CN110637102A - Oxide thin film and oxide sintered body for sputtering target for producing the same - Google Patents
Oxide thin film and oxide sintered body for sputtering target for producing the same Download PDFInfo
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- CN110637102A CN110637102A CN201980002388.XA CN201980002388A CN110637102A CN 110637102 A CN110637102 A CN 110637102A CN 201980002388 A CN201980002388 A CN 201980002388A CN 110637102 A CN110637102 A CN 110637102A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- 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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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
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Abstract
An oxide thin film comprising Nb, Mo and O, wherein the content ratio (atomic ratio) of Nb to Mo is 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8, and the content ratio (atomic ratio) of O to a metal (Nb + Mo) is 1.5 < O/(Nb + Mo) < 2.0. Further, an oxide sintered body comprising Nb, Mo and O, wherein the content ratio of Nb to Mo is (Atomic ratio) of 0.1 or more and Nb/(Nb + Mo) or less and 0.8 or less, the content ratio (atomic ratio) of O to metal (Nb + Mo) of 1.5 or more and O/(Nb + Mo) or less and 2.1 or less, and MoO2XRD peak intensity I of phase belonging to (-111) planeMoO2With background intensity IBGSatisfy the relationship of IMoO2/IBGIs greater than 3. The present invention addresses the problem of providing an oxide thin film having the following excellent properties: low reflectance and transmittance, excellent light absorption ability, solubility in an etching solution, easy processing, high weather resistance, and resistance to change with time.
Description
Technical Field
The present invention relates to an oxide thin film having light absorbing ability and an oxide sintered body for a sputtering target used for producing the thin film.
Background
In a liquid crystal display, a plasma display, an organic Electroluminescence (EL) display, a touch panel, a solar cell, and the like, a transparent conductive film containing ITO (indium tin oxide) is used as a wiring member. ITO has excellent transmittance for visible light and low resistivity in oxide, and is therefore an excellent material as a wiring member. However, when the area of the display or the panel is increased, the resistance is increased, and the problem that the display or the panel cannot cope with the increase in area arises.
Therefore, it is studied to use a metal thin film having low resistivity as a wiring member instead of the ITO film. However, when a metal thin film is used as the wiring member, the metal thin film reflects visible light, which causes a problem of lowering visibility of the display and the panel. In order to solve this problem, it has been studied to form a film capable of absorbing reflected light in the vicinity of a thin metal film, thereby suppressing reflection of light by the thin metal film and improving visibility.
As for a film for reducing reflection of light, for example, patent document 1 discloses the use of an oxide film containing any one of Cu and Fe and any one of Ni and Mn as a film for reducing the metallic luster of a wiring pattern of a touch panel screen. Patent document 2 discloses that a black layer containing oxygen, copper, nickel, and molybdenum is formed together with a wiring layer made of copper foil or the like.
Patent documents 3 to 5 relate to a solar light absorbing layer for solar energy utilization and a light absorbing layer used for a black matrix layer of a liquid crystal display, and disclose a light absorbing layer composed of two layers in which a metal as an absorbing component is dispersed in an oxide matrix. The total layer thickness is in the range of 180nm to 455nm, has a light transmittance (light transmittance) of less than 1% in the wavelength range of 380nm to 780nm, and has a light reflectance (light transmittance) of less than 6%.
In addition to this, phase shift photomasks are known for applications requiring light transmittance, reflectance, and film thickness. The phase shift photomask is used for the purpose of improving resolution by interference of light. The phase shift photomask film is required to have a specific film thickness, a specific transmittance (about several percent), and a low reflectance depending on the wavelength of the laser light to be used. In addition, there is also a need for films that reduce light reflection in decorative applications.
