperature range is 300℃~1200℃ (for example, 300℃~750℃, 750℃~1200℃, 300℃~600℃, 600℃~900℃, 900℃~1200℃, 300℃~1000℃, 300℃~800℃, 400℃~1200℃, 600℃~1200℃, 800℃~1200℃, 400℃~ The temperature can be 1100℃, 600℃~1000℃, 800℃~1000℃, 800℃~900℃, 900℃~1000℃, 800℃~850℃, 850℃~900℃, 900℃~950℃, 950℃~1000℃, 800℃~950℃, 850℃~1000℃, or 850℃~950℃. In some examples, the temperature is 800℃ or higher. In some examples, the temperature is 1000℃ or lower. In some examples, the temperature is 800℃~1000℃. In some examples, the temperature is 800℃~950℃. In some examples, the temperature is 850℃~950℃. In some examples, the temperature is 900℃.

[0084] This method may include, for example, metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), hydride vapor deposition (HVPE), pulsed laser deposition (PLD), low-pressure chemical vapor deposition (LPCVD), mist CVD, or a combination thereof. In some examples, this method includes mist CVD.

[0085] In some examples, the method involves depositing a composition onto a substrate. Examples of substrates include, but are not limited to, LiGa5O8, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, or combinations thereof.

[0086] Numerous embodiments of the present invention have been described. Needless to say, it is understood that various modifications can be made without departing from the spirit and scope of the invention. Therefore, other embodiments are within the scope of the following claims.

[0087] The following examples are intended to further illustrate specific embodiments of the devices and methods described herein and are not intended to limit the scope of the claims. [Examples]

[0088] The following examples are provided below to illustrate the methods and results according to the subject matter disclosed herein. These examples are not intended to include all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the invention that would be apparent to those skilled in the art.

[0089] While we strive to ensure accuracy in numerical values ​​(e.g., quantity, temperature, etc.), please allow for a certain degree of error and deviation. Unless otherwise specified, parts refer to parts by weight, temperature to °C or ambient temperature, and pressure to atmospheric pressure or near atmospheric pressure. There are many variations and combinations of measurement conditions, such as component concentration, temperature, pressure, and other measurement ranges and conditions that can be used to optimize the described process.

[0090] Example 1: Ultra-wide bandgap oxide semiconductor with p-type conductivity Beta-gallium oxide (β-Ga2O3) has emerged as a promising material for future power devices due to its ultrawide bandgap (approximately 4.9 eV), high critical field (EC), controllable doping, and availability of high-quality large-diameter wafers [1]. While n-type β-Ga2O3 can be readily obtained by Si or Sn doping, the existence of p-type β-Ga2O3 has not yet been reported. One potential approach to fabricating β-Ga2O3 devices with pn junctions involves using a heterojunction between β-Ga2O3 and another p-type semiconductor. In this case, oxide materials are preferred as the p-type semiconductor because they can prevent interfacial oxidation reactions that occur when non-oxide materials are used, enabling more efficient device fabrication methods. In recent developments, p-type nickel oxide (with a bandgap of 3.4–4 eV) has been used to fabricate pn junction diodes with β-Ga2O3 [2]. Since its initial report, NiO / Ga2O3pn diodes have achieved voltage withstand voltages (BV) of several kilovolts and low differential specific on-resistances (RON,SP) [3-5]. However, the performance of these devices is significantly limited by the relatively small bandgap of NiO.

[0091] Recently, there has been renewed interest in LiGaO2 as a potential ultra-wide bandgap semiconductor material. LiGaO2 is a transparent ceramic material whose applications in the fields of piezoelectricity and nonlinear optics have been previously studied [6-10]. It can be grown as a bulk single crystal and is suitable as a lattice-matched substrate for GaN epitaxial growth [11-16]. LiGaO2 has a wurtzite-based crystal structure and can be considered an I-III-VI2 analog of the II-VI material ZnO. This crystal structure is characterized by an ordered arrangement of Li and Ga atoms on a wurtzite-based cation sublattice, and its ground state is represented by the Pna21 space group (β-LiGaO2). Furthermore, mixed alloy systems of ZnO and LiGaO2, and ZnO / LiGaO2 heterojunctions have also been studied [17-19]. Recent studies have shown that LiGaO2 can be doped n-type with Si or Ge, which raises expectations for its potential application as an ultra-wide bandgap semiconductor [20-24]. From this perspective, LiGaO2 may offer certain advantages compared to β-Ga2O3, such as a simpler tetrahedral crystalline structure and potentially a wider band gap.

[0092] In this specification, Li exhibits high p-type conductivity. x Ga y O z This describes an ultrawide bandgap semiconductor called [material name]. This material was obtained using a customized mist chemical vapor deposition (CVD) technique. x Ga y O zThin films can be deposited on GaN on a sapphire template, as well as on on-axis and off-cut c-sapphire substrates, using a mist CVD chamber. To prepare the precursor solution, gallium acetylacetate (Ga(acac)3[CH3COCH=C(O-)CH3]3Ga, 99.99%) and lithium acetoacetate (C4H5LiO3, 99.95%) are dissolved in deionized (DI) water. The Ga / Li molar ratio is adjusted to approximately 1. The solution is used to generate atomized particles using an ultrasonic generator operating at 1.7 MHz. The atomized particles are then supplied into the growth chamber using argon (Ar) as the carrier gas. The growth substrate is loaded into the growth chamber, and the growth temperature can be widely adjusted between 800 and 1000°C. A series of material characterization techniques confirmed that the films grown on each substrate exhibited a spinel cubic structure known as LiGa5O8. It was found that the p-type conductive films have a wide range of Li compositions, including both Li-poor and Li-rich conditions.

[0093] LiGa5O8 is a complex oxide compound belonging to the spinel group of compounds and is structurally isomorphic to MgAl2O4 spinel. Its crystal structure is: Characterized by TIFF2026528797000002.tif17164. In this structure, Li in LiGa5O8 + The ion consists of six equivalent oxygen atoms. 2- They coordinate with ions, resulting in the formation of LiO6 octahedra. These octahedra share angles with six equivalent GaO4 tetrahedra and edges with six equivalent GaO6 octahedra, thereby giving rise to the overall crystalline structure of LiGa5O8.

