WO2023063774A1 - Corps fritté à base d'oxyde de molybdène, et cible de pulvérisation et film mince d'oxyde le comprenant - Google Patents

Corps fritté à base d'oxyde de molybdène, et cible de pulvérisation et film mince d'oxyde le comprenant Download PDF

Info

Publication number
WO2023063774A1
WO2023063774A1 PCT/KR2022/015592 KR2022015592W WO2023063774A1 WO 2023063774 A1 WO2023063774 A1 WO 2023063774A1 KR 2022015592 W KR2022015592 W KR 2022015592W WO 2023063774 A1 WO2023063774 A1 WO 2023063774A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide
sintered body
metal oxide
thin film
weight
Prior art date
Application number
PCT/KR2022/015592
Other languages
English (en)
Korean (ko)
Inventor
황병진
이승이
이효원
장봉중
전봉준
진승현
박재성
양승호
Original Assignee
엘티메탈 주식회사
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 엘티메탈 주식회사 filed Critical 엘티메탈 주식회사
Priority claimed from KR1020220132119A external-priority patent/KR20230054290A/ko
Publication of WO2023063774A1 publication Critical patent/WO2023063774A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • 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
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00

Definitions

  • the present invention relates to an oxide sintered body containing molybdenum oxide as a main component, a sputtering target including the sintered body, and an oxide thin film formed therefrom, and more particularly, to manufacturing a sputtering target used in TFT structures of LCD and OLED. It relates to a molybdenum oxide-based sintered body with improved sinterability and density characteristics by adding a specific (semi)metal oxide in a predetermined range, a sputtering target, and an oxide thin film formed therefrom.
  • FPD flat panel displays
  • LEDs light emitting diodes
  • OLEDs organic light emitting diodes
  • ITO indium oxide-tin oxide
  • ITO composition is used to form a conductive thin film having high visible light transmittance and electrical conductivity.
  • ITO compositions have excellent low-reflectance performance, they are not economically viable, so research on materials that replace all or part of indium oxide continues.
  • molybdenum oxide is a difficult-to-sinter material that is difficult to sinter itself.
  • a molybdenum oxide-based ceramic material that is difficult to sinter and has a low density
  • foreign matter is generated due to the generation of nodules, which inevitably leads to deterioration of physical properties of the thin film.
  • Patent Document 1 Republic of Korea Patent Publication No. 10-2020-0069314
  • the present invention has been made to solve the above problems, and by adding a specific (semi)metal oxide in a predetermined range to difficult-to-sinterable molybdenum oxide, which is a main raw material, sinterability is improved and high density can be secured even when sintered in a non-pressurized state. It is a technical task to provide a novel molybdenum oxide-based sintered body that can be used, a sputtering target including the sintered body, and an oxide thin film formed therefrom.
  • the present invention MoO 2 And MoO 3 Molybdenum oxide containing at least one of (M1); niobium oxide (M2); and a metal oxide (M3) containing at least one kind of alkaline earth metal, and provides an oxide sintered body containing at least 70% by weight of molybdenum oxide (M1) based on the total weight of the sintered body.
  • the metal oxide M3 may include a first metal oxide M3-1 including at least one of Ca and Mg.
  • the first metal oxide (M3-1) may include at least one selected from the group consisting of CaCO 3 and MgO.
  • the metal oxide (M3) may include a first metal oxide (M3-1); and a second metal oxide (M3-2) containing at least one metal selected from the group consisting of Co, Si, Y, and Ga.
  • the second metal oxide (M3-2) may include at least one selected from the group consisting of Co 3 O 4 , SiO 2 , Y 2 O 3 , and Ga 2 O 3 . there is.
  • the metal oxide (M3) may be included in an amount greater than 0 wt% and less than 10.0 wt% based on 100 wt% of the sintered body.
  • the molybdenum oxide (M1) and the niobium oxide (M2) are included in 90.0% by weight or more and less than 100% by weight based on 100% by weight of the oxide sintered body, and the molybdenum oxide (M1 ) and the niobium oxide (M2) may be in a weight ratio of 50:50 to 90:10.
  • the oxide sintered body molybdenum oxide (M1); niobium oxide (M2); And the metal oxide (M3) may be mixed and molded, and then non-pressure sintered.
  • the oxide sintered body may have a specific resistance of 1 ⁇ 10 -2 ⁇ cm or less and a relative density of 80% or more.
  • the present invention provides a sputtering target comprising the above-mentioned pressure-free sintered body.
  • the present invention provides an oxide thin film formed from the sputtering target.
  • the molybdenum oxide-based sintered body and sputtering target according to the present invention can be usefully applied to forming electrodes or wires used in TFT structures of LCDs and OLEDs.
  • Example 1 is a photograph showing the structure change of a sintered body according to the heat treatment temperature using the molded body of Example 9 to which a metal oxide (M3) is added.
  • Example 3 is a SEM photograph showing the fractured surface of the powder structure of the mixed raw materials, the structure of the non-pressurized sintered body prepared in Example 9, and the structure of the pressed sintered body prepared in Comparative Example 5, respectively.
