CN118119575A - Molybdenum oxide-based sintered body, sputtering target material comprising same, and oxide thin film - Google Patents
Molybdenum oxide-based sintered body, sputtering target material comprising same, and oxide thin film Download PDFInfo
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- CN118119575A CN118119575A CN202280069188.8A CN202280069188A CN118119575A CN 118119575 A CN118119575 A CN 118119575A CN 202280069188 A CN202280069188 A CN 202280069188A CN 118119575 A CN118119575 A CN 118119575A
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- oxide
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- metal oxide
- molybdenum
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 61
- 238000005477 sputtering target Methods 0.000 title claims abstract description 22
- 239000010409 thin film Substances 0.000 title claims description 25
- 239000013077 target material Substances 0.000 title abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 104
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 70
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 25
- 238000001272 pressureless sintering Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- 239000010408 film Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 22
- 238000000465 moulding Methods 0.000 claims description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical group 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 230000000052 comparative effect Effects 0.000 description 42
- 238000005245 sintering Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000002019 doping agent Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000002706 hydrostatic effect Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- -1 MoO 2 Chemical compound 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007780 powder milling Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
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Abstract
The invention provides an oxide sintered body containing molybdenum oxide as a main component, a sputtering target material containing the sintered body and an oxide film formed by the same. In the present invention, by adding a specific (quasi) metal oxide in a predetermined range to molybdenum oxide and niobium oxide which are difficult to sinter, sinterability can be improved and high density characteristics can be ensured even when pressureless sintering is performed.
Description
Technical Field
The present invention relates to an oxide sintered body containing molybdenum oxide as a main component, a sputtering target containing the same, and an oxide thin film formed therefrom, and more particularly, to a molybdenum oxide-based sintered body, a sputtering target, and an oxide thin film formed therefrom, which simultaneously improve sinterability and density characteristics by adding a specific (quasi) metal oxide in a predetermined range when preparing a target for sputtering of TFT structures for LCDs and OLEDs.
Background
In general, a conductive film having a low reflectance is used for a flat panel display (FLAT PANEL DISPLAY; "FPD"), a touch screen panel, a solar cell, and a light emitting diode (organic LIGHT EMITTING diode; "OLED").
A representative material thereof is indium tin oxide (In 2O3-SnO2) ("ITO"), and an ITO composition is used to form a conductive film having high visible light transmittance as well as conductivity. Such an ITO composition has excellent low reflectance properties, but due to poor economic efficiency, materials replacing all or part of indium oxide are continuously being studied.
However, such studies are focused on low reflectivity of the thin film formed by the target material, and it is necessary to consider the characteristics of chemical resistance, heat resistance, which can improve the reliability of the thin film in long-term use.
On the other hand, molybdenum oxide is a difficult-to-sinter substance that is difficult to sinter. As described above, when a molybdenum oxide-based ceramic material which is difficult to sinter and has a low density is used, it is difficult to not only construct a high-density (for example, a relative density of 90% or more) target, but also when sputtering is performed using the prepared target, foreign substances are generated due to back deposition (back depo.) and nodules (nodule), and thus, the physical properties of the thin film are inevitably degraded.
Prior art literature
Patent document 1: korean laid-open patent No. 10-2020-0069314
Disclosure of Invention
Technical problem
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a novel molybdenum oxide-based sintered body, which can improve sinterability and ensure high density even when sintering is performed in a pressureless state by adding a specific (quasi) metal oxide in a predetermined range to a refractory molybdenum oxide as a main raw material, a sputtering target including the sintered body, and an oxide thin film formed thereby.
Other objects and advantages of the present invention will be more clearly explained by the following detailed description of the invention and the scope of the invention claimed.
Technical proposal
In order to solve the above-described problems, the present invention provides an oxide sintered body including: molybdenum oxide (M1) containing at least one of MoO 2 and MoO 3; niobium oxide (M2); and a metal oxide (M3) containing at least one alkaline earth metal, wherein the content of the molybdenum oxide (M1) is 70 weight percent or more with respect to the total weight of the sintered body.
In an embodiment of the present invention, the metal oxide (M3) may include a first metal oxide (M3-1) including at least one of Ca and Mg.
In an embodiment of the present invention, the first metal oxide (M3-1) may include one or more selected from the group consisting of CaCO 3 and MgO.
In one embodiment of the present invention, the metal oxide (M3) may comprise a first metal oxide (M3-1); and a second metal oxide (M3-2) containing one or more metals selected from the group consisting of Co, si, Y and Ga.
In an embodiment of the present invention, the second metal oxide (M3-2) may include one or more selected from the group consisting of Co 3O4、SiO2、Y2O3 and Ga 2O3.
In an embodiment of the present invention, the content of the metal oxide (M3) may be more than 0wt% and 10.0 wt% or less based on 100wt% of the sintered body.
In an embodiment of the present invention, the content of the molybdenum oxide (M1) and the niobium oxide (M2) may be 90.0 wt% or more and less than 100 wt% based on 100 wt% of the oxide sintered body, and the content ratio of the molybdenum oxide (M1) and the niobium oxide (M2) may be 50:50 wt% to 90:10 wt%.
In one embodiment of the present invention, the oxide sintered body may be formed by mixing and molding a molybdenum oxide (M1), a niobium oxide (M2), and a metal oxide (M3) and then pressureless sintering the mixture.
