Hafnium-based ferroelectric devices and their performance regulation methods

Abstract

The present disclosure provides a hafnium-based ferroelectric device and a performance regulation method, which can be applied to the technical field of ferroelectric film modification. The device comprises: 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 remanent polarization parameter of the hafnium-based ferroelectric film is improved by using particle beam irradiation without forming the top electrode layer; and the ferroelectric induction layer is used to induce the hafnium-based ferroelectric film to generate ferroelectricity without forming the top electrode layer, thereby facilitating the regulation of the remanent polarization parameter using the particle beam without forming the top electrode layer.

Description

Technical Field

[0001] This disclosure relates to the field of ferroelectric thin film technology, and more specifically, to a hafnium-based ferroelectric device and a method for regulating its performance. Background Technology

[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 advantages such as high compatibility with semiconductor processes and mature manufacturing processes, bringing new opportunities for the development of ferroelectric memory technology.

[0003] In realizing the present invention, the inventors discovered that the modification of hafnium-based ferroelectric thin films in hafnium-based ferroelectric devices is ineffective. Summary of the Invention

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

[0005] One aspect of this disclosure provides a hafnium-based ferroelectric device, comprising: a substrate layer; a bottom electrode layer on the substrate layer; a hafnium-based ferroelectric thin film on the bottom electrode layer; a ferroelectric induction layer on the hafnium-based ferroelectric thin film; and a top electrode layer on the ferroelectric induction layer; wherein the remanent polarization parameter of the hafnium-based ferroelectric thin film is improved by particle beam irradiation without the formation of the top electrode layer; the ferroelectric induction layer is used to induce ferroelectricity in the hafnium-based ferroelectric thin film without the formation of the top electrode layer, thereby facilitating the adjustment of the remanent polarization parameter by particle beam without the formation of the top electrode layer.

[0006] According to embodiments of this disclosure, the material of the ferroelectric induction layer includes a metal oxide; the thickness of the ferroelectric induction layer is 1-5 nm.

[0007] According to embodiments of this disclosure, the metal oxide of the ferroelectric induction layer is Al2O3 or ZrO2.

[0008] Another aspect of this disclosure provides a method for performance regulation of a hafnium-based ferroelectric device, comprising: depositing a bottom electrode layer on a substrate; depositing a hafnium-based material thin film on the bottom electrode layer; depositing a ferroelectric induction layer on the hafnium-based material thin film to obtain a first intermediate device; rapidly annealing the first intermediate device to obtain a second intermediate device including a hafnium-based ferroelectric thin film, wherein the hafnium-based ferroelectric thin film is a hafnium-based material thin film with ferroelectric properties; irradiating the second intermediate device with a particle beam to adjust the remanent polarization parameter of the hafnium-based ferroelectric thin film to obtain a third intermediate device including a target hafnium-based ferroelectric thin film, wherein the target hafnium-based ferroelectric thin film is a hafnium-based ferroelectric thin film with adjusted remanent polarization parameter; and forming a top electrode layer on the third intermediate device to obtain the target hafnium-based ferroelectric device with regulated performance.

[0009] According to embodiments of this disclosure, a third intermediate device comprising a target hafnium-based ferroelectric thin film is obtained by irradiating a second intermediate device with a particle beam to adjust the remanent polarization parameter of the hafnium-based ferroelectric thin film. The method includes: 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 thin film, thereby adjusting the remanent polarization parameter of the hafnium-based ferroelectric thin film to obtain the target hafnium-based ferroelectric thin film.

[0010] According to embodiments of this disclosure, a target hafnium-based ferroelectric thin film is obtained by irradiating the ferroelectric induction layer of a 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 thin film, thereby adjusting the remanent polarization parameter of the hafnium-based ferroelectric thin film. This includes: 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 thin film, thereby adjusting the charge state of intrinsic oxygen vacancies in the hafnium-based ferroelectric thin film, and thus adjusting the remanent polarization parameter.

[0011] According to embodiments of this disclosure, the irradiated particle beam includes a neutron beam, a proton beam, and a He beam. 2+ One of the following: ion beam, argon ion beam, and electron beam; the irradiation energy range of the neutron beam is 1 × 10⁻⁶. -9 MeV~10 MeV; the irradiation energy range of the proton beam is 1×10⁻⁶. -1 keV ~10 MeV; the irradiation energy range of the electron beam is 1×10⁻⁶. -1 keV~10 MeV; He 2+ The irradiation energy range of the ion beam is 10 keV to 1 MeV; the irradiation energy range of the argon ion beam is 400 keV to 2 MeV.

