Oxide material and preparation method and application thereof

Abstract

The invention discloses an oxide material and a preparation method and application thereof. The preparation method of the oxide material comprises the following steps that a doping agent containing chalcogenide elements is adopted, the chalcogenide elements are doped in wide band gap oxide in an ion implantation mode, the oxide material is obtained, and the wide band gap oxide comprises at least one of aluminum oxide, gallium oxide, zinc oxide or titanium oxide. According to the method, the surface band gap of the oxide is regulated and controlled through ion implantation of chalcogenide elements, accurate control over the doping concentration and depth can be achieved, the optical and electrical characteristics of the oxide can be remarkably adjusted, and the application prospect is good.

Description

Technical Field

[0001] The present invention belongs to the technical field of optoelectronic materials, and particularly relates to an oxide material, a preparation method thereof, and an application thereof. Background Art

[0002] Wide bandgap oxide materials such as alumina are widely used in microelectronics, optical windows, high-k gate oxides, and nonlinear optics due to their excellent chemical stability, high dielectric constant, high hardness, and optical transparency. The corundum structure of wide bandgap oxide materials such as alumina endows them with strong crystal stability, and their bandgap width is about 9 eV, which is the core advantage in high-performance materials. However, the wide bandgap characteristic of alumina also limits its flexible application in the optoelectronic field, especially the regulation of electronic and optical properties is relatively difficult.

[0003] In practical applications, the effective regulation of the surface bandgap is crucial for the performance of materials in optoelectronic devices. At present, the method of regulating oxide properties by doping or alloying has become a research hotspot. For example, the alloying research of gallium oxide, zinc oxide, and titanium oxide with alumina has shown a large bandgap regulation range. However, the alloying process often requires complex growth processes, and the precise control of doping concentration is challenging. The traditional doping methods of wide bandgap oxides usually directly introduce impurity elements into raw materials, such as crystal growth doping (vapor deposition doping) or thermal diffusion method, etc. These methods usually rely on doping during the crystal growth process, and the doping elements usually enter the material through solid-phase diffusion or vapor-phase diffusion. Therefore, it is difficult to precisely control the doping concentration and depth (such as the thermal diffusion method is prone to excessive diffusion of doping elements), and usually only overall doping can be achieved, which is difficult to meet the requirements of surface property regulation.

[0004] It can be seen that in the related technologies, it is difficult to achieve high-precision control of doping concentration and depth by conventional doping or alloying methods to regulate the properties of wide bandgap oxides, which to a certain extent limits the application of wide bandgap oxides in the optoelectronic field. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the above-mentioned prior art. For this purpose, the present invention provides a preparation method of an oxide material, which can regulate the surface bandgap of the oxide by ion implanting chalcogen elements, not only can achieve precise control of doping concentration and depth, but also can significantly regulate its optical and electrical properties, and has good application prospects.

[0006] The present invention also provides an oxide material.

[0007] The present invention also provides an optoelectronic material.

[0008] The present invention also provides an optoelectronic device.

[0009] In a first aspect of the present invention, a method for preparing an oxide material is provided, comprising the following steps: using a chalcogen - containing dopant, doping chalcogen elements into a wide - bandgap oxide by ion implantation to obtain the oxide material, wherein the wide - bandgap oxide comprises at least one of aluminum oxide, gallium oxide, zinc oxide, or titanium oxide.

[0010] The method for preparing an oxide material according to an embodiment of the present invention has at least the following beneficial effects:

[0011] Ion implantation technology is a surface modification technology with precise dose control and high lateral uniformity. By using ion implantation technology, the present invention can achieve high - concentration doping without changing the overall crystal structure of the wide - bandgap oxide (such as alpha - aluminum oxide, sapphire). Moreover, chalcogen elements have a high substitution ability for oxygen or metal sites (such as aluminum sites), and are ideal dopants. Even with high - dose ion implantation, they are not easily prone to lattice damage or introducing high - concentration point defects (especially defects related to oxygen vacancies). Therefore, by using a chalcogen - containing dopant and doping chalcogen elements into a wide - bandgap oxide by ion implantation, the present invention can not only achieve precise control of doping concentration and depth, but also significantly adjust the optical and electrical properties of the wide - bandgap oxide.

