CN115819083B - Molybdenum oxide-based sintered body, thin film using the sintered body, thin film transistor including the thin film, and display device - Google Patents
Molybdenum oxide-based sintered body, thin film using the sintered body, thin film transistor including the thin film, and display device Download PDFInfo
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- 239000010409 thin film Substances 0.000 title claims abstract description 43
- 229910000476 molybdenum oxide Inorganic materials 0.000 title claims abstract description 39
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910044991 metal oxide Inorganic materials 0.000 claims description 41
- 150000004706 metal oxides Chemical class 0.000 claims description 41
- 239000010408 film Substances 0.000 claims description 35
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 238000005477 sputtering target Methods 0.000 claims description 11
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 7
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000001579 optical reflectometry Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 16
- 239000000843 powder Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 238000005245 sintering Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 238000004544 sputter deposition Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- -1 MoO 2 Chemical compound 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000007580 dry-mixing Methods 0.000 description 1
- 239000007772 electrode material Substances 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
- 238000011068 loading method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
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Abstract
The present invention relates to a molybdenum oxide-based sintered body having low reflection and excellent chemical resistance and heat resistance, a thin film using the sintered body, a thin film transistor including the thin film, and a display device.
Description
Technical Field
The present invention relates to a molybdenum oxide-based sintered body having low reflection and excellent chemical resistance and heat resistance, a thin film using the sintered body, a thin film transistor including the thin film, and a display device.
Background
In general, flat panel displays (FPD, flat panel display), touch screen panels, solar cells, light emitting diodes (LED, light emitting diode), organic light emitting diodes (OLED, organic light emitting diode) use conductive films with low reflectivity.
As a representative material, indium tin oxide (ITO, in) 2 O 3 -SnO 2 ) The indium tin oxide composition is used for forming a conductive film with high visible light transmittance and high conductivity. Although such an indium tin oxide composition has excellent low reflection properties, it has a problem of low economy, and thus, there is a continuing study on materials that replace all or part of indium oxide.
However, in such studies, a portion of interest mainly relates to low reflectivity of a thin film formed of a target, and therefore, when used for a long time, it is actually necessary to consider characteristics of chemical resistance, heat resistance, and the like in order to increase the reliability of the thin film.
Prior art literature
Patent literature
Patent document 0001: korean laid-open patent No. 10-2008-0058390
Disclosure of Invention
Technical problem
On the other hand, the present inventors have noted that the existing molybdenum oxide target material exhibits low reflection characteristics, but is relatively poor in heat resistance and chemical resistance.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a sintered body for a sputtering target, a metal oxide thin film formed by the sintered body, and a thin film transistor and a display device each having the metal oxide thin film formed thereon, each of which is formed by mixing a specific metal oxide and a metal in a predetermined range with molybdenum oxide as main materials.
Other objects and advantages of the present invention will become more apparent from the following detailed description and the scope of the invention as claimed.
Technical proposal
In order to achieve the above technical object, the present invention provides an oxide sintered body comprising: molybdenum oxide comprising MoO 2 And MoO 3 Above MoO 2 MoO (MoO) 3 In MoO (MoO) 2 The content of (2) is 50 to 90 weight percent; metal oxide M1 selected from Nb 2 O 5 、Ta 2 O 5 、ZrO 2 、TiO 2 、SnO 2 WO (WO) 3 More than one kind of the group; and a metal M2 which is at least 70 weight percent or more of molybdenum oxide relative to the total weight of the corresponding sintered body, and is selected from one or more of Mo, ti, cr, W and Cu.
According to an embodiment of the present invention, the above metal M2 may be contained in an amount of 1.0 to 5.0 weight percent with respect to 100 weight percent of the corresponding oxide sintered body.
According to an embodiment of the present invention, the oxide sintered body includes 95.0 to 99.0 weight percent of the molybdenum oxide and the metal oxide M1 with respect to 100 weight percent of the corresponding oxide sintered body, and the content ratio of the molybdenum oxide to the metal oxide M1 may be 75:25 to 90:10 weight ratio.
According to an embodiment of the present invention, the oxide sintered body has a resistivity of 1×10 -2 The relative density may be 95% or more at an Ω cm or less.
The present invention also provides a sputtering target comprising the sintered body.
The present invention also provides an oxide thin film made of the sputtering target.
According to an embodiment of the present invention, the oxide film may be used for one of the gate layer, the source layer and the drain layer.