  • Example 4 is a SEM photograph showing the polished surface of the structure of the non-pressurized sintered body prepared in Example 9 and the structure of the pressurized sintered body prepared in Comparative Example 5, respectively.
  • FIG 11 is a graph showing the change in shrinkage according to the sintering temperature of the non-pressurized sintered body prepared in Examples 13 to 18.
  • Example 13 is an XRD graph showing each crystal structure of the non-pressurized sintered body prepared in Example 9 and the pressed sintered body prepared in Comparative Examples 1 and 5.
  • Example 16 is an image of an etching evaluation result of a double film prepared with the compositions of Example 9 and Comparative Example 1.
  • MoO 2 -Nb 2 O 5 material used as a conventional n-type semiconductor thin film is generally manufactured through a pressure sintering method.
  • the pressure sintering method it is not suitable in terms of mass productivity as the manufacturing process cost increases according to the equipment value.
  • the present invention is a molybdenum oxide-based sintered body that can simultaneously improve sinterability and secure high density by using a small amount of a specific dopant (M3) that assists sinterability in a difficult-to-sinter material having molybdenum oxide and niobium oxide as basic compositions. And it can provide a sputtering target using the same.
  • M3 specific dopant
  • the alkaline earth metal-based oxide dopant (M3) used in the present invention assists in securing the sintering driving force of MoO 2 /MoO 3 -Nb 2 O 5 , which is a sinter-resistant material, so that even if pressureless sintering is performed, the temperature drop effect is reduced. sintering density can be improved.
  • the molybdenum oxide sintered body of the present invention may have superior density and resistivity compared to a sintered body that does not contain a specific metal oxide (M3), and in particular, even if a pressureless sintered body is formed only by heat treatment without pressure, Density characteristics and resistivity characteristics equivalent to or higher than those of the oxide sintered body subjected to conventional pressure sintering (eg, HP, HIP, etc.) can be secured.
  • a pressureless sintered body is formed only by heat treatment without pressure
  • Density characteristics and resistivity characteristics equivalent to or higher than those of the oxide sintered body subjected to conventional pressure sintering eg, HP, HIP, etc.
  • it is very excellent in terms of size and mass production of the sintered body, and has the advantage of low equipment cost.
  • the particle size of the crystal grains constituting the oxide sintered body of the present invention is larger than the grain size of the molybdenum oxide sintered body pressure-sintered by simultaneously applying a predetermined pressure and heat treatment, it is more advantageous in terms of reaction.
  • the pressurized sintered body is in the form of forcibly aggregating the initial raw materials by high pressure, so the size of the particles hardly increases, whereas the sintered body according to the present invention increases the size of the particles by the reaction It can be seen that has increased, and especially in the mutual reaction between different types of elements, it can be seen that it is advantageous in terms of reaction because the particles are combined in a complex form.
  • the molybdenum oxide target according to the present invention secures sinterability by adding a dopant, and can provide a high-density sintered target capable of sputtering even by non-pressure sintering.
  • An example of the present invention is a metal oxide sintered body for producing a target for sputtering containing molybdenum oxide as a main component.
  • This sintered body is distinguished from the conventional sintered body in that it contains a metal oxide (M3) containing at least one alkaline earth metal as an essential component.
  • the oxide sintered body MoO 2 And MoO 3 Molybdenum oxide containing at least one of (M1); niobium oxide (M2); and a metal oxide (M3) containing at least one kind of alkaline earth metal, and at least 70% by weight of molybdenum oxide (M1) based on the total weight of the sintered body.
  • the formed thin film has low reflection characteristics and at the same time, heat resistance and chemical resistance are improved through optimization of the ratio and composition of molybdenum oxide.
  • the density is improved by adding a small amount of a specific dopant (M3), pressure sintering is not required, and a Mo-Nb-O-based sputtering target, which is a difficult-to-sinter material, can be manufactured.
  • Molybdenum oxide contained in the oxide sintered body according to the present invention is a main component constituting the sintered body.
  • Molybdenum oxide (M1) is a component having a form in which oxygen is bonded to molybdenum, such as MoO 2 , MoO 3 , and MoO 4 .
  • molybdenum oxide (M1) MoO 2 , MoO 3 , or MoO 2 and Mixtures of MoO 3 may be used.
  • MoO 2 and MoO 3 as molybdenum oxide, the mixing ratio between them is not particularly limited and can be properly adjusted within a conventional content range known in the art.
  • MoO 3 has a melting point of about 800°C, it volatilizes at a high temperature of 1000°C or higher. Accordingly, in the present invention, it is preferable to use MoO 2 as the molybdenum oxide.