Patent document 6 describes a black matrix thin film in which the Nb content is 1 to 35 wt%, and the remainder is substantially Mo, and a part or the whole of the thin film is present in the form of a compound of any one or two or more of an oxide, a nitride, and a carbide. However, patent document 6 does not specifically disclose the content ratio of oxygen or the like, and it is not clear at all what degree of reflectance and transmittance can be obtained.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2016 + 160448
Patent document 2: japanese patent laid-open publication No. 2017-41115
Patent document 3: japanese patent laid-open publication No. 2016-504484
Patent document 4: japanese patent laid-open publication No. 2016-502592
Patent document 5: japanese patent laid-open publication No. 2016-522317
Patent document 6: japanese patent laid-open No. 2000-214308
Disclosure of Invention
Problems to be solved by the invention
The present invention addresses the problem of providing an oxide thin film that is suitable for preventing reflection of light, has good etching processability and weather resistance, and has light absorption capability, and an oxide sintered body for a sputtering target that is suitable for forming the oxide thin film.
Means for solving the problems
The oxide thin film according to the embodiment of the present invention contains Nb, Mo, and O (oxygen), and is characterized in that the content ratio (atomic ratio) of Nb to Mo is 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8, and the content ratio (atomic ratio) of O to the metal (Nb + Mo) is 1.5 < O/(Nb + Mo) < 2.0.
Further, the oxide sintered body according to the embodiment of the present invention contains Nb, Mo, and O (oxygen), and is characterized in that the content ratio (atomic ratio) of Nb to Mo is 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8, the content ratio (atomic ratio) of O to the metal (Nb + Mo) is 1.5 < O/(Nb + Mo) < 2.1, and MoO2XRD peak intensity I of phase belonging to (-111) planeMoO2With background intensity IBGSatisfy the relationship of IMoO2/IBG＞3。
Effects of the invention
According to the present invention, an oxide thin film having both good processability by etching and weather resistance and having light absorption ability suitable for preventing reflection of light can be obtained. Further, an oxide sintered body for a sputtering target suitable for forming the oxide thin film can be obtained.
Drawings
Fig. 1 is an explanatory diagram of the reflectance of light incident from the thin film side (film side reflectance).
Fig. 2 is an explanatory diagram of the reflectance of light incident from the glass substrate side (substrate-side reflectance).
Detailed Description
It is considered to use a metal film as the light absorption film. However, in this case, although the light absorption is high and the transmittance can be reduced, metal reflection peculiar to metal occurs, and it is difficult to reduce the reflectance. In addition, it is also considered that an oxide film is formed on a metal film, but the manufacturing process is increased, thereby lowering the production efficiency. On the other hand, it is considered to use an oxide film as the light absorbing film. In this case, although surface reflection is suppressed because metal reflection does not occur, the transmittance increases because the light absorption is lower than that of a metal film, and the reflected light from a lower metal electrode or the like becomes conspicuous, which may deteriorate visibility.
In this connection, among the oxides, NbO2、MoO2The material has relatively low visible light transmittance and relatively low reflectance, and is considered to be useful as a light absorbing film. However, in the case of using NbO alone2In the case of a film, the film has a problem that the film is less likely to change with time and is excellent in weather resistance, while the film is difficult to dissolve in an etching solution other than Hydrogen Fluoride (HF) and is difficult to process by etching. On the other hand, in the case of MoO alone2In the case of the film, even if hydrogen peroxide (H) for metal wiring is used2O2) Such an etching solution can be processed by etching, but has a problem of poor weather resistance.
Therefore, the oxide thin film according to the embodiment of the present invention contains, in a specific ratio: NbO which has good weather resistance but is difficult to process by etching2And MoO that can be processed by etching but has poor weather resistance2. That is, the oxide thin film according to the embodiment of the present invention contains Nb, Mo, and O (oxygen), and is characterized in that the content ratio (atomic ratio) of Nb to Mo is 0.1 or more and Nb/(Nb + Mo) or less and 0.8 or less, and the content ratio (atomic ratio) of O to the metal (Nb + Mo) is 1.5 < O/(Nb + Mo) < 2.0.