[25]

[0094] LiGa5O8 is of great interest in research, particularly due to its luminescence properties when doped with transition metal (MT) impurities and rare earth (RE) impurities [26-28]. For example, Cr 3+ When doped with Cr, it exhibits sustained luminescence properties, and is expected to have applications in biomedical imaging. The structure, electronic, and optical properties of LiGa5O8 are different when undoped and when Cr3+ Both doped and undoped LiGa5O8 have been studied using density functional theory (DFT) [28,29]. Theoretical calculations suggest a band gap of approximately 5.7 eV, indicating that LiGa5O8 may be an ultrawide bandgap semiconductor. However, to date, there are no experimental reports on the growth of thin films of undoped LiGa5O8.

[0095] This specification describes the CVD growth of LiGa5O8, which is either Li-poor or Li-rich and exhibits p-type conductivity. This is a significant finding, as no ultrawide bandgap oxide semiconductors with p-type conductivity have been demonstrated.

[0096] Figures 1A to 1D show the surface morphology of LiGa5O8 samples grown on GaN on a sapphire template at different growth temperatures. From the corresponding AFM images shown in Figures 2A to 2D, it can be confirmed that the smoothest surface is obtained at a growth temperature of 900°C. The surface roughness RMS is determined to be approximately 1.60 nm. As shown in Figure 3A, the thickness of the film obtained at 900°C is estimated to be approximately 60 nm from the cross-sectional TEM image. A sharp interface between the grown film and the GaN layer can be observed. The atomic-resolution HAADF-STEM image in Figure 3B also shows that the grown film has a spinel cubic crystal structure. Figure 4 shows the XRD spectrum of the same sample. The XRD peaks at approximately 34.55°, 41.68°, and 72.86° are attributed to GaN and sapphire peaks originating from the substrate, while the presence of a LiGa5O8 peak at approximately 58.46° can be observed. Note that other peaks around 18.74° and 38.01° are also prominent, suggesting the possibility of rotated crystalline regions being present within the grown film.

[0097] Similar surface morphologies were observed in LiGa5O8 samples grown on c-sapphire substrates loaded together. Figures 5A to 5D show planar SEM images and corresponding AFM images of LiGa5O8 samples grown at 850°C on on-axis and 6° off-cut c-plane sapphire substrates. It is noteworthy that the use of an off-cut angle can improve the surface morphology of films grown on sapphire substrates. As shown in Figures 6A to 6B, cross-sectional TEM imaging and atomic-resolution HAADF STEM images of the sample grown on an on-axis c-sapphire substrate confirm a film thickness of approximately 96 nm and a spinel cubic crystal structure similar to that of the sample grown on a GaN template. More importantly, Hall measurements suggest robust p-type conductivity in this sample, as shown in Table 1. [Table 1] TIFF2026528797000003.tif67165

[0098] The atomic composition of the grown films was investigated using X-ray photoelectron spectroscopy (XPS). Figures 7A to 7F show the Li 1s, Ga 3s, and O 1s peaks obtained from two example LiGa5O8 films grown on GaN on a sapphire template at 900°C (Figures 7A to 7C show Li-rich conditions, and Figures 7D to 7F show Li-poor conditions). The curves were fitted with Voigt peak shapes assuming a Shirley background. Next, the Li / Ga, Li / O, and Ga / O atomic ratios were derived using the fitted peak areas. As shown in Table 2, all samples grown on the three types of substrates had a Li / Ga / O ratio of approximately 1:5:8, indicating either a Li-rich or Li-poor composition. [Table 2] TIFF2026528797000004.tif86165

[0099] Given the successful demonstration of p-type conductivity in Li-rich and Li-poor LiGa5O8, several device designs are proposed for power device applications. Figure 8A shows n - -Ga2O3 drift layer, n +Figure 8B shows a LiGa5O8-Ga2O3 MOSFET. Figure 8C shows a LiGa5O8-Ga2O3 trench MOSFET. Figure 8D shows a LiGa5O8-Ga2O3 current-aperture vertical electron transistor (CAVET). In these designs, the main structure is based on an n-Ga2O3 / p-LiGa5O8 heterojunction.

