High-flux antiferroelectric-dielectric energy storage solid solution thin film and preparation method thereof

Abstract

The application discloses a high-flux antiferroelectric-dielectric energy storage solid solution film, which comprises a substrate, a bottom electrode layer and an antiferroelectric-dielectric layer which are sequentially grown on the substrate; the substrate is a rigid base SrTiO3; the bottom electrode layer is a SrRuO3 film; the antiferroelectric-dielectric layer is a solid solution film which is alternately grown by a PbZrO3 antiferroelectric layer and a SrTiO3 dielectric layer; the composition of the PbZrO3 antiferroelectric layer decreases in a ladder form along a horizontal direction, and the composition of the SrTiO3 dielectric layer increases in a ladder form along the horizontal direction. The application optimizes the antiferroelectric characteristics of the high-flux film by changing the growth parameters such as the laser emission number ratio of PbZrO3 and SrTiO3 and the cycle period, so that a lower leakage current density and better performance are realized, and the application is expected to be applied to the application fields of energy storage films and capacitors.

Description

Technical Field

[0001] This invention relates to the field of electronic materials technology, and more specifically to a high-throughput antiferroelectric-dielectric energy storage solid solution thin film and its preparation method. Background Technology

[0002] Functional oxide films, due to their diverse electrical, optical, thermal, mechanical, and magnetic properties, as well as unique multi-field coupling characteristics, have extremely broad application prospects and potential in devices such as memory, sensors, microelectronics, and energy harvesting and storage systems. With the rapid development of science and technology and the increasing diversification of daily life needs, the requirements for the performance, flexibility, and miniaturization of oxide films are becoming increasingly stringent. To this end, researchers have employed various methods to improve their performance and develop new materials. These traditional methods are crucial for controlling and improving oxide films for practical applications. However, traditional methods mainly rely on scientific intuition and frequent trial-and-error experimental strategies, leading to a significant consumption of time and resources from initial research to practical adoption. Furthermore, they focus on the preparation of single-ratio components, resulting in poor stability. Therefore, a new method is urgently needed that allows for the preparation of oxide films with compositional gradients while precisely adjusting the composition.

[0003] With the advent of the big data era and artificial intelligence, it has become possible to realize compositional gradient changes through materials genomics technology, replacing traditional methods. By integrating computation, experimentation, big data analysis, and other disciplines, high-throughput design and experimentation of materials can be achieved. Materials genomics technology comprises three main parts: high-throughput computational simulation, high-throughput experiments, and materials databases. Among these, high-throughput experiments are an indispensable step in materials research, undertaking the tasks of providing a large amount of basic data and experimental evidence for materials computational simulation, as well as enriching materials databases, providing analytical materials, and enabling rapid screening. Compared with traditional methods, high-throughput experiments allow for continuous adjustment of compositional gradients and structures, obtaining multidimensional data, promoting the discovery of new material systems, and significantly shortening investigation time. In 1965, the use of compositional gradient distribution technology to rapidly prepare the phase diagram of Fe-Cr-Ni ternary alloys in a single step was first proposed, which was the prototype of high-throughput experiments. However, due to limitations in computer technology and other related technologies, it was not widely adopted. It wasn't until the 1990s that Xiang Xiaodong et al. at Lawrence Berkeley National Laboratory in the United States used improved high-throughput experiments to test various material systems and achieved a series of results. Subsequently, high-throughput experiments have been widely applied to the development and industrialization of inorganic oxide thin films for catalysis, luminescence, magnetism, and alloying. However, most oxide thin films still face several challenges and difficulties: the first obvious challenge is the inhomogeneity of oxide films, which can introduce inhomogeneities in stress, defects, and other properties, leading to serious impacts on their applications; even if the homogeneity of the film can be achieved as much as possible, it is inevitably very difficult to ensure that the composition of the oxide film can be systematically changed while keeping all other parameters constant.

[0004] Therefore, how to provide a high-flux antiferroelectric-dielectric energy storage solid solution film that can reduce leakage current density is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention

[0005] In view of this, the present invention provides a high-throughput antiferroelectric-dielectric energy storage solid solution film, which can prepare high-throughput films with rich different compositions under the same substrate, thereby achieving lower leakage current density and better performance, and is expected to be applied to energy storage films and capacitors.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A high-throughput antiferroelectric-dielectric energy storage solid solution film includes: a substrate, and a bottom electrode layer and an antiferroelectric-dielectric layer sequentially grown on the substrate; the antiferroelectric-dielectric layer is a solid solution film consisting of alternating PbZrO3 antiferroelectric layers and SrTiO3 dielectric layers; the composition of the PbZrO3 antiferroelectric layer decreases stepwise in the horizontal direction, and the composition of the SrTiO3 dielectric layer increases stepwise in the horizontal direction.

[0008] Preferably, the substrate is a rigid SrTiO3 substrate with an orientation of

[111] and an area of ​​1.5 cm × 1.5 cm.