[0012] According to embodiments of this disclosure, the particle fluence rate of the neutron beam ranges from 1 × 10⁻⁶. 5 n / cm 2 / s ~1×10 14 n / cm 2 / s; the particle fluence rate of the proton beam ranges from 1×10⁻⁶. 7 p / cm 2 / s~1×10 16 p / cm 2 / s; the particle fluence rate of the electron beam ranges from 1×10⁻⁶. 7 p / cm 2 / s ~1×10 16 p / cm 2 / s; 60The fluence rate of Co γ rays ranges from 1×10⁻⁶. 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 × 10⁻⁶. 8 ions / cm 2 / s ~1×10 15 ions / cm 2 / s; Argon ion beam flux range is 5×10 15 ~1.4×10 16 ions / cm 2 .

[0013] According to embodiments of this disclosure, the irradiation angle of the particle beam ranges from 5° to 90°.

[0014] According to embodiments of this disclosure, a hafnium-based ferroelectric thin film is obtained by rapidly annealing an intermediate device to impart ferroelectric properties to the hafnium-based material thin film. The process includes rapidly annealing the intermediate device for a duration ranging from 10 s to 50 s and a heating temperature ranging from 400 ℃ to 700 ℃.

[0015] According to embodiments of this disclosure, by inducing the ferroelectricity of a hafnium-based ferroelectric thin film using a ferroelectric induction layer during the fabrication of a hafnium-based ferroelectric device, the influence of the low-energy particle beam on the hafnium-based ferroelectric thin film can be enhanced when irradiating it with a low-energy particle beam, thereby improving the adjustment effect on the remanent polarization parameter of the hafnium-based ferroelectric thin film. Based on this, compared to the prior art, this disclosure improves the modification effect of the hafnium-based ferroelectric thin film when using a particle beam to modify it, and can achieve irradiation modification of the hafnium-based ferroelectric thin film with lower energy than related technologies. Attached Figure Description

[0016] The above and other objects, features and advantages of this disclosure will become clearer from the following description of embodiments with reference to the accompanying drawings, in which:

[0017] Figure 1 A schematic diagram of the structure of a hafnium-based ferroelectric device according to an embodiment of the present disclosure is shown.

[0018] Figure 2 A flowchart illustrating a method for performance regulation of hafnium-based ferroelectric devices according to an embodiment of the present disclosure is shown.

[0019] Figure 3 The diagram illustrates the change in coercive electric field strength parameters before and after irradiating a hafnium-based ferroelectric thin film with a particle beam.

[0020] Figure 4 The diagram illustrates the change in residual polarization parameters before and after irradiating a hafnium-based ferroelectric thin film with a particle beam. Detailed Implementation

[0021] The embodiments of the present disclosure will now 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 disclosure. In the following detailed description, numerous specific details are set forth to provide a thorough understanding of the embodiments of the present disclosure for ease of explanation. However, it will be apparent that one or more embodiments may be practiced without these specific details. Furthermore, descriptions of well-known structures and techniques are omitted in the following description to avoid unnecessarily obscuring the concepts of the present disclosure.

[0022] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

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

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

[0025] In the embodiments disclosed herein, the collection, updating, analysis, processing, use, transmission, provision, disclosure, and storage of data (e.g., including but not limited to user personal information) comply with relevant laws and regulations, are used for legitimate purposes, and do not violate public order and good morals. In particular, necessary measures have been taken to prevent unauthorized access to user personal information data and to safeguard user personal information security, network security, and national security.

[0026] In the embodiments disclosed herein, user authorization or consent is obtained before acquiring or collecting user personal information.

