Doped hafnium oxide material, preparation method of doped hafnium oxide material, device and preparation method of device
By doping hafnium oxide with metal elements, a doped hafnium oxide material of Hf0.5X0.5+mO2 was prepared, which solved the problems of low polarization, low dielectric constant and easy fatigue of existing hafnium oxide-based ferroelectric materials, and realized the fabrication of high-performance ferroelectric memory.
Patent Information
- Application Number
- CN202510754086.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-06
- Publication Date
- 2025-12-30
AI Technical Summary
Existing hafnium oxide-based ferroelectric materials suffer from low spontaneous polarization, low dielectric constant, high coercivity, and susceptibility to fatigue, which limits their performance improvement in ferroelectric memory and related devices.
By doping hafnium oxide with metal elements of chemical valence states of +3 to +5, Hf0.5X0.5+mO2-doped hafnium oxide material was prepared. By using atomic layer deposition and annealing to control the formation of polar phases, devices with high polarization, high dielectric constant and low coercivity were fabricated.
The polarization performance of hafnium oxide material was improved to 2Pr>120μC/cm2, the dielectric constant was increased to ε>140, the coercive field was reduced to Ec<2MV/cm, and the fatigue characteristics were excellent, with a cycle life of more than 1×1012.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of electronic information materials and devices, and in particular to a doped hafnium oxide material and its preparation method, as well as a device and its preparation method. Background Technology
[0002] Ferroelectric materials, which possess spontaneous polarization that can be reversed under an external field, are key materials for fabricating dielectric layers in memory and semiconductor devices. However, the fabrication processes of commercially widely used traditional perovskite-structured multi-component oxide ferroelectric materials, such as lead titanate and bismuth titanate, are poorly compatible with complementary metal-oxide-semiconductor (CMOS) processes. Furthermore, the ferroelectricity of these materials decreases or even disappears when their thickness is reduced to the nanoscale, making it difficult to further reduce the node size of ferroelectric memory technologies and limiting further improvements in the storage density and other performance characteristics of ferroelectric memories.
[0003] In recent years, ferroelectricity has been discovered in hafnium oxide-based materials used as high-k layers in semiconductor processes. This material maintains ferroelectricity even when its thickness is reduced to the nanoscale. Not only is it compatible with semiconductor processes, but its ferroelectricity is also unaffected by size, making it a key material for developing high-density ferroelectric devices. However, current hafnium oxide-based ferroelectric materials exhibit relatively low remanent polarization (2P). r <60μC / cm 2 It has a low dielectric constant (ε<40) and a high coercive field (E). c >2MV / cm) and easy fatigue (number of cycles <1×10 10 All of these are inferior to currently available commercial ferroelectric materials used in ferroelectric memory, such as lead zirconate titanate (2P). r >100μC / cm 2 ,ε>150,E c <2MV / cm). The poor performance of hafnium oxide-based materials is one of the limiting factors for their application in ferroelectric memory and related devices.
[0004] Therefore, existing technologies still need to be improved and developed. Summary of the Invention
[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a doped hafnium oxide material and its preparation method, as well as a device and its preparation method, in order to solve the problems of low spontaneous polarization, low dielectric constant, high coercive field and easy fatigue of existing hafnium oxide-based ferroelectric materials.
[0006] The technical solution of the present invention is as follows:
[0007] A doped hafnium oxide material, wherein the hafnium oxide material is doped with a metal element with a chemical valence range of +3 to +5, and the chemical formula of the doped hafnium oxide material is Hf. 0.5 X0.5+m O2, where X is a metallic element and m is -0.4 to 0.8.
[0008] The doped hafnium oxide material wherein the metal element is selected from one or more of Ba, Zr, Al, La, and Y.
[0009] The doped hafnium oxide material, wherein when the doped hafnium oxide material is doped with two metal elements, the atomic ratio between the two metal elements is 1:(0.1-0.7); and when the doped hafnium oxide material is doped with three metal elements, the atomic ratio between the three metal elements is 1:(0.1-0.7):(0.1-0.7).