[0009] The beneficial effects of the above technical solution are as follows: Although the thin film exhibits antiferroelectric properties with double hysteresis loops in the

[100] /

[110] /

[111] orientation of the SrTiO3 substrate, the thin film on the

[111] SrTiO3 substrate exhibits a higher maximum polarization than other orientations. For example, the (111) oriented PbZrO3 thin film has a lower angle θ between the applied electric field direction and the polar axis of the ferroelectric rhombohedral phase

[111] compared to the (100) oriented PbZrO3 configuration. Therefore, the polarization projection along the applied electric field direction is larger for the (111) PbZrO3 thin film, and thus, the PbZrO3 sample with preferential orientation in the (111) direction has higher polarization than the PbZrO3 sample with other orientation directions. In addition, the area size of 1.5cm × 1.5cm was chosen because a large-area high-throughput thin film was to be prepared to facilitate further research.

[0010] Preferably, the bottom electrode layer is a SrRuO3 thin film; the thickness of the bottom electrode layer is 5-9 nm.

[0011] Preferably, the thickness of the bottom electrode layer is 7–9 nm.

[0012] Preferably, the antiferroelectric-dielectric layer comprises 7 to 20 cycles and has a thickness of 25 to 75 nm.

[0013] This invention also provides a method for preparing a high-throughput antiferroelectric-dielectric energy storage solid solution thin film, specifically comprising:

[0014] 1) The substrate is bonded and then placed directly above the main target on the substrate stage in the growth chamber of the high-throughput pulsed laser deposition method. The distance between the SrTiO3 substrate and the target is 60-70 cm.

[0015] 2) A bottom electrode layer is grown on the substrate using a high-throughput pulsed laser deposition process;

[0016] 3) An antiferroelectric-dielectric layer is grown on the bottom electrode layer using a high-throughput pulsed laser deposition process;

[0017] 4) Perform cooling post-treatment.

[0018] Preferably, the specific parameters of the high-throughput pulsed laser deposition process in step 2) are: deposition chamber vacuum degree ≤ 8 × 10⁻⁶ -7Pa, deposition temperature 690~710℃, oxygen partial pressure 70~85mTorr, laser energy 320~340 mJ, pulsed laser frequency 4~6Hz, deposition rate 20~35℃ / min, laser focal length -20~10mm, deposition rate 4~7nm / min.

[0019] Preferably, the specific steps of the high-throughput pulsed laser deposition process in step 3) are as follows:

[0020] a. Place the PbZrO3 target and the SrTiO3 target on two adjacent target sites respectively;

[0021] b. Set the relevant parameters as follows: Deposition chamber vacuum degree ≤ 2 × 10 -7 Pa, deposition temperature 750~780℃, oxygen partial pressure 190~200mTorr, deposition rate 25~35℃ / min, laser focal length -15~5mm, deposition rate 5~10nm / min;

[0022] c. Move the substrate stage to a safe height, with the X-axis and Y-axis positions of the moved substrate stage being -3 to -1 mm and 0 to 2 mm, respectively;

[0023] d. First layer gradient: The substrate stage is rotated to the first position (0°), and the mask is moved along the X-axis and Y-axis to the deposition position and the high-throughput starting position, respectively, with moving speeds of 4-6 mm / s and 5-8 mm / s. The substrate stage is lowered to the deposition position, and the main target is switched to the PbZrO3 target. The relevant parameters are set as follows: laser energy 280-300 mJ, pulsed laser frequency 4-6 Hz, number of laser shots 1700-1900, laser focal length -15-5 mm, target rotation speed 16-18°, and mask Y-axis moving speed 0.12-0.2 mm / s.

[0024] e. Second layer gradient: Move the substrate stage to a safe height, rotate the substrate stage to the second position (180°), move the mask Y-axis to the high-throughput starting position at a moving speed of 5-8 mm / s, lower the substrate stage to the deposition position, switch the main target to the SrTiO3 target, and set the relevant parameters including laser energy 280-300 mJ, pulsed laser frequency 4-6 Hz, laser number of shots 1700-1900, laser focal length -15-5 mm, target rotation speed 16-18°, and mask Y-axis moving speed 0.15-0.2 mm / s;

[0025] f. Move the mask along the Y-axis to the high-throughput starting position, move the substrate stage to a safe height, and complete one deposition.

[0026] g. Repeat steps d to f 7 to 20 times to obtain the antiferroelectric-dielectric layer.

[0027] Preferably, the specific steps of the cooling post-treatment in step 4) are as follows:

[0028] a. Place at 750–780℃ and 190–200 mTorr oxygen partial pressure for 5–30 min;

[0029] b. Cool to room temperature at a rate of 2–5 °C / min.

