CN116791201A - High-conductivity ruthenium metal film and preparation method thereof - Google Patents
High-conductivity ruthenium metal film and preparation method thereof Download PDFInfo
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- CN116791201A CN116791201A CN202210250648.9A CN202210250648A CN116791201A CN 116791201 A CN116791201 A CN 116791201A CN 202210250648 A CN202210250648 A CN 202210250648A CN 116791201 A CN116791201 A CN 116791201A
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- ruthenium metal
- ruthenium
- metal layer
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 62
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 23
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001659 ion-beam spectroscopy Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000004549 pulsed laser deposition Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000010408 film Substances 0.000 description 28
- 239000010410 layer Substances 0.000 description 17
- 239000010409 thin film Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 230000005641 tunneling Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- -1 platinum group metals Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The application relates to a high-conductivity ruthenium metal film and a preparation method thereof. According to an embodiment, a method of forming a ruthenium metal film may include epitaxially or epitaxially growing a ruthenium metal layer on a substrate having a perovskite crystal structure using metallic ruthenium or ruthenium oxide as a growth source or target. The surface of the substrate may be a (110) crystal plane, the ruthenium metal layer formed is a single crystal ruthenium metal layer, and the surface thereof is a (002) crystal plane. The substrate may comprise LaAlO 3 。
Description
Technical Field
The present application relates generally to the field of materials, and more particularly, to a high-conductivity ruthenium metal film and a method for preparing the same.
Background
Ruthenium is one of six platinum group metals, has lower resistivity and better chemical stability, and meanwhile, has excellent catalytic activity, so that the ruthenium has wide application in the fields of electronic information, electrochemistry and the like. In addition to the catalytic action, the metallic ruthenium thin film is widely used in semiconductor devices of the electronic information industry, as a copper bonding layer/diffusion barrier layer in integrated circuits, as an intermediate layer/seed layer in magnetic recording media, and in addition, has wide application in the aspects of oxidation-resistant protective layer materials, electrical contact materials and the like.
Metallic ruthenium has a close-packed hexagonal structure at normal temperature, and has lattice parameters of a=b=270.59 pm, c= 428.15pm, axis angles α=β=90°, and γ=120°. Ruthenium has a melting point of up to about 2310 ℃ and requires deposition at relatively high temperatures, typically at Si, glass, al 2 O 3 、TiO 2 And the like, and amorphous and polycrystalline samples are obtained, and it is difficult to obtain metallic ruthenium having a good single crystal morphology.
Disclosure of Invention
The application provides a method for preparing a ruthenium metal film, which can prepare a high-quality metal ruthenium film in a single crystal form, and the obtained ruthenium film has high conductivity and is suitable for being used in various applications.
One aspect of the present application provides a method of forming a ruthenium metal film comprising epitaxially or epitaxially growing a ruthenium metal layer on a substrate having a perovskite crystal structure using metallic ruthenium or ruthenium oxide as a growth source or target.
In some embodiments, the ruthenium metal layer is a single crystal ruthenium metal layer
In some embodiments, the surface of the substrate having a perovskite crystal structure is a (110) crystal plane and the surface of the single crystal ruthenium metal layer is a (002) crystal plane.
In some embodiments, the substrate having a perovskite crystal structure comprises LaAlO3.
In some embodiments, the substrate having a perovskite crystal structure has a lattice match with the single crystal ruthenium metal layer within a range of ±3%.
In some embodiments, the ruthenium metal layer has a room temperature resistivity of 20 μΩ cm or less, preferably 10 μΩ cm or less.
In some embodiments, the method further comprises: argon, nitrogen or oxygen is used as carrier gas in the epitaxial or epitaxial growth of ruthenium metal layers.
In some embodiments, the gas pressure is below 1Pa and the temperature is in the range of 250-750deg.C when epitaxially or epitaxially growing a ruthenium metal layer on a substrate having a perovskite crystal structure.
In some embodiments, the ruthenium metal layer is epitaxially or epitaxially grown using a physical vapor deposition process including magnetron sputtering, pulsed laser deposition, or ion beam sputtering.
In another aspect, the application also provides a single crystal ruthenium metal layer prepared according to the above method.
The foregoing and other features and advantages of the application will be apparent from the following description of particular embodiments, as illustrated in the accompanying drawings.
Drawings
Fig. 1 shows a crystal structure diagram of a substrate for preparing a ruthenium metal thin film according to an embodiment of the application.
FIG. 2 shows an X-ray diffraction pattern of a ruthenium metal thin film prepared according to an embodiment of the application.
Fig. 3 shows a scanning tunneling micrograph of a ruthenium metal film prepared according to an embodiment of the application.
FIG. 4 shows a graph of resistivity of ruthenium metal thin films prepared according to an embodiment of the application as a function of temperature.