[0010] The doped hafnium oxide material, wherein the polar phase structure of the doped hafnium oxide material includes one or more of the following: a polar orthorhombic phase with point groups Pca21 and Pnm21, and a polar rhombohedral phase with space point groups R3 and R3m.
[0011] A method for preparing a doped hafnium oxide material, comprising the following steps:
[0012] Provide a substrate with a first buffer layer;
[0013] The deposition sequence of hafnium, metal element X, and oxygen was set, and the hafnium oxide was grown on the first buffer layer of the substrate using atomic layer deposition. After annealing, the doped hafnium oxide material was obtained.
[0014] The method for preparing the doped hafnium oxide material, wherein the deposition sequence includes one or more of X-oxy-hafnium-oxygen, hafnium-oxy-X-oxygen, oxygen-X-oxy-hafnium, and oxygen-hafnium-oxygen-X; or, the deposition sequence includes one or more of hafnium-oxygen, oxygen-hafnium, X-oxygen, and oxygen-X combined with one or more of X-oxy-hafnium-oxygen, hafnium-oxy-X-oxygen, oxygen-X-oxy-hafnium, and oxygen-hafnium-oxygen-X.
[0015] The method for preparing the doped hafnium oxide material, wherein in the atomic layer deposition method, the deposition temperature is 200–300°C, and the growth rate of the hafnium element and the metal element X is [missing information].
[0016] The method for preparing the doped hafnium oxide material, wherein the growth cycle of growing on the first buffer layer of the substrate using atomic layer deposition is 10 to 100 times; and the thickness of the doped hafnium oxide material is 2 to 30 nm.
[0017] A device based on doped hafnium oxide material includes a silicon wafer, a bottom electrode, a first buffer layer, a doped hafnium oxide material layer, a second buffer layer, and a top electrode stacked sequentially from bottom to top.
[0018] The device wherein the thickness of the first buffer layer is 0.1–10 nm; the thickness of the second buffer layer is 0.1–10 nm; and the materials of the first and second buffer layers are independently selected from one or more of hafnium oxide, zirconium oxide, aluminum oxide, titanium oxide, titanium nitride, titanium tantalum, and gallium nitride.
[0019] The device wherein the material of the top electrode includes one or more of titanium nitride, tungsten, gold, silver, platinum, titanium, and copper; the thickness of the top electrode is between 10 and 200 nm; and / or the material of the bottom electrode includes one or more of titanium nitride, tungsten, gold, silver, platinum, titanium, and copper; the thickness of the bottom electrode is between 10 and 200 nm.
[0020] A method for fabricating a device, comprising the following steps:
[0021] A first buffer layer is deposited on a silicon wafer with a bottom electrode;
[0022] The deposition order of hafnium, metal element X and oxygen is set, and the hafnium oxide layer is grown on the first buffer layer using atomic layer deposition to obtain a doped hafnium oxide layer.
[0023] A second buffer layer is prepared on the doped hafnium oxide layer;
[0024] A top electrode is fabricated on the second buffer layer and then annealed to obtain the device.
[0025] The method for fabricating the device, wherein the annealing temperature is 400–800°C, the annealing time is 10–600 s, the heating rate of the annealing is 20–70°C / s, and the cooling rate of the annealing is 0.5–5°C / s.
[0026] Beneficial effects: This invention provides a doped hafnium oxide material and its preparation method, as well as a device and its preparation method. The hafnium oxide material is doped with a metal element with a chemical valence range of +3 to +5, and the chemical formula of the doped hafnium oxide material is Hf. 0.5 X 0.5+m O2, where X is a metallic element and m is -0.4 to 0.8. Since hafnium has a +4 valence, this invention utilizes metallic elements with valences lower or higher than +4 to dope hafnium oxide, providing additional charge centers in the material and thus facilitating the formation of the polar phase. If the metallic element is an equivalent +4 valence dopant, the formation energy of the polar phase will be reduced, thereby increasing the content of the polar phase. Furthermore, devices based on this doped hafnium oxide material simultaneously exhibit high polarization (2P). r >120μC / cm 2 High dielectric constant (ε>140), low coercive field (Ec <2MV / cm) and high fatigue properties (cycle count >1×10⁻⁶). 12 (The excellent characteristics of) Attached Figure Description
[0027] Figure 1 This is a schematic diagram of the phase content structure of the hafnium oxide doped in Examples 1-4;
[0028] Figure 2 The X-ray diffraction pattern and hysteresis loop diagram of aluminum-doped hafnium oxide prepared in Example 1 are shown.
