A hafnium-based ferroelectric thin film oxygen defect content control method

Abstract

The application relates to a hafnium-based ferroelectric film oxygen defect content control method, which comprises the following steps: configuring a hafnium-based ferroelectric film preparation raw material; setting a growth oxygen regulation parameter; preparing a hafnium-based ferroelectric film by using the hafnium-based ferroelectric film preparation raw material according to the growth oxygen regulation parameter; setting an annealing oxygen regulation parameter; performing an annealing operation on the hafnium-based ferroelectric film according to the annealing oxygen regulation parameter; setting a reannealing oxygen regulation parameter; and performing a reannealing operation on the hafnium-based ferroelectric film according to the reannealing oxygen regulation parameter. The hafnium-based ferroelectric film oxygen defect content control method provided by the application effectively regulates the oxygen content in the device from three aspects of growth oxygen, annealing oxygen and reannealing oxygen, meets the manufacturing process of the back end, and is beneficial to the research and development of hafnium-based ferroelectric memory chips.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oxygen defect content control, and particularly relates to a hafnium-based ferroelectric film oxygen defect content control method. BACKGROUND

[0002] When oxide, nitride and other thin film materials are prepared by using an ALD (atomic layer deposition) method, the oxygen, nitrogen and other element contents and distributions in the thin film play a decisive role in the performance of the thin film, especially the element content during layer-by-layer deposition plays a key role in the formation of phase structure, defect distribution at local, internal and interface, and further affects the device phase structure. Therefore, how to adjust the element content of each layer, especially the oxygen content, is an important research direction.

[0003] The existing deposition method cannot realize layer-by-layer (about 0.1 nm, atomic layer) regulation (0-100% content) of the oxygen content in the thin film, and thus cannot accurately regulate the oxygen defects. In addition, different oxygen source materials provide different valence states of oxygen, and the thin films deposited by combining different valence states of oxygen with the precursors have different oxygen contents and different oxygen defect concentrations. These affect the phase structure formation, defect concentration and distribution, and device reliability.

[0004] The hafnium-based ferroelectric film crystallization needs to be subjected to rapid annealing (RTA), and the oxygen atmosphere in the annealing process is also very important. The pressure of the existing rapid annealing method is usually about 100 Pa, and only the atmosphere (oxygen, nitrogen, argon or mixed gas) can be changed, and the pressure is not taken as an important influencing factor for research.

[0005] The formation of the hafnium oxide ferroelectric phase needs a certain oxygen defect, and thus the oxygen defect is an important factor affecting the ferroelectric characteristics. However, there is no very suitable and convenient method for realizing the regulation of the element content of a single atomic layer, especially the regulation of the oxygen content at the electrode / ferroelectric interface, in the atomic layer deposition process. SUMMARY

[0006] Therefore, the present application provides a hafnium-based ferroelectric film oxygen defect content control method.

[0007] Specifically, the present application is realized by the following technical scheme:

[0008] According to a first aspect of the present application, a hafnium-based ferroelectric film oxygen defect content control method is provided, and the method comprises the following steps:

[0009] Configuring hafnium-based ferroelectric film preparation raw materials;

[0010] Setting growth oxygen regulation parameters;

[0011] Preparation of a hafnium-based ferroelectric film by using the hafnium-based ferroelectric film preparation raw materials according to the growth oxygen regulation parameters.

[0012] setting an annealing oxygen regulation parameter;

[0013] performing an annealing operation on the hafnium-based ferroelectric thin film according to the annealing oxygen regulation parameter;

[0014] setting a re-annealing oxygen regulation parameter;

[0015] performing a re-annealing operation on the hafnium-based ferroelectric thin film according to the re-annealing oxygen regulation parameter.

[0016] Optionally, the configuration of the hafnium-based ferroelectric thin film preparation raw material comprises the steps of:

[0017] configuring a substrate;

[0018] configuring an electrode;

[0019] configuring a precursor;

[0020] configuring at least two oxygen sources (oxygen sources include H2O, H2O2, O2, O3, etc.).

[0021] Optionally, the setting of the growth oxygen regulation parameter comprises the steps of:

[0022] setting the number of precursor-nitrogen circulation;

[0023] setting the circulation parameter of at least two oxygen sources for each deposited layer;

[0024] setting the oxygen source content of the precursor;

[0025] setting the oxygen source content of each deposited layer.