[0012] Furthermore, in the present invention, by adjusting the dose and energy of ion implantation, uniform doping and depth - controllable distribution of chalcogen elements on the surface of the wide - bandgap oxide can be achieved, significantly improving its optical and electrical properties, providing a new idea for the application of wide - bandgap oxides in the optoelectronic field, and having good application prospects.

[0013] In addition, the preparation cost of the present invention is low: compared with the high - cost doping crystal growth process (such as the Czochralski method), the ion implantation process can directly dope on the existing wide - bandgap oxide substrate (such as a sapphire substrate) without the need to additionally prepare a monocrystalline material with overall doping, greatly reducing the material production cost; ion implantation technology has high efficiency and repeatability, strong industrial adaptability, and can realize batch production, providing a more economical solution for industrial application. The ion implantation equipment required by the present invention is widely used in the semiconductor processing field, and the existing equipment can realize the doping process without large - scale modification, reducing the process development cost and having strong equipment adaptability.

[0014] In some embodiments of the present invention, the energy of the ion beam can be selected according to actual needs. For example, the ion implantation method can be selected as a low-energy ion beam implantation method or a higher-energy ion beam implantation method. Among them, compared with the higher-energy ion beam implantation method (such as the implantation acceleration voltage is above 120 kV), the low-energy ion beam implantation method has a lower implantation energy, which can reduce surface damage and achieve shallow doping. Optionally, in the low-energy ion beam implantation method, the implantation acceleration voltage is below 100 kV.

[0015] In some embodiments of the present invention, the wide-bandgap oxide includes alumina.

[0016] Through the above embodiments, the present invention regulates the surface bandgap of alumina (such as Alpha-alumina, sapphire) by ion implantation, realizing precise regulation of the surface bandgap of alumina. It has strong bandgap regulation ability, significantly improving its optical and electrical properties, and providing a new idea for the application of sapphire in the optoelectronic field. Specifically, this method injects chalcogen element ions (such as selenium ions) into the alumina single crystal to control the surface bandgap and electrical and optical properties of alumina. It is possible to achieve uniform doping and depth-controllable distribution of selenium on the surface of alumina by adjusting the ion implantation dose and energy.

[0017] For example, after the ultra-wide bandgap material is implanted with chalcogen elements (such as implanted with selenium), the bandgap width decreases significantly. In some embodiments of the present invention, it is measured that the bandgap of the oxide material obtained with different implantation doses gradually decreases from 7.27 eV to 5.81 eV, and the regulation range is as high as 1.46 eV, indicating that the present invention can significantly adjust the electronic structure of alumina. And compared with traditional doping methods (such as crystal growth doping or thermal diffusion method), the preparation method in the present invention has a wider bandgap regulation range for wide-bandgap oxides, and the depth and concentration distribution of element doping are more controllable: the ion implantation technology adopted in the present invention can achieve precise positioning of doping elements in the material by precisely controlling parameters such as implantation energy and dose, can control the depth and concentration distribution of doping elements, and can achieve a wider bandgap regulation range. Through this precise control, doping can be carried out in a relatively wide depth range to meet the requirements of different applications for bandgap adjustment, significantly improving the flexibility and controllability of preparation.

[0018] By regulating the bandgap and optical properties of alumina, the present invention provides a broader prospect for its application in optoelectronic devices (such as high-efficiency photocatalytic materials, optical windows, ultraviolet detectors, etc.), which helps to promote the progress of green energy and optoelectronic technology.

[0019] In the present invention, in addition to c-plane obliquely cut alumina single crystal, alumina of other planes can also be selected, such as r-plane and m-plane. In some embodiments of the present invention, the alumina is selected from at least one of c-plane alumina, r-plane alumina or m-plane alumina.

