Hafnium-based ferroelectric device and performance regulation and control method thereof

Abstract

The invention provides a hafnium-based ferroelectric device and a performance regulation and control method. The hafnium-based ferroelectric device and the performance regulation and control method can be applied to the technical field of ferroelectric film modification. The device comprises a substrate layer; the bottom electrode layer is positioned on the substrate layer; the hafnium-based ferroelectric film is positioned on the bottom electrode layer; the ferroelectric induction layer is positioned on the hafnium-based ferroelectric film; a top electrode layer on the ferroelectric induction layer; wherein the remanent polarization parameter of the hafnium-based ferroelectric film is improved by using particle beam irradiation adjustment under the condition that the top electrode layer is not formed; the ferroelectric induction layer is used for inducing the hafnium-based ferroelectric film to generate ferroelectricity under the condition that the top electrode layer is not formed, so that particle beams are used for adjusting remanent polarization parameters under the condition that the top electrode layer is not formed.

Description

Technical Field

[0001] The present disclosure relates to the technical field of ferroelectric thin films, and more specifically, to a hafnium-based ferroelectric device and a method for controlling its performance. Background Art

[0002] Memory is one of the three pillars of the semiconductor industry, and hafnium-based ferroelectric materials have become one of the key candidate materials for the next generation of new ferroelectric memory due to their high compatibility with semiconductor processes and mature preparation processes, bringing new opportunities for the development of ferroelectric storage technology.

[0003] In the process of realizing the concept of the present disclosure, the inventors found that the effect of modifying the hafnium-based ferroelectric thin film in the hafnium-based ferroelectric device is poor. Summary of the invention

[0004] In view of this, the present disclosure provides a hafnium-based ferroelectric device and a method for controlling its performance.

[0005] One aspect of the present disclosure provides a hafnium-based ferroelectric device, comprising: a substrate layer; a bottom electrode layer located on the substrate layer; a hafnium-based ferroelectric film located on the bottom electrode layer; a ferroelectric induction layer located on the hafnium-based ferroelectric film; and a top electrode layer located on the ferroelectric induction layer; wherein the residual polarization intensity parameter of the hafnium-based ferroelectric film is improved by adjusting by using particle beam irradiation without forming the top electrode layer; the ferroelectric induction layer is used to induce the hafnium-based ferroelectric film to generate ferroelectricity without forming the top electrode layer, thereby facilitating adjusting the residual polarization intensity parameter by using a particle beam without forming the top electrode layer.

[0006] According to an embodiment of the present disclosure, the material of the ferroelectric induction layer includes metal oxide; and the thickness of the ferroelectric induction layer is 1-5 nm.

[0007] According to an embodiment of the present disclosure, the metal oxide of the ferroelectric inductive layer is Al2O3 or ZrO2.

[0008] Another aspect of the present disclosure provides a performance control method for a hafnium-based ferroelectric device, comprising: depositing a bottom electrode layer on a substrate layer; depositing a hafnium-based material film on the bottom electrode layer; depositing a ferroelectric induction layer on the hafnium-based material film to obtain a first intermediate device; obtaining a second intermediate device including a hafnium-based ferroelectric film by rapidly annealing the first intermediate device, wherein the hafnium-based ferroelectric film is a hafnium-based material film having ferroelectricity; irradiating the second intermediate device with a particle beam to adjust the residual polarization intensity parameter of the hafnium-based ferroelectric film to obtain a third intermediate device including a target hafnium-based ferroelectric film, wherein the target hafnium-based ferroelectric film is a hafnium-based ferroelectric film with adjusted residual polarization intensity parameter; forming a top electrode layer on the third intermediate device to obtain a target hafnium-based ferroelectric device after performance control.

[0009] According to an embodiment of the present disclosure, a third intermediate device including a target hafnium-based ferroelectric film is obtained by irradiating a second intermediate device with a particle beam and adjusting the residual polarization intensity parameters of the hafnium-based ferroelectric film, comprising: irradiating a ferroelectric induction layer of the second intermediate device with a particle beam so that the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameters of the hafnium-based ferroelectric film and obtaining a target hafnium-based ferroelectric film.

[0010] According to an embodiment of the present disclosure, the ferroelectric induction layer of the second intermediate device is irradiated with a particle beam so that the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameters of the hafnium-based ferroelectric film and obtaining a target hafnium-based ferroelectric film, including: irradiating the ferroelectric induction layer of the second intermediate device with a particle beam so that the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, adjusting the charged state of intrinsic oxygen vacancies in the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameters.