The present invention also provides a display device including the oxide thin film.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the embodiment of the present invention, by adding a specific metal oxide M1 and a metal 2 in a prescribed range to a mixture of molybdenum oxide as main components, the sinterability of the molybdenum oxide-based sintered body can be improved and a high density can be ensured.
The film made of the sintered body has low reflection characteristics and excellent heat resistance and chemical resistance. Thus, the operation reliability of the thin film transistor or the display device made of the above thin film can be ensured.
In addition, other effects of the present invention can be clearly understood by those skilled in the art to which the present invention pertains from the following detailed contents or in the course of carrying out the present invention.
Drawings
Fig. 1 is a graph showing that the reflectance after the hydrogen heat treatment varies based on whether or not the metal M2 is contained.
Detailed Description
The present invention will be described in detail below.
All terms (including technical and scientific terms) used in this specification have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Also, terms defined in a dictionary generally used should be interpreted as having the same meaning as the related art having on the text, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In the entire specification, when a certain portion "includes" other structural elements, unless the specific contrary is stated, the other structural elements are also included, and other structural elements are not excluded. In the present specification, "above" or "upper" means not only above or below the target portion but also other portions in the middle thereof, and does not mean above with respect to the gravitational direction. In the present specification, the terms "first", "second", and the like are used only to distinguish structural elements, and do not indicate any order or importance.
Sintered body and sputtering target
In one example of the present invention, a metal oxide sintered body is used for producing a sputtering target containing molybdenum oxide as a main component.
According to one embodiment, the sintered body includes: molybdenum oxide comprising MoO 2 And MoO 3 Above MoO 2 MoO (MoO) 3 In MoO (MoO) 2 The content of (2) is 50 to 90 weight percent; metal oxide M1 selected from Nb 2 O 5 、Ta 2 O 5 、ZrO 2 、TiO 2 、SnO 2 WO (WO) 3 More than one kind of the group; and a metal M2 containing at least 70 wt% or more of molybdenum oxide as a main component, based on the total weight of the sintered body.
In the case of forming a thin film using the above metal oxide sintered body as a target, the formed thin film has low reflection characteristics, and at the same time, heat resistance and chemical resistance are improved by optimizing the proportion and composition of molybdenum oxide.
The components are described in detail below.
Molybdenum oxide as a component of molybdenum combined with oxygen, e.g. MoO 2 、MoO 3 、MoO 4 Etc. The molybdenum oxide in the invention comprises MoO 2 、MoO 3 。
For MoO constituting the above molybdenum oxide 2 And MoO 3 Content of MoO 2 50 to 90 weight percent MoO 3 From 10 to 50 weight percent. In MoO 2 In the case where the content is less than 50% by weight, the content is due to MoO 3 The increase in the content causes a decrease in the sintering density, and therefore, when a thin film is evaporated, chemical stability is not desirable. On the other hand, in MoO 2 In the case where the content is more than 90 weight%, the sintered density may be due to MoO 2 The increase in the content increases, but as the strength of the target decreases, cracks may be generated in the target. On the other hand, according to MoO 2 /MoO 3 The weight percentage shows that the proportion is 1-16.
One of the additive components contained in the oxide sintered body of the present invention is a metal oxide M1, and the metal oxide M1 is Nb 2 O 5 、Ta 2 O 5 、ZrO 2 、TiO 2 、SnO 2 WO (WO) 3 More than one kind of the group.
The metal oxide M1 is used as an oxidation dopant to improve properties such as chemical resistance and heat resistance, and the chemical resistance and heat resistance of molybdenum oxide can be improved by adding the metal oxide. In the following description, nb will be denoted by the reference numeral M1 2 O 5 、Ta 2 O 5 、ZrO 2 、TiO 2 、SnO 2 WO (WO) 3 More than one component of the composition.
The other additive component included in the oxide sintered body of the present invention is at least one metal M2 selected from the group consisting of Mo, ti, cr, W and Cu.
The metal M2 has an effect of improving the sintering property and density of molybdenum oxide as a metal dopant, and can improve the chemical resistance, heat resistance, and other properties of molybdenum oxide by adding the metal. In the following description, one or more components of Mo, ti, cr, W and Cu will be denoted by reference numeral M2.