  • One of the additive components included in the oxide sintered body according to the present invention is niobium oxide (M2).
  • Niobium oxide (M2) is an oxide dopant that improves chemical resistance and heat resistance, and chemical resistance and heat resistance of molybdenum oxide can be improved by adding the metal oxide.
  • the niobium oxide is not particularly limited as long as it has a form in which oxygen is bonded to niobium, and may be, for example, Nb 2 O 5 . In the following description, the niobium oxide component is symbolized and expressed as M2.
  • Another of the additive components included in the oxide sintered body according to the present invention is a metal oxide (M3) containing at least one kind of alkaline earth metal.
  • the metal oxide M3 may include at least one of Ba, Ca, Mg, and Sr, and may specifically include the first metal oxide M3-1 including at least one of Ca and Mg.
  • the metal oxide M3 may include at least one of Ba, Ca, Mg, and Sr, and may specifically include the first metal oxide M3-1 including at least one of Ca and Mg.
  • the first metal oxide (M3-1) serves as a dopant to show a density increasing effect by assisting the sinterability of the difficult-to-sinterable molybdenum oxide. Chemical resistance and heat resistance characteristics of molybdenum oxide may be improved by adding the first metal oxide.
  • the first metal oxide (M3-1) is not particularly limited as long as it has a form in which oxygen is bonded to at least one element (A) of Ca and Mg, and is, for example, 1 selected from the group consisting of CaCO 3 and MgO. May include more than one species.
  • the metal oxide (M3) may include a first metal oxide (M3-1); and a second metal oxide (M3-2) containing at least one metal selected from the group consisting of Co, Si, Y, and Ga.
  • the second metal oxide (M3-2) may serve to increase the sinterability of molybdenum oxide by assisting the above-described first metal oxide.
  • the second metal oxide (M3-2) is not particularly limited as long as it has a form in which oxygen is bonded to at least one element of Co, Si, Y, and Ga.
  • Co 3 O 4 , SiO 2 , Y 2 It may include one or more selected from the group consisting of O 3 , and Ga 2 O 3 .
  • the mixing ratio thereof is not particularly limited, and for example, the weight ratio is 1: 0.3 to 2.5. , More specifically, it may be 1: 0.5 to 2.0 weight ratio.
  • the metal oxide sintered body including the above-described molybdenum oxide (M1), niobium oxide (M2), and (semi)metal oxide (M3) contains molybdenum oxide (M1) and niobium oxide (M2) based on 100% by weight of the sintered body. 90% by weight or more and less than 100% by weight, and (semi)metal oxide (M3) may be included in more than 0% by weight and less than 10% by weight. More specifically, 95.0 to 99.5% by weight of molybdenum oxide (M1) and niobium oxide (M2); and 0.5 to 5.0 wt% of (semi)metal oxide (M3).
  • the content ratio of molybdenum oxide (M1) and niobium oxide (M2) is 50:50 to 90:10 weight ratio, specifically 70:30 to 90:10 weight ratio, more specifically 75:25 to 90:10 weight ratio can be configured.
  • the ratio of molybdenum oxide occupies 70% by weight or more in the entire metal oxide sintered body, it may have low reflection characteristics when deposited as a thin film.
  • the oxide sintered body according to the present invention configured as described above has a relative density of 80% or more, even when pressure-free sintering is performed, and specifically may be 90% or more.
  • the upper limit is not particularly limited.
  • the specific resistance of the oxide sintered body is 1 ⁇ 10 -2 ⁇ cm or less, and the lower limit thereof is not particularly limited.
  • the size (D50) of crystal grains included in the oxide sintered body is not particularly limited, and may be, for example, 1 to 30 ⁇ m.
  • the crystal grain size of the sintered body prepared under pressurized conditions may be 1 to 3 ⁇ m
  • the crystal grain size of the sintered body prepared under non-pressurized conditions may be 3 to 30 ⁇ m.
  • the particle size of the crystal grains constituting the oxide sintered body of the present invention is larger than the particles of the molybdenum oxide sintered body artificially pressurized by pressing the powder by HP or HIP. Accordingly, there is an advantage that it is more advantageous in terms of reaction.
  • the average grain diameter (D 50 ) constituting the non-pressurized sintered body of the present invention may satisfy the condition of Equation 1 below.
  • G N is the average grain diameter (D 50 ) of the oxide sintered body subjected to non-pressure heat treatment at 1,400 ⁇ 200 ° C. for 2 hours,
  • G P is the average grain diameter (D 50 ) of the oxide sintered body subjected to pressure heat treatment for 2 hours under conditions of 30 MPa and 830° C.
  • the average grain diameter (D 50 ) constituting the unpressurized sintered body according to Equation 1 may be 5.0 or more, more specifically 10.0 or more.
  • the average grain diameter (D 50 ) of the oxide sintered body subjected to non-pressure heat treatment may be 3 to 30 ⁇ m
  • the average grain diameter (D 50 ) of the oxide sintered body subjected to pressure heat treatment may be 1 ⁇ m to 3 ⁇ m.
  • the sputtering target according to another embodiment of the present invention an oxide sintered body containing the above-described molybdenum oxide as a main component; and a backing plate bonded to one surface of the sintered body to support the sintered body.