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

[0028] Building upon this, the inventors discovered that annealing the hafnium-based thin film after depositing a top electrode layer on it can impart ferroelectricity, resulting in a hafnium-based ferroelectric thin film. In this case, modification of the hafnium-based ferroelectric thin film can only be achieved by irradiating it with a high-energy particle beam. Simultaneously, through simulation, the inventors found that a low-energy particle beam is more effective at inducing oxygen vacancies (V0) within the hafnium-based ferroelectric thin film. O Defect generation occurs. However, the presence of the top electrode layer can obstruct the low-energy particle beam during irradiation, reducing the irradiation effect and thus decreasing the ability to adjust the remanent polarization parameters. Based on this, the inventors discovered that by depositing a ferroelectric induction layer based on a metal oxide on a hafnium-based thin film, providing a certain mechanical clamping stress to the hafnium-based thin film, and then annealing the hafnium-based thin film to induce its ferroelectricity, a hafnium-based ferroelectric thin film is obtained. Irradiating the hafnium-based ferroelectric thin film to adjust the remanent polarization parameters can improve the effect of the low-energy particle beam on the remanent polarization parameters, thereby enhancing the modification effect on the hafnium-based ferroelectric thin film.

[0029] Based on this, in order to at least partially solve the technical problems existing in the related art, the embodiments of this disclosure provide 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; and a top electrode layer located on the ferroelectric induction layer; wherein the remanent polarization intensity parameter of the hafnium-based ferroelectric thin film is improved by adjusting it by particle beam irradiation without forming the top electrode layer; the ferroelectric induction layer is used to induce ferroelectricity in the hafnium-based ferroelectric thin film without forming the top electrode layer, thereby facilitating the adjustment of the remanent polarization intensity parameter by particle beam without forming the top electrode layer.

[0030] Figure 1 A schematic diagram of the structure of a hafnium-based ferroelectric device according to an embodiment of the present disclosure is shown.

[0031] like Figure 1As shown, the device 100 in this embodiment includes a substrate layer 110, a bottom electrode layer 120 on the substrate layer 110, a hafnium-based ferroelectric thin film 130 on the bottom electrode layer 120, a ferroelectric induction layer 140 on the hafnium-based ferroelectric thin film 130, and a top electrode layer 150 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 or different materials, which is not limited here.

[0032] According to embodiments of this disclosure, the substrate 110 can provide mechanical support for the device 100. To ensure the stability and reliability of the device 100, the thickness, flatness, and material properties of the substrate 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, and is used to provide a current path so that current can pass smoothly through the hafnium-based ferroelectric thin film 130.

[0034] According to embodiments of this disclosure, the hafnium-based ferroelectric thin film 130 can be made of hafnium dioxide doped with other elements, thereby exhibiting excellent ferroelectric properties. Hafnium oxide-based ferroelectric crystals can be prepared by selectively doping with elements such as Zr, La, Al, Si, Ga, and Y. Therefore, the material of the hafnium-based ferroelectric thin film 130 includes one of Zr-doped HfO2, La-doped HfO2, Al-doped HfO2, Si-doped HfO2, Ga-doped HfO2, and Y-doped HfO2. The thickness of the hafnium-based ferroelectric thin film 130 ranges from 5 nm to 50 nm.

[0035] The inventors discovered that the intrinsic oxygen vacancy V in hafnium-based ferroelectric thin film 130 O With increasing concentration, the room-temperature stable phase structure of hafnium-based ferroelectric thin film 130 transforms from the original monoclinic m-phase (P21 / c) structure to a tetragonal t-phase (P42 / nmc) structure. Stabilizing the intermediate t-phase structure of hafnium-based ferroelectric thin film 130 helps to reduce the polarization reversal barrier and can increase the ferroelectric phase to a certain extent, thereby improving the remanent polarization intensity parameter. Simultaneously, intrinsic oxygen vacancies V... O Charged to become V O 2+ It also helps to reduce the polarization reversal barrier of hafnium-based ferroelectric thin film 130, thereby affecting the residual polarization intensity parameters.

[0036] According to embodiments of this disclosure, the particle beam may include neutrons, protons, and He. 2+Ions, such as argon ions, can produce radiation effects, that is, they can induce particles that produce displacement radiation and ionization radiation effects, either separately or simultaneously. Radiation effects can influence specific crystal phase structures within the hafnium-based ferroelectric thin film by altering the microscopic physical properties of oxygen vacancies, thus selectively regulating the remanent polarization parameters of the hafnium-based ferroelectric thin film 130. Ionization radiation effects can increase the intrinsic oxygen vacancies V0 of the hafnium-based ferroelectric thin film 130. O Charging reduces the polarization reversal barrier to some extent; meanwhile, the displacement radiation effect can create new point defects to alter the intrinsic oxygen vacancy V. O The concentration stabilizes the intermediate t-phase structure, further increasing the ferroelectric phase. Therefore, the remanent polarization parameter of the hafnium-based ferroelectric thin film 130 can be selectively controlled by adjusting the energy, flux, and incident angle of the irradiated ions.