[0020] In some embodiments of the present invention, the chalcogen element includes at least one of S, Se or Te. Among them, the consumption of Se doping element is small during the ion implantation process, and there is no high temperature or chemical pollution emission in the process, which more meets the requirements of sustainable manufacturing; using Te doping can further reduce the bandgap of wide bandgap oxides (such as alumina) and enhance its optical absorption ability; while using S doping may have a more significant impact on the electrical properties of the surface of wide bandgap oxides (such as alumina).

[0021] In some embodiments of the present invention, the preparation method includes: taking a wide bandgap oxide matrix material, using a chalcogen element-containing substance as a dopant, and doping the chalcogen element into the wide bandgap oxide matrix material by ion implantation to obtain the oxide material.

[0022] In some embodiments of the present invention, the ion implantation dose range is 1×10 14 ions / cm 2 to 9×10 16 ions / cm 2 , such as optionally 5×10 14 ions / cm 2 to 5×10 16 ions / cm 2 .

[0023] Through the above embodiments, it is more conducive to obtaining a more moderate doping concentration and better crystal integrity.

[0024] In some embodiments of the present invention, the implantation depth of the ion implantation is 0-500 nm, such as optionally 0.1-50 nm.

[0025] In some embodiments of the present invention, the peak value of the ion implantation depth is 5-20 nm, such as optionally about 15 nm, to maximize the surface effect and minimize the bulk lattice damage. Unless otherwise specified, the peak value of the ion implantation depth in the present invention refers to the implantation depth at the maximum value of the doping ion implantation concentration in the oxide material.

[0026] In some embodiments of the present invention, the wide bandgap oxide matrix material is undoped c-plane α-Al2O3 single crystal, which makes the uniformity and stability of the initial surface of the wide bandgap oxide better, thereby enhancing the consistency of the material properties after doping. Optionally, the purity of the c-plane α-Al2O3 single crystal is more than 98%, such as 99.99% - 99.999% can be selected. Using high-purity single crystal alumina, such as between 99.99% (4N) and 99.999% (5N), electronic grade, can better reduce impurity interference and has a better element doping effect.

[0027] In some embodiments of the present invention, in the ion implantation step, the vacuum degree of the system is above 10 -5 Pa, so as to better reduce the introduction of pollutants during doping and be more conducive to the cleanliness of the experimental conditions.

[0028] In some embodiments of the present invention, in the ion implantation step, the implantation acceleration voltage is 20 - 100 kV, preferably 50 - 60 kV, in order to achieve a better ion distribution depth and minimize crystal damage.

[0029] In some embodiments of the present invention, the temperature of the ion implantation is 0 - 300 °C, such as 5 - 40 °C can be selected.

[0030] In some embodiments of the present invention, the chalcogen element ions are implanted at an angle of 12° or less with respect to the normal direction of the surface to be ion implanted of the wide bandgap oxide matrix material. Optionally, the chalcogen element ions are implanted at an angle of 2° - 12° with respect to the normal direction of the surface to be ion implanted of the wide bandgap oxide matrix material.

[0031] In some embodiments of the present invention, in the preparation method, it further includes: after doping the wide bandgap oxide matrix material with chalcogen elements by ion implantation, annealing the obtained material to obtain the oxide material.

[0032] In some embodiments of the present invention, the annealing temperature is 300 - 900 °C.

[0033] In some embodiments of the present invention, the annealing time is 1 - 30 min.

[0034] Through the above embodiments, after the ion implantation step, the material is gently annealed to repair the non-ideal defects introduced during the implantation process and at the same time stabilize the chemical state of the doped elements.

[0035] In some embodiments of the present invention, the annealing atmosphere condition is a protective atmosphere or a vacuum state. Optionally, the protective atmosphere can be a nitrogen atmosphere.

