Molybdenum oxide sputtering target material and preparation method and application thereof

Abstract

The invention discloses a molybdenum oxide sputtering target material and a preparation method and application thereof. Comprising the following raw materials in parts by weight: 60-90 parts of a molybdenum-containing compound; 10-30 parts by weight of a metal oxide M1; 5-20 parts by weight of metal M2; the molybdenum-containing compound is selected from at least one of MoO2, MoO3, Mo4O11 or MoN; the metal oxide M1 is selected from at least one of TaO2, Ta2O5, NbO and Nb2O5; and the metal M2 is selected from at least one of Cu, Zn, Al, Mg, Ca or Ba. According to the method, the molybdenum-containing compound, the metal oxide M1 and the metal M2 are used as raw materials, sintering at normal pressure and low temperature is achieved by introducing the metal M2, and the molybdenum oxide target material with high density and good conductivity can still be obtained.

Description

Technical Field

[0001] This invention relates to the field of target technology, and in particular to a molybdenum oxide sputtering target, its preparation method, and its application. Background Technology

[0002] MoO3 is a cathode electrochromic material with a similar color-changing mechanism to WO3, but its color display is softer than that of WO3 films. Its color development can be controlled by applying a potential to the electrode to adjust the absorbance of the film at a given wavelength. Non-stoichiometric molybdenum oxide (MoOx, 2 < x < 3) is an N-type metal oxide semiconductor with high carrier mobility and good conductivity. Molybdenum oxide films are generally obtained through magnetron sputtering, using a molybdenum target in an argon-oxygen mixed atmosphere. The desired sub-stoichiometric molybdenum oxide film is obtained by adjusting the gas ratio. However, the sputtering atmosphere ratio is difficult to precisely control, and the high cost of metallic molybdenum targets makes this sputtering process inefficient. Therefore, molybdenum oxide targets are used instead to improve sputtering efficiency and quality.

[0003] However, due to the relatively low sublimation temperature (700℃) of MoO3, it is currently difficult to densify MoO3 at high temperatures. Related technologies employ methods such as reducing the saturated vapor pressure of MoO3 under high pressure and shortening the sintering time, aiming to reduce the low density phenomenon caused by component volatilization.

[0004] Therefore, it is necessary to develop a molybdenum oxide target material that can be sintered under normal pressure and has high density and conductivity. Summary of the Invention

[0005] The present invention aims to at least solve one of the technical problems existing in the prior art. To this end, the first aspect of the present invention provides a molybdenum oxide sputtering target, which can be sintered at room temperature and has the characteristics of high density and conductivity.

[0006] A second aspect of the present invention also provides a method for preparing a molybdenum oxide sputtering target.

[0007] A third aspect of the present invention also provides an application of a molybdenum oxide sputtering target.

[0008] The molybdenum oxide sputtering target provided according to a first aspect embodiment of the present invention comprises the following raw materials in parts by weight: Contains 60-90 parts by weight of molybdenum compound; Metal oxide M110~30 parts by weight; Metal M2: 5-20 parts by weight; The molybdenum-containing compound is selected from MoO2, MoO3, and Mo4O. 11 Or at least one of MoN; The metal oxide M1 is selected from at least one of TaO2, Ta2O5, NbO, or Nb2O5; The metal M2 is selected from at least one of Cu, Zn, Al, Mg, Ca, or Ba.

[0009] According to a preferred embodiment of the present invention, the molybdenum oxide sputtering target comprises the following raw materials in parts by weight: Contains 60-80 parts by weight of molybdenum compound; Metal oxide M115~30 parts by weight; Metal M2: 8-15 parts by weight.

[0010] According to a preferred embodiment of the present invention, the metal oxide M1 is selected from Nb2O5 and / or Ta2O5.

[0011] According to a preferred embodiment of the present invention, the metal M2 includes Ca or Ca and at least one selected from Al, Mg or Zn.

[0012] The molybdenum oxide sputtering target according to embodiments of the present invention has at least the following beneficial effects: This invention uses molybdenum-containing compounds, metal oxide M1, and metal M2 as raw materials. By introducing metal M2, it achieves high density and good conductivity molybdenum oxide targets even during sintering at ambient pressure and relatively low temperatures. This is because metal M2 has high wettability, filling the pores in the sintered green body during low-temperature sintering, thus achieving the goal of densification of the target material at a lower sintering temperature. Furthermore, the introduction of metal M2 can also form a metal-ceramic system, which can improve density and sintering activity.

[0013] Furthermore, the present invention introduces metal oxide M2 ​​to ensure the low reflectivity of this material in the visible light wavelength range.