In one embodiment of the present invention, the oxide sintered body may have a specific resistance of 1×10 -2 Ω cm or less and a relative density of 80% or more.
The present invention also provides a sputtering target comprising the pressureless sintered body.
The present invention also provides an oxide thin film formed from the sputtering target.
ADVANTAGEOUS EFFECTS OF INVENTION
According to an embodiment of the present invention, by adding a (quasi) metal oxide containing a specific element in a prescribed range to a molybdenum oxide that is difficult to sinter, it is possible to improve the sinterability of a molybdenum oxide sintered body and ensure a high density even in a pressureless state.
Therefore, the molybdenum oxide-based sintered body and the sputtering target of the present invention can be usefully applied to electrodes or wirings forming TFT structures for LCDs as well as OLEDs.
The effects of the present invention are not limited to those exemplified above, and more various effects are also included in the present specification.
Drawings
Fig. 1 is an image showing the change in the structure of a sintered body of the molded body of example 9 using the metal oxide (M3) added according to the heat treatment temperature.
Fig. 2 is an image showing the change in the structure of the sintered body of the molded body of comparative example 1 using the metal oxide (M3) not added according to the heat treatment temperature.
Fig. 3 is an SEM image showing fracture surfaces of the powder structure of the mixed raw materials, the structure of the pressureless sintered body prepared in example 9, and the structure of the pressureless sintered body prepared in comparative example 5, respectively.
Fig. 4 is an SEM image of a polished surface showing the structure of the pressureless sintered body prepared in example 9 and the structure of the pressured sintered body prepared in comparative example 5, respectively.
Fig. 5 is a graph showing the relative densities of pressureless sintered bodies prepared in examples 1 to 6 with sintering temperature.
Fig. 6 is a graph showing the relative densities of pressureless sintered bodies prepared in examples 7 to 12 with sintering temperature.
Fig. 7 is a graph showing the relative densities of pressureless sintered bodies prepared in examples 13 to 17 with sintering temperature.
Fig. 8 is a graph showing the relative densities of the sintered bodies prepared in comparative examples 1 to 4 with sintering temperature.
Fig. 9 is a graph showing shrinkage rate changes with sintering temperature of the pressureless sintered bodies prepared in examples 1 to 6.
Fig. 10 is a graph showing shrinkage rate changes with sintering temperature of the pressureless sintered bodies prepared in examples 7 to 12.
Fig. 11 is a graph showing shrinkage rate changes with sintering temperature of the pressureless sintered bodies prepared in examples 13 to 18.
Fig. 12 is a graph showing shrinkage rate changes with sintering temperature of the oxide sintered bodies prepared in comparative examples 1 to 4.
Fig. 13 is an XRD chart showing the respective crystal forms of the pressureless sintered body prepared in example 9 and the pressured sintered bodies prepared in comparative examples 1 and 5.
Fig. 14 is a graph showing the sheet resistance characteristics of unit films prepared from the components of example 1, example 9 and comparative example 1.
FIG. 15 is a graph showing the average reflectance results in the visible light range (380 to 740nm wavelength) of the double films prepared from the components of example 1, example 9 and comparative example 1.
Fig. 16 is an image of the etching evaluation result of the double film prepared from the components of example 9 and comparative example 1.
Detailed Description
Hereinafter, the present invention will be described in detail.
All terms (including technical and scientific terms) used in this specification can be used in the meanings commonly understood by one of ordinary skill in the art to which this invention belongs. And, unless specifically defined otherwise, terms defined in commonly used dictionaries should not be interpreted as being idealized or overly formal.
In addition, throughout the specification, when a certain portion "includes" a certain structural element, unless specifically stated to the contrary, it means that other structural elements may also be included, but not excluded. In the present specification, "above" or "upper" refers not only to the case of being located above or below the object portion but also to the case of having another portion in between, and does not necessarily mean to be located above in the direction of gravity. Moreover, in the description of the present invention, the terms "first," "second," and the like are used to distinguish structural elements from each other and do not denote any order or importance.
MoO 2-Nb2O5 materials used as existing n-type (n-type) semiconductor thin films are generally prepared by a pressure sintering method. However, when the pressure sintering method is applied, the production process cost increases due to the equipment value, and thus mass production is not suitable. Also, there is a limitation in increasing the size of the sintering aid due to the preparation process in which high pressure is applied.
In order to solve the above problems, when the MoO 2-Nb2O5 material is pressureless sintered, it is difficult to apply because of the limited increase in the sintering density, and when the sintering temperature is raised, the density is lowered due to the increase in the amount of melting and volatilization. That is, heat is required as a driving force during sintering, and in general, the higher the heat is, the more advantageous the sintering property (densification) is to be ensured, whereas the problem such as volatilization is rather occurred for part of the raw material, and the density is lowered.
Accordingly, the present invention can provide a molybdenum oxide-based sintered body and a sputtering target using the same, which can achieve improvement of sinterability while securing high density by using a small amount of a specific dopant (M3) contributing to sinterability in a difficult-to-sinter material having molybdenum oxide and niobium oxide as basic components.