  • the backing plate is a substrate for supporting the sintered body for the sputtering target, and a conventional backing plate known in the art may be used without limitation.
  • the material constituting the backing plate and its shape are not particularly limited.
  • molybdenum oxide (M1); niobium oxide (M2); preparing a raw material powder comprising; a metal oxide (M3) containing at least one kind of alkaline earth metal (A); (ii) preparing a molded body using the raw material powder ('step S20'); (iii) preparing a sintered body by sintering the molded body at 1,200 to 1,600 ° C. for 1 to 20 hours without pressure ('S30 step'); may be configured to include.
  • step S10 raw material powder including molybdenum oxide (M1), niobium oxide (M2), and (semi)metal oxide (M3) containing at least one kind of alkaline earth metal (A) is prepared.
  • M3-1 powder selected from the group consisting of molybdenum oxide (M1), niobium oxide (M2), CaCO 3 and MgO, if necessary, second metal oxide (M3-2)
  • each powder is put into a mixer and pulverized and mixed to prepare a mixture.
  • additives known in the art such as a binder, a dispersing agent, and an antifoaming agent, may be further included as needed.
  • the amount of the additive can be properly adjusted within a conventional range known in the art, and for example, 0.01 to 10% by weight relative to the total weight of the powder in the slurry (eg, 100% by weight) may be used.
  • Mixing and grinding of the raw material powder is not particularly limited, and may be performed using a conventional ball mill, attrition mill, bead mill, or the like known in the art.
  • the mixed raw material powder may be subjected to a dry ball mill process using zirconia balls.
  • the zirconia balls can be weighed 1 to 3 times the amount of powder, and the ball mill can be performed at a speed of 100 to 300 rpm for 10 to 36 hours.
  • step S10 in order to mix and pulverize the raw material powder through a wet ball mill, pre-measured elemental powder is introduced using a prepared PE cylinder, and about 2 to 4 times the amount of the raw material, preferably A zirconia ball of 3 times the weight is added. After that, distilled water or pure water is added at a level of about 1.5 times the raw material to proceed with the ball mill.
  • the wet pulverized mixture is dried in a dry oven, and ball milling is performed again to obtain a dried raw material powder.
  • the drying conditions are not particularly limited, and for example, drying may be performed at about 90 to 110 ° C. for about 10 to 15 hours in a dry oven.
  • the dried mixture is subjected to a ball mill again to obtain dry raw material powder. If necessary, the zirconia balls and powder are separated by filtering through a mesh of about 90 to 110 mesh, specifically, 100 mesh.
  • a molded body is manufactured from the prepared raw material powder, and more specifically, a molded body having a predetermined standard is manufactured through a process of putting the raw material powder into a molding machine and molding it.
  • the molding process may be carried out twice.
  • the primary molding process may use a uniaxial molding machine
  • the secondary molding process may use an isostatic pressure molding machine.
  • Conditions in the primary molding and secondary molding processes are not particularly limited and may be appropriately adjusted within common conditions known in the art.
  • the pressure at the time of primary molding after inputting the raw material powder into the uniaxial molding machine is not particularly limited, and may specifically be 10 MPa or more per unit area.
  • the pressure at the time of secondary molding after the primary molded body is put into the isostatic pressure molding machine is not particularly limited, and may be, for example, 200 MPa or more per unit area, and preferably 200 to 300 MPa.
  • a primary molded body is manufactured using a 20 ⁇ standard STS mold according to the weight of the determined powder.
  • the pressure may proceed under the minimum pressure condition constituting the shape, for example, about 10 MPa, and the time may proceed at a level of holding for 1 minute.
  • the secondary molding was carried out for several hours under the condition of 200 MPa using hydrostatic pressure molding (CIP).
  • CIP hydrostatic pressure molding
  • the second hydrostatic pressure proceeds with an organic solvent including water, it can proceed in a state in which it is put into an acrylic-based sealing material (eg, a bag).
  • step S30 a sintered body is prepared by sintering the manufactured molded body under predetermined conditions.
  • the sintering conditions are not particularly limited and may be appropriately adjusted within common conditions known in the art.
  • it may be pressure-free sintering at 1,200 to 1,600 ° C. for 1 to 20 hours, and specifically for 1 to 4 hours.
  • the sintering may be performed under an oxygen atmosphere or under inert conditions.
  • the prepared molded body is put into an alumina crucible of a certain standard and sintering is performed.
  • the weight, diameter, height, etc. of the molded body and the sintered body were measured and each physical property was compared (see Table 2 and FIGS. 9 to 12 below).
