CN115332443A - Method for improving durability of hafnium-based ferroelectric device and hafnium-based ferroelectric device - Google Patents
Method for improving durability of hafnium-based ferroelectric device and hafnium-based ferroelectric device Download PDFInfo
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Abstract
The invention provides a method for improving the durability of a hafnium-based ferroelectric device and the hafnium-based ferroelectric device, wherein the method comprises the following steps: preparing a hafnium-based thin film on a substrate; forming a metal electrode on the hafnium-based thin film to form a hafnium-based device; carrying out thermal annealing on the hafnium-based thin film to enable the crystal of the hafnium-based thin film to have antiferroelectric characteristics, so as to obtain the hafnium-based antiferroelectric thin film and form a hafnium-based ferroelectric device; and applying electric field circulation to the hafnium-based antiferroelectric film to ensure that the hafnium-based antiferroelectric film obtains remanent polarization and simultaneously improves durability. The invention makes the hafnium-based antiferroelectric film obtain the remanent polarization by applying electric field circulation, so that the hafnium-based antiferroelectric film can meet the remanent polarization and obtain better durability.
Description
Technical Field
The invention relates to the technical field of integrated circuit devices, in particular to a method for improving the durability of a hafnium-based ferroelectric device and the hafnium-based ferroelectric device.
Background
In the big data era driven by artificial intelligence and internet of things, the explosive growth of data volume puts higher requirements on the computing and storing capability of integrated circuits. The traditional storage technology is composed of three-level structures of static memory (SRAM), dynamic memory (DRAM) and FlASH memory (FlASH) and performs complementation and balance of various performances, and the storage architecture is gradually difficult to satisfy the storage of mass data in the big data era and the execution of high-speed and high-bandwidth memory access tasks such as deep learning. Therefore, there is a need for a nonvolatile memory device that realizes higher speed, lower power consumption, higher density, and new functions such as memory integration, using new technology, which is mainly characterized by new materials, new principles, and new architectures.
Currently, several new memory technology routes have been proposed in the academic and industrial fields, including Resistive Random Access Memory (RRAM), phase change memory (PCRAM), spin electron memory (STT-MRAM), and various ferroelectric memory devices. The ferroelectric memory devices including ferroelectric transistors (fefets), ferroelectric memories (ferams) and Ferroelectric Tunnel Junctions (FTJ) have advantages of high memory density, fast read/write speed, low memory power consumption, and the like. Early development of such devices was mainly based on perovskite structures such as PZT, BTO, and other ferroelectric materials. However, the traditional perovskite ferroelectric material has the problems of incompatibility with the CMOS process, poor micro-shrinkage performance, environmental pollution and the like, and has the challenge in the process production below 130 nm. In 2011, germany NamLab discovered the ferroelectric properties of hafnium oxide (HfO 2), a high-k material that has been well-established in CMOS technology, and unlike conventional PZT and BTO ferroelectric materials, a hafnium-based ferroelectric thin film is not only compatible with CMOS processes, but also exhibits ferroelectric properties at a nanoscale (< 30 nm), with excellent scaling characteristics. Therefore, the new material can perfectly solve all bottleneck problems of the traditional perovskite ferroelectric material, and is expected to lead the development of a novel ferroelectric memory device. Semiconductor industry observations point to the ongoing development of new generation ferroelectric memory devices that will change the next generation memory landscape.
However, the device durability of general storage (such as embedded storage) or integrated storage device surpassing SRAM and DRAM in future>10 16 There is a significant gap in performance in terms of power consumption and durability.
Disclosure of Invention
The invention aims to provide a method for improving the durability of a hafnium-based ferroelectric device and the hafnium-based ferroelectric device, aiming at the problem of poor durability of the existing hafnium-based iron memory and ferroelectric transistor.
According to an aspect of the present invention, there is provided a method of improving endurance of a hafnium-based ferroelectric device, the method comprising:
preparing a hafnium-based thin film on a substrate;
forming a metal electrode on the hafnium-based thin film to form a hafnium-based device;
carrying out thermal annealing on the hafnium-based thin film to enable the crystal of the hafnium-based thin film to have antiferroelectric characteristics, so as to obtain the hafnium-based antiferroelectric thin film and form a hafnium-based ferroelectric device;
and applying electric field circulation to the hafnium-based antiferroelectric film to ensure that the hafnium-based antiferroelectric film obtains remanent polarization and simultaneously improves durability.
Further, the method for preparing the hafnium-based thin film on the substrate comprises the following steps: the preparation method of the hafnium-based film comprises any one of atomic layer deposition, magnetron sputtering and laser pulse deposition.