In the metal oxide sintered body including the above molybdenum oxide, the metal oxide M1, and the metal M2, 95.0 to 99.0 weight percent of the molybdenum oxide and the metal oxide are included with respect to 100 weight percent of the corresponding sintered body; comprising 1.0 to 5.0 weight percent of metal M2. Wherein, the content ratio of the molybdenum oxide and the metal oxide M1 can be 75:25 to 90:10 weight ratio. When the proportion of molybdenum oxide occupies 75 weight percent or more with respect to the total weight of the corresponding metal oxide sintered body, low reflection characteristics can be obtained in the case of vapor deposition of a thin film.
The oxide sintered body of the present invention formed in the above manner has a relative density of 95% or more, and the upper limit thereof is not limited. And the resistivity of the oxide sintered body was 1×10 -2 The lower limit of Ω cm or less is not limited. The crystal grain size included in the oxide sintered body is not limited, and may be, for example, 1 μm to 20 μm, specifically, 1 μm to 10 μm.
Furthermore, a sputtering target according to still another embodiment of the present invention includes: an oxide sintered body containing the molybdenum oxide as a main component; and a backing plate bonded to one surface of the sintered body for supporting the sintered body.
Among them, the backing plate used as a substrate for supporting the sintered body for sputtering target can be used without limitation. In this case, the material constituting the pad and the shape thereof are not particularly limited.
Oxide sintered body and method for producing sputtering target
The following describes a method for producing an oxide sintered body and a sputtering target according to an embodiment of the present invention. However, the method is not limited to the following production method, and the steps of each step may be changed or mixed as needed.
As a preferred embodiment, the above preparation method may include: a first step (i) of mixing molybdenum oxide, at least one metal oxide M1 and at least one metal M2; a second step (ii) of sintering the mixed raw material powder; a third step (iii) of processing a sintered body obtained by sintering the material powder; and a fourth step (iv) of welding the sintered body to the backing plate to complete the target.
The above-described production method will be described below in terms of the respective steps.
First, in a first step, a mixture of MoO according to a desired chemical composition 2 And MoO 3 Molybdenum oxide powder; nb (Nb) 2 O 5 、Ta 2 O 5 、ZrO 2 、TiO 2 、SnO 2 WO (WO) 3 More than one metal oxide M1 in the powder; and one or more metals M2 of Mo, ti, cr, W and Cu are weighed and mixed.
Specifically, the above raw material powder contains 95.0 to 99.0 weight percent of molybdenum oxide and metal oxide M1;1.0 to 5.0 weight percent of metal M2, the mixing ratio of the molybdenum oxide and the metal oxide M1 may be 75:25 to 90:10 weight ratio. In this case, in the molybdenum oxide powder, moO 2 The proportion of (c) may be 50 to 90 weight percent.
According to one embodiment, in the first step described above, the molybdenum oxide and the metal oxide M1 are weighed so that (MoO 2 +MoO 3 +M1)/(MoO 2 +MoO 3 ) The proportion by weight is changed to 1.03% to 1.30%.
Next, a metal powder M2 is added to the mixed raw material powder, and the metal powder M2 is weighed so that the metal powder M2 (MoO 2 +MoO 3 +M1+M2)/(MoO 2 +MoO 3 The proportion of +m1) by weight becomes 1.03% to 1.3%. Wherein MoO 2 Content of (2) and MoO 3 The content of (2) is the same in the numerator and denominator, respectively. A dry ball milling process may be performed on the mixed powder using zirconia balls.
Zirconia balls can be weighed 1 to 3 times the amount of powder and ball milling can be performed at a speed of 100 to 300rpm for 7 to 9 hours. After dry ball milling is completed, powder mixing can be completed by sieving.
Subsequently, in the second step, in order to sinter the mixed powder, a carbon sheet of 0.1mm to 0.5mm may be wound into the inside of the carbon mold and the lower punch and 100g to 300g of the mixed powder may be charged. After loading the powder, the carbon sheet was covered and an upper punch was set.
If the preparation of the sintering mold is completed through the process as described above, the sintering mold may be loaded into the hot press to perform the sintering process. During sintering, the heating rate is 2-10 ℃/min, the highest heat treatment temperature is 700-900 ℃, and the sintering can be maintained for 1-3 hours. In the process of raising and maintaining the temperature, the pressure can be maintained at 20 Mpa-50 Mpa.
Then, in the third step, the sintered body after the sintering is taken out and processed. Specifically, after taking out the sintered body, taking out the carbon sheets on the upper and lower parts of the target, and polishing the surface of the target. In order to remove the carbon sheet, the upper and lower portions may be processed by 1mm or more, respectively.