[0030] As can be seen from the above technical solution, compared with the prior art, the present invention provides a high-throughput antiferroelectric-dielectric energy storage solid solution thin film and its preparation method, which has the following beneficial effects:

[0031] (1) This invention takes a perovskite oxide SrRuO3 thin film as the bottom electrode as the premise, and uses a PbZrO3 antiferroelectric layer and a SrTiO3 dielectric layer as the main components to prepare a high-flux antiferroelectric-dielectric energy storage solid solution film with a step-like variation along the horizontal direction. SrTiO3 is beneficial to reduce the leakage current density of PbZrO3, making its polarization intensity performance better.

[0032] (2) The high-throughput antiferroelectric-dielectric energy storage solid solution film prepared by the present invention has a rich gradient film with different components under the same substrate, and has excellent performance. It can quickly and conveniently screen out the component with the best performance, providing new opportunities for the application and development of thin film materials in the future.

[0033] (3) By using a high-throughput pulsed laser deposition system and an automatic mask system, this invention optimizes the antiferroelectric properties of high-throughput thin films by changing the laser emission ratio and cycle period of PbZrO3 and SrTiO3. The high-throughput antiferroelectric-dielectric energy storage solid solution thin film prepared has a lower leakage current density and is expected to be applied to energy storage films and capacitors. Attached Figure Description

[0034] To more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0035] Figure 1 The polarization intensity-voltage and current-voltage plots are for comparative examples 1, 2 and 3 of the antiferroelectric energy storage films.

[0036] Figure 2 The polarization intensity-voltage diagrams are for the high-throughput antiferroelectric-dielectric energy storage solid solution films of Examples 1, 2 and 3.

[0037] Figure 3This is a schematic diagram of the sample of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film of Example 3.

[0038] Figure 4 This is a flowchart illustrating the preparation process of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film in Example 3.

[0039] Figure 5 This is a top view of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film of Example 3.

[0040] Figure 6 This is a polarization intensity-voltage diagram of different component positions of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film in Example 3.

[0041] Figure 7 The image shows the current-voltage diagrams at different component positions of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film in Example 3.

[0042] Figure 8 The diagram shows the saturation polarization, residual polarization, and current intensity-location points of different components in the high-throughput antiferroelectric-dielectric energy storage solid solution thin film of Example 3.

[0043] Figure 9 TEM images of component positions 1 and 9 of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film of Example 3. Detailed Implementation

[0044] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0045] Example 1

[0046] A high-throughput antiferroelectric-dielectric energy storage solid solution film includes: a substrate, and a bottom electrode layer and an antiferroelectric-dielectric layer sequentially grown on the substrate; the antiferroelectric-dielectric layer is a solid solution film consisting of alternating PbZrO3 antiferroelectric layers and SrTiO3 dielectric layers; the composition of the PbZrO3 antiferroelectric layer decreases stepwise in the horizontal direction, and the composition of the SrTiO3 dielectric layer increases stepwise in the horizontal direction.

[0047] The substrate is a rigid SrTiO3 substrate with an orientation of

[111] and an area of ​​1.5cm × 1.5cm.

[0048] The bottom electrode layer is a SrRuO3 thin film with a thickness of 5 nm.

[0049] The antiferroelectric-dielectric layer comprises 7 cycles with a thickness between 25 and 50 nm, with the leftmost layer having a thickness of 25 nm and the rightmost layer having a thickness of 50 nm.

[0050] This embodiment also provides a method for preparing a high-throughput antiferroelectric-dielectric energy storage solid solution thin film, specifically including:

[0051] 1) The substrate is bonded and then placed directly above the main target on the substrate stage in the growth chamber of the high-throughput pulsed laser deposition method. The distance between the SrTiO3 substrate and the target is 60cm.

[0052] 2) A bottom electrode layer is grown on the substrate using a high-throughput pulsed laser deposition process;

[0053] 3) An antiferroelectric-dielectric layer is grown on the bottom electrode layer using a high-throughput pulsed laser deposition process;

[0054] 4) Perform cooling post-treatment.

[0055] The specific parameters for the pulsed laser deposition process in step 2) are: the vacuum level of the deposition chamber is 8 × 10⁻⁶. -7 Pa, deposition temperature 690℃, oxygen partial pressure 70mTorr, laser energy 320mJ, pulsed laser frequency 4Hz, deposition rate 20℃ / min, laser focal length -20mm, deposition rate 4nm / min.

[0056] Step 3) The specific steps of the pulsed laser deposition process are as follows:

[0057] a. Place the PbZrO3 target and the SrTiO3 target on two adjacent target sites respectively;

[0058] b. Set the relevant parameters as follows: Deposition chamber vacuum degree is 2×10 -7 Pa, deposition temperature 750℃, oxygen partial pressure 190mTorr, deposition rate 25℃ / min, laser focal length -15mm, deposition rate 5nm / min;

[0059] c. Move the substrate stage to a safe height, with the X-axis and Y-axis positions of the moved substrate stage at -3mm and 0mm respectively;

[0060] d. First layer gradient: The substrate stage is rotated to the first position (0°), and the mask is moved along the X and Y axes to the deposition position and the high-throughput starting position, respectively, with moving speeds of 4 mm / s and 5 mm / s. The substrate stage is lowered to the deposition position, and the main target is switched to the PbZrO3 target. The relevant parameters are set as follows: laser energy 280 mJ, pulsed laser frequency 4 Hz, number of laser shots 1700, laser focal length -15 mm, target rotation speed 16°, and mask Y-axis moving speed 0.12 mm / s.