Further, the method for preparing the hafnium-based thin film on the substrate comprises the following steps: the thickness of the hafnium-based film is 0.1-100nm.
Further, the method for preparing the hafnium-based thin film on the substrate comprises the following steps: the hafnium-based thin film is made of hafnium oxide as a basic material, the doping element is any one of Zr, si, ge, al, Y, la and N, and the doping concentration range is 0-100% according to the atomic weight ratio of the doping element to the hafnium element.
Further, forming a metal electrode on the hafnium-based thin film to form a hafnium-based device, wherein: the hafnium-based device is any one of a capacitor, a transistor, and a tunnel junction.
Further, the hafnium-based thin film is subjected to thermal annealing to enable crystals of the hafnium-based thin film to have antiferroelectric properties, so that the hafnium-based antiferroelectric thin film is obtained, and a hafnium-based antiferroelectric device is formed, wherein: the temperature of the thermal annealing is 300-1300 ℃.
Further, the method for preparing the hafnium-based thin film on the substrate comprises the following steps: the substrate is made of metal materials or semiconductor materials.
Further, the semiconductor material is any one of Si, ge, siC and a thin film semiconductor, and the metal material is any one of TiN, taN and W.
Further, the applying the electric field cycle to the hafnium-based antiferroelectric thin film includes: the applied electric field is a direct current electric field or an alternating current electric field for circulation, wherein the voltage amplitude of the direct current electric field is 0.5V-20V, and the time is 1ps-100h; the voltage amplitude of the alternating current electric field is 0.5V-20V, the cycle frequency is 1Hz-100MHz, the waveform comprises any one of triangular wave, sine wave and square wave, and the time is 1ps-100h.
According to a second aspect of the present invention, there is provided a hafnium-based ferroelectric device prepared by the above method for improving the durability of a hafnium-based ferroelectric device.
Compared with the prior art, the invention has the following beneficial effects:
the invention can make the hafnium-based antiferroelectric film obtain the remanent polarization by preparing the hafnium-based antiferroelectric film and applying electric field circulation to the hafnium-based antiferroelectric film, and the hafnium-based antiferroelectric film can obtain more than 10 under the condition of having the remanent polarization 12 Durability of one cycle.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
fig. 1 is a schematic flow chart of a method for improving the endurance of a hafnium-based ferroelectric device according to an embodiment of the present invention;
fig. 2 is a schematic diagram illustrating a concept of improving endurance of a hafnium-based ferroelectric device according to an embodiment of the present invention;
fig. 3 is a schematic diagram illustrating the effect of improving the endurance of a hafnium-based ferroelectric device according to an embodiment of the present invention.
In the figure: 1 is a substrate, 2 is a first TiN metal film, 3 is a hafnium-based film, 4 is a photoresist, and 5 is a second TiN metal film.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention. In the description of the embodiments of the present invention, it should be noted that the terms "first", "second", and the like in the description and the claims of the present invention are used for distinguishing similar objects, and are not necessarily used for describing a particular order or sequence. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein.
An embodiment of the present invention provides a method for improving durability of a hafnium-based ferroelectric device, and referring to fig. 1, the method includes:
and 4, applying electric field circulation to the hafnium-based antiferroelectric film to ensure that the hafnium-based antiferroelectric film obtains remanent polarization and simultaneously improves durability.
As shown in fig. 2, the hafnium-based antiferroelectric material (i.e., the hafnium-based antiferroelectric thin film) formed by crystallizing a hafnium-based thin film through thermal annealing to have antiferroelectric properties has good durability, but has no remanent polarization, and the ferroelectric material has good remanent polarization and insufficient durability. By applying electric field cycling to the hafnium-based antiferroelectric thin film, it is possible to shift the film to ferroelectric characteristics, obtain remanent polarization, and maintain high durability.
In some embodiments, a hafnium-based thin film is prepared on a substrate, wherein: the substrate is formed by using a metal material or a semiconductor material. Preferably, the semiconductor material is any one of Si, ge, siC, and a thin film semiconductor. The metal material is any one of TiN, taN and W.
In some embodiments, a hafnium-based thin film is prepared on a substrate, wherein: the preparation method of the hafnium-based thin film comprises any one of atomic layer deposition, magnetron sputtering and laser pulse deposition. The thickness of the hafnium-based thin film is related to the deposition rate of the thin film, and may be given according to practical needs, and preferably, the thickness of the hafnium-based thin film is 0.1-100nm, and the formation of the hafnium-based antiferroelectric characteristics is promoted by the thin film of 0.1-100nm.
