CN-122003093-A - Double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric film material, preparation method and application

CN122003093ACN 122003093 ACN122003093 ACN 122003093ACN-122003093-A

Abstract

The application belongs to the technical field of ferroelectric materials, and particularly relates to a double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric film material, a preparation method and application thereof; according to the preparation method of the double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric film material, the HZO film and the double-aluminum-layer oxide film are prepared through an atomic layer deposition process, the double-aluminum-layer oxide film is doped in the HZO film material, the tetragonal phase and the monoclinic phase are effectively promoted to generate orthogonal ferroelectric phases in an annealing process, so that the ferroelectric performance of the ferroelectric film material is improved, the residual polarization intensity, the coercive electric field and the cycle stability and the fatigue life are superior, and the technical problem that the ferroelectric performance of the hafnium-zirconium oxide ferroelectric film material in the prior art is lower is solved.

Inventors

YAO LULU
WANG KAI
LIU GANG
JIA LEI
YAO CHENG
MENG SEN
YI CHENGQIAN
CAI HANSHENG
WU YONGCONG
Hu taishan

Assignees

南方电网科学研究院有限责任公司
深圳供电局有限公司

Dates

Publication Date: 20260508
Application Date: 20260211

Claims (10)

1. The preparation method of the double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric film material is characterized by comprising the following steps of: S1, synthesizing a hafnium zirconium oxide film on a substrate through an atomic layer deposition process; Step S2, sequentially carrying out pulse and purge on at least one aluminum precursor and at least one oxygen reactant through an atomic layer deposition process to synthesize a single aluminum layer oxide film on the hafnium-zirconium oxide composite film; S3, repeating the step S2, and synthesizing a double-aluminum-layer oxide film on the single-aluminum-layer oxide film; s4, repeating the step S1, and synthesizing a hafnium zirconium oxide film on the double-aluminum-layer oxide film; s5, repeating the steps S1-S4 for 1-4 times to synthesize a double-aluminum-layer-doped hafnium-zirconium oxide film material; and S6, annealing the hafnium-zirconium oxide film material doped with the double aluminum layers to synthesize the hafnium-zirconium oxide ferroelectric film material doped with the double aluminum layers.
2. The method for preparing a double aluminum layer doped hafnium zirconium oxide ferroelectric thin film material according to claim 1, wherein step S1 specifically comprises: Step S11, sequentially pulsing and purging at least one hafnium precursor and at least one oxygen reactant through an atomic layer deposition process to synthesize a hafnium oxide film on a substrate; Step S12, sequentially pulsing and purging at least one zirconium precursor and at least one oxygen reactant through an atomic layer deposition process to synthesize a hafnium-zirconium oxide film on the hafnium oxide film; And step S13, repeating the steps S1-S2 for 2-8 times to synthesize the hafnium-zirconium oxide composite film.
3. The method for preparing a double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric thin film material according to claim 1, wherein in the step S1-S5, the temperature of the atomic layer deposition process is 250-300 ℃, the carrier gas is nitrogen, and the flow rate is 50-100 sccm.
4. The method for preparing a double aluminum layer doped hafnium zirconium oxide ferroelectric thin film material according to claim 2, wherein in step S1, the hafnium precursor is selected from at least one of tetra (methyl ethylamino) hafnium, tetra (dimethylamino) hafnium, tetra (ethylmethylamino) hafnium, cyclopentadienyl hafnium, hafnium tetrachloride, hafnium trifluoroacetylacetonate, and hafnium tert-butoxide; the zirconium precursor is at least one of tetra (methyl ethyl amino) zirconium, tetra (dimethylamino) zirconium, tetra (ethylamino) zirconium, zirconium tetrachloride and tetraisopropoxy zirconium; the oxygen reactant is at least one selected from water, hydrogen peroxide and ozone; in the step S2, the aluminum precursor is at least one selected from trimethylaluminum, triethylaluminum and aluminum isopropoxide; the oxygen reactant is at least one selected from water, hydrogen peroxide and ozone.
5. The preparation method of the double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric film material is characterized in that in the step S1, the pulse time of a hafnium precursor in the process of synthesizing a hafnium-zirconium oxide film is 0.4-0.6S, the nitrogen purging time is 4-6S, the pulse time of an oxygen reactant is 0.1-0.2S, and the nitrogen purging time is 4-6S; The pulse time of the zirconium precursor is 0.4-0.6 s, the nitrogen purging time is 4-6 s, the pulse time of the oxygen reactant is 0.1-0.2 s, and the nitrogen purging time is 4-6 s; in the step S2, the pulse time of the aluminum precursor is 0.015-0.05S, the nitrogen purging time is 4-6S, the pulse time of the oxygen reactant is 0.1-0.2S, and the nitrogen purging time is 4-6S in the process of synthesizing the single aluminum oxide film.
6. The method for preparing a double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric thin film material according to claim 1, wherein in the step S6, the annealing is a rapid thermal annealing RTA process, the temperature is 450-550 ℃, the time is 50-70S, and the atmosphere is nitrogen.
7. A double-aluminum-layer doped hafnium zirconium oxide ferroelectric thin film material, which is prepared by the preparation method according to any one of claims 1 to 6.
8. Use of a double aluminum layer doped hafnium zirconium oxide ferroelectric thin film material as claimed in any one of claims 1 to 6 in the field of ferroelectric memories, negative capacitance transistors or ferroelectric tunneling junction memories.
9. A ferroelectric capacitor, comprising the double aluminum layer doped hafnium zirconium oxide ferroelectric thin film material as claimed in any one of claims 1 to 6, and a top electrode deposited on the double aluminum layer doped hafnium zirconium oxide ferroelectric thin film material of the hafnium zirconium oxide ferroelectric thin film material; The base in the double-aluminum-layer doped hafnium zirconium oxide ferroelectric film material comprises a substrate and a bottom electrode, wherein the bottom electrode is deposited on the substrate.
10. A ferroelectric memory, comprising the ferroelectric capacitor and the transistor according to claim 9; the transistor and the ferroelectric capacitor are electrically connected.