[0036] In some embodiments of the present invention, the dopant further includes a doping element A, and the element A includes at least one of the elements N, Mg or Ti.

[0037] On the basis of injecting chalcogen elements, co-doping with the doping element A is combined to further optimize the performance of the material. For example, the co-doping of Se and Ti can simultaneously improve the optical and mechanical properties of sapphire.

[0038] In some embodiments of the present invention, when the dopant includes chalcogen elements and the element A, the method and number of ion implantation are not limited. For example, it can be selected as multiple injections or the method of simultaneously injecting chalcogen elements and the element A. Optionally, the multiple injection method can be injecting chalcogen elements first and then injecting the element A, or injecting the element A first and then injecting chalcogen elements, etc.

[0039] In a second aspect of the present invention, an oxide material is proposed, which is obtained by using the preparation method of the above-mentioned oxide material.

[0040] In a third aspect of the present invention, the application of the above-mentioned oxide material in the preparation of optoelectronic devices is proposed.

[0041] In a fourth aspect of the present invention, an optoelectronic material is proposed, which includes the above-mentioned oxide material.

[0042] In a fifth aspect of the present invention, an optoelectronic device is proposed, which includes the above-mentioned oxide material or the above-mentioned optoelectronic material. Description of the Drawings

[0043] The present invention will be further described below in conjunction with the drawings and embodiments, where:

[0044] Figure 1 It is a test result diagram of the microstructure and element distribution of the oxide material in Example 5 of the present invention;

[0045] Figure 2 It is a test result diagram of the band gap of the alumina matrix material of the present invention and the oxide materials in Examples 1-5;

[0046] Figure 3 It is a SIMS test result diagram of the alumina matrix material of the present invention and the oxide materials in Examples 1-5. Detailed Embodiments

[0047] The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the purpose, features and effects of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts shall fall within the scope of protection of the present invention.

[0048] For the experimental methods without specific conditions in the following examples and comparative examples, they are generally carried out according to the conventional conditions in the art or according to the conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as the conventional market.

[0049] Example 1

[0050] This example discloses an oxide material. By using selenium as a dopant and injecting selenium ions into the substrate material alumina by ion implantation, an oxide material is obtained. Specifically, the preparation process of the oxide material specifically includes:

[0051] Take undoped alumina single crystal (Alpha-alumina, sapphire) as the substrate material, with a size of 10×10 mm 2 , and a thickness of 0.5 mm. Use pure selenium particles (analytical, purity 99.99%, 4N) as the dopant. To avoid the channeling effect, the selenium ions are injected at an angle of 10° with respect to the normal direction of the surface of the substrate material (the surface to be ion implanted). The selenium ion implantation dose is 5×10 14 ions / cm 2 , the implantation acceleration voltage is 50 kV, and the whole process is completed at room temperature under a vacuum of 10 -5 Pa.

[0052] This example also discloses an optoelectronic material, including the oxide material prepared in this example.

[0053] This example also discloses an optoelectronic device, including the optoelectronic material or the oxide material of this example.

[0054] Example 2

[0055] This example discloses an oxide material, which is only different from Example 1 in that: the selenium implantation dose is different. In this example, the selenium ion implantation dose is 1×10 15 ions / cm 2 , and other conditions are the same as those in Example 1.

[0056] This example also discloses an optoelectronic material, including the oxide material prepared in this example.

[0057] This example also discloses an optoelectronic device, including the optoelectronic material or the oxide material of this example.

[0058] Example 3

[0059] This example discloses an oxide material, which is only different from Example 1 in that: the selenium implantation dose is different. In this example, the selenium ion implantation dose is 5×10 15ions / cm 2 , and other conditions are the same as those in Example 1.

[0060] This example also discloses an optoelectronic material, including the oxide material obtained in this example.

[0061] This example also discloses an optoelectronic device, including the optoelectronic material of this example or the oxide material of this example.