[0014] According to a second aspect of the present invention, a method for preparing a molybdenum oxide sputtering target is provided, comprising the following steps: S1. Mix molybdenum-containing compound, metal oxide M1 and metal M2, and granulate to obtain particulate matter; S2. The particulate matter is pressed and molded to obtain a target blank; S3. The target blank is sintered to obtain the target blank.

[0015] According to a preferred embodiment of the present invention, in step S3, the sintering temperature is 1000℃~1500℃. For example, it includes 1000℃, 1050℃, 1100℃, 1200℃, 1300℃, 1400℃, 1500℃, or any sub-range composed of two values.

[0016] According to a preferred embodiment of the present invention, in step S3, the sintering temperature is 1100℃~1300℃. For example, it includes 1100℃, 1150℃, 1200℃, 1250℃, 1300℃, or any sub-range composed of two values.

[0017] According to a preferred embodiment of the present invention, in step S3, the sintering time is 1h to 30h. For example, it includes 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 15h, 20h, 25h, 30h, or any sub-range composed of two values.

[0018] According to a preferred embodiment of the present invention, in step S3, the sintering is atmospheric pressure sintering.

[0019] In this invention, "atmospheric pressure" refers to one standard atmosphere.

[0020] According to a preferred embodiment of the present invention, in step S2, the pressing pressure includes 20 MPa to 300 MPa. For example, it includes 20 MPa, 30 MPa, 40 MPa, 50 MPa, 60 MPa, 70 MPa, 80 MPa, 100 MPa, 120 MPa, 150 MPa, 200 MPa, 250 MPa, 300 MPa, or any sub-range of two values. This effectively prevents cracking of the molded blank.

[0021] According to a preferred embodiment of the present invention, in step S1, the mixing method includes at least one of wet sand milling, dry ball milling, or asymmetric dry mixing.

[0022] According to a preferred embodiment of the present invention, the wet sand milling conditions include: using 0.3~0.8mm zirconia beads, a water-to-material mass ratio of (1~2):1, a ball-to-material mass ratio of (0.5~1):10, and a ball milling time of 8~24h.

[0023] According to a preferred embodiment of the present invention, in step S1, the granulation method includes at least one of spray drying granulation, drum granulation, or vibrating screen granulation.

[0024] According to a preferred embodiment of the present invention, the parameters of the spray granulation include at least: drying tower inlet air temperature of 190~230℃, outlet air temperature of 90~105℃, and atomizer speed of 6000~8000rpm.

[0025] According to a preferred embodiment of the present invention, in step S1, the particle size of the particulate matter is 20~80μm, and the loose packing density is ≥1.3g / cm³. 3Therefore, when the particle size is within the above range, it results in better density during sintering.

[0026] According to a preferred embodiment of the present invention, in step S2, the target blank includes a planar target blank or a tubular target blank; wherein, the planar target blank has a length of (500~1800) * width of (250~550), and the tubular target blank has a length of (500~800) * inner diameter of (150~165) * outer diameter of (185~200).

[0027] According to a preferred embodiment of the present invention, in step S2, the pressing is isostatic pressing, with a pressure of 200~300 MPa and a molding time of 1~3 hours.

[0028] According to a preferred embodiment of the present invention, the sintering is carried out in an inert atmosphere or a reducing atmosphere.

[0029] According to a preferred embodiment of the invention, the inert atmosphere comprises nitrogen and / or argon. This prevents the oxidation of metal M2.

[0030] According to a preferred embodiment of the present invention, the preparation method further includes grinding and bonding.

[0031] The method for preparing molybdenum oxide sputtering targets according to embodiments of the present invention has at least the following beneficial effects: This invention uses molybdenum-containing compounds, metal oxide M1, and metal M2 as raw materials to prepare molybdenum oxide targets through mixing, granulation, pressing, and sintering. The introduction of metal M2 in this method enables the preparation of molybdenum oxide targets with high density and high conductivity at normal pressure and relatively low sintering temperature. The preparation method of this invention can be used for large-scale industrial production.

[0032] The third aspect of the present invention provides the application of the molybdenum oxide sputtering target described in the first aspect of the present invention in the preparation of molybdenum oxide thin films.