[0011] According to an embodiment of the present disclosure, the irradiation particle beam includes a neutron beam, a proton beam, He 2+ One of ion beam, argon particle beam and electron beam; the irradiation energy range of neutron beam is 1×10 -9 MeV~10 MeV; the irradiation energy range of the proton beam is 1×10 -1 keV ~10 MeV; the irradiation energy range of the electron beam is 1×10 -1 keV~10 MeV; He 2+ The irradiation energy range of the ion beam is 10 keV ~1 MeV; the irradiation energy range of the argon particle beam is 400 keV ~2 MeV.

[0012] According to the embodiment of the present disclosure, the particle fluence rate of the neutron beam ranges from 1×10 5 n / cm 2 / s ~1×10 14 n / cm 2 / s; the particle fluence rate range of the proton beam is 1×10 7 p / cm 2 / s~1×10 16 p / cm 2 / s; the particle fluence rate of the electron beam ranges from 1×10 7 p / cm 2 / s ~1×10 16 p / cm 2 / s; 60The Co γ-ray fluence rate range is 1×10 5 p / cm 2 / s~1×10 15 p / cm 2 / s;He 2+ The particle fluence rate of the ion beam ranges from 1×10 8 ions / cm 2 / s ~1×10 15 ions / cm 2 / s; the flux range of argon particle beam is 5×10 15 ~1.4×10 16 ions / cm 2 .

[0013] According to an embodiment of the present disclosure, the irradiation angle range of the particle beam is 5°~90°.

[0014] According to an embodiment of the present disclosure, the hafnium-based material film is made ferroelectric by rapidly annealing the intermediate device to obtain a hafnium-based ferroelectric film, including: rapidly annealing the intermediate device, the annealing time ranges from 10 s to 50 s, and the heating temperature ranges from 400°C to 700°C.

[0015] According to the embodiments of the present disclosure, by inducing the ferroelectricity of the hafnium-based ferroelectric film using a ferroelectric induction layer during the preparation of the hafnium-based ferroelectric device, the influence of the low-energy particle beam on the hafnium-based ferroelectric film can be enhanced when the hafnium-based ferroelectric film is irradiated with a low-energy particle beam, and the effect of regulating the residual polarization intensity parameters of the hafnium-based ferroelectric film is improved. Based on this, compared with the prior art, the present disclosure improves the modification effect of the hafnium-based ferroelectric film when the hafnium-based ferroelectric film is modified using a particle beam, and can achieve irradiation modification of the hafnium-based ferroelectric film at a lower energy than the related art. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The above and other objects, features and advantages of the present disclosure will become more apparent through the following description of the embodiments of the present disclosure with reference to the accompanying drawings, in which:

[0017] Figure 1 The structural diagram of a hafnium-based ferroelectric device according to an embodiment of the present disclosure is schematically shown.

[0018] Figure 2 The flowchart of the performance control method of the hafnium-based ferroelectric device according to the embodiment of the present disclosure is schematically shown.

[0019] Figure 3 The schematic diagram shows the change of the coercive electric field intensity parameters before and after the hafnium-based ferroelectric film is irradiated with a particle beam.

[0020] Figure 4 A schematic diagram showing the change in the remanent polarization intensity parameter of the hafnium-based ferroelectric film before and after irradiation with a particle beam. DETAILED DESCRIPTION

[0021] Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings. However, it should be understood that these descriptions are exemplary only and are not intended to limit the scope of the present disclosure. In the following detailed description, for ease of explanation, many specific details are set forth to provide a comprehensive understanding of the embodiments of the present disclosure. However, it is apparent that one or more embodiments may also be implemented without these specific details. In addition, in the following description, descriptions of known structures and technologies are omitted to avoid unnecessary confusion of the concepts of the present disclosure.

[0022] The terms used herein are only for describing specific embodiments and are not intended to limit the present disclosure. The terms "comprise", "include", etc. used herein indicate the existence of the features, steps, operations and / or components, but do not exclude the existence or addition of one or more other features, steps, operations or components.

[0023] All terms (including technical and scientific terms) used herein have the meanings commonly understood by those skilled in the art unless otherwise defined. It should be noted that the terms used herein should be interpreted as having a meaning consistent with the context of this specification and should not be interpreted in an idealized or overly rigid manner.

[0024] When using expressions such as "at least one of A, B, and C, etc.", they should generally be interpreted according to the meaning of the expression commonly understood by those skilled in the art (for example, "a system having at least one of A, B, and C" should include but is not limited to a system having A alone, B alone, C alone, A and B, A and C, B and C, and / or A, B, C, etc.).