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

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

[0039] According to embodiments of this 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 embodiments of this disclosure, by inducing the ferroelectricity of the hafnium-based ferroelectric thin film 130 using a ferroelectric induction layer 140 during the fabrication of the hafnium-based ferroelectric device 100, the influence of the low-energy particle beam on the hafnium-based ferroelectric thin film 130 can be enhanced when irradiating the hafnium-based ferroelectric thin film 130 with a low-energy particle beam, thereby improving the adjustment effect on the remanent polarization intensity parameter of the hafnium-based ferroelectric thin film 130. Based on this, compared to the prior art, this disclosure improves the modification effect of the hafnium-based ferroelectric thin film 130 when modifying it with a particle beam, and can achieve irradiation modification of the hafnium-based ferroelectric thin film 130 with a lower energy than related technologies.

[0041] According to embodiments of this disclosure, the ferroelectric induction layer 140 is made of a metal oxide. Furthermore, since the ferroelectric induction layer is an oxide thin film, compared to a metal thin film electrode, the oxide thin film generates in-plane stress to prevent the hafnium-based ferroelectric thin film from transforming from a metastable orthorhombic / tetragonal (o / t) phase to a monoclinic (m) phase during annealing and cooling, while also avoiding the formation of additional oxygen vacancy defects at the interface with the hafnium-based ferroelectric thin film.

[0042] According to embodiments of this 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, as well as the doping elements and film thickness of the hafnium-based ferroelectric thin film 130, it is beneficial to adjust the ferroelectric properties of the hafnium-based ferroelectric thin film 130, thereby improving the cycle durability of the hafnium-based ferroelectric device 100.

[0043] According to embodiments of this disclosure, the metal oxide of the ferroelectric induction 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 embodiments of this disclosure, by setting the thickness and material of the top electrode layer 150 and the bottom electrode layer 120, as well as the doping elements of the substrate layer 110, it is beneficial to control the conductivity of the electrodes, thereby helping to obtain a more stable and reliable hafnium-based ferroelectric device 100.

[0045] Based on the hafnium-based ferroelectric device 100 described above, embodiments of this disclosure also provide a method for regulating the performance of the hafnium-based ferroelectric device 100, which will be described below based on... Figure 2 The performance control method of the device 100 in the above embodiment will be described.

[0046] Figure 2 A flowchart illustrating a method for performance regulation of hafnium-based ferroelectric devices according to an embodiment of the present disclosure is shown.

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

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

[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 a hafnium-based material thin film to obtain the first intermediate device.

[0051] In operation S240, a second intermediate device including a hafnium-based ferroelectric thin film is obtained by rapidly annealing the first intermediate device, wherein the hafnium-based ferroelectric thin film is a hafnium-based material thin film with ferroelectric properties.

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

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

[0054] According to embodiments of this disclosure, the bottom electrode layer can be deposited using a magnetron sputtering method, for example, the deposition process can last from 5 to 30 minutes. Preferably, it can last 10 minutes.

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

[0056] According to embodiments of this disclosure, an intermediate device is obtained by depositing a ferroelectric induction layer on a hafnium-based thin film, and the first intermediate device is annealed to impart ferroelectricity to the hafnium-based thin film, thus avoiding the use of a top electrode layer, which is a metallic material, to induce ferroelectricity in the hafnium-based thin film. Therefore, when using a low-energy particle beam to irradiate the hafnium-based ferroelectric thin film, the influence of the low-energy particle beam on the hafnium-based ferroelectric thin film is enhanced, improving the adjustment effect on the coercive electric field parameters of the hafnium-based ferroelectric thin film. Based on this, compared to the prior art, this disclosure improves the modification effect of the hafnium-based ferroelectric thin film when using a particle beam to modify it, and can achieve irradiation modification of the hafnium-based ferroelectric thin film with lower energy than related technologies.