[0029] Figure 3 The X-ray diffraction pattern of zirconium-doped hafnium oxide prepared in Example 2 is shown below.
[0030] Figure 4 A comparison of the polarization properties and dielectric constant properties of hafnium oxide with different phase contents;
[0031] Figure 5 A comparison chart of the fatigue performance of hafnium oxide with different phase contents;
[0032] Figure 6 A comparison diagram of the coercive fields of hafnium oxide with different phase contents. Detailed Implementation
[0033] This invention provides a doped hafnium oxide material and its preparation method, as well as a device and its preparation method. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
[0034] It will be understood by those skilled in the art that, unless otherwise defined, all terms used herein (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. It should also be understood that terms such as those defined in general dictionaries should be understood to have the same meaning as in the context of the prior art, and should not be interpreted in an idealized or overly formal sense unless specifically defined as herein.
[0035] This invention provides a doped hafnium oxide material, wherein the hafnium oxide material is doped with a metal element with a chemical valence range of +3 to +5, and the chemical formula of the doped hafnium oxide material is Hf. 0.5 X 0.5+m O2, where X is a metallic element and m is -0.4 to 0.8.
[0036] In this embodiment, doping hafnium oxide with a metal element of a valence lower than or higher than +4 provides additional charge centers in the material, thereby facilitating the formation of the polar phase. If the metal element is an equivalent +4 dopant, the formation energy of the polar phase is reduced, thus increasing the content of the polar phase. Furthermore, the doped hafnium oxide material and device simultaneously exhibit high polarization (2P). r >120μC / cm 2 High dielectric constant (ε>140), low coercive field (E c <2MV / cm) and high fatigue properties (cycle count >1×10⁻⁶). 12 (The excellent characteristics of)
[0037] Specifically, when this doped hafnium oxide material is applied to a device, the base electrode provides a confinement effect, and a buffer layer between the electrode and the hafnium oxide is used. Combined with the annealing process and the deposition order of different elements, the formation energy of the polar phase is reduced, and the formation of the polar phase is promoted. Finally, a doped hafnium oxide thin film containing only different polar phases and no non-polar phase is obtained.
[0038] In some embodiments, the metal element is selected from, but not limited to, one or more of Ba, Zr, Al, La, and Y. Since hafnium has a +4 valence, the valence states of the aforementioned metal elements are all below or above +4. Using them to dope hafnium oxide can provide additional charge centers in the material, thereby facilitating the formation of polar phases.
[0039] In some embodiments, when the doped hafnium oxide material is doped with two metal elements, the atomic ratio between the two metal elements is 1:(0.1 to 0.7); when the doped hafnium oxide material is doped with three metal elements, the atomic ratio between the three metal elements is 1:(0.1 to 0.7):(0.1 to 0.7).
[0040] Specifically, the atomic ratio of hafnium to metallic element X, Hf:X = 0.5:0.5+m, where m ranges from -0.4 to 0.8. If it is a single-element doping, m represents the content of that single element; if it is a two-element doping, m represents the sum of the contents of both elements. The atomic ratio of the two metallic elements A and B is A:B = 1:C, where C ranges from 0.1 to 0.7. Within this range, hafnium oxide exhibits optimal polarization, dielectric constant, and fatigue characteristics.
[0041] In addition, the present invention also provides a method for preparing a doped hafnium oxide material, comprising the following steps:
[0042] Step S10: Provide a substrate with a first buffer layer;
[0043] Step S20: Set the deposition order of hafnium, metal element X and oxygen, grow it on the first buffer layer of the substrate using atomic layer deposition, and obtain doped hafnium oxide material after annealing.