[0100] References 1. SJPearton et al. “A review of Ga2O3 materials, processing, and devices,” Appl. Phys. Rev. 5(1), 011301 (2018). 2. Y. Kokubu et al. “All-oxide pn heterojunction diodes comprising p-type NiO and n-type β-Ga2O3,” Appl. Phys. Express 9(9), 091101 (2016). 3. X.Lu et al.“1-kV Sputtered p-NiO / n-Ga2O3Heterojunction Diodes With an Ultra-Low Leakage Current Below 1uA / cm 2 ,”IEEE Electron Device Lett. 41(3), 449-452(2020). 4. Y.Wang et al. “2.41kV Vertical P-NiO / n-Ga2O3Heterojunction Diodes With a Record Baliga's Figure-of-Merit of 5.18GW / cm 2 ,”IEEE Trans. Power Electron. 37(4), 3743-3746(2022). 5. B.Wang et al.“2.5kV Vertical Ga2O3Schottky Rectifier With Graded Junction Termination Extension,”IEEE Electron Device Lett. 44(2),221-224(2023)。 6. A.Boonchun et al.“First-principles study of the elasticity,piezoelectricity,and vibrational modes in LiGaO2compared with ZnO and GaN,”Phys. Rev. B 81(23),235214(2010)。 7. S.N. Gupta et al.“Surface acoustic wave properties of lithium gallium oxide,”J. Appl. Phys. 47(3),858-860(1976)。 8. S.Nanamatsu et al.“Piezoelectric, elastic and dielectric properties of LiGaO2,”Jpn. J.Appl. Phys. 11(6),816(1972)。 9. P.Knoll, and H.Kuzmany,“Nonlinear-optical properties and signs of the Raman tensor for LiGaO2,”Phys. Rev. B 29(4),2221-2226(1984)。 10. S.N.Rashkeev et al.“Theoretical evaluation of LiGaO2for frequency upconversion to ultraviolet,”JOSA B 16(12),2217-2222(1999)。 11. T.Ishii et al.“Single-crystal growth of LiGaO2for a substrate of GaN thin films,”J. Cryst. Growth 186(3),409-419(1998)。 12. M.Marezio,“The crystal structure of LiGaO2,”Acta Crystallogr. 18(3),481-484(1965)。 13. A.Christensen et al.“Heat dissipation in high-power GaN electronics on thermally resistive substrates,” IEEE Trans. Electron Devices 52(8),1683-1688(2005)。 14. W.A.Doolittle et al.“MBE growth of high quality GaN on LiGaO2for high frequency, high power electronic applications,”Solid-State Electron. 44(2),229-238(2000)。 15. K.Sakurada et al.“Low temperature epitaxial growth of GaN films on LiGaO2substrates,”Appl. Phys. Lett. 90(21),211913(2007)。 16. C.Chen et al.“Growth and characterization of β-LiGaO2single crystal,”J.Cryst. Growth 402,325-329(2014)。 17. I.Ohkubo et al.“Heteroepitaxial growth of β-LiGaO2thin films on ZnO,”J. Appl. Phys.92(9),5587-5589(2002)。 18. T.Omata et al.“Wide band gap semiconductor alloy:x(LiGaO2) 1 / 2 -(1-x)ZnO,” J.Appl. Phys.103(8),083706(2008)。 19. T.Omata et al.“Zn2LiGaO4,Wurtzite-Derived Wide Band Gap Oxide,”Jpn. J.Appl. Phys.50(3R),031102(2011)。 20. A.Boonchun et al.“First-principles study of point defects in LiGaO2,”J.Appl. Phys.126(15),155703(2019)。 21. A.Boonchun et al. in Oxide-Based Mater. Devices II (SPIE,2011),pp.129-134。 22. K.Dabsamut et al.“First-principles study of n-and p-type doping opportunities in LiGaO2,”J.Phys. Appl. Phys.53(27),274002(2020)。 23. C.A.Lenyk et al.“Lithium and gallium vacancies in LiGaO2crystals,”J.Appl. Phys.124(13),135702(2018)。 24. D.Skachkov et al.“Computational study of electron paramagnetic resonance spectra for Li and Ga vacancies in LiGaO2,”J.Phys. Appl. Phys.53(17),17LT01(2020)。 25. J.Ahman et al.“Structure of LiGa5O8,”Acta Chem.Scand.50(5),391-394(1996)。 26. F. Liu et al. “Photostimulated near-infrared persistent luminescence as a new optical read-out from Cr 3+ -doped LiGa5O8,”Sci.Rep.3(1),1554(2013). 27. L.Ao et al. “Structure characterization and microwave dielectric properties of LiGa5O8ceramic with low-εr and low loss,” J.Eur. Ceram. Soc.40(15), 5498-5503(2020). 28. OMSousa et al. “Theoretical study of the structural, energetic, electronic and magnetic properties of the host matrix LiGa5O8doped with Cr 3+ ,”J.Solid State Chem.289,121472(2020). 29. OMDe Sousa, “Study of the structural, electronic, and optical properties of the host matrices of LiAl5O8and LiGa5O8via DFT,” Comput. Theor. Chem. 1123, 96-101 (2018).

[0101] Example 2: Experimental determination of band offset at the UWBG p-LiGa5O8 / Ga2O3 interface Abstract: LiGa5O8, a recently discovered ultrawide bandgap semiconductor exhibiting p-type conductivity at room temperature, was grown on a (010)β-Ga2O3 substrate. The LiGa5O8 thin film grown on an insulating Ga2O3 substrate using mist chemical vapor deposition (M-CVD) had a hole concentration of approximately 2.31 × 10⁻¹⁶. 18 cm -3 The hole mobility is approximately 2.07 cm.2 The value is / V·s. A comprehensive evaluation of the characteristics of the obtained heterostructure was performed. Smooth and uniform film growth was observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM) imaging. Cross-sectional scanning transmission electron microscopy (STEM) observation and X-ray diffraction (XRD) confirmed that the spinel-type cubic crystal structure of LiGa5O8 grew along the

[0110] direction. Furthermore, the valence band and conduction band offset at the p-LiGa5O8 / β-Ga2O3 heterointerface was determined by X-ray photoelectron spectroscopy (XPS). From the determined band alignment at the LiGa5O8 / β-Ga2O3 interface, it became clear that a type II (staggered) heterojunction was formed. This experimental measurement provides a valuable parameter for the band offset at the heterointerface, which will be useful in future efforts to design and manufacture power electronics devices based on β-Ga2O3 ultrawide bandgap semiconductors.

[0102] Introduction: Over the past decade, the excellent high-power switching capabilities of beta-phase gallium oxide (β-Ga2O3) based diodes and transistors [A1-A3] have been remarkably demonstrated, highlighting their potential in advanced power electronics [A1, A4-A13]. Despite this progress, a significant obstacle to the widespread adoption of β-Ga2O3 is its inherent lack of ability to support effective p-type conductivity. This limitation stems from the fact that valence band flatness and hole self-binding lead to polaron formation [A14, A15]. To overcome this challenge, various p-type semiconductors are combined with n-Ga2O3 to form pn junctions [A16-A23]. These materials include SiC, GaN, SnO, Cu2O, CuI, and especially NiO. NiO stands out as a promising candidate due to its relatively wide bandgap range of 3.6–4.0 eV and its affinity with β-Ga2O3 [A20–A22, A26]. Recent advances in p-NiO / n-Ga2O3 pn diodes have demonstrated excellent voltage withstand capability and relative on-resistance [A18, A20, A24, A25]. However, the overall performance of these devices is currently limited by the thermal instability of the sputtered NiO layer [A26] and the relatively small bandgap of NiO compared to Ga2O3. This indicates a pressing need to explore other p-type semiconductors with ultra-wide bandgaps.

[0103] In recent developments, LiGa5O8, characterized by its ultrawide bandgap semiconductor with an experimentally measured bandgap of approximately 5.36 eV, has been demonstrated to exhibit p-type conductivity at room temperature. This breakthrough makes LiGa5O8 the widest bandgap p-type oxide semiconductor confirmed to date [A27]. Belonging to the spinel group of compounds, LiGa5O8 is structurally isomorphic to MgAl2O4 spinel, sharing a common structure. LiGa5O8 is found in pure and Cr 3+Both the doped and undoped versions have been studied using density functional theory (DFT) with the full-potential reinforced plane-wave (FP-LAPW) method [A28, A29], suggesting an indirect band gap of approximately 5.7 eV and a direct band gap approximately 0.1 eV higher. Recent reports have shown very close band gap values ​​using the CGA / QSGW method, suggesting that Si is a potential n-type dopant [A30]. High-crystal-quality LiGa5O8 thin films were grown on c-plane sapphire substrates and GaN-on-sapphire substrates using mist chemical vapor deposition (M-CVD). These films were 10 15 cm -3 ~10 18 cm -3 It exhibited robust p-type conductivity in the hole concentration range [A27]. This finding suggests that p-LiGa5O8 is likely to be adopted in Ga2O3-based device designs in future power electronics. This specification reports on the M-CVD growth of p-type LiGa5O8 thin films on a Ga2O3 substrate and the experimental measurement of the band offset at the LiGa5O8 / Ga2O3 heterointerface by X-ray photoelectron spectroscopy (XPS).