[0057] According to embodiments of this disclosure, a hafnium-based ferroelectric thin film is obtained by rapidly annealing an intermediate device to impart ferroelectric properties to the hafnium-based material thin film. The process includes rapidly annealing the intermediate device for a duration ranging from 10 s to 50 s and a heating temperature ranging from 400 ℃ to 700 ℃.

[0058] According to embodiments of this disclosure, by rapidly annealing intermediate devices, the intermediate devices can be brought to a stable state, thereby improving the overall performance of the devices.

[0059] According to embodiments of this disclosure, a third intermediate device comprising a target hafnium-based ferroelectric thin film is obtained by irradiating a second intermediate device with a low-energy particle beam to adjust the remanent polarization parameter of the hafnium-based ferroelectric thin film. This includes 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 thin film, thereby adjusting the remanent polarization parameter of the hafnium-based ferroelectric thin film to obtain the target hafnium-based ferroelectric thin film.

[0060] According to the embodiments of this disclosure, since the ferroelectric induction layer has low blocking ability for low-energy particle beams and the blocking effect on low-energy particle beams is small, 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 low-energy particle beam on the adjustment of the remanent polarization intensity parameter of hafnium-based ferroelectric thin film is improved, and the modification effect of hafnium-based ferroelectric thin film is enhanced.

[0061] According to embodiments of this disclosure, a target hafnium-based ferroelectric thin film is obtained by irradiating the ferroelectric induction layer of a 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 thin film, thereby adjusting the remanent polarization parameter of the hafnium-based ferroelectric thin film. This includes: 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 thin film, thereby adjusting the charge state of intrinsic oxygen vacancies in the hafnium-based ferroelectric thin film, and thus adjusting the remanent polarization parameter.

[0062] According to the embodiments of this disclosure, since the ferroelectric induction layer has low blocking ability for low-energy particle beams and the low-energy particle beams are less affected by the blocking, 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 low-energy particle beams on the charging state of intrinsic oxygen vacancies in hafnium-based ferroelectric thin films is improved, and the modification effect on hafnium-based ferroelectric thin films is enhanced.

[0063] According to embodiments of this disclosure, the particle beam includes a neutron beam, a proton beam, and a He beam. 2+ One of the following: ion beam, argon ion beam, and electron beam; the irradiation energy range of the neutron beam is 1 × 10⁻⁶. -9 MeV~10 MeV; the irradiation energy range of the proton beam is 1×10⁻⁶. -1 keV ~10 MeV; the irradiation energy range of the electron beam is 1×10⁻⁶. -1 keV~10 MeV; He 2+The irradiation energy range of the ion beam is 10 keV to 1 MeV; the irradiation energy range of the argon ion beam is 400 keV to 2 MeV.

[0064] According to embodiments of this disclosure, the particle fluence rate of the neutron beam ranges from 1 × 10⁻⁶. 5 n / cm 2 / s ~1×10 14 n / cm 2 / s; the particle fluence rate of the proton beam ranges from 1×10⁻⁶. 7 p / cm 2 / s~1×10 16 p / cm 2 / s; the particle fluence rate of the electron beam ranges from 1×10⁻⁶. 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 × 10⁻⁶. 8 ions / cm 2 / s ~1×10 15 ions / cm 2 / s; the particle flux range of the argon ion beam is 5 × 10⁻⁶. 15 ~1.4×10 16 ions / cm 2 .

[0065] According to embodiments of this disclosure, the irradiation angle of the particle beam ranges from 5° to 90°.

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

[0067] To better understand the contents of this disclosure, the invention will be described below through specific embodiments.

[0068] (1) Fabrication of hafnium-based ferroelectric devices. The structure of hafnium-based ferroelectric devices includes ZrO2 / HZO / W. First, W was deposited as the bottom electrode on a lightly doped Si substrate using magnetron sputtering for 10 min, with a thickness of 50 nm to 100 nm. Then, a hafnium-based ferroelectric thin film with a thickness of 10 nm to 50 nm was grown on the surface of the bottom electrode using atomic layer deposition. Next, a 1 nm thick ZrO2 ferroelectric induction layer was deposited using atomic layer deposition, and the entire device was rapidly annealed at a temperature of 400 °C to 700 °C for 10 s to 50 s. The fabricated devices were labeled as the irradiation group and the control group, respectively.