  • the pressure-free sintered body manufactured through this process may have a relative density of 80% or more, specifically 90% or more.
  • the upper limit is not particularly limited.
  • each upper and lower portion of the target may be processed by 1 mm or more.
  • a productized sputtering target is manufactured through diffusion bonding and final processing commonly known in the art.
  • the sintered body obtained in step S30 is bonded to a backing plate.
  • indium can be used as an adhesive, and it is preferable to have a bonding rate of 95% or more.
  • a final sputtering target may be obtained by processing to a final target thickness using processing equipment and performing bead and/or arc spray treatment on the surface of the backing plate.
  • a metal oxide target may be manufactured through the above process.
  • the target density of the prepared target is 90% or more, and specifically, it is preferable to be 95% or more.
  • Another example of the present invention is a metal oxide thin film deposited using the molybdenum oxide-based target described above.
  • a metal oxide thin film may be formed by performing sputtering using the above-described sintered body as a target material.
  • the oxide thin film is manufactured by sputtering the above-described oxide target, and thus has substantially the same composition as the target. Accordingly, an oxide thin film having a relative density of 90% or more and excellent resistivity of 1 ⁇ 10 -2 ⁇ cm or less can be formed.
  • specific metal oxides and metals are added in a predetermined range to molybdenum oxide, which is the main raw material, but chemical resistance and heat resistance characteristics can be improved through optimization of the molybdenum oxide ratio and composition.
  • the metal oxide thin film according to the present invention may be formed (deposited) using a conventional sputtering method known in the art.
  • a conventional sputtering method known in the art.
  • the manufacturing method after mounting the above-mentioned molybdenum oxide pressure-free sintered sputtering target, it includes depositing at room temperature under an oxygen and / or argon atmosphere in a vacuum chamber. At this time, sputtering may be performed using DC sputter.
  • the substrate and sputtering device used conventional ones known in the art may be used without limitation. Specifically, it can be formed while supplying oxygen or oxygen and high-purity argon gas into a vacuum chamber at a rate of 80 to 110 sccm (standard cubic centimeters per minute), and specifically supplied at a rate of 95 to 105 sccm, forming a film It can be deposited at room temperature (RT) without applying temperature to the substrate.
  • the power density of the DC sputter may be 1.0 to 2.0 W/cm 2
  • the thickness of the metal oxide thin film may be 300 to 500 ⁇ , but is not particularly limited thereto.
  • the oxide thin film obtained as described above can be used in various ways in the manufacture of semiconductor devices, and for example, it can be applied for forming wires or electrodes in the manufacture of semiconductors.
  • the metal oxide thin 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).
  • TFT thin film transistor
  • the molybdenum oxide-based sputtering target and the oxide thin film formed therefrom according to the present invention described above have high density and excellent resistivity characteristics even under no pressure, they are connected to TFT structures of LCDs and OLEDs or electron injection layers of organic electroluminescent devices. resistance can be kept low. Accordingly, the oxide thin film described above may be used in various display devices such as liquid crystal display devices or organic light emitting display devices, information transmission devices such as flat panel displays such as LCD, PDP, OLED, and LED; surface light source lighting devices such as OLED and LED touch panels; It can also be applied without limitation to mobile phones, tablets and/or information delivery devices using the same.
  • display devices such as liquid crystal display devices or organic light emitting display devices, information transmission devices such as flat panel displays such as LCD, PDP, OLED, and LED; surface light source lighting devices such as OLED and LED touch panels; It can also be applied without limitation to mobile phones, tablets and/or information delivery devices using the same.
  • the oxide sintered body of Examples 1 to 17 was produced by heat treatment without pressure at about 1,200 to 1,600 ° C. for 2 hours using a heat treatment facility.
  • a molded body was manufactured in the same manner as in the above embodiment. Thereafter, heat treatment was performed at about 1200 to 1600 ° C. for 2 hours using a heat treatment facility to produce sintered bodies of Comparative Examples 1 to 4, respectively.
  • Molybdenum oxide (M1) and niobium oxide (M2) were weighed in the ratio of the composition shown in Table 1 above.
  • the weighed powder was put into a 1L plastic container, and alumina balls were added in an amount three times the amount of the powder.
  • the alumina ball used was a 3-10 mm ball.
  • dry mixing was performed for 8 hours at a speed of 170 to 230 rpm in a ball mill machine. The obtained dry powder was pressurized and sintered by a hot press.
  • the sintered body of Comparative Example 5 was prepared through the process as described above.