[0104] Results and Discussion: LiGa5O8 thin films were synthesized on a semi-insulating Fe-doped (010)Ga2O3 substrate using a specially designed mist CVD system. Gallium acetylacetate (Ga(acac)3, [CH3COCH=C(O-)CH3]3Ga) was used as the Ga raw material, and lithium acetoacetate (C4H5LiO3) was used as the Li raw material. Pure O2 was used as the oxygen source, and argon (Ar) gas was used as the carrier gas during the film deposition process. The growth temperature was always maintained at 850°C, and the growth pressure was kept at atmospheric pressure. A detailed explanation of the growth conditions is published in another document [A27]. For the XPS measurements described later, two LiGa5O8 samples were grown on the (010)Fe-doped Ga2O3 substrate with different growth times to thicknesses of approximately 50 nm and approximately 2 nm. A 50 nm thick film was used to probe bulk LiGa5O8, and a 2 nm thick sample was used to probe the LiGa5O8 / Ga2O3 heterostructure interface.

[0105] X-ray diffraction (XRD) analysis was performed using Bruker's high-performance XRD system D8 Discover. Scanning transmission electron microscopy (STEM) observation was performed using the probe-corrected Themis STEM function of Thermofisher. Surface morphology was investigated using scanning electron microscopy (SEM) with FEI's Apreo LoVac (low vacuum mode) analysis SEM. Atomic force microscopy (AFM) using Bruker's Icon 3 AFM was employed to measure surface roughness. X-ray photoelectron spectroscopy (XPS) evaluation was performed using ThermoFisher's XPS system Nexsa G2. Net carrier concentration and associated electron-hole mobility were measured at room temperature using Ecopia's Hall effect measurement system HMS-3000. Details of the instruments used for characterization are reported in another document [A27]. (010) To characterize the conductivity of a LiGa5O8 thin film grown on a Fe-doped β-Ga2O3 substrate, Hall measurements were performed at room temperature. The measured hole concentration was approximately 2.31 × 10⁻⁶. 18 cm -3 Therefore, the hole mobility is approximately 2.07 cm. 2 The value was / V·s. Detailed measurement results regarding the p-type conductivity of the LiGa5O8 film are published in other literature [A27]. The surface morphology and surface roughness of the LiGa5O8 sample grown on a (010)Fe-doped β-Ga2O3 substrate are shown in the supplementary materials, as characterized. Figure 15A is a planar SEM image of the film surface, and Figure 15B is the corresponding 2μm×2μm AFM image. In the SEM image, a smooth and uniform surface can be observed. The root mean square (RMS) value of the surface roughness obtained from the AFM is approximately 1.27 nm, confirming that it is a smooth and high-quality surface. Furthermore, in the AFM image shown in Figure 9B, a striped surface feature can be seen. A similar groove structure along the

[0001] direction has also been reported in β-Ga2O3 films grown on the same substrate [A31].

[0106] The thickness and crystal quality of the grown LiGa5O8 film were probed using cross-sectional STEM. Figure 9A shows a high-angle annular dark-field STEM image. Continuous film growth along the cross-section can be observed. The thickness of the grown film was estimated to be approximately 160 nm, resulting in a growth rate of approximately 1.8 nm / min. A clear interface exists between the grown film and the (010)Fe-doped β-Ga2O3 substrate. The atomic-resolution image in Figure 9B shows that the film has a spinel-type cubic crystal structure. Further characterization identified this cross-section as corresponding to the

[0110] region, which is supported by atomic modeling and XRD analysis. The lattice mismatch between LiGa5O8 and (010)β-Ga2O3 is estimated to be approximately 4.8%. Furthermore, signs of dislocations are observed in the LiGa5O8 film, which is thought to be alleviating strain within the film. Dislocations also affect the local structure of LiGa5O8.

[0107] The crystal quality and film orientation of the grown sample were analyzed by XRD measurement. As shown in Figure 10, the XRD peaks at approximately 30.85° and 61.44° are due to (010)Ga2O3 peaks originating from the substrate. LiGa5O8 is clearly visible at approximately 63.88°. Due to the peak in TIFF2026528797000006.tif17164, perpendicular to the (110) direction is observed in the cross-section. TIFF2026528797000007.tif17164 It is important to further confirm the growth of the LiGa5O8 film. Although the peak intensity is relatively low due to the thin film thickness, the clearly appearing peaks clearly indicate that a high-quality LiGa5O8 thin film is being grown as a single crystal. To better understand the crystal quality and orientation of the LiGa5O8 film, another sample with a larger film thickness was grown and analyzed using XRD. Figures 16A and 16B show the results of the XRD 2θ-ω scan and rocking curve scan of a LiGa5O8 film grown with a thickness of approximately 400 nm on a (010)Fe-doped β-Ga2O3 substrate. This shows TIFF2026528797000008.tif17164. Low-angle peaks can be observed by increasing the signal intensity in XRD.

[0108] The atomic composition of the LiGa5O8 film was probed by XPS measurement. Figures 11A to 11C show the Li 1s, Ga 3s, and O 1s peaks obtained from the LiGa5O8 sample grown on a (010)β-Ga2O3 substrate. Assuming a Shirley background, the peaks were fitted to the Voigt peak shape. The atomic ratios of Li / Ga, Li / O, and Ga / O were then determined using the ratio of the areas of the fitted peaks, and were found to be approximately 0.15, 0.11, and 0.72, respectively. This sample can be judged to be stoichiometrically slightly Li-poor and O-poor.

[0109] The band gap of the grown LiGa5O8 film was determined by the inelastic energy loss spectrum of the XPS peak at the O 1s core level. The rise of the inelastic loss spectrum at kinetic energies lower than the core level peak (higher binding energies) corresponds to the band gap energy [A32]. Figure 12 shows the O 1s core level spectrum of the LiGa5O8 film. The band gap estimated by measuring the rise of the energy loss peak was 5.4 ± 0.12 eV, which is in good agreement with the value obtained from optical transmission measurements

[27] .