[0069] (2) Irradiation treatment. The irradiated devices are exposed to irradiation conditions, and charged ions or uncharged particles are selected as the radiation source. In this embodiment, uncharged particles (atmosphere) neutrons are used as the incident source, the incident energy is selected as 1 MeV, the beam size is 5000 nm × 400 nm, and the average injection amount is 4 × 10⁻⁶. 9 p / cm 2 The incident angle is 90°. For example, the incident angle can be determined based on the plane in which 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 electrode was patterned before electrical testing was completed.

[0071] (4) Irradiation effect analysis. Compared with the control group, the remanent polarization parameter of the irradiated group was approximately 15 µC / cm. 2 The remanent polarization parameter of the irradiated group of devices after neutron beam irradiation increased by 35%, reaching 23 µC / cm. 2 The coercive electric field strength parameter of the device remains essentially unchanged at 2.55 MV / cm.

[0072] Figure 3 The diagram illustrates the change in coercive electric field strength parameters before and after irradiating a hafnium-based ferroelectric thin film with a particle beam.

[0073] Figure 4 The diagram illustrates the change in residual polarization parameters before and after irradiating a hafnium-based ferroelectric thin film 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 varying irradiation doses, the remanent polarization parameters of hafnium-based ferroelectric devices increase sequentially, while the coercive electric field parameters remain essentially constant. Specifically, E... c+ and E c- P represents the positive and negative coercive electric field strengths, respectively. r+ and P r- These represent the positive and negative remanent polarization intensities, respectively. Furthermore, when the irradiation dose increases sequentially to 4 × 10⁻⁶... 10 n / cm 2 5.2×10 11 n / cm 2 At this point, the remanent polarization parameter of the hafnium-based ferroelectric device begins to decrease. Based on this, it can be concluded that there is a certain range of optimal irradiation conditions for neutron irradiation of hafnium-based ferroelectric devices. By adjusting the neutron flux rate, the remanent polarization parameter of the hafnium-based ferroelectric device can be flexibly controlled, thereby achieving flexible control over the durability of the hafnium-based ferroelectric device.

[0075] According to embodiments of this disclosure, the present disclosure performs device structure design for hafnium-based ferroelectric devices, and prepares materials and devices for hafnium-based ferroelectric devices based on the structural design results. The prepared devices are subjected to irradiation process to obtain target hafnium-based ferroelectric devices. Unirradiated hafnium-based ferroelectric devices correspond to control group devices, and irradiated hafnium-based ferroelectric devices correspond to irradiated group devices. The irradiation process requires setting the type of irradiated ions, the irradiated ion flux rate, the irradiation energy, and the irradiation angle.

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

[0077] The flowcharts and block diagrams in the accompanying drawings illustrate the architecture, functionality, and operation of possible implementations of systems, methods, and computer program products according to various embodiments of the present disclosure. In this regard, each block in a flowchart or block diagram may represent a module, segment, or portion of code containing one or more executable instructions for implementing a specified logical function. It should also be noted that in some alternative implementations, the functions indicated in the blocks may occur in a different order than those indicated in the drawings. For example, two consecutively indicated blocks may actually be executed substantially in parallel, and they may sometimes be executed in reverse order, depending on the functions involved. It should also be noted that each block in a block diagram or flowchart, and combinations of blocks in a block diagram or flowchart, may be implemented using a dedicated hardware-based system that performs the specified function or operation, or using a combination of dedicated hardware and computer instructions. Those skilled in the art will understand that the features described in the various embodiments of the present disclosure can be combined and / or combined in various ways, even if such combinations are not explicitly described in the present disclosure. In particular, the features described in the various embodiments of this disclosure may be combined and / or combined in various ways without departing from the spirit and teachings of this disclosure. All such combinations and / or combinations fall within the scope of this disclosure.

[0078] The embodiments of this disclosure have been described above. However, these embodiments are for illustrative purposes only and are not intended to limit the scope of this disclosure. Although various embodiments have been described above, this does not mean that the measures in the various embodiments cannot be used advantageously in combination. Various substitutions and modifications can be made by those skilled in the art without departing from the scope of this disclosure, and all such substitutions and modifications should fall within the scope of this disclosure.