[0025] In the embodiments of the present disclosure, the collection, updating, analysis, processing, use, transmission, provision, disclosure, storage, etc. of the data involved (for example, including but not limited to user personal information) are in compliance with the provisions of relevant laws and regulations, are used for legitimate purposes, and do not violate public order and good morals. In particular, necessary measures are taken for user personal information to prevent illegal access to user personal information data and maintain the security of user personal information, network security, and national security.

[0026] In the embodiments of the present disclosure, the user's authorization or consent is obtained before obtaining or collecting the user's personal information.

[0027] The inventors have discovered that by using a low-energy particle beam to irradiate a hafnium-based ferroelectric film having a top electrode layer deposited on its upper surface, the residual polarization intensity parameters of the hafnium-based ferroelectric film can be adjusted, thereby achieving modification of the hafnium-based ferroelectric film. However, the modification effect of the hafnium-based ferroelectric film is difficult to meet the demand.

[0028] On this basis, the inventors found that when a top electrode layer is deposited on a hafnium-based material film, annealing the hafnium-based material film can make it ferroelectric, thereby obtaining a hafnium-based ferroelectric film. In this case, the hafnium-based ferroelectric film can be modified by irradiating it with a high-energy particle beam. At the same time, the inventors found through simulation that a low-energy particle beam can more effectively induce oxygen vacancies V in the hafnium-based ferroelectric film. O Defect generation. However, the presence of the top electrode layer will block the low-energy particle beam during the irradiation process, reduce the irradiation effect, and thus reduce the effect of regulating the residual polarization intensity parameters. Based on this, the inventors found that by depositing a ferroelectric induction layer based on metal oxide on a hafnium-based material film, providing a certain mechanical clamping stress to the hafnium-based material film, and then annealing the hafnium-based material film to induce the ferroelectricity of the hafnium-based material film, a hafnium-based ferroelectric film is obtained, and then the hafnium-based ferroelectric film is irradiated to adjust the residual polarization intensity parameters, the regulating effect of the low-energy particle beam on the residual polarization intensity parameters can be improved, thereby achieving an improvement in the modification effect of the hafnium-based ferroelectric film.

[0029] Based on this, in order to at least partially solve the technical problems existing in the related art, an embodiment of the present disclosure provides a hafnium-based ferroelectric device, including: a substrate layer; a bottom electrode layer located on the substrate layer; a hafnium-based ferroelectric thin film located on the bottom electrode layer; a ferroelectric induction layer located on the hafnium-based ferroelectric thin film; a top electrode layer located on the ferroelectric induction layer; wherein the residual polarization intensity parameter of the hafnium-based ferroelectric thin film is improved by adjusting by using particle beam irradiation without forming a top electrode layer; the ferroelectric induction layer is used to induce the hafnium-based ferroelectric thin film to generate ferroelectricity without forming a top electrode layer, thereby facilitating the use of a particle beam to adjust the residual polarization intensity parameter without forming a top electrode layer.

[0030] Figure 1 The structural diagram of a hafnium-based ferroelectric device according to an embodiment of the present disclosure is schematically shown.

[0031] like Figure 1As shown, the device 100 of this embodiment includes a substrate layer 110, a bottom electrode layer 120 located on the substrate layer 110, a hafnium-based ferroelectric thin film 130 located on the bottom electrode layer 120, a ferroelectric induction layer 140 located on the hafnium-based ferroelectric thin film 130, and a top electrode layer 150 located on the ferroelectric induction layer 140. The top electrode layer 150 includes a first top electrode 151 and a second top electrode 152. For example, the first top electrode 151 and the second top electrode 152 may be made of the same material or different materials, which is not limited here.

[0032] According to the embodiments of the present disclosure, the substrate layer 110 can provide mechanical support for the device 100. In order to ensure the stability and reliability of the device 100, the thickness, flatness and material properties of the substrate layer 110 can be set according to actual needs.

[0033] According to an embodiment of the present disclosure, the bottom electrode layer 120 is located between the substrate layer 110 and the hafnium-based ferroelectric thin film 130 to provide a current channel so that current can smoothly pass through the hafnium-based ferroelectric thin film 130 .

[0034] According to an embodiment of the present disclosure, the material of the hafnium-based ferroelectric film 130 may be hafnium dioxide doped with other elements, based on which the hafnium-based ferroelectric film 130 has excellent ferroelectric properties. The preparation of hafnium oxide-based ferroelectric crystals can be achieved by selectively doping elements such as Zr, La, Al, Si, Ga and Y. Based on this, the material of the hafnium-based ferroelectric film 130 includes one of Zr-doped HfO2, La-doped HfO2, Al-doped HfO2, Si-doped HfO2, Ga-doped HfO2 and Y-doped HfO2. And the thickness of the hafnium-based ferroelectric film 130 ranges from 5 nm to 50 nm.