[0110] To experimentally evaluate the band offset between LiGa5O8 grown by mist CVD and β-Ga2O3, two LiGa5O8 samples of specific thicknesses (approximately 2 nm and 50 nm) were used as the LiGa5O8 interface sample and bulk sample, respectively, and XPS measurements were performed on them. For the β-Ga2O3 bulk sample, an Fe-doped β-Ga2O3 substrate with a (010) plane orientation was used. The valence band offset (ΔE) between LiGa5O8 and β-Ga2O3 was determined. V ) is calculated using the Kraut method [A33] and the following formula: TIFF2026528797000009.tif17164

[0111] In this formal system, TIFF2026528797000010.tif17164 represents the binding energy of a specific inner-shell level in a bulk sample of β-Ga2O3 or LiGa5O8. TIFF2026528797000011.tif17164 refers to the binding energy of the same inner shell level measured in a LiGa5O8 / β-Ga2O3 interface sample. TIFF2026528797000012.tif17164 shows the position of the valence band maximum (VBM) in bulk β-Ga2O3 or LiGa5O8. The relative positions of these core levels are determined relative to the Fermi level. Positive ΔE V The value indicates that the VBM of LiGa5O8 is located lower than that of β-Ga2O3. Equation (1) can be calculated by XPS [A34~A37]. The first two terms of this equation are obtained from XPS data obtained from bulk samples of β-Ga2O3 and LiGa5O8. For the third term, XPS analysis of the heterojunction formed between these two materials is used. A key aspect of this analysis is the detection of photoelectrons emanating from the β-Ga2O3 layer underlying the two-layer heterostructure, which is essential for accurately measuring the core levels of the entire structure. However, this process presents challenges due to the limited escape depth of photoelectrons. If the upper LiGa5O8 layer is too thick, it may completely absorb the photoelectrons emitted from the lower β-Ga2O3 layer, hindering detection. Therefore, for effective detection, it is important to maintain the thickness of the upper LiGa5O8 layer to a minimum so that a sufficient number of photoelectrons can escape from the lower β-Ga2O3 layer.

[0112] Figures 13A to 13C show the XPS spectra near the Li 1s peak and Ga 3s peak, along with portions of the XPS spectra indicating the valence band edges of the three samples. During analysis, Voigt peak shape and Shirley background were assumed, and the spectra were calibrated based on the C 1s peak position (284.5 eV). Aside from impurities such as O and C commonly observed in XPS survey spectra, no metallic contaminants were detected, confirming the high purity of the Ga2O3 and LiGa5O8 materials. The 50 nm LiGa5O8 layer in the bulk sample is thick enough to absorb all XPS signals originating from the underlying Ga2O3 substrate. Therefore, the Ga 3s peak in the spectrum of this sample is attributed to the Ga atoms in the upper alloy layer. The binding energy of the Li 1s peak was determined to be 54.90 ± 0.02 eV and 57.22 ± 0.02 eV for the bulk LiGa5O8 sample and the heterointerface sample, respectively. For the Ga 3s peak, the binding energy was 161.17±0.02 eV for the β-Ga2O3 bulk sample and 161.30±0.02 eV for the interface sample. The positions of the valence band maxima for the bulk samples of β-Ga2O3 and LiGa5O8 were found to be 3.35±0.05 eV and 3.24±0.03 eV, respectively. The valence band offset (VBO) between β-Ga2O3 and LiGa5O8 extracted using the core levels of Li 1s and Ga 3s was 1.86±0.09 eV. The experimentally determined valence band alignment of LiGa5O8 and β-Ga2O3 is shown in Figure 14, along with the conduction band alignment considering the band gap of 5.4 eV of LiGa5O8 grown on (010)β-Ga2O3.

[0113] In conclusion, the significant potential for forming pn junctions for power electronics applications by growing p-type LiGa5O8 thin films on (010)Fe-doped β-Ga2O3 substrates using M-CVD was demonstrated. This film has a thickness of approximately 2.31 × 10⁻¹⁶ at room temperature. 18 cm -3 The hole concentration is approximately 2.07 cm 2It exhibits p-type conductivity with a hole mobility of / V·s. Smooth and uniform film growth was observed in both SEM and AFM imaging. The spinel-type cubic crystal structure of LiGa5O8 was revealed by STEM imaging and XRD. The film grew along the direction and exhibited high crystal quality. By examining the rise of inelastic energy loss in the atomic spectra of the inner-shell levels, the band gap of the LiGa5O8 film was determined to be 5.4 ± 0.12 eV, which was in good agreement with the experimental characterization based on light transmission mentioned earlier. Importantly, the valence band offset between LiGa5O8 and β-Ga2O3 was experimentally determined to be 1.86 ± 0.09 eV, indicating type II band alignment. The results of this study give great promise for the adoption of p-LiGa5O8 in the design and fabrication of UWBG Ga2O3-based power devices in future power device technology.

[0114] Supplementary materials: The surface morphology of a typical LiGa5O8 film grown on a (010)Ga2O3 substrate was characterized by SEM and AMF imaging. For a LiGa5O8 film grown on a (010)Fe-doped β-Ga2O3 substrate with a relatively thick film thickness (approximately 400 nm), XRD characteristics were evaluated using 2θ-ω scanning and XRD rocking curves.

[0115] Surface morphology and surface roughness of LiGa5O8 samples grown on (010)Fe-doped β-Ga2O3 substrates: Figures 15A and 15B show the surface morphology and surface roughness of LiGa5O8 samples grown on (010)Fe-doped β-Ga2O3 substrates, as characterized by planar scanning electron microscopy (SEM) observation and atomic force microscopy (AFM) imaging. The samples were grown at 850°C to a thickness of approximately 50 nm.

[0116] XRD Characterization of Thick LiGa5O8 Films Grown on (010)Fe-Doped β-Ga2O3 Substrates: Figure 16A shows the results of an XRD 2θ-ω scan of a LiGa5O8 film with a thickness of approximately 400 nm, grown on a (010)Fe-doped β-Ga2O3 substrate under the same growth conditions as the aforementioned LiGa5O8 sample with a thickness of approximately 160 nm, but with a longer growth period.

[0117] The peaks at approximately 15.11°, 30.85°, and 61.44° are due to the (010)Ga2O3 peak originating from the substrate. The peak at approximately 64.22° is due to LiGa5O8. The intensity of TIFF2026528797000014.tif17164 has increased significantly due to the increased film thickness. Furthermore, the low angles of approximately 15.22° and 47.01° TIFF2026528797000015.tif17164 is observable. Figure 16B shows the rocking curve scan of the same sample. The image TIFF2026528797000016.tif17164 is shown. A full width at half maximum (FWHM) of approximately 0.32° was extracted.