Next, in a fourth step, the processed sintered body is welded to the backing plate.
Preferably, indium can be used as the binder so that the soldering ratio reaches 95% or more.
The metal oxide target can be manufactured by the above-described process. Preferably, the target density of the produced target is 95% or more, in particular 97.5% or more.
Oxide film
In another example of the present invention, the metal oxide thin film is formed by vapor deposition of the molybdenum oxide-based target. Sputtering may be performed using the above sintered body as a target to form the above metal oxide thin film.
The composition of the oxide thin film may vary slightly with the vapor deposition atmosphere, and the oxide target is produced by sputtering, so that the actual composition is the same as that of the target. Thus, a high density and a relative density of more than 95% and a 1X 10 characteristic can be obtained -2 An oxide film having excellent resistance characteristics of Ω cm or less. Further, by adding a specific metal oxide and a metal in a predetermined range to molybdenum oxide as a main material, the proportion and composition of molybdenum oxide can be optimized to improve chemical resistance and heat resistance.
According to one embodiment, the light reflectance change rate Δr of the oxide thin film after heat treatment at a temperature of 350 ℃ for 30 minutes or more may be 30% or less, specifically 20% or less, more specifically 15% or less, as calculated by the following formula 1:
formula 1:
light reflectance change ratio (Δr,%) = (R 2 －R 1 )/R 1 ×100
In the above-mentioned embodiment 1, the first and second heat exchangers,
R 1 for the light reflectance of the film before heat treatment at a wavelength of 550nm,
R 2 is the light reflectivity of the heat-treated film at 550nm wavelength.
Specifically, the oxide film has a light reflectance R at 550nm 1 Is 10.5% or less, more specifically, 10.4% or less. And after heat treatment at a temperature of 350 ℃ for 30 minutes or more, the light reflectance R at a wavelength of 550nm 2 May be 12.5% or less, and more specifically, may be 12% or less. In this case, the light reflectance R 1 、R 2 The lower limit value of the light reflectance change rate Δr is not particularly limited.
On the other hand, the light reflectance is measured based on an average wavelength of 360nm to 740nm and/or a wavelength of 550nm, but is not limited thereto.
The metal oxide film of the present invention can be deposited by a sputtering method generally used in the art. In this case, sputtering may be performed using a direct current sputtering machine (DC sputtering).
The metal oxide film may be used for at least one of a gate layer, a source layer, and a drain layer of a Thin Film Transistor (TFT). In addition, the thin film transistor can be used for display devices such as an organic light emitting diode television (OLED TV), a mobile phone, a tablet personal computer and the like.
As a specific example, the metal oxide thin film of the embodiment of the present invention may be used for a low reflection layer in the lower portion of the gate layer. The thin film having the above-mentioned use not only reduces the reflectance of the substrate but also improves the adhesiveness of the gate electrode.
The substrate may be one of various substrates commonly used in the process of display devices, for example, a glass plate, a metal plate, a plastic film, or the like. Specifically, the substrate may be a transparent front panel for an organic light emitting diode television, a mobile phone or a tablet computer. On the other hand, the gate electrode may be made of a common electrode material such as copper, silver, or the like.
Film deposition can be performed by setting the Power density (Power density) of a DC sputtering machine to 1.0w/cm 2 ～2.0w/cm 2 And is performed under normal temperature conditions in an argon (Ar Gas) atmosphere. At this time, the thickness of the metal oxide film may beTo->However, the present invention is not limited thereto. Further, a copper (Cu) film may be deposited over the metal oxide film. In this case, the copper film can be evaporated to +.>To->Is a thickness of (c).
On the other hand, the measurement of the reflectance may be performed by a method known in the art. As an example, the light reflectance at an average wavelength of 360nm to 740nm and/or a wavelength of 550nm can be measured on the surface of the substrate on which the metal oxide thin film is formed. In this case, the light reflectance is 10.5% or less.
The metal oxide film of the embodiment of the invention has excellent heat resistance and chemical resistance. Although the evaluation of heat resistance and chemical resistance may be performed as follows, it is not limited thereto.