[0035] The inventors have found that the intrinsic oxygen vacancies V O When the concentration increases, the room temperature stable phase structure of the hafnium-based ferroelectric film 130 will change from the original monoclinic m-phase (P21 / c) structure to the tetragonal t-phase (P42 / nmc) structure. Stabilizing the intermediate t-phase structure of the hafnium-based ferroelectric film 130 is beneficial to reducing the polarization reversal barrier of the hafnium-based ferroelectric film 130, and can increase the ferroelectric phase to a certain extent, thereby improving the residual polarization intensity parameter. At the same time, the intrinsic oxygen vacancy V O Charged to V O 2+ It is also beneficial to reduce the polarization reversal barrier of the hafnium-based ferroelectric film 130 , thereby affecting the residual polarization intensity parameters.

[0036] According to an embodiment of the present disclosure, the particle beam may include neutrons, protons, He 2+Ions, argon particles, etc. can produce radiation effects, that is, particles that can induce displacement radiation effects and ionizing radiation effects separately or simultaneously. The radiation effect can affect the specific crystal phase structure by changing the microscopic physical properties of oxygen vacancies inside the hafnium-based ferroelectric film, and specifically adjust the residual polarization intensity parameters of the hafnium-based ferroelectric film 130. The ionizing radiation effect can make the intrinsic oxygen vacancy V O The charge reduces the polarization reversal barrier to a certain extent; at the same time, the displacement radiation effect can create new point defects to change the intrinsic oxygen vacancy V O The concentration stabilizes the intermediate t-phase structure and further increases the ferroelectric phase. Therefore, the magnitude of the residual polarization intensity parameter of the hafnium-based ferroelectric thin film 130 can be selectively adjusted by adjusting the energy, injection amount and incident angle of the irradiated ions.

[0037] According to an embodiment of the present disclosure, the residual polarization parameter of the hafnium-based ferroelectric film 130 is improved by adjusting by using particle beam irradiation without forming a top electrode layer. For example, when the ferroelectric induction layer 140 is covered on the hafnium-based ferroelectric film 130 and the top electrode layer 150 is not formed, the residual polarization parameter of the hafnium-based ferroelectric film 130 can be adjusted by irradiating the hafnium-based ferroelectric film 130 with a particle beam.

[0038] According to an embodiment of the present disclosure, the ferroelectric induction layer 140 is used to induce ferroelectricity in the hafnium-based ferroelectric film 130 without forming the top electrode layer 150 , thereby facilitating adjusting the residual polarization intensity parameters using a particle beam without forming the top electrode layer 150 .

[0039] According to an embodiment of the present disclosure, the top electrode layer 150 includes two top electrodes, which may be made of a conductive material and together with the bottom electrode layer 120 form a complete current channel.

[0040] According to the embodiments of the present disclosure, the ferroelectricity of the hafnium-based ferroelectric film 130 is induced by using the ferroelectric induction layer 140 during the preparation of the hafnium-based ferroelectric device 100, so that when the hafnium-based ferroelectric film 130 is irradiated with a low-energy particle beam, the influence of the low-energy particle beam on the hafnium-based ferroelectric film 130 can be enhanced, and the effect of adjusting the residual polarization intensity parameter of the hafnium-based ferroelectric film 130 is improved. Based on this, compared with the prior art, the present disclosure improves the modification effect of the hafnium-based ferroelectric film 130 when the hafnium-based ferroelectric film 130 is modified using a particle beam, and the irradiation modification of the hafnium-based ferroelectric film 130 can be achieved with lower energy than the related art.

[0041] According to an embodiment of the present disclosure, the material of the ferroelectric induction layer 140 includes a metal oxide. On this basis, since the ferroelectric induction layer is an oxide film, compared with the metal film electrode, the oxide film can generate in-plane stress to prevent the hafnium-based ferroelectric film from transforming from a metastable orthorhombic / tetragonal (o / t) phase to a monoclinic (m) phase during annealing and cooling, and can also avoid the formation of additional oxygen vacancy defects at the interface with the hafnium-based ferroelectric film.

[0042] According to the embodiment of the present disclosure, the thickness of the ferroelectric induction layer 140 is 1-5 nm. By setting the material and thickness of the ferroelectric induction layer 140, and setting the doping element and film thickness of the hafnium-based ferroelectric film 130, it is helpful to adjust the ferroelectric properties of the hafnium-based ferroelectric film 130, thereby improving the cycle durability of the hafnium-based ferroelectric device 100.