The oxide thin film according to the embodiment of the present invention satisfying the above composition range of 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8 has desired optical properties, film resistance, and amorphousness. On the other hand, when Nb/(Nb + Mo) is less than 0.1, the desired weather resistance cannot be obtained, and when Nb/(Nb + Mo) is more than 0.8, the desired processability by etching cannot be obtained. The preferable content ratio of Nb to Mo is 0.1 < Nb/(Nb + Mo) < 0.5. When the content ratio O/(Nb + Mo) of O and the metal (Nb + Mo) is 1.5 or less, the reflectance increases, and when O/(Nb + Mo) is 2.0 or more, the transmittance increases, and desired optical characteristics cannot be obtained. Therefore, the composition is set within the above composition range.
In addition, the oxide thin film according to the embodiment of the present invention preferably has an average reflectance of 30% or less with respect to incident light in a visible light region (wavelength: 380nm to 780nm) when a thin film having a thickness of 100 nm. + -.10 nm is formed on a glass substrate. Here, the "average" reflectance means a value obtained by measuring reflectance for every 5nm in the above wavelength range and calculating the average value thereof.
The reflectance includes reflectance of light incident from the thin film side (film side reflectance) as shown in fig. 1 and reflectance of light incident from the glass substrate side (substrate side reflectance) as shown in fig. 2, but in the present disclosure, the reflectance refers to only the film side reflectance. The reflected light includes specular reflected light and diffuse reflected light, but in the present disclosure, the reflected light refers to a relative total light reflectance obtained by combining the specular reflected light and the diffuse reflected light.
In addition, in the oxide thin film according to the embodiment of the present invention, when a thin film having a film thickness of 100 nm. + -.10 nm is formed on a glass substrate, the average transmittance of incident light in the visible light region (wavelength: 380nm to 780nm) is preferably 20% or less. Here, the "average" transmittance means a value obtained by measuring the transmittance for every 5nm in the above wavelength range and calculating the average value thereof.
With such a level of reflectance and transmittance, light reflected from the display and metal wiring (copper foil and the like) inside the panel can be sufficiently absorbed, and a reduction in visibility can be suppressed. Further, the low reflectance required for the use as a phase shift photomask can be satisfied.
Incidentally, the transmittance is related to the film thickness of the oxide thin film, and generally decreases as the film thickness increases. As described above, in the embodiment of the present invention, the transmittance is defined when the film thickness of the oxide thin film is 100nm ± 10nm or more, but the value of ± 10nm is set in consideration of the fact that it is difficult to accurately form the film to be 100nm in reality, and even if the film thickness fluctuates by ± 10nm (i.e., 90nm to 110nm), the fluctuation range of the transmittance is theoretically within about ± 1.3%. Even when the variation width of the transmittance is considered, the average transmittance of the oxide thin film according to the embodiment of the present invention satisfies 20% or less.
In addition, the surface resistivity of the oxide thin film according to the embodiment of the present invention is preferably 1.0 × 105Omega/□ or less. In order to suppress light reflection by the metal wiring, an oxide thin film functioning as a light absorbing film is laminated adjacent to the metal wiring, but when the resistivity of the oxide thin film is high, a sufficient current does not flow through the metal wiring. Therefore, the surface resistivity of the oxide thin film is preferably set within the above range.
The oxide thin film according to the embodiment of the present invention is excellent in weather resistance, and the rate of change in the average transmittance and the average reflectance in the visible light region (wavelength: 380nm to 780nm) before and after the constant temperature and humidity test is preferably 30% or less. The rate of change in surface resistivity before and after the constant temperature and humidity test is preferably 30% or less.
Here, the constant temperature and humidity test in the present disclosure is as follows: the oxide thin film sample formed on the substrate was placed in a chamber a (temperature 40 ℃ to humidity 90%) and a chamber B (temperature 85 ℃ to humidity 85%), and transmittance, reflectance, and surface resistivity after 120 hours, 500 hours, and 1000 hours were measured, compared with each measured value immediately after film formation, and the change rate thereof was examined.