Specifically, the alkaline earth metal-based oxide dopant (M3) used in the present invention helps to ensure the sintering driving force of MoO 2/MoO3-Nb2O5 as a difficult-to-sinter material, so that the sintering density due to the temperature drop effect can be improved even if pressureless sintering is performed. For example, the molybdenum oxide sintered body of the present invention can have excellent density and electrical resistance characteristics as compared with a sintered body not containing a specific metal oxide (M3), and in particular, even if the pressureless sintered body (pressureless sintered body) is constituted by heat treatment alone without pressurizing, it is possible to secure density characteristics and electrical resistance characteristics at a level equal to or higher than those of an oxide sintered body subjected to conventional pressure sintering (e.g., HP, HIP, etc.). Further, the oxide sintered body is excellent in terms of enlargement of the sintered body and mass production, and has an advantage of low equipment cost, as compared with the pressure sintered oxide sintered body.
Further, the particles of the molybdenum oxide sintered body, which are pressure-sintered by applying a predetermined pressure and heat treatment at the same time, have a larger particle size than the particles of the crystal grains constituting the oxide sintered body of the present invention, and are therefore more advantageous in terms of reaction. For example, as shown in fig. 3 to 4 described below, since the pressurized sintered body is in a form in which the starting materials are forced together by high pressure, the particle size of the sintered body of the present invention is hardly increased, and in contrast to this, it can be seen that the particle size of the sintered body of the present invention is increased by the reaction, and in particular, it can be seen that the particles are in a state of being combined and merged in the interaction between the dissimilar elements, and thus, the present invention is advantageous in terms of the reaction.
When no element is added, the molybdenum oxide target has a very low density and a high specific resistance. As described above, when the target has high electric resistance, there is a problem that plasma is not formed when DC sputtering is performed. In contrast, the molybdenum oxide target of the present invention can provide a high-density target at a level at which sputtering can be performed even by pressureless sintering by adding a dopant (Dopant) to ensure sinterability.
< Oxide sintered compact and sputtering target >
An example of the present invention is a metal oxide sintered body for producing a sputtering target containing molybdenum oxide as a main component. This sintered body differs from the existing sintered body in that it contains a metal oxide (M3) containing at least one alkaline earth metal as an essential component.
In one embodiment, the oxide sintered body includes: molybdenum oxide (M1) containing at least one of MoO 2 and MoO 3; niobium oxide (M2); and a metal oxide (M3) containing at least one alkaline earth metal, wherein the content of the molybdenum oxide (M1) is 70 weight percent or more with respect to the total weight of the sintered body.
When a metal oxide sintered body composed of the above-described components is used as a target to form a thin film, the formed thin film has low reflection characteristics while improving heat resistance and chemical resistance by optimizing the proportion of molybdenum oxide and the components. Further, since the density is increased by adding a small amount of a specific dopant (M3), it is not necessary to use pressure sintering, and thus a Mo-Nb-O-based sputtering target which is a hardly sintered substance can be produced.
Hereinafter, each component will be described in detail.
The molybdenum oxide contained in the oxide sintered body of the present invention is a main component constituting the sintered body.
The molybdenum oxide (M1) is a component having a form in which molybdenum is combined with oxygen, such as MoO 2、MoO3、MoO4. In the present invention, moO 2、MoO3 or a mixture of MoO 2 and MoO 3 may be used as the molybdenum oxide (M1). In this case, when a mixture of MoO 2 and MoO 3 is used as the molybdenum oxide, the mixing ratio therebetween is not particularly limited and may be appropriately adjusted within a conventional content range well known in the art. On the other hand, moO 3 has a melting point of about 800℃and thus volatilizes at a high temperature of 1000℃or higher. Therefore, in the present invention, moO 2 is preferably used as the molybdenum oxide.
One of the additive components contained in the oxide sintered body of the present invention is niobium oxide (M2).
This niobium oxide (M2) is an oxide dopant that improves chemical resistance and heat resistance characteristics, and the chemical resistance and heat resistance characteristics of molybdenum oxide can be improved by the above metal oxide. The niobium oxide is not particularly limited as long as it is a component having a form in which niobium is combined with oxygen, and may be Nb 2O5, for example. In the following description, the niobium oxide component is denoted by the M2 mark.
Another additive component included in the oxide sintered body of the present invention is a metal oxide (M3) containing at least one alkaline earth metal.
For example, the metal oxide (M3) may contain at least one of Ba, ca, mg, and Sr, and specifically, may contain a first metal oxide (M3-1) containing at least one of Ca and Mg.
The first metal oxide (M3-1) acts as a dopant, which exhibits a density-raising effect by contributing to the sinterability of the hard-to-sinter molybdenum oxide. The chemical resistance and heat resistance properties of molybdenum oxide can be improved by adding such a first metal oxide. The first metal oxide (M3-1) is not particularly limited as long as it is a component having a form in which at least one element (a) of Ca and Mg is combined with oxygen, and for example, may contain one or more selected from the group consisting of CaCO 3 and MgO.
For another example, the metal oxide (M3) may include a first metal oxide (M3-1); and a second metal oxide (M3-2) containing one or more metals selected from the group consisting of Co, si, Y and Ga.