[0061] e. Second layer gradient: The substrate stage is moved to a safe height, rotated to the second position (180°), and the mask Y-axis is moved to the high-throughput starting position at a moving speed of 5 mm / s. The substrate stage is lowered to the deposition position, and the main target is switched to SrTiO3 target. The relevant parameters are set as follows: laser energy 280 mJ, pulsed laser frequency 4 Hz, number of laser shots 1700, laser focal length -15 mm, target rotation speed 16°, and mask Y-axis moving speed 0.15 mm / s.

[0062] f. Move the mask along the Y-axis to the high-throughput starting position, move the substrate stage to a safe height, and complete one deposition.

[0063] g. Repeat steps d to f seven times to obtain the antiferroelectric-dielectric layer.

[0064] Step 4) The specific steps of the cooling post-treatment are as follows:

[0065] a. Place at 750℃ and 190mTorr oxygen partial pressure atmosphere for 5 minutes;

[0066] b. Cool to room temperature at a cooling rate of 2℃ / min.

[0067] Example 2

[0068] A high-throughput antiferroelectric-dielectric energy storage solid solution film includes: a substrate, and a bottom electrode layer and an antiferroelectric-dielectric layer sequentially grown on the substrate; the antiferroelectric-dielectric layer is a solid solution film consisting of alternating PbZrO3 antiferroelectric layers and SrTiO3 dielectric layers; the composition of the PbZrO3 antiferroelectric layer decreases stepwise in the horizontal direction, and the composition of the SrTiO3 dielectric layer increases stepwise in the horizontal direction.

[0069] The substrate is a rigid SrTiO3 substrate with an orientation of

[111] and an area of ​​1.5cm × 1.5cm.

[0070] The bottom electrode layer is a SrRuO3 thin film with a thickness of 7 nm.

[0071] The antiferroelectric-dielectric layer comprises 13 cycles and has a thickness between 60 and 75 nm, with the leftmost layer having a thickness of 60 nm and the rightmost layer having a thickness of 75 nm.

[0072] This embodiment also provides a method for preparing a high-throughput antiferroelectric-dielectric energy storage solid solution thin film, specifically including:

[0073] 1) The substrate is bonded and then placed directly above the main target on the substrate stage in the growth chamber of the high-throughput pulsed laser deposition method. The distance between the SrTiO3 substrate and the target is 65cm.

[0074] 2) A bottom electrode layer is grown on the substrate using a high-throughput pulsed laser deposition process;

[0075] 3) An antiferroelectric-dielectric layer is grown on the bottom electrode layer using a high-throughput pulsed laser deposition process;

[0076] 4) Perform cooling post-treatment.

[0077] The specific parameters for the pulsed laser deposition process in step 2) are: the vacuum level of the deposition chamber is 8 × 10⁻⁶. -7 Pa, deposition temperature 700℃, oxygen partial pressure 78mTorr, laser energy 330mJ, pulsed laser frequency 5Hz, deposition rate 27℃ / min, laser focal length -5mm, deposition rate 5nm / min.

[0078] Step 3) The specific steps of the pulsed laser deposition process are as follows:

[0079] a. Place the PbZrO3 target and the SrTiO3 target on two adjacent target sites respectively;

[0080] b. Set the relevant parameters as follows: Deposition chamber vacuum degree is 2×10 -7 Pa, deposition temperature 760℃, oxygen partial pressure 195mTorr, deposition rate 29℃ / min, laser focal length -2mm, deposition rate 8nm / min;

[0081] c. Move the substrate stage to a safe height, with the X-axis and Y-axis positions of the moved substrate stage being -2mm and 1mm respectively;

[0082] d. First layer gradient: The substrate stage is rotated to the first position (0°), and the mask is moved along the X and Y axes to the deposition position and the high-throughput starting position, respectively, with moving speeds of 5 mm / s and 7 mm / s. The substrate stage is lowered to the deposition position, and the main target is switched to the PbZrO3 target. The relevant parameters are set as follows: laser energy 290 mJ, pulsed laser frequency 5 Hz, number of laser shots 1900, laser focal length -2 mm, target rotation speed 17°, and mask Y-axis moving speed 0.16 mm / s.

[0083] e. Second layer gradient: The substrate stage is moved to a safe height, rotated to the second position (180°), and the mask Y-axis is moved to the high-throughput starting position at a moving speed of 7 mm / s. The substrate stage is lowered to the deposition position, and the main target is switched to SrTiO3 target. The relevant parameters are set as follows: laser energy 290 mJ, pulsed laser frequency 5 Hz, number of laser shots 1900, laser focal length -2 mm, target rotation speed 17°, and mask Y-axis moving speed 0.18 mm / s.