  • the structure change of the sintered body according to heat treatment was evaluated using the molded body to which metal oxide was added and not added.
  • FIG. 1 is a photograph showing the structure change of a sintered body according to the heat treatment temperature using the molded body of Example 9 to which metal oxide (M3) is added
  • FIG. 2 is a molded body of Comparative Example 1 to which metal oxide (M3) is not added. This is a photograph showing the change in the structure of the sintered body according to the heat treatment temperature.
  • the molded body to which the metal oxide was added had a relatively large change in structure, such as suppression of pores of the sintered body according to the heat treatment temperature, compared to the molded body to which no metal oxide was added (see FIGS. 1 and 2 below).
  • Example 9 prepared under no pressure
  • Comparative Example 5 prepared under pressure
  • these two types of samples were cut in a size of 10X10X10mm using a metal blade, polished for several minutes using a polishing machine from SiC paper #100 to #2000, and finally prepared using a 1 ⁇ m paste slurry and a microfiber cloth. Thereafter, the sample was immersed at about 200 ° C. for 1 minute using hydrogen peroxide solution so that the surface of the tissue was exposed and heat treated.
  • D average particle diameter
  • C total length of the line
  • M magnification
  • N number of particles on the line.
  • 3 and 4 are SEM photographs showing fractured and polished surfaces of the powder structure of the mixed raw materials, the structure of the non-pressurized sintered body prepared in Example 9, and the structure of the pressed sintered body prepared in Comparative Example 5, respectively.
  • the diameter (D) and height (T) of each molded body were measured using a vernier caliper, and the weight (Mass) was weighed using a scale.
  • the relative density was converted into a percentage of the theoretical density by converting the input amount of each weight into volume%, and the results are shown in Table 2 below.
  • the density of the measured sample was calculated by weight/volume, and was expressed as an average value when several identical samples were produced.
  • each sample had a low relative density because sintering was not applied, and the relative density of each sintered body after sintering (heat treatment) was approximately 96%.
  • the density evaluation of the sintered body after heat treatment was measured in the same manner as in Experimental Example 3 described above.
  • the results of the relative density calculated by measuring the diameter, height and weight of the heat-treated sintered body are shown in FIGS. 5 to 8, respectively.
  • the shrinkage rate 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 results are shown in Figures 9 to 12, respectively.
  • Resistivity characteristics were evaluated for each sintered body sample prepared in Examples 1 to 17 and Comparative Examples 1 to 5.
  • Example 9 and Comparative Example 1 were measured by cutting samples sintered at 1500 ° C, which is an intermediate temperature range, into 10 X 10 X 3 mm (T).
  • samples sintered at 830° C. were cut into the same size and measured.
  • the X-ray diffraction equipment used in the measurement was a Pro MRD product (Malvern panalytical company), and the 2 theta range was measured at 20 to 60 degrees.
  • a unit film was formed by depositing a 4-inch target prepared with the composition of Examples and Comparative Examples at 300 to 500 ⁇ through a DC sputter.
  • a 4-inch Cu target was deposited on the unit film at 4000 to 6000 ⁇ through a DC sputter to prepare a double film.
  • the sheet resistance and reflectance characteristics of the prepared thin film are shown in FIGS. 14 and 15, respectively.
  • Example 14 is a graph showing sheet resistance characteristics of unit films prepared with compositions of Examples 1, 9, and Comparative Example 1; In the case of the thin films of Examples 1 and 9, it was found that they had significantly lower sheet resistance characteristics compared to Comparative Example 1.
  • Examples 1 and 9 are graph of average reflectance measurements in the visible light region (wavelength of 380 to 740 nm) using the double films prepared with the compositions of Examples 1, 9, and Comparative Example 1. Compared to the double film of Comparative Example 1 having an average reflectance exceeding approximately 10%, the double films of Examples 1 and 9 had average reflectance characteristics of 9% or less, indicating that better reflectance characteristics were secured. there was.
  • a photoresist (PR) process was performed on the double films prepared with the compositions of Example 9 and Comparative Example 1. During the PR process, a sample for etching evaluation was prepared by exposure to light to form a line width of 50 to 100 nm. The results are shown in Table 4 and FIG. 16 below.
  • FIG. 16 is an image of an etching evaluation result of a double film prepared with the composition of Example 9 and Comparative Example 1
  • FIG. 16(a) is an image of Example 9
  • 16(b) is an image of Comparative Example 1.
  • the thin film of Example 9 exhibited a significantly lower degree of thin film damage and a lower angle after the etching process compared to Comparative Example 1. Accordingly, it was confirmed that the oxide sintered body according to the present invention had excellent chemical stability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