[0062] Example 4

[0063] This example discloses an oxide material, which is different from that in Example 1 only in that: the selenium implantation dose is different, and the selenium ion implantation dose in this example is 1×10 16 ions / cm 2 , and other conditions are the same as those in Example 1.

[0064] This example also discloses an optoelectronic material, including the oxide material obtained in this example.

[0065] This example also discloses an optoelectronic device, including the optoelectronic material of this example or the oxide material of this example.

[0066] Example 5

[0067] This example discloses an oxide material, which is different from that in Example 1 only in that: the selenium implantation dose is different, and the selenium ion implantation dose in this example is 5×10 16 ions / cm 2 , and other conditions are the same as those in Example 1.

[0068] This example also discloses an optoelectronic material, including the oxide material obtained in this example.

[0069] This example also discloses an optoelectronic device, including the optoelectronic material of this example or the oxide material of this example.

[0070] Test Example

[0071] This test example conducted performance tests on the materials obtained in the examples, specifically including:

[0072] The surface morphologies of the substrate materials and oxide materials in the examples were characterized by scanning electron microscopy, and the element distributions were analyzed by energy dispersive spectroscopy. The chemical states and band gap changes after doping with different doses were analyzed by reflection electron energy loss spectroscopy (REELS). The concentration distribution of selenium ions with depth was tested by time-of-flight secondary ion mass spectrometry. Among them:

[0073] 1) The microscopic test and element distribution test results of the oxide material in Example 5 are as shown in Figure 1As shown, where (a) is the secondary electron image, (b) is the backscattered electron test result image, and (c)-(f) are the EDS-mapping images of C, O, Al, and Se elements.

[0074] 2) The band gaps of the alumina matrix material and the oxide materials in Examples 1-5 were measured by reflection electron energy loss spectroscopy, and the test results are respectively as shown in Figure 2 Figures (a)-(f) therein.

[0075] 3) The SIMS test results of the alumina matrix material and the oxide materials in Examples 1-5 are respectively as shown in Figure 3 Figures (a)-(f) therein, where the solid lines of Se, Al, and O respectively represent the distributions of selenium, aluminum, and oxygen elements in the material to be tested. The vertical axis is the mass spectrometry signal intensity (unit: count, meaningless unit), and the horizontal axis is the implantation depth (nanometers), and its depth is measured by a step gauge. The dotted line in the figure is the selenium ion concentration in the material to be tested, and the vertical axis is on the right side, with the concentration (unit: atoms per cubic centimeter).

[0076] The experimental results show that the preparation method of the oxide material of the present invention significantly reduces the band gap of alumina, effectively realizes the regulation of the surface band gap of wide-bandgap alumina, and verifies the feasibility of adjusting the electronic and optical properties in optoelectronic devices, providing a new idea for the development of high-performance optoelectronic materials. Specifically, the preparation method of the oxide material of the present invention provides a precise and controllable method for optimizing its optoelectronic properties, can achieve more precise doping concentration control, more significant band gap regulation effect (able to reduce by more than 1.5 eV), and reduce crystal damage, further improving the performance of sapphire materials in optoelectronic devices. Among them:

[0077] Regarding the doping depth and concentration: Measured by TOF-SIMS: In the oxide materials of Examples 1-5, the peak value of the Se ion implantation depth is about 12-16 nm, and the Se implantation depth is about 80-120 nm.

[0078] Table 1 SIMS measurement result table

[0079]

[0080]

[0081] Improvement of surface doping uniformity and controllability: The EDS results further verify the uniformity of surface doping of the obtained oxide materials, avoiding the defect of uneven doping in the traditional method.

[0082] Optimization of the optical properties of materials: Along with a significant reduction in the bandgap, the surface of the sapphire sample changes color (from colorless to dark) due to the doping of Se, indicating a significant change in the optical absorption range. This lays the foundation for the application of sapphire in the optoelectronic field (such as in the fields of optical absorbers, photocatalysis, etc.), with significant economic and social benefits, and provides a new solution for the development and practical application of high-performance optoelectronic materials.