[0044] In this embodiment, the hafnium oxide material in thin film form prepared by the above-described method utilizes the confinement effect provided by the substrate electrode, a buffer layer between the electrode and the hafnium oxide, and annealing and different element deposition sequences to reduce the formation energy of the polar phase and promote its formation. Ultimately, a doped hafnium oxide thin film containing only different polar phases and no non-polar phase is obtained. Furthermore, the hafnium oxide material and device prepared based on this process simultaneously exhibit high polarization (2P). r >120μC / cm 2 High dielectric constant (ε>140), low coercive field (E c <2MV / cm) and high fatigue properties (cycle count >1×10⁻⁶). 12 (The excellent characteristics of)
[0045] In some embodiments, the doped hafnium oxide material prepared by the above method has a special polar phase structure, including one or more of the following polar phases: polar orthorhombic phase with point groups Pca21 and Pnm21; and polar rhombohedral phase with space point groups R3 and R3m.
[0046] In some embodiments, the deposition sequence includes one or more of X-oxy-hafnium-oxygen, hafnium-oxygen-X-oxygen, oxygen-X-oxygen-hafnium, and oxygen-hafnium-oxygen-X; or, the deposition sequence includes one or more of hafnium-oxygen, oxygen-hafnium, X-oxygen, and oxygen-X combined with one or more of X-oxy-hafnium-oxygen, hafnium-oxygen-X-oxygen, oxygen-X-oxygen-hafnium, and oxygen-hafnium-oxygen-X. Completion of one deposition sequence represents one growth cycle. A single deposition sequence can be used during fabrication, or multiple deposition sequences can be used together. Hafnium oxide materials and devices fabricated based on this process simultaneously exhibit large polarization (2P). r >120μC / cm 2 High dielectric constant (ε>140), low coercive field (E c <2MV / cm) and high fatigue properties (cycle count >1×10⁻⁶). 12 (The excellent characteristics of)
[0047] In some embodiments, the atomic layer deposition method uses a deposition temperature of 200–300°C, and the growth rates of the hafnium element and the metal element X are [missing information]. The ratio of hafnium to metal elements is controlled by adjusting the growth rate, thereby achieving precise doping.
[0048] In some embodiments, the annealing temperature is 400–800°C, the annealing time is 10–600 s, and the annealing atmosphere is one or more of nitrogen and argon; a polar phase will be formed in the doped hafnium oxide layer after annealing.
[0049] In some embodiments, the growth cycle for growing the first buffer layer of the substrate using atomic layer deposition is 10 to 100 times; the thickness of the doped hafnium oxide material is 2 to 30 nm. The thickness of the doped hafnium oxide material can be precisely controlled by controlling the growth cycle, and within this thickness range, the polar phase is easily formed.
[0050] In addition, the present invention also provides a device based on doped hafnium oxide material, comprising a silicon wafer, a bottom electrode, a first buffer layer, doped hafnium oxide material, a second buffer layer, and a top electrode stacked sequentially from bottom to top.
[0051] In this embodiment, the device with this structure has large polarization (2P). r >120μC / cm 2 High dielectric constant (ε>140), low coercive field (E c <2MV / cm) and high fatigue properties (cycle count >1×10⁻⁶). 12 (The excellent characteristics of)
[0052] In some embodiments, the thickness of the first buffer layer is 0.1 to 10 nm; the thickness of the second buffer layer is 0.1 to 10 nm; and the materials of the first and second buffer layers are independently selected from one or more of hafnium oxide, zirconium oxide, aluminum oxide, titanium oxide, titanium nitride, titanium tantalum, and gallium nitride.
[0053] In some embodiments, the top electrode is made of one or more of titanium nitride, tungsten, gold, silver, platinum, titanium, and copper; the thickness of the top electrode is between 10 and 200 nm; and / or, the bottom electrode is made of one or more of titanium nitride, tungsten, gold, silver, platinum, titanium, and copper; the thickness of the bottom electrode is 10 to 200 nm. Using the above electrodes allows the prepared hafnium oxide material to form a polar phase, thereby exhibiting polarization characteristics.