The second metal oxide (M3-2) can exert an effect of improving the sinterability of the molybdenum oxide by assisting the above-mentioned first metal oxide. The second metal oxide (M3-2) is not particularly limited as long as it is a component having a form in which at least one element of Co, si, Y, and Ga is combined with oxygen, and may contain, for example, one or more selected from the group consisting of Co 3O4、SiO2、Y2O3 and Ga 2O3. In this case, when the first metal oxide (M3-1) and the second metal oxide (M3-2) are used in combination as the metal oxide (M3), the mixing ratio thereof is not particularly limited, for example, a weight ratio of 1:0.3 to 2.5, more specifically, may be a weight ratio of 1:0.5 to 2.0.
In the metal oxide sintered body including the molybdenum oxide (M1), the niobium oxide (M2), and the (quasi) metal oxide (M3), the content of the molybdenum oxide (M1) and the niobium oxide (M2) may be 90 wt% or more and less than 100 wt%, and the content of the (quasi) metal oxide (M3) may be more than 0wt% and 10 wt% or less, based on 100 wt% of the sintered body. More specifically, it is possible to have from 95.0 to 99.5 weight percent of molybdenum oxide (M1) and niobium oxide (M2); and 0.5 to 5.0 weight percent of (quasi) metal oxide (M3). Wherein the content ratio of molybdenum oxide (M1) to niobium oxide (M2) is 50:50 to 90:10 by weight, specifically 70:30 to 90:10 by weight, more specifically 75:25 to 90:10 by weight. In the present invention, when the proportion of molybdenum oxide is 70 weight percent or more of the total metal oxide sintered body, it is possible to have low reflection characteristics when vapor deposited as a thin film.
The oxide sintered body of the invention having the above composition has a relative density of 80% or more, specifically 90% or more even when subjected to pressureless sintering. In this case, the upper limit value thereof is not particularly limited. The specific resistance of the oxide sintered body is 1×10 -2 Ω cm or less, and the lower limit thereof is not particularly limited.
Further, the size (D 50) of crystal grains contained in the oxide sintered body is not particularly limited, and may be, for example, 1 μm to 30 μm. Specifically, the grain size of the sintered body prepared under the pressurized condition may be 1 μm to 3 μm, and the grain size of the sintered body prepared under the pressureless condition may be 3 μm to 30 μm. In particular, the grain size of crystal grains constituting the oxide sintered body of the present invention is larger than that of molybdenum oxide sintered body obtained by press-sintering powder by artificial compacting such as HP or HIP. Thus, there is an advantage in that it is more advantageous in terms of reaction.
In one specific example, the average particle diameter (D 50) constituting the pressureless sintered body of the present invention may satisfy the condition of the following formula 1.
Formula 1:
GN/GP≥3.0
In the above-mentioned formula (i), the water,
G N is the average particle diameter of the oxide sintered body which was heat-treated under no pressure at a temperature of 1400±200 ℃ for 2 hours (D 50),GP is the average particle diameter of the oxide sintered body which was heat-treated under pressure at 30MPa and 830 ℃ for 2 hours (D 50).
Specifically, the pressureless sintered body constituting the above formula 1 may have an average particle diameter (D 50) of 5.0 or more, more specifically, 10.0 or more. For example, the average particle diameter (D 50) of the oxide sintered body subjected to the pressureless heat treatment may be 3 μm to 30 μm, and the average particle diameter (D 50) of the oxide sintered body subjected to the pressurized heat treatment may be 1 μm to 3 μm.
Also, a sputtering target according to another embodiment of the present invention includes: an oxide sintered body containing the molybdenum oxide as a main component; and a back plate bonded to one surface of the sintered body to support the sintered body.
Wherein the backing plate is a substrate supporting a sintered body for sputtering target, conventional backing plates known in the art can be used without limitation. In this case, the material constituting the back plate and its shape are not particularly limited.
< Method for producing oxide sintered compact and sputtering target >
Hereinafter, a method for producing an oxide sintered body and a sputtering target according to an embodiment of the present invention will be described. However, not limited to the following production method, the steps of each process may be changed or selectively mixed according to the need.
As an embodiment of the above preparation method, it may be configured to include: a step (i) of preparing a raw material powder containing molybdenum oxide (M1), niobium oxide (M2), and metal oxide (M3) containing at least one alkaline earth metal (A); a step (ii) of preparing a molded body using the above raw material powder ("step S20"); step (iii), a sintered body is produced by pressureless sintering the above-mentioned molded body at a temperature of 1200 ℃ to 1600 ℃ for 1 hour to 20 hours ("step S30").
Hereinafter, the above preparation method is described by dividing the steps into the following steps.
(I) Preparation of raw material powder ("step S10")
In the above step S10, a raw material powder containing molybdenum oxide (M1), niobium oxide (M2), and (quasi) metal oxide (M3) containing at least one alkaline earth metal (a) is prepared. Specifically, molybdenum oxide (M1), niobium oxide (M2), one or more first metal oxide (M3-1) powders selected from the group consisting of CaCO 3 and MgO, and, as required, second metal oxide (M3-2) powders are weighed to meet target components, and then each powder is put into a mixer to be crushed and mixed to prepare a mixture.
When the above raw material powders are mixed, conventional additives known in the art, such as binders, dispersants, defoamers, and the like, may be further contained as required. In this case, the amount of the additive to be used may be appropriately adjusted within a conventional range known in the art, for example, 0.01 to 10 weight percent may be used with respect to the total weight of the powder in the slurry (for example, 100 weight percent).