[0043] According to an embodiment of the present disclosure, the metal oxide of the ferroelectric inductive layer 140 is Al2O3 or ZrO2; the material of the bottom electrode layer 120 includes at least one of titanium nitride, tungsten, gold and ruthenium; the thickness of the bottom electrode layer 120 ranges from 30 nm to 100 nm; the material of the top electrode layer 150 includes at least one of titanium nitride, tungsten, gold and ruthenium; the thickness of the top electrode layer 150 ranges from 20 nm to 40 nm; and the material of the substrate layer 110 includes doped silicon.

[0044] According to the embodiments of the present disclosure, by setting the thickness and material of the top electrode layer 150 and the bottom electrode layer 120 and the material doping elements of the substrate layer 110 , it is helpful to regulate the electrode conductivity, thereby facilitating obtaining a more stable and reliable hafnium-based ferroelectric device 100 .

[0045] Based on the above hafnium-based ferroelectric device 100, the embodiment of the present disclosure further provides a performance control method for the hafnium-based ferroelectric device 100. Figure 2 The performance control method of the device 100 in the above embodiment is described.

[0046] Figure 2 The flowchart of the performance control method of the hafnium-based ferroelectric device according to the embodiment of the present disclosure is schematically shown.

[0047] like Figure 2 As shown, the method includes operations S210 to S260.

[0048] In operation S210 , a bottom electrode layer is deposited on a substrate layer.

[0049] In operation S220 , a hafnium-based material thin film is deposited on the bottom electrode layer.

[0050] In operation S230 , a ferroelectric induction layer is deposited on the hafnium-based material film to obtain a first intermediate device.

[0051] In operation S240 , a second intermediate device including a hafnium-based ferroelectric thin film is obtained by performing rapid annealing on the first intermediate device, wherein the hafnium-based ferroelectric thin film is a hafnium-based material thin film having ferroelectricity.

[0052] In operation S250, the second intermediate device is irradiated with a low-energy particle beam to adjust the remanent polarization intensity parameters of the hafnium-based ferroelectric film, thereby obtaining a third intermediate device including a target hafnium-based ferroelectric film, wherein the target hafnium-based ferroelectric film is a hafnium-based ferroelectric film with the remanent polarization intensity parameters adjusted.

[0053] In operation S260 , a top electrode layer is formed on the third intermediate device to obtain a target hafnium-based ferroelectric device with adjusted performance.

[0054] According to the embodiments of the present disclosure, the bottom electrode layer electrode may be deposited by magnetron sputtering, for example, the deposition process may take 5 to 30 minutes, preferably 10 minutes.

[0055] According to the embodiments of the present disclosure, a hafnium-based ferroelectric thin film may be grown on the surface of the bottom electrode layer by using methods such as atomic layer deposition (ALD), and a top electrode layer may be deposited by using methods such as magnetron sputtering, photolithography, and patterning.

[0056] According to an embodiment of the present disclosure, a ferroelectric induction layer is deposited on a hafnium-based material film to obtain an intermediate device, and the first intermediate device is annealed to make the hafnium-based material film have ferroelectricity, thereby avoiding the use of a top electrode layer that is a metal material to induce the ferroelectricity of the hafnium-based material film. Thus, when a low-energy particle beam is used to irradiate the hafnium-based ferroelectric film, the influence of the low-energy particle beam on the hafnium-based ferroelectric film is enhanced, and the effect of regulating the coercive electric field parameters of the hafnium-based ferroelectric film is improved. Based on this, compared with the prior art, the present disclosure improves the modification effect of the hafnium-based ferroelectric film when a particle beam is used to modify the hafnium-based ferroelectric film, and can achieve irradiation modification of the hafnium-based ferroelectric film at a lower energy than the related art.

[0057] According to an embodiment of the present disclosure, the hafnium-based material film is made ferroelectric by rapidly annealing the intermediate device to obtain a hafnium-based ferroelectric film, including: rapidly annealing the intermediate device, the annealing time ranges from 10 s to 50 s, and the heating temperature ranges from 400°C to 700°C.

[0058] According to the embodiments of the present disclosure, by performing rapid annealing on the intermediate device, the intermediate device can be brought into a stable state, so as to improve the overall performance of the device.

[0059] According to an embodiment of the present disclosure, a second intermediate device is irradiated with a low-energy particle beam to adjust the residual polarization intensity parameters of the hafnium-based ferroelectric film, thereby obtaining a third intermediate device including a target hafnium-based ferroelectric film, including: irradiating the ferroelectric induction layer of the second intermediate device with a particle beam so that the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameters of the hafnium-based ferroelectric film, and obtaining a target hafnium-based ferroelectric film.