Description

Double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric film material, preparation method and application Technical Field The application belongs to the technical field of ferroelectric materials, and particularly relates to a double-aluminum-layer-doped hafnium-zirconium oxide ferroelectric film material, a preparation method and application thereof. Background The ferroelectric material shows self-polarization below the Curie temperature, the relationship between the polarization intensity and the electric field is a nonlinear electric hysteresis loop, the characteristic enables the ferroelectric material to store charge information, store charges through polarization states, be a core component of a ferroelectric capacitor, can be packaged into a ferroelectric memory (FeRAM) together with components such as a transistor, a circuit and the like, represent binary data in an upward or downward polarization direction through the transistor and the circuit control, enable the ferroelectric material to be superimposed with the external electric field in the polarization inversion process by additionally applying an external electric field, lead to an equivalent capacitance to be a negative value, compensate charges in series with a positive dielectric layer to stabilize a negative capacitance state, can be used as a negative capacitance layer in a grid electrode stack of a negative capacitance transistor (NCFET), internally amplify the grid electrode voltage, overcome the Boltzmann limitation of a traditional Metal Oxide Semiconductor Field Effect Transistor (MOSFET) and reduce the power consumption of the transistor, can be used for constructing a next-generation high-performance logic circuit, can be used as a barrier layer of a ferroelectric tunneling junction, realize the storage characteristic of a high-switching ratio by utilizing the polarization direction of the ferroelectric material, and be used for a next-generation high-density ferroelectric tunneling junction (FTJ-nonvolatile memory) in the ferroelectric memory, and the ferroelectric memory has wide application prospect in the future nonvolatile memory and the ferroelectric memory (the future). The traditional ferroelectric materials such as PZT (lead zirconate titanate) have the problems of lead pollution, poor compatibility with CMOS technology and the like, and ferroelectric films based on HfO 2 series materials are widely paid attention to because of the advantages of no lead, strong CMOS compatibility, controllable thickness and the like, the hafnium zirconium oxide ferroelectric film (HZO film) material prepared by introducing Zr into the HfO 2 ferroelectric film material stabilizes the non-central symmetry orthogonal phase required by ferroelectricity and improves the ferroelectric performance, however, the high-performance ferroelectric phase is difficult to be stably obtained under different technological conditions only by changing the ratio of Hf/Zr, so the doping element regulation becomes an important means for improving the ferroelectric performance of the HZO ferroelectric film material in recent years. The orthogonal phase has a non-centrosymmetric crystal structure, and the oxygen atom migration to form a polar axis is guaranteed to be generated by ferroelectricity, however, the generation of the orthogonal phase in the HZO ferroelectric film material is effectively promoted by doping elements, so that the ferroelectric property of the current HZO ferroelectric film material is lower. Disclosure of Invention In view of the above, the application provides a double-aluminum-layer doped hafnium-zirconium oxide ferroelectric film material, a preparation method and application thereof, which are used for solving the technical problem of lower ferroelectric property of the hafnium-zirconium oxide ferroelectric film material in the prior art. The application provides a preparation method of a double-aluminum-layer doped hafnium zirconium oxide ferroelectric film material, which comprises the following steps: S1, synthesizing a hafnium zirconium oxide film on a substrate through an atomic layer deposition process; Step S2, sequentially carrying out pulse and purge on at least one aluminum precursor and at least one oxygen reactant through an atomic layer deposition process to synthesize a single aluminum layer oxide film on the hafnium-zirconium oxide composite film; S3, repeating the step S2, and synthesizing a double-aluminum-layer oxide film on the single-aluminum-layer oxide film; s4, repeating the step S1, and synthesizing a hafnium zirconium oxide film on the double-aluminum-layer oxide film; s5, repeating the steps S1-S4 for 1-4 times to synthesize a double-aluminum-layer-doped hafnium-zirconium oxide film material; and S6, annealing the hafnium-zirconium oxide film material doped with the double aluminum layers to synthesize the hafnium-zirconium oxide ferroelectric film material doped with the double aluminum layers. Pr