The mixing and pulverizing of the raw material powder are not particularly limited, and may be performed using a conventional ball mill, a grinding mill, a bead mill, or the like, which are well known in the art. For example, the mixed raw material powder may be subjected to a dry ball milling process using zirconia balls. Wherein the weight of the zirconia balls may be 1 to 3 times the amount of the powder, and ball milling may be performed at a speed of 100 to 300rpm for 10 to 36 hours.
As a specific example of the above step S10, in order to mix and crush the raw material powder by the wet ball mill, a pre-weighed elemental powder is added using a prepared PE bucket, and zirconia balls having a weight of about 2 to 4 times, preferably 3 times, the weight of the raw material are added. Then, distilled water or pure water at a level about 1.5 times the level of the raw materials was added thereto for ball milling.
Then, the wet-milled mixture was dried in a dry box, and ball-milled again to obtain a dried raw material powder. In this case, the drying conditions are not particularly limited, and for example, may be dried in a drying oven at a temperature of about 90 ℃ to 110 ℃ for about 10 hours to 15 hours.
Next, the dried mixture was again ball-milled to obtain a dried raw material powder. Filtration is carried out with a sieve of about 90 mesh to 110 mesh, specifically 100 mesh, as required to separate zirconia balls from the powder.
(Ii) Preparation of shaped bodies ("step S20")
In the above step S20, a molded body is prepared from the prepared raw material powder, specifically, the raw material powder is put into a molding machine and a molded body of a predetermined specification is prepared by a molding process.
In order to increase the density of the shaped body, the shaping process can be carried out in two steps. For example, the first molding process may utilize a single axis molding machine and the second molding process may utilize an isostatic molding machine.
The conditions in the above-described first molding and second molding processes are not particularly limited and may be appropriately adjusted under conventional conditions known in the art. For example, the pressure at the time of first molding after the raw material powder is put in the single-axis molding machine is not particularly limited, and specifically may be 10MPa or more per unit area. The pressure at which the molded article obtained by the first molding is placed in the isostatic pressing machine for the second molding is not particularly limited, and may be, for example, 200MPa or more, preferably, 200MPa to 300MPa per unit area.
As a specific example of the above step S20, a first molded body is prepared using an STS material mold having a specification of 20 Φ according to a specified powder weight. In this case, the formation may be performed under a minimum pressure condition capable of forming a shape, for example, under a pressure of about 10MPa for 1 minute. Then, the second molding was performed by hydrostatic molding (CIP) under 200MPa for several hours. In this case, since the second hydrostatic molding is performed together with an organic solvent including water, it can be performed in a state of being put in an acrylic sealing material (for example, a bag).
(Iii) Preparation of sintered body ("step S30")
In the above step S30, a sintered body is prepared by sintering the prepared molded body under a predetermined condition.
In this case, the sintering conditions are not particularly limited, and may be appropriately adjusted under conventional conditions known in the art. For example, pressureless sintering may be performed at a temperature of 1200 ℃ to 1600 ℃ for 1 hour to 20 hours, and specifically, may be performed for 1 hour to 4 hours. The sintering may be performed under an oxygen atmosphere or under inert conditions.
As a specific example of the above step S30, the molded article thus produced is put into an alumina crucible of a predetermined specification and sintered. In this experiment, in order to confirm the difference in characteristics between the molded body before heat treatment and the pressureless sintered body after heat treatment, each physical property was compared by measuring the weight, diameter, height, and the like of the corresponding molded body and sintered body (see table 2 and fig. 9 to 12 below).
The pressureless sintered body produced by this process may have a relative density of 80% or more, specifically, 90% or more. In this case, the upper limit value is not particularly limited.
(Iv) Preparation of sputter target
Then, the sintered body thus sintered is taken out and processed. For example, after taking out the sintered body, the upper and lower portions of the target may be respectively processed to 1mm or more for polishing the surface of the target.
The resulting sputter target is then prepared by diffusion bonding and final processing as is well known in the art.
Specifically, the sintered body obtained in the above step S30 is bonded to a back Plate (Backing Plate). In this case, indium may be used as the binder, and it is preferable to make the binding rate 95% or more. Then, the sputtering target is processed to a final target thickness by using processing equipment, and a final sputtering target is obtained by spraying and/or Arc spraying (Arc spraying) treatment on the surface of the backing plate.
The metal oxide target can be prepared by the above process. The target density of the prepared target is 90% or more, specifically, preferably 95% or more.
< Oxide film >
Another example of the present invention is a metal oxide thin film deposited by using the molybdenum oxide-based target. Such a metal oxide thin film can be formed by sputtering using the sintered body as a target.
The oxide thin film may have a slight difference in composition depending on the vapor deposition atmosphere, but is prepared by sputtering the oxide target, and thus has substantially the same composition as the target. Therefore, an oxide film having a relative density characteristic of 90% or more and an excellent specific resistance characteristic of 1×10 -2 Ω cm or less can be formed. Further, a specific metal oxide and a metal in a predetermined range are added to molybdenum oxide as a main raw material, and chemical resistance and heat resistance characteristics can be improved by optimizing the proportion and composition of molybdenum oxide.
The metal oxide film of the present invention can be formed (evaporated) using a conventional sputtering method known in the art. An example of the preparation method includes a step of performing normal temperature vapor deposition in an oxygen and/or argon atmosphere in a vacuum chamber after the molybdenum oxide pressureless sintered body sputtering target is mounted. In this case, sputtering can be performed by a DC sputtering machine (dispenser).