[0060] According to the embodiments of the present disclosure, since the ferroelectric induction layer has a low blocking ability for low-energy particle beams, the low-energy particle beams are less affected by the blocking. Therefore, when the ferroelectric induction layer of the second intermediate device is irradiated with a low-energy particle beam, the energy loss and particle angle deflection caused by the low-energy particle beam penetrating the layer structure are reduced. Compared with the prior art, the regulating effect of the low-energy particle beam on the residual polarization intensity parameters of the hafnium-based ferroelectric film is improved, thereby achieving an enhanced modification effect on the hafnium-based ferroelectric film.

[0061] According to an embodiment of the present disclosure, the ferroelectric induction layer of the second intermediate device is irradiated with a particle beam so that the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameters of the hafnium-based ferroelectric film and obtaining a target hafnium-based ferroelectric film, including: irradiating the ferroelectric induction layer of the second intermediate device with a particle beam so that the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, adjusting the charged state of intrinsic oxygen vacancies in the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameters.

[0062] According to the embodiments of the present disclosure, since the ferroelectric induction layer has a low blocking ability for low-energy particle beams, the low-energy particle beams are less affected by the blocking. Therefore, when the ferroelectric induction layer of the second intermediate device is irradiated with a low-energy particle beam, the energy loss and particle angle deflection caused by the low-energy particle beam penetrating the layer structure are reduced. Compared with the prior art, the effect of regulating the charged state of the intrinsic oxygen vacancies of the hafnium-based ferroelectric film by the low-energy particle beam is improved, thereby enhancing the modification effect on the hafnium-based ferroelectric film.

[0063] According to an embodiment of the present disclosure, the particle beam includes a neutron beam, a proton beam, a He 2+ One of ion beam, argon particle beam and electron beam; the irradiation energy range of neutron beam is 1×10 -9 MeV~10 MeV; the irradiation energy range of the proton beam is 1×10 -1 keV ~10 MeV; the irradiation energy range of the electron beam is 1×10 -1 keV~10 MeV; He 2+The irradiation energy range of the ion beam is 10 keV ~1 MeV; the irradiation energy range of the argon particle beam is 400 keV ~2 MeV.

[0064] According to the embodiment of the present disclosure, the particle fluence rate of the neutron beam ranges from 1×10 5 n / cm 2 / s ~1×10 14 n / cm 2 / s; the particle fluence rate range of the proton beam is 1×10 7 p / cm 2 / s~1×10 16 p / cm 2 / s; the particle fluence rate of the electron beam ranges from 1×10 7 p / cm 2 / s ~1×10 16 p / cm 2 / s; He 2+ The particle fluence rate of the ion beam ranges from 1×10 8 ions / cm 2 / s ~1×10 15 ions / cm 2 / s; the particle flux range of the argon particle beam is 5×10 15 ~1.4×10 16 ions / cm 2 .

[0065] According to an embodiment of the present disclosure, the irradiation angle range of the particle beam is 5°~90°.

[0066] Based on this, the irradiation parameters of low-energy particle beam irradiation can be set according to actual needs, so as to selectively adjust the charge state and oxygen vacancy concentration of intrinsic oxygen vacancies in the hafnium-based ferroelectric film, thereby reducing the polarization reversal barrier of the hafnium-based ferroelectric film and adjusting the residual polarization intensity parameters.

[0067] In order to better understand the content of the present disclosure, the invention content of the present disclosure is described below through specific embodiments.

[0068] (1) Preparation of hafnium-based ferroelectric devices. The structure of hafnium-based ferroelectric devices includes ZrO2 / HZO / W. First, W is deposited as the bottom electrode on a low-doped Si substrate by magnetron sputtering. The process time is 10 min and the thickness of the bottom electrode is 50 nm ~ 100 nm. Then, a hafnium-based ferroelectric film with a thickness of 10 nm ~ 50 nm is grown on the surface of the bottom electrode by atomic layer deposition. Then, a 1 nm thick ZrO2 ferroelectric induction layer is deposited by atomic layer deposition, and the entire device is rapidly annealed at a temperature of 400℃ ~ 700℃ and a processing time of 10 s ~ 50 s. The prepared devices are marked as irradiation group and control group, respectively.

[0069] (2) Irradiation treatment. Expose the irradiation group devices to irradiation conditions, and select charged ions or uncharged particles as the radiation source. In this embodiment, uncharged particle (atmospheric) neutrons are used as the incident source, the incident energy is selected to be 1 MeV, the beam size is 5000 nm×400 nm, and the average injection amount is 4×10 9 p / cm 2 , the incident angle is 90°. For example, the incident angle can be determined according to the plane where the hafnium-based ferroelectric thin film is located and the incident direction of the low-energy particle beam.