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[0119] Exemplary aspects Taking into consideration the compositions, devices, systems, and methods described herein, specific embodiments of the invention described in more detail are described below. However, the specific embodiments described herein should not be construed as having any limiting effect on any different claims, including different or more general teachings set forth herein, nor should the “specific” embodiments be construed as being somewhat limited in any way other than the literal meaning of the words and phrases used herein.

[0120] Example 1: A composition comprising an ultrawide bandgap oxide semiconductor having p-type conductivity, Li x Ga y O z Includes, The composition wherein the atomic ratio of Li to Ga (e.g., x:y) is 0.0001 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.0001 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

[0121] Example 2: Any example of this specification, particularly the composition described in Example 1, wherein the atomic ratio of Li to Ga (e.g., x:y) is 0.01 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.00625 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

[0122] Example 3: A composition comprising an ultrawide bandgap oxide semiconductor having p-type conductivity, Li x Ga y O z Includes, The composition wherein the atomic ratio of Li to Ga (e.g., x:y) is 0.01 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.00625 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.0.

[0123] Example 4: The composition in any of the examples herein, particularly the composition described in Examples 1 to 3, wherein the atomic ratio of Li, Ga, and O (e.g., x:y:z) is 1:5:8.

[0124] Example 5: The composition in any of the examples herein, particularly the composition described in Examples 1 to 4, wherein the composition contains β-Li x Ga y O z The composition in any of the examples herein, particularly the composition described in Examples 1 to 4, which contains.

[0125] Example 6: The composition in any of the examples herein, particularly the composition described in Examples 1 to 5, wherein the composition contains LiGa5O8.

[0126] Example 7: The composition in any of the examples herein, particularly the composition described in Examples 1 to 6, wherein the composition contains Li-rich LiGa5O8.

[0127] Example 8: The composition in any of the examples herein, particularly the composition described in Examples 1 to 6, wherein the composition contains Li-poor LiGa5O8.

[0128] Example 9: The composition in any of the examples herein, particularly the composition described in Examples 1 to 6, wherein the composition contains O-poor LiGa5O8.

[0129] Example 10: The composition in any of the examples herein, particularly the composition described in Examples 1 to 6, wherein the composition contains O-rich LiGa5O8.

[0130] Example 11: The composition in any of the examples herein, particularly the composition described in Examples 1 to 10, wherein the composition further contains a dopant such as a p-type dopant.

[0131] Example 12: The composition described herein is substantially free of dopants, and is one of the compositions described in any of the examples herein, particularly those described in Examples 1 to 10.

[0132] Example 13: The composition has a carrier concentration (e.g., hole concentration) of 1 × 10¹⁶ per cubic centimeter. 14 ~1 × 10 21 cm -3 The composition is one of the examples described herein, particularly those described in Examples 1 to 12.

[0133] Example 14: The composition has a carrier concentration (e.g., hole concentration) of 1 × 10⁻⁶. 14 ~1 5×10 19 cm -3 For example, 1 × 10 17 ~5×10 18 cm -3 The composition is one of the examples described herein, particularly those described in Examples 1 to 13.

[0134] Example 15: The above composition has a mobility of 0.01 to 100 cm, such as hole mobility. 2 A composition having a Vs of / Vs as described in any of the examples herein, particularly those described in Examples 1 to 14.

[0135] Example 16: The above composition has a mobility of 0.1 to 10 cm, such as hole mobility. 2 / Vs, for example, 0.35~2cm 2 A composition having a Vs of / Vs as described in any of the examples herein, particularly those described in Examples 1 to 15.

[0136] Example 17: The composition described herein exhibits high p-type conductivity, and is one of the compositions described in any of the examples herein, particularly those described in Examples 1 to 16.

[0137] Example 18: A device comprising any of the embodiments of this specification, particularly the compositions described in Examples 1 to 17.

[0138] Example 19: The device further comprises a substrate, wherein the composition is deposited as a layer on the substrate, as described in any embodiment of this specification, particularly the device described in Example 18.

[0139] Example 20: The substrate is any of the embodiments herein, particularly the device described in Example 19, including LiGa5O8, freestanding GaN, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, AlN, AlGaN, diamond, or a combination thereof.

[0140] Example 21: The substrate is any of the embodiments herein, particularly the device described in Example 19 or Example 20, including LiGa5O8, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, or a combination thereof.

[0141] Example 22: The device according to any example herein, particularly Examples 19 to 21, wherein the layer has a surface roughness RMS value of 20 nm or less.

[0142] Example 23: The device according to any example of this specification, particularly Examples 19 to 22, wherein the layer has a surface roughness RMS value of 15 nm or less, 10 nm or less, 5 nm or less, 2.5 nm or less, 1.75 nm or less, or 1.5 nm or less.

[0143] Example 24: The device according to any example of this specification, particularly Examples 19-23, wherein the layer has an average thickness of 10-2000 nm.

[0144] Example 25: The device according to any example of this specification, particularly Examples 19 to 24, wherein the layer has an average thickness of 25 nm to 1000 nm, for example, 50 to 100 nm.

[0145] Example 26: The device includes a vertical PN diode, a MOSFET device such as a power MOSFET or a trench MOSFET, a MESFET device, a MODFET device, a current aperture vertical electron transistor (CAVET) device, or a combination thereof, and is any device described in any example of this specification, particularly the devices described in Examples 18 to 25.

[0146] Example 27: The device includes a vertical PN diode, a MOSFET device such as a power MOSFET or a trench MOSFET, a current aperture vertical electron transistor (CAVET) device, or a combination thereof, and is any device described in any example of this specification, particularly the devices described in Examples 18 to 26.

[0147] Example 28: The device includes a vertical power device and is any device described in any example of this specification, particularly the devices described in Examples 18 to 27.

[0148] Example 29: The device includes an optical device, an electronic device, an optoelectronic device, or a combination thereof, and is any device described in any example of this specification, particularly the devices described in Examples 18 to 28.

[0149] Example 30: The device includes a diode and is any device described in any example of this specification, particularly the devices described in Examples 18 to 29.

[0150] Example 31: The device includes an n-Ga2O3 / p-Li x Ga y O z (e.g., n-Ga2O3 / p-LiGa5O8) heterojunction and is any device described in any example of this specification, particularly the devices described in Examples 18 to 30.