[0026] Optionally, the setting of the circulation parameter of at least two oxygen sources for each deposited layer comprises the steps of:

[0027] setting the number of oxygen source circulation pulses for each deposited layer;

[0028] setting the oxygen source circulation flow rate for each deposited layer;

[0029] setting the oxygen source circulation pulse time for each deposited layer.

[0030] Optionally, the preparation of the hafnium-based ferroelectric thin film according to the growth oxygen regulation parameter using the hafnium-based ferroelectric thin film preparation raw material comprises the steps of:

[0031] obtaining a substrate, an electrode, a precursor, and an oxygen source;

[0032] depositing a bottom electrode on the substrate using the electrode;

[0033] depositing deposited layers on the bottom electrode layer by layer using the precursor and the oxygen source;

[0034] depositing a top electrode on the deposited layer using the electrode;

[0035] patterning the bottom electrode and the top electrode.

[0036] Optionally, the setting the annealing oxygen regulation parameter comprises the steps of:

[0037] setting an annealing pressure;

[0038] setting an annealing time;

[0039] setting a first annealing temperature.

[0040] Optionally, the first annealing temperature is 350-600℃.

[0041] Optionally, the setting the re-annealing oxygen regulation parameter comprises the steps of:

[0042] setting an annealing pressure;

[0043] setting an annealing time;

[0044] setting a second annealing temperature.

[0045] Optionally, the second annealing temperature is 250-600℃.

[0046] Optionally, the annealing pressure is 0.001-100000 Pa, and the annealing time is 10s-3h.

[0047] The technical scheme provided by the application at least brings the following beneficial effects:

[0048] The hafnium-based ferroelectric thin film oxygen defect content control method provided by the application realizes layer-by-layer regulation of oxygen content in the thin film, and obtains a thin film structure with different oxygen gradients; realizes atomic layer regulation of phase structure, defect distribution, etc. in the thin film, and improves the consistency and reliability of two-dimensional or three-dimensional devices; through regulation of oxygen content in the rapid annealing process, re-regulation of oxygen defects in the crystallization process is realized, and a ferroelectric thin film with different oxygen contents (0-100%) is obtained; the device after the failure of the back-end thermal process is subjected to rapid annealing again, the oxygen content level in the thin film is changed, and the oxygen defects and ferroelectric properties are restored to the initial optimal state; the oxygen content in the device is effectively regulated from three aspects of growth oxygen, annealing oxygen and re-annealing oxygen, which meets the manufacturing process of the back-end process and is conducive to the research and development of hafnium-based ferroelectric memory chips. BRIEF DESCRIPTION OF DRAWINGS

[0049] The accompanying drawings, which are incorporated into and form a part of the specification, illustrate an embodiment consistent with the present application and, together with the description, serve to explain the principles of the application.

[0050] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or related technologies will be briefly introduced below. Obviously, those skilled in the art can obtain other drawings based on these drawings without creative effort.

[0051] Figure 1 A schematic flowchart illustrating a method for controlling oxygen defect content in a hafnium-based ferroelectric thin film according to an embodiment of the present invention;

[0052] Figure 2 This is a schematic diagram illustrating the cycle of ALD growth of HZO thin films using tetradiethylmethylaminohafnium (Zr[N(C2H5)CH3]4) and tetradiethylmethylaminozirconium (Hf[N(C2H5)CH3]4) as precursors in a method for controlling oxygen defect content in hafnium-based ferroelectric thin films provided in an embodiment of the present invention.

[0053] Figure 3 This is a schematic diagram of the structure of the first embodiment of the hafnium-based ferroelectric thin film in the method for controlling oxygen defect content of hafnium-based ferroelectric thin films provided in this invention. Oxygen source 1 and oxygen source 2 can be any one of H2O, H2O2, O2, and O3.

[0054] Figure 4 for Figure 3 Schematic diagram of the imprinting effect when greywater is used as an oxygen source;

[0055] Figure 5 for Figure 3 A schematic diagram of the imprinting effect when oxygen is used as an oxygen source;

[0056] Figure 6 This is a schematic diagram of the structure of a second embodiment of a hafnium-based ferroelectric thin film in a method for controlling oxygen defect content in a hafnium-based ferroelectric thin film provided in this invention.