The substrate and the sputtering apparatus used may be conventional ones known in the art without limitation. Specifically, it is formed by supplying oxygen or oxygen and high purity argon gas at a rate of 80 to 110sccm (standard cubic CENTIMETERS PER minutes per minute) in a vacuum tank, specifically, at a rate of 95 to 105sccm, and evaporation can be performed at Room Temperature (RT) without heating the film-forming substrate. Also, the Power density (Power density) of the DC sputtering machine may be 1.0 to 2.0W/cm 2 and the thickness of the metal oxide thin film may be 300 to 500, but is not particularly limited thereto.
The oxide film obtained as described above can be used in various ways in the production of a semiconductor device, for example, can be used for forming a wiring or for forming an electrode in the production of a semiconductor. In particular, the above metal oxide film may be used as at least one of a gate layer, a source layer, and a drain layer of a Thin Film Transistor (TFT). As such, when the thin film of the present invention is used for a barrier layer of a source electrode and a drain electrode included in a thin film transistor, contact resistance can be reduced, and excellent transparency and low refractive index can be provided, and thus physical properties of the thin film transistor can be improved.
Since the molybdenum oxide-based sputtering target material and the oxide thin film formed thereby of the present invention described above have high density and excellent specific resistance characteristics even under no pressure, contact resistance with TFT structures of LCDs and OLEDs or electron injection layers of organic electroluminescent devices can be suppressed to a low level. Therefore, the oxide film described above can also be applied to various display devices such as a liquid crystal display device or an organic electroluminescent display device without limitation; information transmission devices such as flat panel displays like LCD, PDP, OLED, LED; a surface light source lighting device touch screen such as OLED, LED, etc.; such as a mobile phone, a tablet computer, and/or an information transmission device using the same.
Hereinafter, the present invention will be described in detail by way of examples. The following examples are merely illustrative of the present invention and the present invention is not limited to the following examples.
Example 1-example 17: preparation of MoO 2-Nb2O5 -alpha sintered body
The molybdenum oxide (M1), the niobium oxide (M2), and the (quasi) metal oxide (M3) were mixed in the composition ratios shown in table 1 below to prepare molded articles.
When the molded body was prepared, most of the samples were prepared as disks (disks) of 20 Φ, but part of the composition was also prepared as 50 Φ. Then, oxide sintered bodies of examples 1 to 17 were prepared by non-pressure heat treatment at a temperature of about 1200 to 1600 ℃ for 2 hours using a heat treatment apparatus.
TABLE 1
Comparative example 1-comparative example 4: preparation of MoO 2-Nb2O5 and alpha-added sintered body
A molded body was produced by the same method as the above example, except that the composition of the added oxide was changed as shown in table 1 above. Then, sintered bodies of comparative examples 1 to 4 were prepared, respectively, by heat-treating at a temperature of about 1200 to 1600 ℃ for 2 hours using a heat-treating apparatus.
Comparative example 5: preparation of sintered body
Molybdenum oxide (M1) and niobium oxide (M2) were weighed in the composition ratios shown in table 1. The weighed powder was placed in a 1L plastic bucket and alumina balls 3 times the amount of the powder were added. The alumina balls are 3-10 mm balls. After the addition of the weighed powder and balls was completed, dry mixing was performed in a ball mill at a speed of 170 to 230rpm for 8 hours. The resulting dry powder was pressure sintered using a Hot Press (Hot Press). In this case, the internal vacuum condition of the hot press was 30MPa, the heating rate was 3 to 7 ℃, the maximum temperature was 830 ℃, and the sintering was performed for about 2 hours, followed by furnace cooling. The sintered body of comparative example 5 was prepared by the procedure described above.
Experimental example 1: evaluation of the structural change of the molded body according to the heat treatment
The structure change of the sintered body according to the heat treatment was evaluated by using the molded body with and without the metal oxide added.
Fig. 1 is an image showing the change in the structure of the sintered body of the molded body of example 9 using the metal oxide (M3) added according to the heat treatment temperature, and fig. 2 is an image showing the change in the structure of the sintered body of the molded body of comparative example 1 using the metal oxide (M3) not added according to the heat treatment temperature.
As a result of the experiment, it was confirmed that the metal oxide-added molded article has a relatively large structural change with the heat treatment temperature, for example, pores (pore) of the sintered body are suppressed, as compared with the molded article without the metal oxide added (see fig. 1 to 2 described below).
Experimental example 2: evaluation of sintered body evaluation particle size
The sintered bodies heat-treated under pressure and under no-pressure process conditions were used to evaluate their structure change and average particle diameter, respectively.
Specifically, the sintered body of example 9 prepared in the pressureless state and comparative example 5 prepared in the pressurized state were used as the samples. The two samples were cut into 10X 10mm sizes using a blade made of metal, then, after grinding for several minutes from SiC coated abrasive (paper) #100 to #2000 by a polisher, it was finally prepared by using 1 μm of paste and ultrafine fiber cloth. The sample was then soaked with hydrogen peroxide at a temperature of about 200 ℃ for 1 minute and heat treated so that the surface of the tissue could be exposed.