[0033] Other features and advantages of the invention will be set forth in the description which follows, and will be apparent in part from the description, or may be learned by practicing the invention. Attached Figure Description

[0034] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which: Figure 1 This is a SEM image of the cross-sectional microstructure of the molybdenum oxide sputtering target sintered at 1000℃ in Comparative Example 1. Figure 2This is a SEM image of the cross-sectional microstructure of the molybdenum oxide sputtering target sintered at 1500℃ in Comparative Example 1. Figure 3 This is a SEM image of the cross-sectional microstructure of the molybdenum oxide sputtering target of Embodiment 6 of the present invention. Detailed Implementation

[0035] The following are specific embodiments of the present invention, and the technical solutions of the present invention will be further described in conjunction with the embodiments, but the present invention is not limited to these embodiments.

[0036] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0037] Some of the raw materials used in the embodiments and comparative examples of this invention are as follows: Metal oxides M1: MoO2, MoN, Nb2O5, Ta2O5; commercially available; Metal M2: Zn, Al, Mg, Ca: in powder form, purity ≥ 99.95%, D50 particle size 0.5~2μm, BET range 2~5m. 2 / g; commercially available.

[0038] Example 1 This example provides a molybdenum oxide sputtering target, the preparation method of which is as follows: S1. Grinding and Granulation: 70 parts by weight of MoO2, 20 parts by weight of Nb2O5, and 10 parts by weight of metallic Zn are mixed in 150 parts by weight of pure water by grinding for 24 hours to obtain a slurry with a particle size D50 = 0.92 μm. The slurry is then granulated using a spray granulator with an inlet air temperature of 220℃, an outlet air temperature of 100℃, and an atomizer speed of 7000 rpm to obtain spherical powder particles with a D50 = 38.56 μm and a loose packing density of 1.48 g / cm³. 3 ; S2. Pressure forming: The granular powder is loaded into a mold and pressed into shape. The isostatic pressing pressure is 280 MPa to obtain the target material blank. S3. High-temperature sintering: The green blank is placed in a nitrogen atmosphere sintering furnace under normal pressure and subjected to gradient heating. The heating rate from 650℃ to 1100℃ is 0.8℃ / min, and the heating rate from 1100℃ to 1400℃ is 1.5℃ / min. After reaching the sintering temperature, the holding time is 15h. After sintering, the blank is cooled with the furnace to obtain the sintered molybdenum oxide target material. S4. Grinding: The sintered molybdenum oxide target material is processed into the required product size using a cutting machine and a grinding machine to obtain a semi-finished molybdenum oxide target material. S5. Bonding: The semi-finished molybdenum oxide sputtering target is bonded to the metal backing plate or backing tube by heating using molten indium. The gap between the sputtering seams of the target is controlled to be 0.3 mm, and the bonding rate is not less than 98.5%. After manual cleaning of the surface, the finished molybdenum oxide sputtering target is obtained.

[0039] Example 2 This example provides a molybdenum oxide sputtering target, which is prepared in the same way as in Example 1; the difference is that in step S1, there are 70 parts by weight of MoO2, 20 parts by weight of Nb2O5 and 10 parts by weight of metallic Al.

[0040] Example 3 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as in Example 1; the difference is that in step S1, It consists of 70 parts by weight of MoO2, 20 parts by weight of Nb2O5, and 10 parts by weight of metallic Mg.

[0041] Example 4 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as in Example 1; the difference is that in step S1, It consists of 70 parts by weight of MoO2, 20 parts by weight of Nb2O5, and 10 parts by weight of metallic Ca.

[0042] Example 5 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as in Example 1; the difference is that in step S1, It consists of 65 parts by weight of MoO2, 25 parts by weight of Nb2O5, 5 parts by weight of metallic Mg, and 5 parts by weight of metallic Ca.

[0043] Example 6 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as in Example 1; the difference is that in step S1, It consists of 60 parts by weight of MoO2, 30 parts by weight of Nb2O5, 5 parts by weight of metallic Al, and 5 parts by weight of metallic Ca.

[0044] Example 7 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as in Example 1; the difference is that in step S1, It consists of 60 parts by weight of MoO2, 30 parts by weight of Nb2O5, 5 parts by weight of metallic Zn, and 5 parts by weight of metallic Ca.

[0045] Example 8 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as in Example 1; the difference is that in step S1, It consists of 55 parts by weight of MoO2, 15 parts by weight of MoN, 15 parts by weight of Nb2O5, 15 parts by weight of Ta2O5, 5 parts by weight of metallic Al, and 5 parts by weight of metallic Mg.

[0046] Example 9 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as in Example 1; the difference is that in step S1, It consists of 55 parts by weight of MoO2, 15 parts by weight of MoN, 10 parts by weight of Nb2O5, 20 parts by weight of Ta2O5, 2 parts by weight of metallic Ca, and 6 parts by weight of metallic Mg.