La présente invention concerne un corps fritté d'oxyde comprenant un oxyde de molybdène en tant que constituant principal, une cible de pulvérisation comprenant ledit corps fritté, et un film mince d'oxyde formé à partir de celui-ci. La présente invention peut améliorer l'aptitude au frittage tout en garantissant des caractéristiques de haute densité, même lorsqu'un frittage sans pression est effectué, par l'ajout d'un oxyde métallique (ou métalloïde) spécifique à un oxyde de molybdène résistant au frittage et un oxyde de niobium dans une plage prédéterminée.
PCT/KR2022/015592 2021-10-14 2022-10-14 Corps fritté à base d'oxyde de molybdène, et cible de pulvérisation et film mince d'oxyde le comprenant WO2023063774A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2021-0136630 2021-10-14
KR20210136630 2021-10-14
KR1020220132119A KR20230054290A (ko) 2021-10-14 2022-10-14 몰리브덴 산화물계 소결체, 이를 포함하는 스퍼터링 타겟 및 산화물 박막
KR10-2022-0132119 2022-10-14

Publications (1)

Publication Number Publication Date
WO2023063774A1 true WO2023063774A1 (fr) 2023-04-20

Family

ID=85987558

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2022/015592 WO2023063774A1 (fr) 2021-10-14 2022-10-14 Corps fritté à base d'oxyde de molybdène, et cible de pulvérisation et film mince d'oxyde le comprenant

Country Status (1)

Country Link
WO (1) WO2023063774A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4407970A (en) * 1981-08-10 1983-10-04 Tokyo Shibaura Denki Kabushiki Kaisha Sintered body of ceramics and preparation thereof
JPH09157048A (ja) * 1995-12-06 1997-06-17 Hitachi Ltd 複合セラミックスとその製法
KR20190070732A (ko) * 2017-12-13 2019-06-21 엘티메탈 주식회사 고이동도 산화물 소결체 및 이를 포함하는 박막 트랜지스터
KR20200020855A (ko) * 2018-08-09 2020-02-26 제이엑스금속주식회사 산화물 스퍼터링 타깃 및 그 제조 방법, 그리고 당해 산화물 스퍼터링 타깃을 사용하여 성막한 산화물 박막
KR20200069314A (ko) * 2017-10-06 2020-06-16 플란제 에스이 몰리브덴 옥사이드 층의 증착을 위한 타겟 재료