[0070] (3) After the irradiation test, a top electrode W with a thickness of 40 nm was grown on the ferroelectric induction layer of the irradiated group and the control group devices, and the electrical test was completed after the electrode patterning.

[0071] (4) Analysis of irradiation effect. Compared with the control group, the residual polarization intensity parameter of the irradiated group device is about 15 µC / cm 2 After neutron beam irradiation, the residual polarization intensity parameter of the irradiated group devices increased by 35% to 23 µC / cm 2 The coercive electric field strength parameter of the device remains basically unchanged at 2.55 MV / cm.

[0072] Figure 3 The schematic diagram shows the change of the coercive electric field intensity parameters before and after the hafnium-based ferroelectric film is irradiated with a particle beam.

[0073] Figure 4 A schematic diagram showing the change in the remanent polarization intensity parameter of the hafnium-based ferroelectric film before and after irradiation with a particle beam.

[0074] like Figure 3 and Figure 4 As shown, in 2×10 10 n / cm 2 Irradiation dose, 3×10 10 n / cm 2Under the irradiation dose, the remanent polarization intensity parameters of hafnium-based ferroelectric devices increase successively, while the coercive electric field intensity parameters remain basically unchanged. c+ and E c- are the positive and negative coercive electric field strengths, P r+ and P r- are the positive and negative remanent polarization intensities, respectively. Furthermore, when the irradiation dose increases to 4×10 10 n / cm 2 , 5.2×10 11 n / cm 2 When the remanent polarization intensity parameters of the hafnium-based ferroelectric device begin to decrease. Based on this, it can be seen that there is a certain range of optimal irradiation condition values ​​for neutron irradiation of hafnium-based ferroelectric devices. By adjusting the neutron injection rate, the remanent polarization intensity parameters of the hafnium-based ferroelectric device can be flexibly adjusted, thereby achieving flexible regulation of the durability of the hafnium-based ferroelectric device.

[0075] According to the embodiments of the present disclosure, the present disclosure performs device structure design for a hafnium-based ferroelectric device, and prepares materials and devices for the hafnium-based ferroelectric device according to the structural design results, and performs an irradiation process on the prepared device to obtain a target hafnium-based ferroelectric device, wherein the hafnium-based ferroelectric device that has not been irradiated corresponds to a control group device, and the hafnium-based ferroelectric device after irradiation corresponds to an irradiation group device, wherein the irradiation treatment requires setting the irradiation ion type, irradiation ion injection rate, irradiation energy, and irradiation angle.

[0076] According to the embodiments of the present disclosure, macroscopic and microscopic performance tests of control group devices and irradiated group devices can be performed using electrical tests and then microscopic observation and analysis, and irradiation parameters can be optimized based on the performance test results to obtain hafnium-based ferroelectric devices with better performance.

[0077] The flowcharts and block diagrams in the accompanying drawings illustrate the possible implementation architecture, functions and operations of the systems, methods and computer program products according to various embodiments of the present disclosure. In this regard, each box in the flowchart or block diagram may represent a module, a program segment, or a part of a code, and the above-mentioned module, program segment, or a part of the code contains one or more executable instructions for implementing the specified logical function. It should also be noted that in some alternative implementations, the functions marked in the box may also occur in an order different from that marked in the accompanying drawings. For example, two boxes represented in succession can actually be executed substantially in parallel, and they can sometimes be executed in the opposite order, depending on the functions involved. It should also be noted that each box in the block diagram or flowchart, and the combination of boxes in the block diagram or flowchart, can be implemented with a dedicated hardware-based system that performs a specified function or operation, or can be implemented with a combination of dedicated hardware and computer instructions. It can be understood by those skilled in the art that the features recorded in the various embodiments of the present disclosure can be combined and / or combined in a variety of ways, even if such a combination or combination is not explicitly recorded in the present disclosure. In particular, without departing from the spirit and teaching of the present disclosure, the features described in the various embodiments of the present disclosure may be combined and / or combined in a variety of ways. All of these combinations and / or combinations fall within the scope of the present disclosure.

[0078] The embodiments of the present disclosure are described above. However, these embodiments are only for illustrative purposes and are not intended to limit the scope of the present disclosure. Although the embodiments are described above, this does not mean that the measures in the various embodiments cannot be used in combination to advantage. Without departing from the scope of the present disclosure, those skilled in the art may make a variety of substitutions and modifications, which should all fall within the scope of the present disclosure.