In the embodiment of the present invention, the thickness of the oxide thin film is preferably 20nm to 2000 nm. When the film thickness is less than 20nm, the light absorption ability may be lowered, while when the film thickness is more than 2000nm, it takes more time than necessary to form the film, which is not preferable. However, since the film thickness is ultimately determined by the device design, the film thickness is not limited to this film thickness as long as the light absorption capability can be ensured.
The oxide thin film according to the embodiment of the present invention is preferably an amorphous thin film (amorphous thin film). Since the amorphous film has a lower film stress than the crystalline film, film peeling and cracking are less likely to occur during lamination. Therefore, it is particularly suitable for use in flexible devices.
Next, the oxide sintered body according to the embodiment of the present invention will be described in detail.
An oxide sintered body according to an embodiment of the present invention contains Nb, Mo, and O (oxygen), and is characterized in that the content ratio (atomic ratio) of Nb to Mo is 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8, the content ratio (atomic ratio) of O to metal (Nb + Mo) is 1.5 < O/(Nb + Mo) < 2.1, and MoO2XRD peak intensity I of phase belonging to (-111) planeMoO2With background intensity IBGSatisfy the relationship of IMoO2/IBGIs greater than 3. The oxide sintered body having such characteristics can be used as a sputtering target.
The oxide sintered body according to the embodiment of the present invention satisfying the above composition ranges of 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8 and 1.5. ltoreq. O/(Nb + Mo) < 2.1 has a thin film obtained by sputtering deposition and has desired optical characteristics, film resistance and amorphousness. In the above oxide sintered body, when the content ratio of O to metal (Nb + Mo) is 1.5 < O/(Nb + Mo) < 2.1, the content ratio of O to metal (Nb + Mo) is in the range of 1.5 < O/(Nb + Mo) < 2.0 even when oxygen gas is not introduced during sputtering, and desired film characteristics can be obtained in a thin film formed by sputtering using the oxide sintered body (sputtering target).
In the oxide sintered body according to the embodiment of the present invention, MoO2XRD peak intensity I of phase belonging to (-111) planeMoO2With background intensity IBGSatisfy the relationship of IMoO2/IBG> 3, if the above XRD peak intensity ratio satisfies IMoO2/IBGMore than 3, most of the molybdenum (Mo) in the sintered body is MoO2In the case of using such an oxide sintered body, desired optical characteristics can be obtained for a thin film formed by sputtering.
The relative density of the oxide sintered body according to the embodiment of the present invention is preferably 80% or more. When the relative density is 80% or more, the sputtering target can be practically used. The relative density is more preferably 85% or more.
The volume resistivity of the oxide sintered body according to the embodiment of the present invention is preferably 100m Ω · cm or less. The film formation by DC sputtering can be performed due to the decrease in volume resistivity. DC sputtering has a higher film formation rate and an excellent sputtering efficiency than RF sputtering, and can improve throughput. In addition, RF sputtering may be performed depending on the manufacturing conditions, and even in this case, the film deposition rate is improved.
The oxide sintered body according to the embodiment of the present invention can be produced, for example, as follows.
Weighing and mixing NbO2Powder, MoO2Raw powder of the powder to achieve the desired composition. The raw material powder preferably has a purity of 99.9% or more and a particle diameter (D50) of 0.5 to 10 μm. As the mixing method, it is preferable to perform mixing while performing pulverization using a ball mill or the like. It is also contemplated to use Nb as the raw material powder2O5Powder and Mo powder, but because of Nb2O5Since the sintering temperature differs greatly from that of Mo, densification is difficult.
Then, the mixed powder is hot-pressed (uniaxially pressed and sintered) at 1100 to 1200 ℃ and a pressing pressure of 250MPa or more for 5 to 10 hours in an Ar atmosphere. This makes it possible to obtain an oxide sintered body containing Nb, Mo, and O, the relative density of which is 80% or more. The obtained oxide sintered body can be processed into a sputtering target by cutting, polishing, and the like.
The oxide thin film according to the embodiment of the present invention can be produced, for example, as follows.