Claims

1. A hafnium-based ferroelectric device modified by irradiation of particles, comprising: a substrate layer; a bottom electrode layer on the substrate layer; a hafnium-based ferroelectric thin film on the bottom electrode layer; a ferroelectric inducing layer on the hafnium-based ferroelectric thin film; a top electrode layer on the ferroelectric inducing layer; wherein a remnant polarization parameter of the hafnium-based ferroelectric thin film is modified by using a particle beam irradiation without forming the top electrode layer; and the ferroelectric inducing layer is used to induce the hafnium-based ferroelectric thin film to have ferroelectricity without forming the top electrode layer, thereby facilitating the remnant polarization parameter to be adjusted by using the particle beam without forming the top electrode layer.

2. The hafnium-based ferroelectric device of claim 1, wherein, a material of the ferroelectric inducing layer comprises a metal oxide; a thickness of the ferroelectric inducing layer is 1-5 nm.

3. The hafnium-based ferroelectric device of claim 2, wherein the metal oxide of the ferroelectric inducing layer is AI2O3 or ZrO2.

4. A method for performance regulation of a hafnium-based ferroelectric device, comprising: depositing a bottom electrode layer on a substrate layer; depositing a hafnium-based material thin film on the bottom electrode layer; depositing a ferroelectric inducing layer on the hafnium-based material thin film to obtain a first intermediate device; obtaining a second intermediate device comprising a hafnium-based ferroelectric thin film by performing rapid annealing on the first intermediate device, wherein the hafnium-based ferroelectric thin film is the hafnium-based material thin film having ferroelectricity; obtaining a third intermediate device comprising a target hafnium-based ferroelectric thin film by adjusting a remnant polarization parameter of the hafnium-based ferroelectric thin film using a particle beam irradiation on the second intermediate device, wherein the target hafnium-based ferroelectric thin film is the hafnium-based ferroelectric thin film with the adjusted remnant polarization parameter; forming a top electrode layer on the third intermediate device to obtain a target hafnium-based ferroelectric device with regulated performance.

5. The method of claim 4, wherein, the obtaining the third intermediate device comprising the target hafnium-based ferroelectric thin film by adjusting the remnant polarization parameter of the hafnium-based ferroelectric thin film using the particle beam irradiation on the second intermediate device, comprises: adjusting the remnant polarization parameter of the hafnium-based ferroelectric thin film by irradiating the ferroelectric inducing layer of the second intermediate device using the particle beam so that the particle beam penetrates the ferroelectric inducing layer of the second intermediate device to act on the hafnium-based ferroelectric thin film, thereby obtaining the target hafnium-based ferroelectric thin film.

6. The method of claim 5, wherein, the adjusting the remnant polarization parameter of the hafnium-based ferroelectric thin film by irradiating the ferroelectric inducing layer of the second intermediate device using the particle beam so that the particle beam penetrates the ferroelectric inducing layer of the second intermediate device to act on the hafnium-based ferroelectric thin film, thereby obtaining the target hafnium-based ferroelectric thin film, comprises: adjusting a charged state of an intrinsic oxygen vacancy in the hafnium-based ferroelectric thin film by irradiating the ferroelectric inducing layer of the second intermediate device using the particle beam so that the particle beam penetrates the ferroelectric inducing layer of the second intermediate device to act on the hafnium-based ferroelectric thin film, thereby adjusting the remnant polarization parameter.

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

8. The method of claim 7, wherein The particle fluence rate of the neutron beam ranges from 1 x 10 5 n / cm 2 / s to 1 x 10 14 n / cm 2 / s; The particle fluence rate of the proton beam ranges from 1 x 10 7 p / cm 2 / s~1 x 10 16 p / cm 2 / s. The particle fluence of the electron beam ranges from 1 x 10 7 p / cm 2 / s ~ 1 x 10 16 p / cm 2 / s; The He 2+ The particle flux of the ion beam ranges from 1 x 10 8 ions / cm 2 / s ~ 1 x 10 15 ions / cm 2 / s; The argon ion beam has a flux in the range of 5 x 1014 15 1.4 x 1014 16 ions / cm 2 .

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

10. The method of any one of claims 4-6, wherein, The hafnium-based material thin film is provided with ferroelectricity by rapid annealing of the intermediate device, and a hafnium-based ferroelectric thin film is obtained, comprising: The intermediate device is subjected to rapid annealing, and the annealing time ranges from 10 s to 50 s, and the heating temperature ranges from 400 DEG C to 700 DEG C.

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