Further, for measurement of the average particle diameter of the sintered body, each sample was observed with FE-SEM (Hitachi, S-4800) at the same magnification of 1000, 5 lines were drawn randomly on the measured image, and about 100 particles were calculated by a linear fitting method (LINEAR INTERCEPT method) according to the following mathematical formula 2.
Mathematics 2
D＝1.56×C/MN
In the above formula, d=average particle diameter, c=full length of the line, m=magnification, n=number of particles on the line.
Fig. 3 and 4 are SEM images showing the powder structure of the mixed raw materials, the structure of the pressureless sintered body prepared in example 9, and the fracture surface and polished surface of the structure of the pressureless sintered body prepared in comparative example 5, respectively.
As shown in fig. 3 to 4 described below, it can be seen that the pressed sintered body of comparative example 5 is in the form of forcibly bringing together the starting materials by high pressure, and thus the particle size is hardly increased. In contrast, it can be seen that the particle size (grain size) of the sintered body of example 9 is increased by the reaction, and in particular, it is seen that the particles are advantageous in terms of the reaction because they take a form of a combination in the interaction between the dissimilar elements.
Experimental example 3: evaluation of physical Properties of molded articles
The physical properties of each molded body produced in examples 1 to 17 and comparative examples 1 to 4 were evaluated as follows.
Specifically, the diameter (D) and the height (T) of each molded body were measured with a vernier caliper, and the weight (Mass) was measured with a balance. The relative density was calculated by converting the amount of each weight added to a volume percentage and converting the level compared to the theoretical density to a percentage, and the results are shown in table 2. The density of the measured samples was calculated in weight/volume and expressed as an average when preparing a plurality of identical samples.
For reference, each sample in table 2 below had a low relative density because it was not sintered, and the relative density of each sintered body after sintering (heat treatment) exhibited a level of 96%.
TABLE 2
Experimental example 4: evaluation of Density and shrinkage of sintered body
After heat treatment was performed on each of the samples prepared in examples 1 to 17 and comparative examples 1 to 4, the physical property change of each sintered body was measured.
(1) Evaluation of Density after Heat treatment
The density of the sintered body after heat treatment was evaluated by the same measurement as in experimental example 3. For example, the results of the relative density calculated by measuring the diameter, height, and weight of the sintered body after the heat treatment are shown in fig. 5 to 8, respectively, described below.
As a result of the experiment, it was found that in examples 1 to 17, the relative density also increased significantly as the sintering temperature was increased from 1200 ℃ to 1600 ℃ (see fig. 5 to 7). In contrast, in the cases of comparative examples 1 to 4, it was found that the relative density of the molded article was lower or similar with the sintering temperature. In addition, it is found that the slope with the temperature rise is low, and in the case of comparative example 1, the relative density does not further increase even if the temperature rises further (see fig. 8). The sintered density of comparative example 5 was 95 to 97%.
(2) Evaluation of shrinkage before and after Heat treatment
Shrinkage was calculated by measuring the diameter and height of the molded body before heat treatment and the sintered body after heat treatment, respectively. The calculated shrinkage rate results are shown in fig. 9 to 12, respectively, below.
As a result of the experiment, in the cases of comparative examples 1 to 4, the rate of change in shrinkage caused by the heat treatment was not significant (see fig. 12). In contrast, it is understood that in the cases of examples 1 to 17, the rate of change in shrinkage of the sintered body due to the heat treatment was relatively high (see fig. 9 to 11).
Experimental example 5: evaluation of specific resistance of sintered body
The specific resistance characteristics of each of the sintered body samples prepared in examples 1 to 17 and comparative examples 1 to 5 were evaluated.
Specifically, a sample in an intermediate temperature range of 1500 ℃ was used as a sintered body sample. The resistance ratio of the sample was measured by using Loresta-GX MCP-T700 product (Mitsubishi chemical corporation (Mitsubishi chemical)), and the results are shown in Table 3 below.
TABLE 3 Table 3
As shown in table 3 above, it was confirmed that the sintered bodies of examples 1 to 17 containing the prescribed metal oxide as an additive had excellent specific resistance characteristics as compared with the sintered bodies of comparative examples 1 to 5 containing no additive.
Experimental example 6: analysis and evaluation of the Crystal Structure of sintered body
The crystal structure characteristics of each of the sintered body samples prepared in example 9, comparative example 1 and comparative example 5 were evaluated.
Specifically, in example 9 and comparative example 1, the samples sintered at an intermediate temperature range of 1500 ℃ were cut into 10×10×3mm (T) and measured. In comparative example 5, the sample sintered at 830 ℃ was cut into the same size and measured. The X-ray Diffraction (X-ray Diffraction) apparatus used for the measurement was used to measure the temperature of 2theta at 20 to 60 degrees using Pro MRD product (manufactured by Marvin panaceae Co., ltd. (MALVERN PANALYTICAL).
As shown in fig. 13 below, it is clear that the sintered body of comparative example 5 produced by pressure sintering has a crystal structure more similar to that of the original mixed powder, unlike the sintered bodies of comparative example 1 and example 9.
Experimental example 7: evaluation of sheet resistance and reflectance characteristics of film
The properties of films prepared from the respective sintered bodies of example 1, example 9 and comparative example 1 were evaluated as follows.