[0151] Example 32: The device includes n-GaN / p-Li x Ga y O z , n-AlN / p-Li x Ga y O z , n-diamond / p-Lix Ga y O z The devices described in any of the embodiments of this specification, particularly those described in Examples 18-31, including, or combinations thereof.

[0152] Example 33: A method using any of the examples specified herein, particularly the compositions described in Examples 1 to 17.

[0153] Example 34: A method for producing any of the examples of this specification, particularly Examples 1 to 17, comprising contacting a gallium-containing precursor and a lithium-containing precursor at a predetermined temperature in the presence of oxygen or an oxygen-containing precursor to react the gallium-containing precursor, the lithium-containing precursor, and the oxygen or oxygen-containing precursor to form the composition.

[0154] Example 35: The gallium-containing precursor is the method according to any example of this specification, particularly the method according to Example 34, wherein the gallium-containing precursor includes an organometallic Ga-containing precursor.

[0155] Example 36: The gallium-containing precursor comprises Ga(acac)3 ([CH3COCH=C(O-)CH3]3Ga), as described in any of the examples herein, particularly the method of Example 34 or Example 35.

[0156] Example 37: The lithium-containing precursor is the method according to any of the examples herein, particularly those according to Examples 34 to 36, wherein the lithium-containing precursor includes an organometallic Li-containing precursor.

[0157] Example 38: The lithium-containing precursor comprises lithium acetoacetate (C4H5LiO3), as described in any of the examples of this specification, particularly those of Examples 34 to 37.

[0158] Example 39: The method according to any of the embodiments herein, particularly those of Examples 34-38, wherein the gallium-containing precursor and / or the lithium-containing precursor independently comprises a fluid.

[0159] Example 40: The method according to any of the embodiments herein, particularly Examples 34-39, wherein the gallium-containing precursor and / or the lithium-containing precursor are supplied independently with a carrier gas.

[0160] Example 41: The carrier gas is argon, helium, N2, or a combination thereof, as described in any of the embodiments of this specification, particularly the method of Example 40.

[0161] Example 42: The carrier gas is argon, as described in any of the embodiments of this specification, particularly the method of Example 40 or Example 41.

[0162] Example 43: The method according to any example of this specification, particularly the method according to Examples 34 to 42, wherein the temperature is 300°C to 1200°C.

[0163] Example 44: The method according to any of the embodiments herein, particularly those according to Examples 34 to 43, wherein the temperature is 800°C to 1000°C, for example, 800°C to 950°C or 850°C to 950°C.

[0164] Example 45: The method according to any of the embodiments herein, particularly those of Examples 34 to 44, wherein the temperature is 900°C.

[0165] Example 46: The method described herein, particularly the method described in Examples 34 to 45, includes metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), hydride vapor deposition (HVPE), pulsed laser deposition (PLD), low-pressure chemical vapor deposition (LPCVD), mist CVD, or a combination thereof.

[0166] Example 47: The method described above is any of the examples herein, particularly those described in Examples 34 to 46, which include mist CVD.

[0167] Example 48: The method according to any of the examples herein, particularly those according to Examples 34 to 47, comprising depositing the composition onto a substrate.

[0168] Example 49: Any example of this specification, particularly the method of Example 48, wherein the substrate includes LiGa5O8, freestanding GaN, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, AlN, AlGaN, diamond, or a combination thereof.

[0169] Example 50: The substrate is any of the embodiments herein, particularly the method according to Example 48 or Example 49, wherein the substrate is LiGa5O8, GaN on a c-plane sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-plane sapphire), Ga2O3, or a combination thereof.

[0170] Other obvious and unique advantages of the present invention will be apparent to those skilled in the art. It will be understood that certain properties and partial combinations are beneficial and can be used regardless of other properties and partial combinations. It will be understood that all matters in this specification described or shown in the accompanying drawings should be interpreted as illustrative rather than restrictive, since many possible embodiments of the present invention contemplated and within the scope of the claims can be carried out without departing from that scope.

[0171] The methods of the appended claims are not limited by the specific methods described herein, which are intended to be illustrative of some aspects of the claims, and any functionally equivalent methods are intended to be included in the claims. In addition to those shown and described herein, various variations of the methods are intended to be included in the appended claims. Furthermore, although only certain representative method steps disclosed herein are specifically described, other combinations of method steps are also intended to be included in the appended claims, even if not specifically enumerated. Thus, combinations of steps, elements, components, or constituents may be explicitly mentioned herein, but other combinations of steps, elements, components, and constituents are included even if not explicitly mentioned.

Claims

1. A composition comprising an ultrawide bandgap oxide semiconductor having p-type conductivity, Li ｘ Ga ｙ O ｚ Includes, The atomic ratio of Li to Ga (for example, x:y) is between 0.0001 and 1.

0. The atomic ratio of Li to O (for example, x:z) is between 0.0001 and 0.

5. The composition wherein the atomic ratio of Ga to O (for example, y:z) is 0.5 to 1.

0.

2. The composition according to claim 1, wherein the atomic ratio of Li to Ga (e.g., x:y) is 0.01 to 1.0, the atomic ratio of Li to O (e.g., x:z) is 0.00625 to 0.5, and the atomic ratio of Ga to O (e.g., y:z) is 0.5 to 1.

0.

3. A composition comprising an ultrawide bandgap oxide semiconductor having p-type conductivity, Li ｘ Ga ｙ O ｚ Includes, The atomic ratio of Li to Ga (for example, x:y) is between 0.01 and 1.

0. The atomic ratio of Li to O (for example, x:z) is 0.00625 to 0.

5. The composition wherein the atomic ratio of Ga to O (for example, y:z) is 0.5 to 1.

0.

4. The composition according to any one of claims 1 to 3, wherein the atomic ratio of Li, Ga, and O (for example, x:y:z) is 1:5:

8.

5. The composition contains β-Li ｘ Ga ｙ O ｚ and is the composition according to any one of claims 1 to 4.

6. The above composition is LiGa ５ O ８ A composition according to any one of claims 1 to 5, comprising:

7. The above composition is Li-rich LiGa ５ O ８ A composition according to any one of claims 1 to 6, comprising:

8. The above composition is Li-Pua LiGa ５ O ８ A composition according to any one of claims 1 to 6, comprising:

9. The above composition is O-poor LiGa ５ O ８ A composition according to any one of claims 1 to 6, comprising:

10. The above composition is O-rich LiGa ５ O ８ A composition according to any one of claims 1 to 6, comprising:

11. The composition according to any one of claims 1 to 10, further comprising a dopant such as a p-type dopant.

12. The composition according to any one of claims 1 to 10, wherein the composition substantially does not contain a dopant.