[0057] Figure 7 for Figure 6 A schematic diagram showing the relationship between polarization intensity and voltage in hafnium-based ferroelectric thin films;

[0058] Figure 8 This is a schematic diagram of the third embodiment of a hafnium-based ferroelectric thin film in a method for controlling oxygen defect content in a hafnium-based ferroelectric thin film provided in this invention.

[0059] Figure 9 for Figure 8 A schematic diagram showing the relationship between polarization spinor charge and cycle number in hafnium-based ferroelectric thin films;

[0060] Figure 10 This is a schematic diagram illustrating the annealing oxygen adjustment during the annealing operation of a hafnium-based ferroelectric thin film in a method for controlling oxygen defect content in a hafnium-based ferroelectric thin film according to an embodiment of the present invention.

[0061] Figure 11 For Figure 10 The schematic diagram of the relationship between the polarization intensity and the voltage of the hafnium-based ferroelectric thin film;

[0062] Figure 12 The schematic diagram of the annealing oxygen pressure intensity of the hafnium-based ferroelectric thin film after the thermal effect of the back-end process in the hafnium-based ferroelectric thin film oxygen defect content control method provided by the embodiment of the application;

[0063] Figure 13 For Figure 12 The schematic diagram of the relationship between the polarization intensity and the voltage of the hafnium-based ferroelectric thin film. DETAILED DESCRIPTION

[0064] To make the objectives, technical solutions and advantages of the embodiments of the application clearer, the technical solutions in the embodiments of the application will be described below in connection with the drawings of the embodiments of the application. Obviously, the described embodiments are some but not all of the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those of ordinary skill in the art without creative work fall within the protection scope of the application.

[0065] Figure 1 The flowchart of the hafnium-based ferroelectric thin film oxygen defect content control method suitable for the embodiment of the application is schematically shown.

[0066] Referring to Figure 1 The application provides a hafnium-based ferroelectric thin film oxygen defect content control method, which comprises the following steps:

[0067] S1: configuring hafnium-based ferroelectric thin film preparation raw materials;

[0068] Exemplarily, the step of configuring the hafnium-based ferroelectric thin film preparation raw materials comprises the following steps:

[0069] Configuring a substrate;

[0070] Configuring an electrode;

[0071] Configuring a precursor;

[0072] Configuring at least two oxygen sources.

[0073] In the embodiment of the application, electrode materials compatible with CMOS (complementary metal oxide semiconductor) processes are selected, such as Si and Ge semiconductor wafers, W, TiN, TaN, Al, Cu and other conductive metals / nitrides, or Au / W, Si / Ge, Ti / Ni alloy materials. The substrate needs to have good flatness and small roughness to ensure that the device is not easy to break down or has low leakage current, which is conducive to electrical characterization of the device.

[0074] S2: setting growth oxygen regulation parameters;

[0075] Exemplarily, the setting growth oxygen regulation parameters comprises steps of:

[0076] setting precursor-nitrogen cycle number;

[0077] setting at least two oxygen source cycle parameters of each deposition layer;

[0078] setting precursor oxygen source content;

[0079] setting at least two oxygen source contents of each deposition layer.

[0080] In the embodiments of the present application, the precursor-nitrogen cycle number (one cycle of one precursor and one nitrogen purge), the pulse number, time and flow of each oxygen source cycle (cycle number from 0-30, duration from 0-200s, flow from 10-500sccm) (one cycle of one oxygen source and one nitrogen purge), the setting of the precursor content and the oxygen source content of each deposition layer are set to realize the separate control of the oxygen source in the whole deposition process.

[0081] Exemplarily, the setting at least two oxygen source cycle parameters of each deposition layer comprises steps of:

[0082] setting oxygen source cycle pulse number of each deposition layer;

[0083] setting oxygen source cycle flow of each deposition layer;

[0084] setting oxygen source cycle pulse time of each deposition layer.

[0085] In the embodiments of the present application, the oxygen pulse number and oxygen pulse time in each cycle are set to realize the regulation of the oxygen content of each layer, realize the regulation of the element content of single atomic layer (~0.1nm), and then design the thin film with different gradient oxygen contents according to the application requirements.