[0084] f. Move the mask along the Y-axis to the high-throughput starting position, move the substrate stage to a safe height, and complete one deposition.

[0085] g. Repeat steps d to f 13 times to obtain the antiferroelectric-dielectric layer.

[0086] Step 4) The specific steps of the cooling post-treatment are as follows:

[0087] a. Place at 760℃ and 195mTorr oxygen partial pressure for 15 minutes;

[0088] b. Cool to room temperature at a cooling rate of 4℃ / min.

[0089] Example 3

[0090] A high-throughput antiferroelectric-dielectric energy storage solid solution film includes: a substrate, and a bottom electrode layer and an antiferroelectric-dielectric layer sequentially grown on the substrate; the antiferroelectric-dielectric layer is a solid solution film consisting of alternating PbZrO3 antiferroelectric layers and SrTiO3 dielectric layers; the composition of the PbZrO3 antiferroelectric layer decreases stepwise in the horizontal direction, and the composition of the SrTiO3 dielectric layer increases stepwise in the horizontal direction.

[0091] The substrate is a rigid SrTiO3 substrate with an orientation of

[111] and an area of ​​1.5cm × 1.5cm.

[0092] The bottom electrode layer is a SrRuO3 thin film with a thickness of 9 nm.

[0093] The antiferroelectric-dielectric layer comprises 20 cycles and has a thickness between 30 and 66 nm, with the leftmost layer having a thickness of 30 nm and the rightmost layer having a thickness of 66 nm.

[0094] This embodiment also provides a method for preparing a high-throughput antiferroelectric-dielectric energy storage solid solution thin film, specifically including:

[0095] 1) The substrate is bonded and then placed directly above the main target on the substrate stage in the growth chamber of the high-throughput pulsed laser deposition method. The distance between the SrTiO3 substrate and the target is 70cm.

[0096] 2) A bottom electrode layer is grown on the substrate using a high-throughput pulsed laser deposition process;

[0097] 3) An antiferroelectric-dielectric layer is grown on the bottom electrode layer using a high-throughput pulsed laser deposition process;

[0098] 4) Perform cooling post-treatment.

[0099] The specific parameters for the pulsed laser deposition process in step 2) are: the vacuum level of the deposition chamber is 8 × 10⁻⁶.-7 Pa, deposition temperature 710℃, oxygen partial pressure 85mTorr, laser energy 340mJ, pulsed laser frequency 6Hz, deposition rate 35℃ / min, laser focal length 10mm, deposition rate 7nm / min.

[0100] Step 3) The specific steps of the pulsed laser deposition process are as follows:

[0101] a. Place the PbZrO3 target and the SrTiO3 target on two adjacent target sites respectively;

[0102] b. Set the relevant parameters as follows: Deposition chamber vacuum degree is 2×10 -7 Pa, deposition temperature 780℃, oxygen partial pressure 200mTorr, deposition rate 35℃ / min, laser focal length 5mm, deposition rate 10nm / min;

[0103] c. Move the substrate stage to a safe height, with the X-axis and Y-axis positions of the moved substrate stage being -1mm and 2mm respectively;

[0104] d. First layer gradient: The substrate stage is rotated to the first position (0°), and the mask is moved along the X and Y axes to the deposition position and the high-throughput starting position, respectively, with moving speeds of 6 mm / s and 8 mm / s. The substrate stage is lowered to the deposition position, and the main target is switched to the PbZrO3 target. The relevant parameters are set as follows: laser energy 300 mJ, pulsed laser frequency 6 Hz, number of laser shots 1800, laser focal length 5 mm, target rotation speed 18°, and mask Y-axis moving speed 0.2 mm / s.

[0105] e. Second layer gradient: The substrate stage is moved to a safe height, rotated to the second position (180°), and the mask Y-axis is moved to the high-throughput starting position at a moving speed of 8 mm / s. The substrate stage is lowered to the deposition position, and the main target is switched to SrTiO3 target. The relevant parameters are set as follows: laser energy 300 mJ, pulsed laser frequency 6 Hz, number of laser shots 1800, laser focal length 5 mm, target rotation speed 18°, and mask Y-axis moving speed 0.2 mm / s.

[0106] f. Move the mask along the Y-axis to the high-throughput starting position, move the substrate stage to a safe height, and complete one deposition.

[0107] g. Repeat steps d to f 20 times to obtain the antiferroelectric-dielectric layer.

[0108] Preferably, the specific steps of the cooling post-treatment in step 4) are as follows:

[0109] a. Place at 780℃ and 200mTorr oxygen partial pressure atmosphere for 30 minutes;

[0110] b. Cool to room temperature at a rate of 5℃ / min.

[0111] Comparative Example 1

[0112] An antiferroelectric energy storage thin film includes: a substrate, and a bottom electrode layer and an antiferroelectric layer sequentially grown on the substrate; the antiferroelectric layer is a thin film grown from PbZrO3.