13. The aforementioned composition has a carrier concentration (e.g., hole concentration) of 1 × 10¹⁶ per cubic centimeter. １４ ~1 x 10 ２１ cm －３ The composition according to any one of claims 1 to 12.

14. The aforementioned composition has a carrier concentration (e.g., hole concentration) of 1 × 10⁻⁶ １４ ~1 5 x 10 １９ cm －３ For example, 1 x 10 １７ ~5 x 10 １８ cm －３ The composition according to any one of claims 1 to 13.

15. The above composition has a mobility of 0.01 to 100 cm, such as hole mobility. ２ A composition according to any one of claims 1 to 14, wherein the ratio is / Vs.

16. The above composition has a mobility of 0.1 to 10 cm, such as hole mobility. ２ / Vs, for example, 0.35 to 2 cm ２ A composition according to any one of claims 1 to 15, wherein / Vs.

17. The composition according to any one of claims 1 to 16, wherein the composition exhibits high p-type conductivity.

18. A device comprising the composition according to any one of claims 1 to 17.

19. The device according to claim 18, further comprising a substrate, wherein the composition is deposited as a layer on the substrate.

20. The aforementioned substrate is LiGa ５ O ８ , self-propelled GaN, GaN on a c-face sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-face sapphire), Ga ２ O ３ The device according to claim 19, comprising AlN, AlGaN, diamond, or a combination thereof.

21. The aforementioned substrate is LiGa ５ O ８ GaN on a c-face sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-face sapphire), Ga ２ O ３ The device according to claim 19 or claim 20, including, or a combination thereof.

22. The device according to any one of claims 19 to 21, wherein the layer has a surface roughness RMS value of 20 nm or less.

23. The device according to any one of claims 19 to 22, wherein the layer has a surface roughness RMS value of 15 nm or less, 10 nm or less, 5 nm or less, 2.5 nm or less, 1.75 nm or less, or 1.5 nm or less.

24. The device according to any one of claims 19 to 23, wherein the layer has an average thickness of 10 to 2000 nm.

25. The device according to any one of claims 19 to 24, wherein the layer has an average thickness of 25 nm to 1000 nm, for example, 50 to 100 nm.

26. The device is the device according to any one of claims 18 to 25, which includes a vertical PN diode, a MOSFET device such as a power MOSFET or trench MOSFET, a MESFET device, a MODFET device, a current-aperture vertical electron transistor (CAVET) device, or a combination thereof.

27. The device according to any one of claims 18 to 26, wherein the device includes a MOSFET device such as a vertical PN diode, a power MOSFET or a trench MOSFET, a current-aperture vertical electron transistor (CAVET) device, or a combination thereof.

28. The device is the device according to any one of claims 18 to 27, including a vertical power device.

29. The device according to any one of claims 18 to 28, comprising an optical device, an electronic device, an optoelectronic device, or a combination thereof.

30. The device is the device according to any one of claims 18 to 29, comprising a diode.

31. The aforementioned device is n-Ga ２ O ３ / p-Li ｘ Ga ｙ O ｚ (For example, n-Ga ２ O ３ / p-LiGa ５ O ８ The device according to any one of claims 18 to 30, comprising a heterojunction of ).

32. The device is n-GaN / p-Li ｘ Ga ｙ O ｚ , n-AlN / p-Li ｘ Ga ｙ O ｚ n-diamond / p-Li ｘ Ga ｙ O ｚ The device according to any one of claims 18 to 31, including, or a combination thereof.

33. A method of using the composition according to any one of claims 1 to 17.

34. A method for producing the composition according to any one of claims 1 to 17, comprising contacting a gallium-containing precursor and a lithium-containing precursor at a predetermined temperature in the presence of oxygen or an oxygen-containing precursor to react the gallium-containing precursor, the lithium-containing precursor, and the oxygen or oxygen-containing precursor to form the composition.

35. The method according to claim 34, wherein the gallium-containing precursor includes an organometallic Ga-containing precursor.

36. The gallium-containing precursor is Ga(acac) ３ ([CH ３ COCH=C(O-)CH ３ ] ３ The method according to claim 34 or claim 35, comprising Ga).

37. The method according to any one of claims 34 to 36, wherein the lithium-containing precursor includes an organometallic Li-containing precursor.

38. The lithium-containing precursor is lithium acetoacetate (C ４ H ５ LiO ３ The method according to any one of claims 34 to 37, including )

39. The method according to any one of claims 34 to 38, wherein the gallium-containing precursor and / or the lithium-containing precursor independently comprises a fluid.

40. The method according to any one of claims 34 to 39, wherein the gallium-containing precursor and / or the lithium-containing precursor are supplied independently together with a carrier gas.

41. The carrier gas is argon, helium, N ２ The method according to claim 40, including, or a combination thereof.

42. The method according to claim 40 or claim 41, wherein the carrier gas comprises argon.

43. The method according to any one of claims 34 to 42, wherein the temperature is 300°C to 1200°C.

44. The method according to any one of claims 34 to 43, wherein the temperature is 800°C to 1000°C, for example, 800°C to 950°C, or 850°C to 950°C.

45. The method according to any one of claims 34 to 44, wherein the temperature is 900°C.

46. The method according to any one of claims 34 to 45, wherein the method includes metal-organic chemical vapor deposition (MOCVD), molecular beam epitaxy (MBE), hydride vapor deposition (HVPE), pulsed laser deposition (PLD), low-pressure chemical vapor deposition (LPCVD), mist CVD, or a combination thereof.

47. The method described above is the method according to any one of claims 34 to 46, comprising mist CVD.

48. The method according to any one of claims 34 to 47, comprising depositing the composition on a substrate.

49. The aforementioned substrate is LiGa ５ O ８ , self-propelled GaN, GaN on a c-face sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-face sapphire), Ga ２ O ３ The method according to claim 48, comprising AlN, AlGaN, diamond, or a combination thereof.

50. The aforementioned substrate is LiGa ５ O ８ GaN on a c-face sapphire template, on-axis c-sapphire, off-axis c-sapphire (e.g., 6° off-cut c-face sapphire), Ga ２ O ３ The method according to claim 48 or claim 49, including, or a combination thereof.

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