[0086] In the embodiments of the present application, taking the deposition of Hf 0.5 Zr 0.5 O2 (HZO) as an example (Hf[N(CH3)2]4 and Zr[N(CH3)2]4 are precursors, and H2O is an oxygen source), after depositing a layer of Hf[N(CH3)2]4 or Zr[N(CH3)2]4, the pulse number, time and flow of H2O are changed (to realize the regulation of the oxygen content of the layer), then after depositing a layer of Hf[N(CH3)2]4 or Zr[N(CH3)2]4, the pulse number, time and flow of H2O are changed again, and so on, which can realize the gradient (layer by layer) regulation of the initial oxygen content of the thin film.

[0087] S3: preparing a hafnium-based ferroelectric thin film by using the hafnium-based ferroelectric thin film preparation raw material according to the growth oxygen regulation parameter;

[0088] Exemplarily, the step of preparing a hafnium-based ferroelectric thin film by using the hafnium-based ferroelectric thin film preparation raw material according to the growth oxygen regulation parameter comprises the following steps:

[0089] obtaining a substrate, an electrode, a precursor and an oxygen source;

[0090] depositing a bottom electrode on the substrate by using the electrode;

[0091] depositing a deposition layer on the bottom electrode layer by layer by using the precursor and the oxygen source;

[0092] depositing a top electrode on the deposition layer by using the electrode;

[0093] patterning the bottom electrode and the top electrode.

[0094] In the embodiments of the present application, the bottom electrode is deposited on the substrate by using an ALD (atomic layer deposition), a PVD (physical vapor deposition) or the like, the top electrode is grown after the atomic layer deposition, and the electrode is patterned by a photolithography, etching or the like to form a two-dimensional or three-dimensional structure capacitor.

[0095] In the embodiments of the present application, the cycle process of the HZO thin film prepared by using the ALD is as shown in Figure 2 Four diethylmethylammonium hafnium (Hf[N(C2H5)CH3]4) and four diethylmethylammonium zirconium (Hf[N(C2H5)CH3]4) are used as the precursors, and H2O is used as the oxygen source or reducing agent. The liquid Hf and Zr sources are converted into gas by heating, and are combined and reacted with the hydroxyl groups on the surface of the substrate, as shown in Figure 2 The precursors are combined with the surface, and two NMe2-H are removed in N2 blowing, leaving O-Zr-NMe2, as shown in 1(b); then the oxygen source is introduced, and reacts with the O-Zr-NMe2 left on the surface, as shown in Figure 2 (c); by reaction and replacement, the remaining reaction products are blown away under the action of N2, leaving H-O-Zr-O, as shown in Figure 2 (d), which is one complete cycle.

[0096] The above operation is repeated by introducing the Hf source again, as shown in Figure 2e-2h. This is a cycle of Hf and Zr, according to the temperature of the substrate to regulate the growth rate and crystallinity of HZO, a cycle of Hf and Zr growth rate is generally 0.15-0.2 Å / cycle, for different proportions of doping, can be achieved according to the different cycle number. In this cycle can change the oxygen content (oxygen source including oxygen, ozone, water, hydrogen peroxide), by controlling the flow size (10-500sccm) and pulse time (0.1s-500s) to regulate the amount of oxygen in each layer. In addition, it can be in a cycle process into a variety of oxygen sources, can be further optimized and improved oxygen source quality. Because there are three coordination oxygen in the hafnium-based ferroelectric lattice, so there need to be a certain amount of oxygen defects in the film, and can be directly according to the amount of oxygen in the film and the change of hafnium-based film ferroelectric properties, can further optimize the adjustment of the oxygen content of the film in the deposition process.

[0097] S4: setting annealing oxygen regulation parameters;

[0098] Exemplarily, the setting annealing oxygen regulation parameters comprises the steps of:

[0099] setting annealing pressure;

[0100] setting annealing time;

[0101] setting first annealing temperature.

[0102] In the embodiments of the present application, the rapid annealing pressure (0.001 Pa to 100000 Pa), annealing time (10s-3h) and annealing temperature (350-600℃) are changed, so as to realize the further regulation of the oxygen content in the film by the annealing pressure in the film crystallization process; by changing the growth oxygen content and the pressure in the annealing process, the oxygen content in the film after crystallization is adjusted to 0-100%.