Mixing NbO2Sputtering target and MoO2The sputtering target is set in a sputtering device and co-sputtered to form NbO on the substrate2And MoO2The mixed film of (4). At this time, the film composition can be changed by changing the respective sputtering powers at the time of sputtering.
Alternatively, the sputtering target produced by the above method is set in a sputtering apparatus and sputtering is performed, thereby forming NbO on a substrate2And MoO2The mixed film of (4). In this case, the composition of the sputtering target is not completely the same as that of the film,but will be of similar composition. Since the composition of the target is related to the composition of the film, the composition of the target that can obtain a desired film composition can be grasped by setting conditions. In addition, the amount of oxygen in the film can also be adjusted by adjusting the flow rate of oxygen introduced during sputtering.
< film Forming conditions >
A sputtering device: ANELVA SPL-500
Substrate temperature: room temperature (substrate not heated)
Film forming atmosphere: ar or Ar + O2
Air pressure: 0.2 Pa-2.0 Pa
Gas flow rate: 50sccm to 100sccm
Power: 100W-1000W (DC, RF)
Substrate: EagleXG manufactured by corning (phi 4 mm. times.0.7 mm)
The evaluation methods of the oxide thin film and the oxide sintered body according to the embodiments of the present invention are described below, including examples and comparative examples.
(regarding transmittance and reflectance)
The device comprises the following steps: shimadzu corporation spectrophotometer UV-2450
And (3) determining a sample:
samples obtained by forming a film on a glass substrate having a thickness of 0.7mm at a thickness of 100 nm. + -. 10nm, and glass substrates on which no film is formed
The determination method comprises the following steps:
(reflectance) the relative total light reflectance obtained using an integrating sphere (reference sample, specular mirror) was used.
The reflectance of light incident from the thin film side (film side reflectance) includes not only the reflectance from the thin film surface but also the reflectance from the glass substrate (front surface) located at the interface with the thin film and the reflectance from the back surface of the glass substrate.
The reflectance of light incident from the glass substrate side (substrate-side reflectance) includes reflectance from the surface of the glass substrate and reflectance from a thin film located at the interface with the glass substrate.
(transmittance) relative transmittance obtained using a glass substrate as a reference sample.
(composition of film)
The device comprises the following steps: JXA-8500F manufactured by JEOL
The method comprises the following steps: EPMA (Electron Beam micro analyzer)
Acceleration voltage: 5keV to 10keV
Irradiation current: 1.0X 10-8A～1.0×10-9A
At a probe diameter of 10 μm, 5 spots were selected, no dust was attached, the substrate surface was not observed, and a smooth film-formed portion was observed, and spot analysis was performed to calculate the average composition.
(surface resistance of film)
The device comprises the following steps: resistivity measuring device sigma-5 + manufactured by NPS company
The method comprises the following steps: direct current four-probe method
(non-crystallizing Properties of film)
The presence or absence of a diffraction peak by X-ray diffraction of the film formation sample was judged. When no diffraction peak due to the film material was observed by the measurement under the following conditions, it was judged as an amorphous film. Here, the absence of a diffraction peak means that: when the maximum peak intensity in the range of 10-60 DEG 2 theta is set as ImaxAnd I represents an average peak intensity of 20 ° to 25 ° when 2 θ is equal toBGWhen, Imax/IBGCase < 5. In the table, as the criterion for determining the amorphousness, I is satisfiedmax/IBGIf < 5, it is marked as O, and I will not be satisfiedmax/IBGThe case of < 5 was marked as X.
The device comprises the following steps: smart Lab manufactured by Physics Inc
A bulb tube: Cu-K alpha ray
Tube voltage: 40kV
Current: 30mA
The determination method comprises the following steps: 2 theta-theta reflection method
Scanning speed: 20 DEG/min
Sampling interval: 0.02 degree
Measurement range: 10-60 degree
And (3) determining a sample: film formation sample (film thickness of 100nm or more) on glass substrate (EagleXG)
(measurement of film thickness)
Contact pin type height difference meter: dektak8 manufactured by Veeco
The method comprises the following steps: the film thickness was measured from the difference in height between the film-formed surface and the non-film-formed surface of the glass substrate after film formation.