Specifically, 4 inch targets prepared from the compositions of examples and comparative examples were evaporated to dryness by a DC Sputter (Sptter)To form a unit film. And, cu4 inch targets were sputtered by a DC Sputter (Sptter)Sputtering onto the above unit film to prepare a double film. The sheet resistance and reflectance characteristic results of the prepared film are shown in fig. 14 and 15, respectively, below.
Fig. 14 is a graph showing the sheet resistance characteristics of unit films prepared from the components of example 1, example 9 and comparative example 1. It can be seen that the films of example 1 and example 9 have significantly lower sheet resistance characteristics than those of comparative example 1.
FIG. 15 is a graph showing the results of measurement of average reflectance in the visible light range (380 to 740nm wavelength) using the double films prepared from the components of example 1, example 9 and comparative example 1. The double films of comparative example 1 had an average reflectance of more than about 10%, whereas the double films of example 1 and example 9 had an average reflectance characteristic of 9% or less, which is found to ensure more excellent reflectance characteristics.
Experimental example 8: evaluation of chemical stability of film
A Photoresist (PR) process was performed on the double film prepared from the components of example 9 and comparative example 1. In performing the PR process, a sample for evaluating etching is prepared by exposing to light so that a wiring line width of 50nm to 100nm is formed. The results are shown in table 4 and fig. 16.
TABLE 4 Table 4
| Degree of damage (nm) of molybdenum oxide film | Post-etch angle (°) | |
| Comparative example 1 | 1.75 | 51.5 |
| Example 9 | 0 | 48.6 |
Fig. 16 shows the results of dual-mode etching evaluation made of the components of example 9 and comparative example 1, where part (a) of fig. 16 shows the image of example 9, and part (b) of fig. 16 shows the image of comparative example 1.
As shown in table 4 and fig. 16 (a), the thin film of example 9 showed significantly lower damage degree and low angle after the etching process compared with the thin film of comparative example 1. Therefore, it was confirmed that the oxide sintered body of the present invention has excellent chemical stability.
Claims (15)
1. An oxide sintered body characterized in that,
Comprising:
Molybdenum oxide M1 containing at least one of MoO 2 and MoO 3;
niobium oxide M2; and
Metal oxide M3 containing at least one alkaline earth metal,
The content of the molybdenum oxide M1 is 70 weight percent or more with respect to the total weight of the sintered body.
2. The oxide sintered body according to claim 1, wherein the metal oxide M3 includes a first metal oxide M3-1 containing at least one of Ca and Mg.
3. The oxide sintered body according to claim 2, wherein the first metal oxide M3-1 contains at least one selected from the group consisting of CaCO 3 and MgO.
4. The oxide sintered body according to claim 2, wherein the metal oxide M3 comprises:
a first metal oxide M3-1; and
The second metal oxide M3-2 contains one or more metals selected from the group consisting of Co, si, Y and Ga.
5. The oxide sintered body according to claim 4, wherein the second metal oxide M3-2 contains one or more selected from the group consisting of Co 3O4、SiO2、Y2O3 and Ga 2O3.
6. The oxide sintered body according to claim 1, wherein the content of the metal oxide M3 is more than 0 weight percent and 10.0 weight percent or less based on 100 weight percent of the sintered body.
7. The oxide sintered body according to claim 1, wherein the content of the molybdenum oxide M1 and the niobium oxide M2 is 90.0 wt% or more and less than 100 wt%, based on 100 wt% of the oxide sintered body, and the content ratio of the molybdenum oxide M1 and the niobium oxide M2 is 50:50 wt% to 90:10 wt%.
8. The oxide sintered body according to claim 1, wherein the oxide sintered body is obtained by mixing and molding a molybdenum oxide M1, a niobium oxide M2, and a metal oxide M3, and then performing pressureless sintering.
9. The oxide sintered body according to claim 8, wherein,
The average particle diameter D 50 of the oxide sintered body subjected to pressureless sintering satisfies the condition of the following formula 1:
formula 1:
GN/GP≥3.0
In the above-mentioned formula (i), the water,
G N is the average particle diameter D 50 of the oxide sintered body which is subjected to pressureless heat treatment at a temperature of 1400+ -200deg.C for 2 hours,
G P is the average particle diameter D 50 of the oxide sintered body subjected to the heat treatment under pressure at 30MPa and 830 ℃ for 2 hours.
10. The oxide sintered body according to claim 1, wherein the specific resistance is 1x 10 -2 Ω cm or less and the relative density is 80% or more.
11. A sputtering target comprising the oxide sintered body according to any one of claims 1 to 10.
12. An oxide film formed from the sputter target of claim 11.
13. A thin film transistor, wherein the oxide film according to claim 12 is used as any one of a gate layer, a source layer, and a drain layer.
14. A display device comprising the oxide film according to claim 12.
15. A method for producing the oxide sintered body according to claim 1, comprising:
a step (i) of preparing a raw material powder containing molybdenum oxide M1, niobium oxide M2, and metal oxide M3 containing at least one alkaline earth metal;
A step (ii) of preparing a molded body from the above raw material powder; and
And (iii) subjecting the molded article to pressureless heat treatment at a temperature of 1200 to 1600 ℃ for 1 to 20 hours to prepare a sintered body.
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| KR20210136630 | 2021-10-14 | ||
| PCT/KR2022/015592 WO2023063774A1 (en) | 2021-10-14 | 2022-10-14 | Molybdenum oxide-based sintered body, and sputtering target and oxide thin film comprising same |
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