[0113] The substrate is a rigid SrTiO3 substrate with an orientation of

[111] and an area of ​​1.5cm × 1.5cm.

[0114] This comparative example also provides a method for preparing the aforementioned antiferroelectric energy storage thin film, specifically including:

[0115] 1) The substrate is bonded and then placed directly above the main target on the substrate stage in the growth chamber of the high-throughput pulsed laser deposition method. The distance between the SrTiO3 substrate and the target is 60cm.

[0116] 2) A bottom electrode layer is grown on the substrate using a high-throughput pulsed laser deposition process;

[0117] 3) An antiferroelectric layer is grown on the bottom electrode layer using a high-throughput pulsed laser deposition process;

[0118] 4) Perform cooling post-treatment.

[0119] The specific parameters for the pulsed laser deposition process in step 2) are: deposition chamber vacuum degree ≤ 8 × 10⁻⁶ -7 Pa, deposition temperature 690℃, oxygen partial pressure 70mTorr, laser energy 320mJ, pulsed laser frequency 4Hz, deposition rate 20℃ / min, laser focal length -20mm, deposition rate 4nm / min.

[0120] The specific parameters for the pulsed laser deposition process in step 3) are: deposition chamber vacuum degree ≤ 2 × 10⁻⁶ -7 The parameters are: Pa, deposition temperature 750℃, oxygen partial pressure 190mTorr, laser energy 280mJ, pulsed laser frequency 4 Hz, deposition rate 25℃ / min, laser focal length -15mm, deposition rate 5nm / min, laser firing number 36000, and target rotation speed 16°.

[0121] Step 4) The specific steps of the cooling post-treatment are as follows:

[0122] a. Place at 750℃ and 190mTorr oxygen partial pressure atmosphere for 5 minutes;

[0123] b. Cool to room temperature at a cooling rate of 2℃ / min.

[0124] Comparative Example 2

[0125] An antiferroelectric energy storage thin film includes: a substrate, and a bottom electrode layer and an antiferroelectric layer sequentially grown on the substrate; the antiferroelectric layer is a thin film grown from PbZrO3.

[0126] The substrate is a rigid SrTiO3 substrate with an orientation of

[111] and an area of ​​1.5cm × 1.5cm.

[0127] This comparative example also provides a method for preparing the aforementioned antiferroelectric energy storage thin film, specifically including:

[0128] 1) The substrate is bonded and then placed directly above the main target on the substrate stage in the growth chamber of the high-throughput pulsed laser deposition method. The distance between the SrTiO3 substrate and the target is 65cm.

[0129] 2) A bottom electrode layer is grown on the substrate using a high-throughput pulsed laser deposition process;

[0130] 3) An antiferroelectric layer is grown on the bottom electrode layer using a high-throughput pulsed laser deposition process;

[0131] 4) Perform cooling post-treatment.

[0132] The specific parameters for the pulsed laser deposition process in step 2) are: deposition chamber vacuum degree ≤ 8 × 10⁻⁶ -7 Pa, deposition temperature 700℃, oxygen partial pressure 78mTorr, laser energy 332mJ, pulsed laser frequency 5Hz, deposition rate 27℃ / min, laser focal length -7mm, deposition rate 5nm / min.

[0133] The specific parameters for the pulsed laser deposition process in step 3) are: deposition chamber vacuum degree ≤ 2 × 10⁻⁶ -7 The parameters are: Pa, deposition temperature 760℃, oxygen partial pressure 195mTorr, laser energy 290mJ, pulsed laser frequency 5 Hz, deposition rate 30℃ / min, laser focal length -7mm, deposition rate 8nm / min, laser firing number 36000, and target rotation speed 17°.

[0134] Step 4) The specific steps of the cooling post-treatment are as follows:

[0135] a. Place at 760℃ and 195mTorr oxygen partial pressure for 20 minutes;

[0136] b. Cool to room temperature at a rate of 3℃ / min.

[0137] Comparative Example 3

[0138] An antiferroelectric energy storage thin film includes: a substrate, and a bottom electrode layer and an antiferroelectric layer sequentially grown on the substrate; the antiferroelectric layer is a thin film grown from PbZrO3.

[0139] The substrate is a rigid SrTiO3 substrate with an orientation of

[111] and an area of ​​1.5cm × 1.5cm.

[0140] This comparative example also provides a method for preparing the aforementioned antiferroelectric energy storage thin film, specifically including:

[0141] 1) The substrate is bonded and then placed directly above the main target on the substrate stage in the growth chamber of the high-throughput pulsed laser deposition method. The distance between the SrTiO3 substrate and the target is 70cm.

[0142] 2) A bottom electrode layer is grown on the substrate using a high-throughput pulsed laser deposition process;

[0143] 3) An antiferroelectric layer is grown on the bottom electrode layer using a high-throughput pulsed laser deposition process;

[0144] 4) Perform cooling post-treatment.