(processability of film by etching)
As the etching solution, hydrogen peroxide (H) was used2O2) A chemical-like solution. In the etching determination, the case where the etching rate was high was indicated by "o", the case where the etching rate was low was indicated by "Δ", and the case where the film was hardly dissolved was indicated by "x".
(composition of sintered body)
The device comprises the following steps: SPS3500DD manufactured by SII Corp
The method comprises the following steps: ICP-OES (high frequency inductively coupled plasma emission spectrometry)
(relative Density of sintered body)
The dimensional density was calculated by measuring the dimensions (using a vernier caliper) and the weight of the sintered body, and from this dimensional density and the theoretical density of the sintered body, the relative density (%) — dimensional density/theoretical density × 100 was calculated.
The theoretical density is calculated from the mixing ratio of each oxide and the theoretical density of each oxide.
When mixing NbO2The weight of (d) is a (wt%), MoO2When the weight of (b) is b (% by weight),
theoretical density of 100/(a/5.90+ b/6.44)
NbO2Theoretical density of (2): 5.90g/cm3、MoO2Theoretical density of (2): 6.44g/cm3
(XRD analysis of sintered body)
The device comprises the following steps: smart Lab manufactured by Physics Inc
A bulb tube: Cu-K alpha ray
Tube voltage: 40kV
Current: 30mA
The determination method comprises the following steps: 2 theta-theta reflection method
Scanning speed: 20 DEG/min
Sampling interval: 0.02 degree
Measurement range: 10-60 degree
Sample determination position: sputtering surface
Note that, MoO2XRD peak intensity I of phase belonging to (-111) planeMoO2The definition is as follows.
IMoO2＝IMoO2’/IMoO2-BG
IMoO2: XRD peak intensity in the range of 25.5 DEG-2 theta-26.5 DEG
IMoO2-BG: an average XRD intensity in the range of 19.5 DEG to 2 theta to 20.5 deg.
(volume resistivity of sintered body)
The device comprises the following steps: resistivity measuring device sigma-5 + manufactured by NPS company
The method comprises the following steps: DC 4 probe method
[ examples ]
The following description will be made based on examples and comparative examples. It should be noted that the present embodiment is merely an example, and is not limited to this example. That is, the present invention is limited only by the claims and includes various modifications other than the embodiments included in the present invention.
(examples 1-1 to 1-6 and comparative examples 1-1 to 1-2)
Mixing NbO2Target (6 inch diameter) and MoO2The target (phi 6 inches) was set in a sputtering apparatus (ANELVA SPL-500), and NbO was formed on a glass substrate (eagleXG, phi 4 inches) by co-sputtering2And MoO2The mixed film of (4). As described above, the film formation conditions were changed as shown in table 1, and films having the compositions shown in table 1 were produced by changing the powers of the targets during sputtering. In comparative example 1-1, only MoO was used2Sputtering target to form MoO2Film, comparative example 1-2, using only NbO2Sputtering the target to form NbO2And (3) a membrane. Then, with respect to each oxide thin film obtained by changing the composition, the transmittance, the surface reflectance, the back surface reflectance, and the surface resistivity immediately after the film formation (room temperature) were measured, and the results were examinedThe etching property is good. The results are shown in table 1.
As shown in Table 1, the oxide thin films (examples 1-1 to 1-6) in which the content ratio (atomic ratio) of Nb to Mo satisfies 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8 all had the following characteristics: the film has low film resistance, excellent etching processability and non-crystallinity. Examples 1-1 to 1-5 had particularly fast etching rates.
Next, in order to investigate weather resistance, each oxide thin film formed on the substrate under the respective conditions was placed in a chamber a (temperature 40 ℃ to humidity 90%) and a chamber B (temperature 85 ℃ to humidity 85%), and changes in transmittance, surface reflectance, back surface reflectance, and surface resistance after 12 hours, 500 hours, and 1000 hours had elapsed were investigated. The results are shown in Table 2.