[0054] Meanwhile, the present invention also provides a method for fabricating a device, comprising the following steps:
[0055] Step S100: Deposit a first buffer layer on a silicon wafer having a bottom electrode;
[0056] Step S200: Set the deposition order of hafnium, metal element X and oxygen, and grow it on the first buffer layer using atomic layer deposition to obtain a doped hafnium oxide layer;
[0057] Step S300: Prepare a second buffer layer on the doped hafnium oxide layer;
[0058] Step S400: A top electrode is fabricated on the second buffer layer and then annealed to obtain the device.
[0059] In this embodiment, doping hafnium oxide with a metal element of valence lower than or higher than +4 provides additional charge centers in the material, thereby facilitating the formation of a polar phase; the device fabricated using the above method also exhibits high polarization (2P). r >120μC / cm 2 High dielectric constant (ε>140), low coercive field (E c <2MV / cm) and high fatigue properties (cycle count >1×10⁻⁶). 12 (The excellent characteristics of)
[0060] In some embodiments, a bottom electrode is fabricated on a silicon wafer and a top electrode is fabricated on a buffer layer using processes such as magnetron sputtering, electron beam evaporation, and thermal evaporation. Electrodes fabricated using these methods can form a polar phase in the prepared hafnium oxide material, thereby exhibiting polarization characteristics.
[0061] In some embodiments, before step S100, the silicon wafer with the bottom electrode is pretreated, including treatment with plasma, ozone and ultrasound, for a cleaning time of 30 to 500 seconds and a cleaning temperature of 25 to 100°C.
[0062] In some implementations, the methods for depositing dielectric layers include, but are not limited to, magnetron sputtering, atomic layer deposition, etc.
[0063] In some embodiments, in step S300, a buffer layer is prepared on the doped hafnium oxide layer using magnetron sputtering, electron beam evaporation, or thermal evaporation. The magnetron sputtering process parameters are: sputtering power 50–120 W, sputtering temperature 25–100 °C, and sputtering time 10–500 s. For electron beam evaporation, the temperature of the silicon wafer containing the hafnium oxide film is 25–200 °C during electron beam evaporation. For thermal evaporation, the growth rate… Vacuum deposition, vacuum degree less than 10 -6 During thermal evaporation, the temperature of the silicon wafer is 25-200℃.
[0064] In some embodiments, step S400 further includes patterning the top electrode; the patterning of the top electrode is achieved by photolithography, masking, or etching.
[0065] In some embodiments, the annealing temperature is 400–800°C, the annealing time is 10–600 s, the heating rate is 20–70°C / s, and the cooling rate is 0.5–5°C / s; the annealing atmosphere is one or more of nitrogen and argon; a polar phase will be formed in the doped hafnium oxide layer after annealing.
[0066] In a preferred embodiment, the annealing temperature is 600°C, the annealing time is 20–100 s, the heating rate of the annealing is 30°C / s, and the cooling rate of the annealing is 1°C / s.
[0067] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are within the scope of protection of the present invention.
[0068] Example 1
[0069] TiN top and bottom electrodes were fabricated by magnetron sputtering, each with a thickness of 50 nm. The doped hafnium oxide material was made of aluminum, and the deposition sequence was hafnium-oxygen-aluminum-oxygen, resulting in a 10 nm thick hafnium oxide film. The film was annealed at 650 °C for 60 s. 0.7 Al 0.3 A schematic diagram of the phase structure of O2 is shown below. Figure 1 As shown in A, the thin film contains both polar and nonpolar phases.
[0070] The aluminum-doped hafnium oxide prepared in Example 1 was characterized, and its X-ray diffraction pattern was obtained. Figure 2 A) and hysteresis loop diagram ( Figure 2 B) in Figure 2 As shown, o represents the polar phase and m represents the nonpolar phase, indicating the existence of a nonpolar phase.