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4407970A (en) * 1981-08-10 1983-10-04 Tokyo Shibaura Denki Kabushiki Kaisha Sintered body of ceramics and preparation thereof
JPH09157048A (ja) * 1995-12-06 1997-06-17 Hitachi Ltd 複合セラミックスとその製法
KR20200069314A (ko) * 2017-10-06 2020-06-16 플란제 에스이 몰리브덴 옥사이드 층의 증착을 위한 타겟 재료
KR20190070732A (ko) * 2017-12-13 2019-06-21 엘티메탈 주식회사 고이동도 산화물 소결체 및 이를 포함하는 박막 트랜지스터
KR20200020855A (ko) * 2018-08-09 2020-02-26 제이엑스금속주식회사 산화물 스퍼터링 타깃 및 그 제조 방법, 그리고 당해 산화물 스퍼터링 타깃을 사용하여 성막한 산화물 박막

Similar Documents

Publication Publication Date Title
WO2018190674A1 (fr) Film de revêtement céramique et son procédé de formation
KR101627491B1 (ko) 산화물 소결물체와 그 제조 방법, 타겟, 및 그것을 이용해 얻어지는 투명 도전막 및 투명 도전성 기재
KR101184353B1 (ko) 투명도전막, 투명도전막 제조용 소결체 타겟, 투명도전성기재 및 이를 이용한 표시 디바이스
KR20120103594A (ko) 스퍼터링 타겟 및 그것을 이용한 박막 트랜지스터
KR20070080813A (ko) 산화물 소결체 및, 이를 이용하여 얻어지는 산화물막, 이를포함하는 투명기재
JP2007224386A (ja) 透明導電膜製造用焼結体ターゲット及びそれを用いて製造される透明導電膜、透明導電性基材
EP2524905A1 (fr) CORPS FRITÉ EN OXYDE In-Ga-O, CIBLE, FILM MINCE SEMI-CONDUCTEUR EN OXYDE, ET PROCÉDÉS DE FABRICATION CORRESPONDANTS
US20210355033A1 (en) Oxide sintered body, sputtering target and oxide semiconductor film
CN110330332A (zh) 一种无烧结助剂低温烧结压电陶瓷材料及其制备方法
WO2023063774A1 (fr) Corps fritté à base d'oxyde de molybdène, et cible de pulvérisation et film mince d'oxyde le comprenant
WO2023063771A1 (fr) Corps fritté à base d'oxyde de molybdène, cible de pulvérisation le comprenant, et film mince d'oxyde
KR20160133429A (ko) 산화물 소결체 및 산화물 투명 도전막
WO2021132893A1 (fr) Verre résistant au plasm et son procédé de fabrication
KR20060017799A (ko) 밝은 색채의 ｅｓｄ 안전 세라믹 재료
WO2013073802A1 (fr) Film conducteur transparent ayant une stabilité thermique supérieure, cible pour film conducteur transparent et procédé de fabrication de film conducteur transparent
TWI805567B (zh) 氧化物半導體膜、薄膜電晶體、氧化物燒結體及濺鍍靶材
WO2019117559A1 (fr) Film mince de métal de transition-dichalcogénure et son procédé de fabrication
WO2018034422A1 (fr) Composite de mandrin sous vide et procédé de préparation correspondant
CN112512991A (zh) 晶体化合物、氧化物烧结体、溅射靶、晶质及无定形氧化物薄膜、薄膜晶体管及电子设备
KR20230054290A (ko) 몰리브덴 산화물계 소결체, 이를 포함하는 스퍼터링 타겟 및 산화물 박막
WO2021015474A1 (fr) Composant d'appareil de gravure au plasma destiné à fabriquer un semiconducteur comprenant un corps fritté composite et son procédé de fabrication
WO2023059071A1 (fr) Compact fritté d'oxyde de molybdène, film mince utilisant un compact fritté, transistor à film mince comprenant un film mince, et dispositif d'affichage
JP6326560B1 (ja) 酸化物焼結体及びスパッタリングターゲット
KR20220081691A (ko) 텅스텐 산화물 소결체, 스퍼터링 타겟 및 산화물 박막
KR20230095476A (ko) 몰리브덴 산화물 소결체, 스퍼터링 타겟

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22881401

Country of ref document: EP

Kind code of ref document: A1