[0103] S5: annealing operation is performed on the hafnium-based ferroelectric film according to the annealing oxygen regulation parameters;

[0104] In the embodiments of the present application, the annealing operation is performed according to the annealing oxygen regulation parameters.

[0105] S6: setting re-annealing oxygen regulation parameters;

[0106] Exemplarily, the setting re-annealing oxygen regulation parameters comprises the steps of:

[0107] setting annealing pressure;

[0108] setting annealing time;

[0109] setting second annealing temperature.

[0110] In the embodiments of the present application, the device is subjected to a 400-degree 3-hour back-end thermal process, then rapid annealing is performed again and the pressure (0.001 Pa to 100000 Pa), annealing time (10 s-3 hour) and annealing temperature (250-600 DEG C) are changed, so as to further regulate the oxygen content in the failed ferroelectric thin film and restore the oxygen level and ferroelectric characteristics.

[0111] S7: performing a reannealing operation on the hafnium-based ferroelectric thin film according to the reannealing oxygen regulation parameters.

[0112] In the embodiments of the present application, the reannealing operation is performed according to the reannealing oxygen regulation parameters.

[0113] As shown in Figures 3-5 When the hafnium-based ferroelectric thin film is subjected to growth oxygen regulation, two kinds of oxygen sources are in different layers (for example, water is used in the lower layer and oxygen is used in the upper layer), at this time, the imprint effect can be weakened and the polarization retention characteristics can be improved.

[0114] As shown in Figures 6-7 When the hafnium-based ferroelectric thin film is subjected to growth oxygen regulation, two kinds of oxygen sources are in the same layer, but the contents are different, and the oxygen content of each layer is different, at this time, the advantages of the two kinds of oxygen sources can be utilized to improve the oxygen distribution and improve the polarization strength.

[0115] As shown in Figures 8-9 When the hafnium-based ferroelectric thin film is subjected to growth oxygen regulation, since the interface oxygen loss is the main obstacle leading to device breakdown, increasing the interface oxygen content can greatly improve the cycle number of the device.

[0116] As shown in Figures 10-11 When the hafnium-based ferroelectric thin film is subjected to annealing oxygen regulation, a constant pressure value is set, then a temperature rising and falling process is performed, so as to regulate the oxygen content of the thin film during the annealing process. Through the determination of the oxygen content of the grown thin film, the annealing pressure can be increased or decreased, so that the thin film can absorb / release oxygen during the crystallization process.

[0117] As shown in Figures 12-13 When the hafnium-based ferroelectric thin film is subjected to annealing oxygen regulation after the back-end process thermal effect, the back-end process thermal effect (furance) can cause the oxygen content in the thin film to increase, leading to ferroelectric domain pinning, thereby causing the polarization charge to drop, the serious flip speed to slow down and other problems; by reducing the pressure (0.01 Pa) during the reannealing, the ferroelectric performance can be restored.

[0118] The hafnium-based ferroelectric thin film oxygen defect content control method provided by the present application has the following advantages:

[0119] Multi-level oxygen regulation: This method realizes multi-level and fine control of oxygen defect content in hafnium-based ferroelectric thin films through oxygen regulation in three stages of growth, primary annealing and secondary annealing.

[0120] Optimization of ferroelectric characteristics: By precisely regulating the oxygen defect content, this method is expected to significantly improve the ferroelectric performance of hafnium-based ferroelectric thin films, providing strong support for the development of high-performance electronic devices.

[0121] Technical challenge response: In response to the difficulty of element content regulation in the atomic layer deposition process, this method provides a practical solution with high technical innovation and practicality.

[0122] The hafnium-based ferroelectric thin film oxygen defect content control method provided in the present application realizes layer-by-layer regulation of oxygen content in the thin film, obtaining thin film structures with different oxygen gradients; realizes atomic layer regulation of phase structure, defect distribution, etc. in the thin film, improving the consistency and reliability of two-dimensional or three-dimensional devices; through oxygen content adjustment in the rapid annealing process, the oxygen defects in the crystallization process are re-regulated, and ferroelectric thin films with different oxygen contents (0-100%) are obtained; the device after the failure of the back-end thermal process is re-annealed, the oxygen content level in the thin film is changed, and the oxygen defects and ferroelectric characteristics are restored to the initial optimal state; the oxygen content inside the device is effectively regulated from three aspects of growth oxygen, annealing oxygen and secondary annealing oxygen, which meets the manufacturing process of the back-end process and is conducive to the research and development of hafnium-based ferroelectric memory chips. This method has high technical innovation and application value in the field of electronic material preparation, and provides strong support for the development of new electronic devices.