[0047] Example 10 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as in Example 1; the difference is that in step S1, It consists of 40 parts by weight of MoO2, 30 parts by weight of MoN, 10 parts by weight of Nb2O5, 10 parts by weight of Ta2O5, 3 parts by weight of metallic Zn, 5 parts by weight of metallic Ca, and 2 parts by weight of metallic Mg.

[0048] Example 11 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as that in Example 1; the difference is that in step S1: It consists of 70 parts by weight of MoO2, 20 parts by weight of Nb2O5, and 10 parts by weight of metallic Cu.

[0049] Comparative Example 1 This example provides a molybdenum oxide sputtering target, the preparation method of which is the same as that in Example 1; the difference is that in step S1: It consists of 70 parts by weight of MoO2 and 30 parts by weight of Nb2O5.

[0050] Performance testing The cross-sectional microstructures of the molybdenum oxide sputtering targets sintered at 1000℃ and 1500℃ in Comparative Example 1 were analyzed by SEM, and the results are as follows: Figure 1 and Figure 2 As shown, the molybdenum-oxygen sintered body without metal additives is difficult to achieve a high density and still has relatively obvious voids at 1500℃.

[0051] The cross-sectional microstructure of the molybdenum oxide sputtering target of Example 6 of the present invention was analyzed by SEM, and the results are as follows: Figure 3 As shown, this invention, by introducing metal M2, not only fills the voids between particles during the sintering process but also greatly improves the sintering activity.

[0052] Furthermore, the dimensional shrinkage, loss on ignition (calculated as: loss on ignition = (weight before sintering - weight after sintering) / weight before sintering * 100%), relative density, and bulk resistivity of the molybdenum oxide sputtering target were tested before and after sintering for Examples 1-11 and Comparative Example 1. The shrinkage of each sintered body was obtained by measuring its dimensions before and after sintering, while the relative density of the sintered body was conveniently calculated using Archimedes' principle of water displacement. The bulk resistivity was measured using a four-probe resistance meter. The molybdenum oxide sputtering target was polished to remove the surface volatile layer to accurately obtain the bulk resistivity. The results are shown in Table 1.

[0053] Table 1

[0054] As can be seen from the data in Table 1, the introduction of metal M2 in this invention can effectively improve sintering activity, make the sintered body shrinkage effect obvious, effectively improve the relative density, and the addition of metal M2 can form heterojunction in the sintered body structure, giving it a lower bulk resistivity.

[0055] The present invention has been described in detail above with reference to the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A molybdenum oxide sputtering target, characterized in that, Including the following raw materials by weight: Contains 60-90 parts by weight of molybdenum compound; Metal oxide M110~30 parts by weight; Metal M2: 5-20 parts by weight; The molybdenum-containing compound is selected from MoO2, MoO3, and Mo4O. 11 Or at least one of MoN; The metal oxide M1 is selected from at least one of TaO2, Ta2O5, NbO, or Nb2O5; The metal M2 is selected from at least one of Cu, Zn, Al, Mg, Ca, or Ba.

2. The molybdenum oxide sputtering target according to claim 1, characterized in that, Including the following raw materials by weight: Contains 60-80 parts by weight of molybdenum compound; Metal oxide M115~30 parts by weight; Metal M2: 8-15 parts by weight.

3. A method for preparing the molybdenum oxide sputtering target as described in claim 1 or 2, characterized in that, Includes the following steps: S1. Mix molybdenum-containing compound, metal oxide M1 and metal M2, and granulate to obtain particulate matter; S2. The particulate matter is pressed and molded to obtain a target blank; S3. The target blank is sintered to obtain the target blank.

4. The preparation method according to claim 3, characterized in that, In step S3, the sintering temperature is 1000℃~1500℃.

5. The preparation method according to claim 3, characterized in that, In step S3, the sintering time is 1h to 30h.

6. The preparation method according to claim 3, characterized in that, In step S2, the pressure for pressing and molding includes 200 MPa to 300 MPa.

7. The preparation method according to claim 3, characterized in that, In step S1, the mixing method includes at least one of wet sand milling, dry ball milling, or asymmetric dry mixing.

8. The preparation method according to claim 3, characterized in that, In step S1, the granulation method includes at least one of spray drying granulation, drum granulation, or vibrating screen granulation.

9. The preparation method according to claim 3, characterized in that, In step S1, the particle size of the particulate matter is 20~80μm, and the loose packing density is ≥1.3g / cm³. 3 .

10. The use of the molybdenum oxide sputtering target as described in claim 1 or 2 in the preparation of molybdenum oxide thin films.

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