[0083] In summary, the present invention provides a method for regulating the surface bandgap of wide-bandgap oxides through ion implantation. By means of ion implantation technology, precise regulation of the surface bandgap of wide-bandgap oxides (such as sapphire) is achieved, significantly improving their optical and electrical properties, and providing a new technical path for their efficient application in the optoelectronic field. For example, by using selenium ions as dopants and combining optimized implantation parameters (such as an implantation angle of 10°, an acceleration voltage of 50 kV, and gradient dose control), the technical problems of uneven doping concentration, uncontrollable depth, and limited bandgap regulation range in traditional doping methods are better solved. In addition, optionally, the present invention can further utilize SRIM simulation to guide the implantation design and accurately characterize the chemical state and bandgap change of the doped sample through reflection electron energy loss spectroscopy, achieving for the first time the regulation effect of a significant reduction in the bandgap from 9 eV to 5.81 eV. Compared with traditional methods, the present invention not only has high precision, low damage, and high repeatability in the process, but also significantly expands the application range of wide-bandgap oxides (such as sapphire materials), providing new ideas and technical support for the functional design of wide-bandgap oxides.

[0084] Unless otherwise specified, the "about" in the present invention actually means that the allowable error is within the range of ±5%. For example, about 100 is actually 100 ± 5% × 100. The "normal temperature" and "room temperature" in the present invention are about 20 - 30 °C unless otherwise specified. The "between... and..." in the present invention includes the endpoints. For example, "between 2 and 3" includes the endpoint values 2 and 3.

[0085] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the knowledge scope of those of ordinary skill in the art to which the present invention pertains, various changes can be made without departing from the purpose of the present invention. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other without conflict.

Claims

1. A method for preparing an oxide material, characterized in that, It includes the following steps: using a chalcogen-containing dopant, doping chalcogen elements into a wide-bandgap oxide by ion implantation to obtain the oxide material, wherein the wide-bandgap oxide includes at least one of aluminum oxide, gallium oxide, zinc oxide or titanium oxide.

2. The method for preparing an oxide material according to claim 1, wherein The chalcogen elements include at least one of S, Se or Te.

3. The preparation method of the oxide material according to claim 1, wherein The ion implantation dose ranges from 1×10 14 ions / cm 2 to 9×10 16 ions / cm 2 ; and / or, the implantation depth of the ion implantation is 0 to 500 nm; and / or, the peak of the ion implantation depth is 5 to 20 nm; and / or, in the ion implantation step, the vacuum degree of the system is above 10 -5 Pa; and / or, in the ion implantation step, the implantation acceleration voltage is 20 to 100 kV; and / or, the temperature of the ion implantation is 0 to 300 °C.

4. The preparation method of the oxide material according to claim 1, characterized in that, In the preparation method, it further includes: after doping chalcogen elements into the wide-bandgap oxide matrix material by ion implantation, annealing the obtained material to obtain the oxide material.

5. The preparation method of the oxide material according to claim 4, wherein The annealing temperature is 300-900 °C; and / or the annealing time is 1-30 min.

6. The preparation method of the oxide material according to claim 1, characterized in that, The dopant further includes doping element A, and the element A includes at least one of element N, Mg or Ti.

7. An oxide material, characterized in that, It is obtained by using the preparation method of the oxide material according to any one of claims 1-6.

8. Application of the oxide material obtained by the preparation method of the oxide material according to any one of claims 1-6 or the oxide material according to claim 7 in the preparation of optoelectronic devices.

9. An optoelectronic material, characterized in that, It includes the oxide material obtained by the preparation method of the oxide material according to any one of claims 1-6 or the oxide material according to claim 7.

10. An optoelectronic device, characterized in that, It includes the oxide material obtained by the preparation method of the oxide material according to any one of claims 1-6 or the oxide material according to claim 7 or the optoelectronic material according to claim 9.

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