In some embodiments, a hafnium-based thin film is prepared on a substrate, wherein: the basic material of the hafnium-based thin film is hafnium oxide which can generate polarization property and is compatible with a CMOS (complementary metal oxide semiconductor) process, the doping element is any one of Zr, si, ge, al, Y, la and N, and the doping of the elements can promote the hafnium-based thin film to form antiferroelectric characteristics; according to the atomic weight ratio of the doping element to the hafnium element, the doping concentration range of the doping element is 0% to 100%, which can be given according to actual needs.
In some embodiments, a metal electrode is formed on a hafnium-based thin film to form a hafnium-based device, wherein: the hafnium-based device is any one of a capacitor, a transistor and a tunnel junction; the material of the electrode on top of the hafnium-based thin film includes TiN, au, ag, al, taN and RuO 2 And the like, which are advantageous for the formation of antiferroelectric properties of hafnium-based thin films.
In some specific embodiments, the hafnium-based thin film is thermally annealed to make the crystals have antiferroelectric properties, and various parameters are adjusted to form a tetragonal-based antiferroelectric crystal structure, so as to obtain the hafnium-based antiferroelectric thin film and form a hafnium-based antiferroelectric device, where: the annealing temperature is set according to the parameters of doping element type, doping concentration, upper and lower electrodes, film thickness and the like, and preferably, the thermal annealing temperature is 300-1300 ℃.
In some embodiments, an electric field cycle is applied to the hafnium-based antiferroelectric film, wherein: the amplitude, mode, application time, frequency and waveform of the electric field are given according to actual needs. Preferably, the applying of the electric field cycle to the hafnium-based thin film comprises: the applied electric field is a direct current electric field or an alternating current electric field for circulation, wherein the voltage amplitude of the direct current electric field is 0.5V-20V, and the time is 1ps-100h; the voltage amplitude of the alternating current electric field is 0.5V-20V, the cycle frequency is 1Hz-100MHz, the waveform comprises any one of triangular wave, sine wave and square wave, the time is 1ps-100h, and the electric field cycle can enable the hafnium-based antiferroelectric film to obtain the remanent polarization.
In the embodiment of the invention, the property of the hafnium-based antiferroelectric device is prepared and regulated, so that the antiferroelectric film material can obtain residual polarization while maintaining high polarization reversal cycle durability, the regulation of the hafnium-based antiferroelectric material is realized by regulating the initial property and cycle number of antiferroelectric characteristics, and the frequency, amplitude and period of applied electric field cycle are given as required. 6nm Hf as shown in FIG. 3 0.2 Zr 0.8 O 2 The antiferroelectric thin film passes through 10 8 The residual polarization intensity Pr of the obtained material is nearly 20 mu C/cm by the loop electric circulation 2 Durability can exceed 10 12 One cycle, hf without antiferroelectric properties 0.5 Zr 0.5 O 2 The hafnium-based ferroelectric thin film has two orders of magnitude higher durability.
In one embodiment, a method for improving the endurance of a hafnium-based ferroelectric device comprises: preparing a hafnium-based antiferroelectric film on a semiconductor or metal substrate; spin-coating photoresist on the hafnium-based antiferroelectric film and exposing for patterning; then depositing a metal film and stripping photoresist to form a metal electrode; then, a rapid annealing furnace is adopted to carry out thermal annealing on the hafnium-based antiferroelectric film so as to crystallize the hafnium-based antiferroelectric film; and finally, applying a certain amount of alternating current electric field circulation to the hafnium-based antiferroelectric film by adopting a ferroelectric analyzer. Specifically, referring to fig. 1, the method includes:
s1, preparing a first TiN metal film 2 with the thickness of 30nm on a semiconductor silicon substrate 1 by adopting a magnetron sputtering process;
s2, preparing 6nm Hf on the first TiN metal film 2 by adopting an atomic layer deposition process 0.5 Zr 0.5 O 2 A Zr-doped hafnium-based thin film 3;
s3, spin-coating a photoresist 4 on the hafnium-based film 3;
s4, patterning the photoresist 4 by adopting a UV exposure technology;
s5, depositing a 30nm second TiN metal film 5 on the hafnium-based film 3 by adopting a magnetron sputtering process;
s6, stripping the photoresist 4 by using lift off technology to form a metal electrode of 40 μm x 40 μm;
s7, adopting a rapid annealing furnace to carry out 550 ℃ N 2 The atmosphere thermal annealing causes the hafnium-based film 3 to form antiferroelectricity;
s8, adopting a ferroelectric data acquisition analyzer to perform triangular wave alternating current electric field circulation 10 with the frequency of 1Hz and the amplitude of 3V 10 And (3) obtaining the remanent polarization of the hafnium-based antiferroelectric film.