As shown in Table 2, the oxide thin films (examples 1-2 to 1-5) had a transmittance, a reflectance and a change with time (change rate) in surface resistance of 30% or less, and were excellent in weather resistance.
On the other hand, the oxide thin film containing only Mo (comparative example 1-1) was poor in weather resistance, and the transmittance and the like were significantly increased with the passage of time. In addition, the oxide thin films containing only Nb (comparative examples 1 to 3) were hardly dissolved in the etching solution.
(examples 2-1 to 2-4 and comparative example 2-1)
Preparing NbO with purity of more than 99.9% and particle size of 0.5-10 μm2Powder and MoO2The powders were weighed so as to be in a predetermined ratio as shown in table 3, and mixed and pulverized by a ball mill. Next, the resultant was sintered at a temperature of 1200 ℃ and a surface pressure of 250kgf/cm in an argon atmosphere3Next, the obtained mixed powder was subjected to hot press sintering to prepare an oxide sintered body. Mixing, crushing and sintering were performed under the same conditions except that only the weight ratio was adjusted.
The evaluation results of the obtained oxide sintered body are shown in table 3. As shown in Table 3, the MoO of any of the examples2XRD peak intensity I of phase belonging to (-111) planeMoO2With background intensity IBGAll satisfy IMoO2/IBGIs greater than 3. The relative density is 80% or more, and the volume resistivity is 100 m.OMEGA.cm or less. On the other hand, regarding comparative example 2-1, MoO2XRD peak intensity ratio of phase 1.7, MoO2And (4) disappearing.
Next, the oxide sintered bodies obtained in examples and comparative examples were processed into sputtering targets, and sputtering deposition was performed using the targets. The optical properties of the obtained sputtered films are shown in table 3. Films obtained by sputtering deposition using the oxide sintered bodies obtained in the examples each had the following characteristics: the average transmittance and the average reflectance were low, and excellent light absorption ability was exhibited.
[ Industrial Applicability ]
The oxide thin film according to the embodiment of the present invention has the following excellent characteristics: low transmittance and reflectance, excellent light absorption ability, and high weather resistance, and can be processed by etching, and is not easily changed with time. In addition, the oxide sintered body according to the embodiment of the present invention has a high density, and thus can be used as a sputtering target. The oxide thin film according to the embodiment of the present invention is very useful as a light-absorbing film for preventing reflection of light by metal wiring used in a liquid crystal display, a plasma display, an organic EL display, a touch panel, a solar cell, or the like, and is also very useful as a photomask material or a decorative material.
Claims (12)
1. An oxide thin film comprising Nb, Mo and O, wherein the content ratio (atomic ratio) of Nb to Mo is 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8, and the content ratio (atomic ratio) of O to a metal (Nb + Mo) is 1.5 < O/(Nb + Mo) < 2.0.
2. The oxide thin film according to claim 1, wherein the oxide thin film has an average reflectance of 30% or less in a visible light region (wavelength: 380nm to 780 nm).
3. The oxide thin film according to claim 1 or 2, wherein the oxide thin film has an average transmittance of 20% or less in a visible light region (wavelength: 380nm to 780 nm).
4. The oxide thin film according to any one of claims 1 to 3, wherein the oxide thin film has a surface resistivity of 1.0 x 105Omega/□ or less.
5. The oxide thin film according to any one of claims 1 to 4, wherein a change rate of an average reflectance in a visible light region (wavelength: 380nm to 780nm) before and after a constant temperature and humidity test of the oxide thin film is 30% or less.
6. The oxide thin film according to any one of claims 1 to 5, wherein a change rate of an average transmittance in a visible light region (wavelength: 380nm to 780nm) before and after a constant temperature and humidity test of the oxide thin film is 30% or less.
7. The oxide thin film according to any one of claims 1 to 6, wherein a rate of change in surface resistivity of the oxide thin film before and after a constant temperature and humidity test is 30% or less.