[0145] The specific parameters for the pulsed laser deposition process in step 2) are: deposition chamber vacuum degree ≤ 8 × 10⁻⁶ -7 Pa, deposition temperature 710℃, oxygen partial pressure 85mTorr, laser energy 340mJ, pulsed laser frequency 6Hz, deposition rate 35℃ / min, laser focal length 10mm, deposition rate 7nm / min.

[0146] The specific parameters for the pulsed laser deposition process in step 3) are: deposition chamber vacuum degree ≤ 2 × 10⁻⁶ -7 The parameters are: Pa, deposition temperature 780℃, oxygen partial pressure 200mTorr, laser energy 300mJ, pulsed laser frequency 6 Hz, deposition rate 35℃ / min, laser focal length 5mm, deposition rate 10nm / min, laser firing number 36000, and target rotation speed 18°.

[0147] Step 4) The specific steps of the cooling post-treatment are as follows:

[0148] a. Place at 780℃ and 200mTorr oxygen partial pressure atmosphere for 30 minutes;

[0149] b. Cool to room temperature at a rate of 5℃ / min.

[0150] Figure 1The figures show the polarization intensity-voltage and current-voltage diagrams for the antiferroelectric energy storage films of Comparative Examples 1, 2, and 3. It is evident that Comparative Examples 1, 2, and 3 are typical antiferroelectric energy storage films. However, the hysteresis loop in Comparative Example 1 has relatively more leakage points, while the saturation and residual polarization values ​​of Comparative Example 3 are significantly lower than those of Comparative Example 2. Therefore, the process parameters of Comparative Example 2 are optimal. Thus, the high-throughput antiferroelectric-dielectric energy storage solid solution films of Examples 1-3 are obtained by optimizing the process parameters based on Comparative Example 2.

[0151] Figure 2 The following are polarization-voltage diagrams for the high-throughput antiferroelectric-dielectric energy storage solid solution thin films of Examples 1, 2, and 3. It is readily apparent that Example 3 exhibits superior saturation polarization compared to Examples 1 and 2, making it more suitable for use as an energy storage device. Therefore, the following tests (including...) Figures 3-8 All of these are based on Example 3.

[0152] Figure 3 This is a schematic diagram of the high-throughput antiferroelectric-dielectric energy storage solid solution film of Example 3. A PbZrO3 high-throughput film with a gradient along the horizontal direction was first prepared on an STO

[111] substrate, and then a high-throughput SrTiO3 film with a reverse gradient was deposited on it. After 20 cycles, a PbZrO3-SrTiO3 high-throughput antiferroelectric-dielectric film was finally obtained.

[0153] Figure 4 This is a flowchart illustrating the preparation process of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film in Example 3. As target A (PbZrO3) undergoes high-throughput deposition under the movement of the automated mask system, the target is then rotated to target B (SrTiO3), the substrate stage rotates 180°, and the target A deposition operation is repeated to achieve a composite deposition effect of PbZrO3-SrTiO3.

[0154] Figure 5 This is a top view of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film of Example 3. To facilitate subsequent testing, we defined nine equidistant regions, designated as positions 1 to 9.

[0155] Figure 6 The image shows polarization intensity-voltage plots at different component positions of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film in Example 3. It is evident that the linearity of the polarization intensity-voltage curve of the high-throughput thin film improves with decreasing PbZrO3 content and increasing SrTiO3 content. This indicates that the addition of SrTiO3 helps reduce the leakage current density of PbZrO3, resulting in better polarization performance and benefiting the application of energy storage thin films and capacitors.

[0156] Figure 7This is a current-voltage diagram showing the different component positions of the high-flux antiferroelectric-dielectric energy storage solid solution film in Example 3. It is clear that as the PbZrO3 content decreases and the SrTiO3 content increases, the peak current of the high-flux film decreases further and remains antiferroelectric. Figure 6 The results are consistent.

[0157] Figure 8 This is a plot showing the saturation polarization, remanent polarization, and current intensity at different component positions of the high-throughput antiferroelectric-dielectric energy storage solid solution thin film in Example 3. It is evident that as the PbZrO3 content decreases and the SrTiO3 content increases, the saturation polarization, remanent polarization, and current intensity all continuously decrease, exhibiting a gradient change along the horizontal direction. This demonstrates good suppression of linearity and leakage current, resulting in superior performance and promising applications in energy storage thin films and capacitors.

[0158] Figure 9 The images show TEM images of composition positions 1 and 9 of the high-throughput antiferroelectric-dielectric energy storage solid solution film in Example 3. From the images, we can see that the entire film is in a relatively uniform solid solution state from position 1 to position 9. The film thickness also varies from 30 nm at position 1 to 66 nm at position 9. This difference in thickness is due to the higher number of laser pulses used for SrTiO3 deposition at position 9, resulting in a faster SrTiO3 growth rate. This demonstrates that the entire high-throughput antiferroelectric-dielectric energy storage solid solution film is a uniform film with distinct layers and a smooth surface.