Claims

1. A hafnium-based ferroelectric device modified by irradiated particles, comprising: substrate layer; a bottom electrode layer disposed on the substrate layer; A hafnium-based ferroelectric thin film located on the bottom electrode layer; A ferroelectric induction layer located on the hafnium-based ferroelectric thin film; a top electrode layer located on the ferroelectric inductive layer; Wherein, the residual polarization intensity parameter of the hafnium-based ferroelectric film is improved by using particle beam irradiation adjustment without forming the top electrode layer; the ferroelectric induction layer is used to induce the hafnium-based ferroelectric film to produce ferroelectricity without forming the top electrode layer, thereby facilitating the use of the particle beam to adjust the residual polarization intensity parameter without forming the top electrode layer.

2. The hafnium-based ferroelectric device according to claim 1, wherein: The material of the ferroelectric induction layer includes metal oxide; The thickness of the ferroelectric induction layer is 1-5 nm.

3. The hafnium-based ferroelectric device according to claim 2, wherein: The metal oxide of the ferroelectric induction layer is Al2O3 or ZrO2.

4. A method for controlling the performance of a hafnium-based ferroelectric device, comprising: depositing a bottom electrode layer on the substrate layer; Depositing a hafnium-based material film on the bottom electrode layer; Depositing a ferroelectrically inductive layer on the hafnium-based material film to obtain a first intermediate device; By performing rapid annealing on the first intermediate device, a second intermediate device including a hafnium-based ferroelectric thin film is obtained, wherein the hafnium-based ferroelectric thin film is a hafnium-based material thin film having ferroelectricity; irradiating the second intermediate device with a particle beam to adjust the remanent polarization intensity parameter of the hafnium-based ferroelectric film, thereby obtaining a third intermediate device including a target hafnium-based ferroelectric film, wherein the target hafnium-based ferroelectric film is a hafnium-based ferroelectric film with the remanent polarization intensity parameter adjusted; A top electrode layer is formed on the third intermediate device to obtain a target hafnium-based ferroelectric device with adjusted performance.

5. The method according to claim 4, wherein: The method of irradiating the second intermediate device with a particle beam to adjust the residual polarization intensity parameter of the hafnium-based ferroelectric film to obtain a third intermediate device including a target hafnium-based ferroelectric film comprises: The target hafnium-based ferroelectric film is obtained by irradiating the ferroelectric induction layer of the second intermediate device with the particle beam so that the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameters of the hafnium-based ferroelectric film.

6. The method according to claim 5, wherein: The method of irradiating the ferroelectric induction layer of the second intermediate device with the particle beam so that the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameter of the hafnium-based ferroelectric film and obtaining the target hafnium-based ferroelectric film, comprises: By using the particle beam to irradiate the ferroelectric induction layer of the second intermediate device, the particle beam penetrates the ferroelectric induction layer of the second intermediate device and acts on the hafnium-based ferroelectric film, thereby adjusting the charged state of the intrinsic oxygen vacancies in the hafnium-based ferroelectric film, thereby adjusting the residual polarization intensity parameter.

7. The method according to any one of claims 4 to 6, wherein The irradiation particle beam includes neutron beam, proton beam, He 2+ one of an ion beam, an argon particle beam and an electron beam; The irradiation energy range of the neutron beam is 1×10 -9 MeV~10MeV; The irradiation energy range of the proton beam is 1×10 -1 keV ~10MeV; The irradiation energy range of the electron beam is 1×10 -1 keV~10 MeV; He 2+ The ion beam irradiation energy ranges from 10 keV to 1 MeV; The irradiation energy range of the argon ions is 400 keV~2 MeV.

8. The method according to claim 7, wherein: The particle fluence rate of the neutron beam ranges from 1×10 5 n / cm 2 / s~1×10 14 n / cm 2 / s; The particle fluence rate of the proton beam ranges from 1×10 7 p / cm 2 / s~1×10 16 p / cm 2 / s; The particle fluence rate of the electron beam ranges from 1×10 7 p / cm 2 / s ~1×10 16 p / cm 2 / s; He 2+ The particle fluence rate of the ion beam ranges from 1×10 8 ions / cm 2 / s ~1×10 15 ions / cm 2 / s; The argon ion flux range is 5×10 15 ~1.4×10 16 ions / cm 2 .

9. The method according to any one of claims 4 to 6, wherein The irradiation angle of the particle beam ranges from 5° to 90°.

10. The method according to any one of claims 4 to 6, wherein: The method of making the hafnium-based material film have ferroelectricity by rapidly annealing the intermediate device to obtain the hafnium-based ferroelectric film comprises: The intermediate device is subjected to rapid annealing, the annealing time ranges from 10 s to 50 s, and the heating temperature ranges from 400° C. to 700° C.

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