8. The oxide thin film according to any one of claims 1 to 7, wherein the oxide thin film has a film thickness of 20nm to 2000 nm.
9. The oxide thin film according to any one of claims 1 to 8, wherein the oxide thin film is an amorphous thin film.
10. An oxide sintered body comprising Nb, Mo and O, characterized in that the content ratio (atomic ratio) of Nb to Mo is 0.1. ltoreq. Nb/(Nb + Mo). ltoreq.0.8, the content ratio (atomic ratio) of O to metal (Nb + Mo) is 1.5 < O/(Nb + Mo) < 2.1, MoO2XRD peak intensity I of phase belonging to (-111) planeMoO2With background intensity IBGSatisfy the relationship of IMoO2/IBG＞3。
11. The oxide sintered body according to claim 10, wherein the relative density of the oxide sintered body is 80% or more.
12. The oxide sintered body according to claim 10 or 11, wherein a volume resistivity of the oxide sintered body is 100m Ω · cm or less.
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| CN115819083A (en) * | 2021-09-16 | 2023-03-21 | Lt金属株式会社 | Molybdenum oxide-based sintered body, thin film using the sintered body, thin film transistor including the thin film, and display device |
| CN114845861B (en) * | 2019-12-18 | 2024-03-15 | Ａｇｃ株式会社 | Transparent substrate with multilayer film |
| PL443400A1 (en) * | 2023-01-02 | 2024-07-08 | Politechnika Gdańska | Method for producing crystalline layers of molybdenum trioxide |
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| KR102315283B1 (en) * | 2020-12-10 | 2021-10-21 | 엘티메탈 주식회사 | Metal oxide thin film containing molybdenum oxide as the main component, and thin film transistors and display devices in which such thin films are formed |
| KR102315308B1 (en) * | 2020-12-10 | 2021-10-21 | 엘티메탈 주식회사 | Metal oxide sintered body containing molybdenum oxide as the main component and sputtering target comprising the same |
| CN114916228B (en) * | 2020-12-10 | 2023-08-15 | Lt金属株式会社 | Metal oxide sintered body containing molybdenum oxide as main component and sputtering target material containing same |
| TWI839845B (en) * | 2021-10-06 | 2024-04-21 | 南韓商Ｌｔ金屬股份有限公司 | Molybdenum oxide based sintered body, sputtering target, oxide thin film using the sintered body, and thin film transistors and display devices including the thin films |
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| WO1997008359A1 (en) * | 1995-08-23 | 1997-03-06 | Asahi Glass Company Ltd. | Target, process for production thereof, and method of forming highly refractive film |
| JP2001073125A (en) * | 1999-09-08 | 2001-03-21 | Nikko Materials Co Ltd | Co-Ta ALLOY SPUTTERING TARGET AND ITS PRODUCTION |
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| CN114845861B (en) * | 2019-12-18 | 2024-03-15 | Ａｇｃ株式会社 | Transparent substrate with multilayer film |
| CN115819083A (en) * | 2021-09-16 | 2023-03-21 | Lt金属株式会社 | Molybdenum oxide-based sintered body, thin film using the sintered body, thin film transistor including the thin film, and display device |
| CN115819083B (en) * | 2021-09-16 | 2024-03-15 | Lt金属株式会社 | Molybdenum oxide-based sintered body, thin film using the sintered body, thin film transistor including the thin film, and display device |
| PL443400A1 (en) * | 2023-01-02 | 2024-07-08 | Politechnika Gdańska | Method for producing crystalline layers of molybdenum trioxide |
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| JP6767723B2 (en) | 2020-10-14 |
| KR102225493B1 (en) | 2021-03-10 |
| JPWO2019176552A1 (en) | 2020-04-16 |
| TWI700382B (en) | 2020-08-01 |
| WO2019176552A1 (en) | 2019-09-19 |
| TW201938823A (en) | 2019-10-01 |
| KR20210019126A (en) | 2021-02-19 |
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