In the method for improving the durability of the hafnium-based ferroelectric device in the above embodiment of the present invention, the hafnium-based antiferroelectric thin film is prepared on the semiconductor or metal substrate to form structures such as a ferroelectric capacitor, a transistor, a tunnel junction, and the like, and an alternating current electric field is applied to circulate so that the hafnium-based antiferroelectric thin film obtains a remnant polarization, and the hafnium-based antiferroelectric thin film satisfies the remnant polarization and obtains better durability.
The embodiment of the invention also provides a hafnium-based ferroelectric device, which is prepared by adopting the method for improving the durability of the hafnium-based ferroelectric device; the hafnium-based antiferroelectric thin film can obtain better durability while satisfying the remanent polarization, thereby effectively improving the durability of the hafnium-based ferroelectric device.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The above-described preferred features may be used in any combination without conflict with each other.
Claims (10)
1. A method of improving the durability of a hafnium-based ferroelectric device, comprising:
preparing a hafnium-based thin film on a substrate;
forming a metal electrode on the hafnium-based thin film to form a hafnium-based device;
carrying out thermal annealing on the hafnium-based thin film to enable the crystal of the hafnium-based thin film to have antiferroelectric characteristics, so as to obtain the hafnium-based antiferroelectric thin film and form a hafnium-based ferroelectric device;
and applying electric field circulation to the hafnium-based antiferroelectric film to ensure that the hafnium-based antiferroelectric film obtains remanent polarization and simultaneously improves durability.
2. The method of claim 1, wherein said fabricating a hafnium-based thin film on a substrate, wherein: the preparation method of the hafnium-based film comprises any one of atomic layer deposition, magnetron sputtering and laser pulse deposition.
3. The method of improving the endurance of a hafnium based ferroelectric device according to claim 1, wherein said preparing a hafnium based thin film on a substrate, wherein: the thickness of the hafnium-based film is 0.1-100nm.
4. The method of improving the endurance of a hafnium based ferroelectric device according to claim 1, wherein said preparing a hafnium based thin film on a substrate, wherein: the hafnium-based thin film is made of hafnium oxide as a basic material, the doping element is any one of Zr, si, ge, al, Y, la and N, and the doping concentration range is 0-100% according to the atomic weight ratio of the doping element to the hafnium element.
5. The method of claim 1, wherein said forming a metal electrode on said hafnium-based thin film forms a hafnium-based device, wherein: the hafnium-based device is any one of a capacitor, a transistor, and a tunnel junction.
6. The method of claim 1, wherein the hafnium-based thin film is thermally annealed to crystallize the hafnium-based thin film to have antiferroelectric properties, thereby obtaining a hafnium-based antiferroelectric thin film, and forming a hafnium-based antiferroelectric device, wherein: the temperature of the thermal annealing is 300-1300 ℃.
7. The method of improving the endurance of a hafnium based ferroelectric device according to claim 1, wherein said preparing a hafnium based thin film on a substrate, wherein: the substrate is made of a metal material or a semiconductor material.
8. The method of improving the durability of a hafnium based ferroelectric device according to claim 7, wherein the semiconductor material is any one of Si, ge, siC and thin film semiconductor; the metal material is any one of TiN, taN and W.
9. The method of claim 1, wherein said applying an electric field cycle to said hafnium-based antiferroelectric thin film comprises: the applied electric field is a direct current electric field or an alternating current electric field for circulation; wherein the content of the first and second substances,
the voltage amplitude of the direct current electric field is 0.5-20V, and the time is 1ps-100h;
the voltage amplitude of the alternating current electric field is 0.5V-20V, the cycle frequency is 1Hz-100MHz, and the waveform comprises any one of triangular wave, sine wave and square wave.
10. A hafnium-based ferroelectric device, prepared by the method for improving the durability of a hafnium-based ferroelectric device according to any one of claims 1 to 9.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116845056A (en) * | 2023-07-03 | 2023-10-03 | 上海交通大学 | High-performance hafnium oxide-based ferroelectric capacitor and preparation method thereof |
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| CN116845056A (en) * | 2023-07-03 | 2023-10-03 | 上海交通大学 | High-performance hafnium oxide-based ferroelectric capacitor and preparation method thereof |
| CN116845056B (en) * | 2023-07-03 | 2024-02-27 | 上海交通大学 | High-performance hafnium oxide-based ferroelectric capacitor and preparation method thereof |
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