Detailed Description
Hereinafter, exemplary embodiments according to the present application will be described in detail with reference to the accompanying drawings. Note that the figures may not be drawn to scale. It will be apparent that the described embodiments are only some of the embodiments of the present application and not all of the embodiments of the present application, and that the present application is not limited by the example embodiments described herein.
The application provides a method for preparing a single-crystal ruthenium metal film, which utilizes a substrate with a perovskite crystal structure to form the ruthenium metal film by a film physical vapor deposition method. The method of the application can prepare a high-quality single-crystal ruthenium metal film, and the obtained ruthenium metal film has good surface uniformity, continuity and compactness, and has high conductivity due to excellent crystal quality, so that the method is suitable for being used in various applications.
Fig. 1 shows a schematic diagram of perovskite crystal structure. Perovskite originally refers to CaTiO 3 Which has a cubic crystal structure as shown in fig. 1. Many can be represented by the formula ABO 3 The materials represented also have such a crystal structure, and thus they are all referred to as perovskite crystal structures in which a atoms occupy the vertex positions of the cube, B atoms occupy the body-centered positions of the cube, and O atoms occupy the face-centered positions of the cube.
In an embodiment of the present application, a material having a perovskite crystal structure is used as a substrate, and a ruthenium metal layer is formed thereon. As described above, the substrate material may be ABO 3 Where a comprises a rare earth or alkaline earth metal and B comprises a transition metal or Al, which is sometimes considered a transition metal, although it belongs to group IIIA elements. Can select proper substrate material ABO 3 The lattice matching degree of the substrate and the single crystal ruthenium metal layer is made to be in the range of + -5%, more preferably in the range of + -3%. In some embodiments, the substrate may be LaAlO 3 And (5) a crystal.
In some embodiments, the (110) crystal plane of the substrate having the perovskite crystal structure may be used as a growth surface for growing the single crystal ruthenium thin film. For example, can be in LaAlO 3 A single crystal ruthenium film is grown on the (110) crystal face of the crystal.
Methods of growing single crystal ruthenium films may include various thin film physical vapor deposition methods such as, but not limited to, magnetron sputtering, pulsed laser deposition, ion beam sputtering, etc., as these processes are well known in the relevant arts and will not be described in detail herein. In these processes, metallic ruthenium or ruthenium oxide materials may be used as a growth source or target. It is to be understood that although ruthenium oxide is used as a target, a metallic ruthenium thin film can be formed instead of a ruthenium dioxide thin film because ruthenium element has excellent chemical stability, is not easily oxidized, and by selecting an appropriate substrate.
When the physical vapor deposition process is used for epitaxial or oriented growth of the ruthenium metal film on the substrate, the vacuum can be pumped first, then carrier gas is introduced, and the deposition process is carried out under the preset air pressure. For example, a common argon or nitrogen gas may be used as the carrier gas, or oxygen gas may also be used as the carrier gas. Due to the excellent chemical stability of ruthenium element, a ruthenium dioxide film is not formed even when a small amount of oxygen is used as a carrier gas. The pressure of the carrier gas may be below 1Pa, for example, 100 mTorr, 200mTorr, or 500 mTorr. The growth temperature may be in the range of 250-750 ℃, preferably 300-700 ℃.
It will be appreciated that the selection of an appropriate substrate is important for film formation quality. However, in addition to the lattice matching, other factors such as flatness of the grown crystal planes, affinity of the grown interfaces, etc. are also very important. The application utilizes perovskite crystal substrate, especially LaAlO 3 And (3) a substrate, and taking the (110) crystal face as a growth surface, so as to obtain the ruthenium metal film with a high-quality monocrystalline structure. FIG. 2 shows the process in LaAlO 3 An X-ray diffraction (XRD) graph of the ruthenium metal film obtained by growth on a (110) crystal face of the substrate is obtained, the growth process is magnetron sputtering, the target material is ruthenium dioxide, the carrier gas is argon, the pressure is 200mTorr, and the temperature is about 420 ℃. As can be seen from FIG. 2, the XRD profile of the resulting sample has only one Ru (002) peak, indicating that a good quality single crystal or highly oriented ruthenium metal layer is obtained, with no defects or impurity formation. Fig. 3 is a scanning tunneling micrograph of the sample clearly showing a high quality single crystal ruthenium film formed on the substrate, which film has a highly uniform orientation structure, wherein the surface of the ruthenium film is the (002) crystal plane. As shown in FIG. 3, the formed single crystal ruthenium film is of a continuous single crystal structure, has good consistency and compactness, and is far superior to the film forming quality in the prior art.
Fig. 4 shows the resistivity as a function of temperature measured for the sample shown in fig. 3. As can be seen from the experimental data of FIG. 4, the resistivity of the single crystal ruthenium metal thin film at room temperature was about 9.7. Mu. Ohm cm or less, which is superior to the room temperature resistivity of the Pt metal, which is 10.1. Mu. Ohm cm or less. This indicates that ruthenium thin films of good single crystal structure have smaller resistivity. It is understood that when different substrate materials are selected, the single crystal quality of the ruthenium metal film formed varies due to the difference in lattice matching, and thus the resistivity of the ruthenium metal film may fluctuate, for example, may exceed 10 μΩ cm, but in general, the resistivity of the ruthenium metal film formed on the perovskite crystal structure substrate is 20 μΩ cm or less.