For evaluating the heat resistance, a method of heat-treating a film deposited in the above manner in an atmosphere of 200 to 400 ℃ for 30 minutes or more may be used. Typically, the heat treatment may be performed in a vacuum heat treatment furnace and/or a hydrogen heat treatment furnace. After heat treatment, can be observed byThe heat resistance was evaluated by observing the change in the characteristics of the film. As an example of the heat resistance index, reflectance R after heat treatment 2 And reflectance R before heat treatment 1 Difference (R) 2 －R 1 ) It is approximately 1.5% or less, specifically, 1.2% or less. The evaluation may also be performed based on the reflectance change rate Δr calculated by the above equation 1.
Also, in order to evaluate chemical resistance, a micro pattern may be formed on the formed thin film using a photolithography method and a cross section of the formed micro pattern may be observed. Specifically, a photoresist (Positive PR Strip) having a thickness of 1 μm to 2 μm is coated on the film of the present invention formed of two layers of metal oxide and copper, and then baked (back) at a temperature of 60℃to 80℃for 0.5 hours to 2 hours to cure the photoresist. Subsequently, an alignment mask (PRMask) is exposed to form a pattern having a prescribed line width. Such a pattern may be etched (etching) to form a two-layer micropattern comprised of metal oxide and copper. After the photoresist is removed from the substrate having the micropattern formed in the above-described manner, a cross section of the metal oxide in the micropattern may be observed using FIB-SEM. Thus, the film of the present invention does not generate residues even after etching, and thus chemical resistance can be evaluated.
The present invention will be described in detail with reference to examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited to the following examples.
Example 1
Weigh the powder so that MoO 2 /MoO 3 The weight percentage ratio becomes 6.8, (MoO) 2 +MoO 3 +Nb 2 O 5 +Mo)/(MoO 2 +MoO 3 +Nb 2 O 5 ) The weight percentage ratio was changed to 1.05. The weighed powder was placed in a 1L plastic cylinder and alumina balls were put in an amount of three times the amount of the powder. Alumina balls of 3mm to 10mm are used. When the weighed powder and balls were put into the mixer, dry mixing was performed at a speed of 170rpm to 230rpm for 8 hours by a ball mill. Subsequently, the obtained dry powder was pressure sintered by a Hot Press (Hot Press). In this case, the internal vacuum condition of the hot press was 10 - 1 the temperature rising speed is 3-7 ℃, the highest temperature is 750-800 ℃, the maintaining time is 1-3 hours, and after sintering, furnace cooling is carried out.
The measurement results show that: the metal oxide sintered body of example 1 obtained in the above manner had a sintered density of 97.6% and a resistivity of 1.15X10 -3 Ωcm。
Example 2
Except for using MoO 2 /MoO 3 The weight percentage ratio becomes 6.6, (MoO) 2 +MoO 3 +Nb 2 O 5 +Mo)/(MoO 2 +MoO 3 +Nb 2 O 5 ) A sintered body of example 2 was produced in the same manner as in example 1 above, except that the weight percentage ratio was changed from 1.05 to 1.08.
The measurement results show that: the sintered body of example 2 obtained in the above manner had a sintered density of 97.8% and a resistivity of 1.2X10 -3 Ωcm。
Example 3
Except for using MoO 2 /MoO 3 The weight percentage ratio was changed to 6.5, (MoO) 2 +MoO 3 +Nb 2 O 5 +Mo)/(MoO 2 +MoO 3 +Nb 2 O 5 ) A sintered body of example 3 was produced in the same manner as in example 1 above, except that the weight percentage ratio was changed from 1.05 to 1.18.
The measurement results show that: the sintered body of example 3 obtained in the above manner had a sintered density of 99.9% and a resistivity of 1.07×10 -3 Ωcm。
Comparative example 1
Except that Mo metal is not used (MoO) 2 +MoO 3 +Nb 2 O 5 )/(MoO 2 +MoO 3 +Nb 2 O 5 ) A sintered body of comparative example 1 was produced in the same manner as in example 1 above except that the powder was weighed in a proportion of 1 by weight.
The measurement results show that: the sintered body of comparative example 1 obtained in the above manner had a sintered density of 96.1% and a resistivity of 1.27×10 -3 Ωcm。
Experimental example 1: evaluation of physical Properties of sintered body
Table 1 below shows the physical properties of the sintered bodies prepared in examples 1 to 3 and comparative example 1.
TABLE 1
As shown in Table 1 above, in both the examples and comparative examples, the resistivity was a reference value of 1X 10 -2 Omega cm or less, and the target density is 95% or more. However, it was confirmed that examples 1 to 3 were superior to comparative example 1 in terms of target density, and that the resistivity was also lower than comparative example 1. From this, it is understood that examples 1 to 3, in which the target density is relatively high, are more stable in terms of plasma formation when the thin film is evaporated.