[0071] Example 2
[0072] A magnetically controlled top electrode and a TiN bottom electrode were fabricated, both with a thickness of 50 nm. The buffer layer was made of alumina with a thickness of 2 nm. The doped hafnium oxide material was made of zirconium, and the deposition sequence was hafnium-oxygen-zirconium-oxygen, with a film thickness of 15 nm and a composition of Hf. 0.5 Zr 0.7 O2; after annealing at 550℃ for 60s, its phase structure diagram is shown below. Figure 1 As shown in B, the thin film is entirely composed of polar orthorhombic / rhombohedral phases.
[0073] The zirconium-doped hafnium oxide prepared in Example 2 was characterized, and its X-ray diffraction pattern is shown below. Figure 3 As shown, 'o' represents the polar phase, indicating that the Hf prepared in this embodiment... 0.5 Zr 0.7 O2 is entirely polar.
[0074] Example 3
[0075] A magnetically controlled top electrode and a bottom electrode (W) are fabricated, each with a thickness of 100 nm. The buffer layer is made of zirconium oxide and has a thickness of 1 nm. The doped hafnium oxide material contains yttrium and zirconium metals, deposited in the order hafnium-oxygen-yttrium-oxygen-zirconium-oxygen, with a film thickness of 20 nm and a composition of Hf. 0.5 Y 0.1 Zr 0.6 O2, annealed at 600℃ for 90s, has the following phase structure diagram: Figure 1 As shown in C, the thin film has orthogonal polarity and rhombohedral phase.
[0076] Example 4
[0077] Pt top electrode and Au bottom electrode were prepared by electron beam evaporation. Both the top and bottom electrodes were 80 nm thick. The buffer layer was made of hafnium oxide with a thickness of 3 nm. The doped hafnium oxide material was aluminum, and the deposition sequence was hafnium-oxygen-aluminum-oxygen. The film was 10 nm thick and composed of Hf. 0.8 Y 0.2 O2, annealed at 650℃ for 30s, has the following phase structure diagram: Figure 1 As shown in D, the thin film is entirely a polar phase.
[0078] The devices prepared in Examples 1 and 2 were characterized, and the polarization properties and dielectric constant properties of hafnium oxide with different phase contents were compared. Figure 4 As shown; the fatigue properties of hafnium oxide with different phase contents are compared to, for example... Figure 5 As shown; the coercive field pairs of hafnium oxide with different phase contents, for example Figure 6 As shown, doped hafnium oxide films containing a nonpolar phase exhibit low polarization and dielectric constant due to the purity of the nonpolar phase, which is also the reason for the low polarization and dielectric constant in similar current works. However, the fully polar doped hafnium oxide film prepared based on the process of this invention exhibits performance improvements of more than double compared to similar works reported in the literature, representing the highest values for this type of work to date. The nonpolar phase leads to a transition from the polar phase to the nonpolar phase during fatigue testing, resulting in poor fatigue performance. The fully polar doped hafnium oxide film prepared by this invention achieves a cycle test result of 1×10⁻⁶. 12 The number of times exceeded the standard for commercial memory (>1×10). 12 Meanwhile, the coercive field of the doped hafnium oxide film based on the all-polar phase is also relatively small.
[0079] In summary, this invention provides a doped hafnium oxide material and its preparation method, as well as a device and its preparation method. The hafnium oxide material is doped with a metal element with a chemical valence range of +3 to +5, and the chemical formula of the doped hafnium oxide material is Hf. 0.5 X 0.5+m O2, where X is a metallic element and m is -0.4 to 0.8. Since hafnium has a +4 valence, this invention utilizes metallic elements with valences lower or higher than +4 to dope hafnium oxide, providing additional charge centers in the material and thus facilitating the formation of the polar phase. If the metallic element is an equivalent +4 valence dopant, the formation energy of the polar phase will be reduced, thereby increasing the content of the polar phase. Furthermore, devices based on this doped hafnium oxide material simultaneously exhibit high polarization (2P). r >120μC / cm 2 High dielectric constant (ε>140), low coercive field (E c <2MV / cm) and high fatigue properties (cycle count >1×10⁻⁶). 12 (The excellent characteristics of)
[0080] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.