[0159] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on its differences from other embodiments. Similar or identical parts between embodiments can be referred to interchangeably. For the apparatus disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the description is relatively simple; relevant parts can be referred to the method section.

[0160] The above description of the disclosed embodiments enables those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A high-throughput antiferroelectric-dielectric energy storage solid solution thin film, characterized in that, Includes: a substrate, and a bottom electrode layer and an antiferroelectric-dielectric layer sequentially grown on the substrate; The antiferroelectric-dielectric layer is a solid solution film formed by alternating growth of PbZrO3 antiferroelectric layer and SrTiO3 dielectric layer; the composition of the PbZrO3 antiferroelectric layer decreases stepwise in the horizontal direction, and the composition of the SrTiO3 dielectric layer increases stepwise in the horizontal direction. The bottom electrode layer is a SrRuO3 thin film; the thickness of the bottom electrode layer is 5~9 nm; The antiferroelectric-dielectric layer comprises 7 to 20 cycles and has a thickness of 25 to 75 nm. The method for preparing a high-throughput antiferroelectric-dielectric energy storage solid solution thin film specifically includes: 1) The substrate is bonded and then placed directly above the main target on the substrate stage in the high-throughput pulsed laser deposition growth chamber. The distance between the SrTiO3 substrate and the target is 60~70 cm. 2) A bottom electrode layer is grown on the substrate using a high-throughput pulsed laser deposition process; 3) An antiferroelectric-dielectric layer is grown on the bottom electrode layer using a high-throughput pulsed laser deposition process; 4) Perform cooling post-treatment; Step 3) The specific steps of the high-throughput pulsed laser deposition process are as follows: a. Place the PbZrO3 target and the SrTiO3 target on two adjacent target sites respectively; b. Set the relevant parameters as follows: Deposition chamber vacuum degree ≤ 2 × 10 -7 Pa, deposition temperature 750~780℃, oxygen partial pressure 190~200mTorr, deposition rate 25~35℃ / min, laser focal length -15~5 mm, deposition rate 5~10 nm / min; c. Move the substrate stage to a safe height, with the X-axis and Y-axis positions of the moved substrate stage being -3 to -1 mm and 0 to 2 mm, respectively. d. First layer gradient: The substrate stage is rotated to the first position, and the mask is moved along the X-axis and Y-axis to the deposition position and the high-throughput starting position, respectively, with moving speeds of 4~6 mm / s and 5~8 mm / s. The substrate stage is lowered to the deposition position, and the main target is switched to the PbZrO3 target. The relevant parameters are set as follows: laser energy 280~300 mJ, pulsed laser frequency 4~6 Hz, number of laser shots 1700~1900, laser focal length -15~5 mm, target rotation speed 16~18°, and mask Y-axis moving speed 0.12~0.2 mm / s. e. Second layer gradient: Move the substrate stage to a safe height, rotate the substrate stage to the second position, move the mask Y-axis to the high-throughput starting position at a moving speed of 5~8 mm / s, lower the substrate stage to the deposition position, switch the main target to the SrTiO3 target, and set the relevant parameters including laser energy 280~300 mJ, pulse laser frequency 4~6 Hz, laser number of shots 1700~1900, laser focal length -15~5 mm, target rotation speed 16~18°, and mask Y-axis moving speed 0.15~0.2 mm / s; f. Move the mask along the Y-axis to the high-throughput starting position, move the substrate stage to a safe height, and complete one deposition. g. Repeat steps d to f 7 to 20 times to obtain the antiferroelectric-dielectric layer.

2. The high-throughput antiferroelectric-dielectric energy storage solid solution thin film according to claim 1, characterized in that, The substrate is a rigid SrTiO3 substrate with an orientation of [111] and an area of ​​1.5 cm × 1.5 cm.

3. The high-throughput antiferroelectric-dielectric energy storage solid solution thin film according to claim 1, characterized in that, The thickness of the bottom electrode layer is 7~9 nm.

4. The high-throughput antiferroelectric-dielectric energy storage solid solution thin film according to claim 1, characterized in that, Step 2) The specific parameters of the high-throughput pulsed laser deposition process are: deposition chamber vacuum degree ≤ 8 × 10⁻⁶ -7 Pa, deposition temperature 690~710℃, oxygen partial pressure 70~85 mTorr, laser energy 320~340 mJ, pulsed laser frequency 4~6 Hz, deposition rate 20~35℃ / min, laser focal length -20~10 mm, deposition rate 4~7 nm / min.

5. A high-throughput antiferroelectric-dielectric energy storage solid solution thin film according to claim 1, characterized in that, Step 4) The specific steps of the cooling post-treatment are as follows: a. Place at 750~780℃ and 190~200 mTorr oxygen partial pressure atmosphere for 5~30 min; b. Cool to room temperature at a cooling rate of 2~5℃ / min.

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