As described above, the present application can form a metal ruthenium thin film having a good single crystal structure, and the high quality epitaxial single crystal ruthenium metal film grown on a perovskite substrate has wide application in oxide electronics and spintronics, in particular, thin film resistors, ferroelectric random access memories, dynamic random access memories, magnetic tunnel junctions, organic thin film transistors, magnetic thermoelectric devices such as spin Seebeck effect devices, supercapacitors, electrochemical cells, photoelectrolysis water, and electrodes of fuel cells, etc., as well as wide application in the fields of traditional electronic information, electrochemistry, etc.
The basic principles of the present application have been described above in connection with specific embodiments, however, it should be noted that the advantages, benefits, effects, etc. mentioned in the present application are merely examples and not intended to be limiting, and these advantages, benefits, effects, etc. are not to be considered as essential to the various embodiments of the present application. Furthermore, the specific details disclosed herein are for purposes of illustration and understanding only, and are not intended to be limiting, as the application is not necessarily limited to practice with the above described specific details.
The block diagrams of the devices, apparatuses, devices, systems referred to in the present application are only illustrative examples and are not intended to require or imply that the connections, arrangements, configurations must be made in the manner shown in the block diagrams. As will be appreciated by one of skill in the art, the devices, apparatuses, devices, systems may be connected, arranged, configured in any manner. Words such as "including," "comprising," "having," and the like are words of openness and mean "including but not limited to," and are used interchangeably therewith. The terms "or" and "as used herein refer to and are used interchangeably with the term" and/or "unless the context clearly indicates otherwise. The term "such as" as used herein refers to, and is used interchangeably with, the phrase "such as, but not limited to.
It is also noted that in the apparatus, devices and methods of the present application, the components or steps may be disassembled and/or assembled. Such decomposition and/or recombination should be considered as equivalent aspects of the present application.
The previous description of the disclosed aspects is provided to enable any person skilled in the art to make or use the present application. Various modifications to these aspects will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other aspects without departing from the scope of the application. Thus, the present application is not intended to be limited to the aspects shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
The foregoing description has been presented for purposes of illustration and description. Furthermore, this description is not intended to limit embodiments of the application to the form disclosed herein. Although a number of example aspects and embodiments have been discussed above, a person of ordinary skill in the art will recognize certain variations, modifications, alterations, additions, and subcombinations thereof.
Claims (10)
1. A method of forming a ruthenium metal film comprising epitaxially or epitaxially growing a ruthenium metal layer on a substrate having a perovskite crystal structure using metallic ruthenium or ruthenium oxide as a growth source or target.
2. The method of claim 1, wherein the ruthenium metal layer is a single crystal ruthenium metal layer.
3. The method according to claim 2, wherein the surface of the substrate having a perovskite crystal structure is a (110) crystal plane and the surface of the single-crystal ruthenium metal layer is a (002) crystal plane.
4. The method of claim 1, wherein the substrate having a perovskite crystal structure comprises LaAlO 3 。
5. The method of claim 1, wherein the substrate having a perovskite crystal structure has a lattice match with the single crystal ruthenium metal layer within ±3%.
6. The method of claim 1, wherein the ruthenium metal layer has a room temperature resistivity of 20 μΩ cm or less, preferably 10 μΩ cm or less.
7. The method of claim 1, further comprising:
argon, nitrogen or oxygen is used as carrier gas in the epitaxial or epitaxial growth of ruthenium metal layers.
8. The method according to claim 1, wherein the gas pressure at the time of epitaxially or epitaxially growing the ruthenium metal layer on the substrate having the perovskite crystal structure is 1Pa or less and the temperature is in the range of 250 to 750 ℃.
9. The method of claim 1, wherein the ruthenium metal layer is epitaxially or epitaxially grown using a physical vapor deposition process including magnetron sputtering, pulsed laser deposition, or ion beam sputtering.
10. A single crystal ruthenium metal layer formed according to the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210250648.9A CN116791201A (en) | 2022-03-15 | 2022-03-15 | High-conductivity ruthenium metal film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210250648.9A CN116791201A (en) | 2022-03-15 | 2022-03-15 | High-conductivity ruthenium metal film and preparation method thereof |
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| Publication Number | Publication Date |
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| CN116791201A true CN116791201A (en) | 2023-09-22 |
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| CN202210250648.9A Pending CN116791201A (en) | 2022-03-15 | 2022-03-15 | High-conductivity ruthenium metal film and preparation method thereof |
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| Country | Link |
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| CN (1) | CN116791201A (en) |
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- 2022-03-15 CN CN202210250648.9A patent/CN116791201A/en active Pending
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