Claims
1. A doped hafnium oxide material, characterized in that, The hafnium oxide material is doped with a metal element having a valence ranging from +3 to +5 valence, and the doped hafnium oxide material has a chemical formula of Hf 0.5 X 0.5+m O2, wherein X is a metal element, and m is -0.4 to 0.
8.
2. The doped hafnium oxide material of claim 1, wherein, The metal element is selected from one or more of Ba, Zr, Al, La, Y.
3. The doped hafnium oxide material of claim 1, wherein, When the doped hafnium oxide material is doped with two metal elements, the atomic ratio between the two metal elements is 1:(0.1-0.7); when the doped hafnium oxide material is doped with three metal elements, the atomic ratio between the three metal elements is 1:(0.1-0.7):(0.1-0.7).
4. The doped hafnium oxide material of claim 1, wherein, The polar phase structure of the doped hafnium oxide material comprises one or more of a polar orthorhombic phase with point group Pca21 and Pnm21, and a polar rhombohedral phase with space point group R3, R3m.
5. A method of producing a doped hafnium oxide material as claimed in any one of claims 1 to 4, characterized in that, The method comprises the steps of: providing a substrate with a first buffer layer; setting a deposition sequence of the hafnium element, the metal element X, and the oxygen element, and growing on the first buffer layer of the substrate by atomic layer deposition, to obtain the doped hafnium oxide material after annealing.
6. The method of claim 5, wherein the method further comprises: The deposition sequence comprises one or more of X-oxygen-hafnium-oxygen, hafnium-oxygen-X-oxygen, oxygen-X-oxygen-hafnium, oxygen-hafnium-oxygen-X; or, the deposition sequence comprises one or more of hafnium-oxygen, oxygen-hafnium, X-oxygen, oxygen-X in combination with one or more of X-oxygen-hafnium-oxygen, hafnium-oxygen-X-oxygen, oxygen-X-oxygen-hafnium, oxygen-hafnium-oxygen-X.
7. The method of claim 5, wherein the method further comprises: In the atomic layer deposition method, the deposition temperature is 200 to 300°C, and the growth rate of the hafnium element and the metal element X is 8. The method of claim 5, wherein the doped hafnium oxide material is prepared by a method comprising: depositing a hafnium precursor on a substrate; and exposing the hafnium precursor to a reactive gas to form the doped hafnium oxide material. The growing cycle of growing on the first buffer layer of the substrate by atomic layer deposition is 10-100 times; the thickness of the doped hafnium oxide material is 2-30 nm.
9. A device based on the doped hafnium oxide material of any of claims 1-4, wherein, The device comprises, from bottom to top, a silicon wafer, a bottom electrode, a first buffer layer, a doped hafnium oxide material layer, a second buffer layer, and a top electrode.
10. The device of claim 9, wherein, The thickness of the first buffer layer is 0.1-10 nm; the thickness of the second buffer layer is 0.1-10 nm; the material of the first buffer layer and the second buffer layer is independently selected from one or more of hafnium oxide, zirconium oxide, aluminum oxide, titanium oxide, titanium nitride, titanium tantalum, gallium nitride.
11. The device of claim 10, wherein, The material of the top electrode comprises one or more of titanium nitride, tungsten, gold, silver, platinum, titanium, copper; the thickness of the top electrode is between 10-200 nm; and / or, the material of the bottom electrode comprises one or more of titanium nitride, tungsten, gold, silver, platinum, titanium, copper; the thickness of the bottom electrode is 10-200 nm.
12. A method of manufacturing a device as claimed in any one of claims 9-11, characterized in that The method comprises the steps of: depositing a first buffer layer on a silicon wafer with a bottom electrode; setting a deposition sequence of the hafnium element, the metal element X, and the oxygen element, and growing on the first buffer layer by atomic layer deposition to obtain a doped hafnium oxide layer; preparing a second buffer layer on the doped hafnium oxide layer; preparing a top electrode on the second buffer layer, to obtain the device after annealing.
13. The method of producing a device according to claim 12, wherein The temperature of the annealing process is 400-800℃, the time of the annealing process is 10-600s, the heating rate of the annealing process is 20-70℃ / s, and the cooling rate of the annealing process is 0.5-5℃ / s.