Experimental example 2: evaluation of physical Properties of film
After forming a thin film using the sintered bodies prepared in examples 1 to 3 and comparative example 1 as a target, the heat resistance of the thin film can be evaluated in the following manner.
Specifically, a thin film of a low reflection layer in the lower portion of the gate layer was prepared using each sintered body. Such films are used to improve the adhesion of the low reflection and gate electrode to the substrate (glass).
The low reflection film was formed at 0.5w/cm by using a DC sputtering machine 2 ～3.6w/cm 2 The Power density (Power density) of the sintered body of examples 1 to 3 and comparative example 1 was deposited on a transparent glass substrate in an argon atmosphere to form a thin film, and the deposited thin film had a thickness of
Subsequently, an electrode is formed on the above film. The electrode was sputtered at 0.5w/cm using a DC sputtering machine via a copper target 2 ～3.6w/cm 2 Power density (Power density) of (A) is formed under an argon atmosphere, and the film thickness is
In this state, after the initial reflectance of the thin film was measured on the surface of the glass substrate, the film was heat-treated at a temperature of 350 ℃ for 30 minutes or more in a vacuum heat treatment furnace, and then the reflectance was measured again to compare the two reflectances. In this case, the reflectance was calculated based on the reflectance values at the average wavelength of 360nm to 740nm and/or at the wavelength of 550nm, and the results thereof are shown in table 2 below.
TABLE 2
As shown in table 2 above, although the initial reflectance of comparative example 1 was relatively excellent, the reflectance thereof was greatly increased after heat treatment.
In contrast, the initial reflectances of examples 1 to 3 were all excellent, and the reflectance after heat treatment was not greatly changed. In particular, in the case of examples, the change between the reflectance and the initial reflectance was 10% or less after heat treatment at a temperature of 350 ℃ for 30 minutes or more in the hydrogen heat treatment furnace, and it was found that the film characteristics were more excellent than those of the comparative examples.
Claims (7)
1. An oxide sintered body characterized in that,
the raw materials comprise:
molybdenum oxide comprising MoO 2 And MoO 3 Above MoO 2 MoO (MoO) 3 In MoO (MoO) 2 Is 50 to 90 weight percent MoO 3 Is present in an amount of 10 to 50 weight percent;
metal oxide M1 selected from Nb 2 O 5 、Ta 2 O 5 、ZrO 2 、TiO 2 、SnO 2 WO (WO) 3 More than one kind of the group; and
metal M2 is at least one selected from the group consisting of Mo, ti, cr, W and Cu,
at least 70 weight percent or more of molybdenum oxide relative to the total weight of the corresponding sintered body;
the mixing ratio of the molybdenum oxide and the metal oxide M1 is 75:25 to 90:10 by weight, (MoO 2 + MoO 3 + M1) / (MoO 2 + MoO 3 ) The proportion by weight is 1.03% to 1.30%, and (MoO) 2 + MoO 3 + M1 + M2) / (MoO 2 + MoO 3 The proportion of +M1) is 1.03 to 1.3% by weight;
the oxide sintered body has a resistivity of 1×10 -2 Omega cm or less, and a relative density of 95% or more.
2. A sputtering target comprising the sintered body according to claim 1.
3. An oxide film made from the sputtering target of claim 2.
4. The oxide film according to claim 3, wherein,
after heat treatment at a temperature of 350 ℃ for 30 minutes or more, the light reflectance change rate Δr is 30% or less, which is calculated by the following formula 1:
formula 1:
light reflectance change ratio (Δr,%) = (R 2 －R 1 ）/R 1 ×100
In the above-mentioned embodiment 1, the first and second heat exchangers,
R 1 for the light reflectance of the film before heat treatment at a wavelength of 550nm,
R 2 is the light reflectivity of the heat-treated film at 550nm wavelength.
5. The oxide film according to claim 3, wherein,
light reflectivity R at 550nm wavelength before heat treatment 1 Is less than or equal to 10.5 percent,
after heat treatment at a temperature of 350 ℃ for 30 minutes or more, the light reflectance R at a wavelength of 550nm 2 Is less than 12.5%.
6. A thin film transistor, wherein the oxide film according to claim 3 is used as one of a gate layer, a source layer, and a drain layer.
7. A display device comprising the oxide film according to claim 3.
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