[0123] It should be noted that in the present application, the terms "upper", "lower", "left", "right", "front", "back", "top", "bottom", "inner", "outer", "vertical", "horizontal", "lateral", "longitudinal" and the like indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings. These terms are mainly used to better describe the present application and its embodiments, and are not intended to limit the indicated devices, elements or components to have a specific orientation, or to be constructed and operated in a specific orientation.

[0124] In addition, in addition to indicating the orientation or positional relationship, the above-mentioned terms can also be used to indicate other meanings, for example, the term "upper" can also be used to indicate a certain attachment relationship or connection relationship in some cases. For those skilled in the art, the specific meaning of these terms in the present application can be understood according to the specific situation.

[0125] In addition, the terms "mounting", "arrangement", "provided with", "connected", "linked" should be interpreted broadly. For example, it can be fixed connection, detachable connection, or integral structure; it can be mechanical connection, or electrical connection; it can be direct connection, or indirect connection through intermediate medium, or internal communication between two devices, elements or components. For those skilled in the art, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0126] In addition, the terms "first", "second", etc. are mainly used to distinguish different devices, elements or components (the specific types and structures can be the same or different), and are not intended to indicate or imply the relative importance and quantity of the indicated devices, elements or components. Unless otherwise stated, the meaning of "a plurality of" is two or more.

[0127] The above is only a specific embodiment of the present application, which enables those skilled in the art to understand or implement the present application. Various modifications of these embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features applied herein.

Claims

1. A hafnium-based ferroelectric thin film oxygen defect content control method, characterized by, The method comprises the steps of: configuring hafnium-based ferroelectric thin film preparation raw materials; the raw materials comprise a substrate, electrodes, a precursor, and at least two different types of oxygen sources; setting growth oxygen regulation parameters; the growth oxygen regulation parameters comprise precursor-nitrogen circulation quantity, precursor oxygen source content, the type of oxygen source used by each deposition layer, and the number of oxygen source circulation pulses, the flow rate, and the pulse time of the layer; wherein different types of oxygen sources are used in different deposition layers, and the number of oxygen source circulation pulses, the flow rate, and the pulse time of the layer are independently adjusted to achieve gradient regulation of the initial oxygen content of the thin film and further control the gradient distribution of oxygen defects; preparing a hafnium-based ferroelectric thin film from the hafnium-based ferroelectric thin film preparation raw materials according to the growth oxygen regulation parameters; setting first annealing oxygen regulation parameters; the first annealing oxygen regulation parameters comprise annealing pressure, annealing time, and first annealing temperature; performing an annealing operation on the hafnium-based ferroelectric thin film according to the first annealing oxygen regulation parameters; setting re-annealing oxygen regulation parameters; the re-annealing oxygen regulation parameters comprise annealing pressure, annealing time, and second annealing temperature; performing a re-annealing operation on the hafnium-based ferroelectric thin film according to the re-annealing oxygen regulation parameters; the step of preparing a hafnium-based ferroelectric thin film from the hafnium-based ferroelectric thin film preparation raw materials according to the growth oxygen regulation parameters comprises the steps of: obtaining a substrate, electrodes, a precursor, and at least two different types of oxygen sources; depositing a bottom electrode on the substrate using the electrodes; depositing deposition layers on the bottom electrode layer by layer using the precursor and at least two different types of the oxygen sources; depositing a top electrode on the deposition layers using the electrodes; patterning the bottom electrode and the top electrode.

2. The hafnium-based ferroelectric thin film oxygen deficiency content control method according to claim 1, characterized by, The first annealing temperature is 350-600°C.

3. The hafnium-based ferroelectric thin film oxygen deficiency content control method of claim 1, wherein The second annealing temperature is 250-600°C.

4. The hafnium-based ferroelectric thin film oxygen deficiency content control method of claim 1, wherein, The annealing pressure is 0.001-100,000 Pa, and the annealing time is 10 s-3 h.

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