Rotating niobium oxide target material, method for manufacturing the same, and use thereof

Abstract

The application belongs to the technical field of rotating niobium oxide target material, and discloses a rotating niobium oxide target material, which comprises a niobium oxide main body layer and an inner lining pipe. The niobium oxide main body layer comprises a niobium oxide working surface layer and a metal transition bottom layer, and is provided with a functional gradient intermediate layer between the niobium oxide working surface layer and the metal transition bottom layer. The functional gradient intermediate layer is composed of Nb2O5 and TiO2, the content of Nb2O5 at the contact end of the metal transition bottom layer is greater than or equal to 45 wt% and less than or equal to 55 wt%, the content of Nb2O5 at the contact end of the niobium oxide working surface layer is greater than or equal to 95 wt% and less than or equal to 100 wt%, and the content of Nb2O5 gradually increases from the contact end of the metal transition bottom layer to the contact end of the niobium oxide working surface layer. The composition of the functional gradient intermediate layer gradually changes, the coefficient of thermal expansion continuously transitions, the thermal stress is small, the interface between the niobium oxide working surface layer and the functional gradient intermediate layer is not easily damaged, the interface between the functional gradient intermediate layer and the metal transition bottom layer is not easily damaged, and therefore the niobium oxide main body layer is not easily peeled off from the inner lining pipe.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of rotating niobium oxide target, more particularly, to a rotating niobium oxide target, a preparation method and application thereof. BACKGROUND

[0002] The rotating niobium oxide target has excellent high-temperature resistance, electrical insulation and optical transparency, and the thin film obtained by sputtering is widely used in the fields of semiconductors, optoelectronics, coatings, flat panel displays and the like. The basic structure of the existing rotating niobium oxide target includes a niobium oxide main layer and an inner lining tube, and the niobium oxide main layer is mainly composed of a niobium oxide working surface layer and a metal transition bottom layer. The current rotating niobium oxide target has the disadvantage that the niobium oxide working surface layer is easy to peel off from the metal transition bottom layer, because: the niobium oxide working surface layer in the niobium oxide main layer is a ceramic phase, and has a low thermal expansion coefficient of about 7.1x10 -6 / K, while the metal transition layer and the inner lining tube are metal phases, and have a high thermal expansion coefficient of about 12.5x10 -6 / K, and the difference between the thermal expansion coefficients of the niobium oxide working surface layer and the metal transition layer is as high as 5-6, and the two directly contact each other, which generates a large thermal stress, so the interface between the niobium oxide working surface layer and the metal transition bottom layer is easily damaged, and thus the niobium oxide working surface layer is easy to peel off from the metal transition bottom layer, and further causes the niobium oxide main layer to peel off from the inner lining tube. SUMMARY

[0003] The present application provides a rotating niobium oxide target, the thermal expansion coefficient of the niobium oxide main layer of which is close to that of the inner lining tube, and the bonding strength is better than that of the prior art, or the niobium oxide main layer is not easy to decompose at high temperature, and the composition is uniform.

[0004] Another object of the present application is to provide a preparation method of the rotating niobium oxide target.

[0005] To solve the above technical problems, the technical scheme provided by the present application is as follows:

[0006] A rotating niobium oxide target, comprising a niobium oxide main layer and an inner lining tube, the niobium oxide main layer comprising a niobium oxide working surface layer and a metal transition bottom layer, and the niobium oxide main layer being provided with a functional gradient intermediate layer between the niobium oxide working surface layer and the metal transition bottom layer; the functional gradient intermediate layer is composed of Nb2O5 and TiO2, the content of Nb2O5 at the contact end of the metal transition bottom layer is ≥45wt% and ≤55wt%, and the content of Nb2O5 at the contact end of the niobium oxide working surface layer is ≥95wt% and ≤100wt%, and the content of Nb2O5 gradually increases from the contact end of the metal transition bottom layer to the contact end of the niobium oxide working surface layer.

[0007] The application adds a functional gradient intermediate layer in the existing niobium oxide main layer, wherein the content of Nb2O5 gradually changes from 45wt% to 50wt% to 95wt% to 100wt%, and the surface of Nb2O5 is coated with a SiO2 nano layer, and the following technical effects are achieved.

[0008] The niobium oxide main layer has high bonding strength with the inner lining pipe and is not easy to peel off from the inner lining pipe.

[0009] The additional functional gradient intermediate layer gradually changes in composition and continuously transitions in thermal expansion coefficient, so that the niobium oxide main layer has low difference in thermal expansion coefficient and small thermal stress, the interface between the niobium oxide working surface layer and the functional gradient intermediate layer is not easy to be damaged, the interface between the functional gradient intermediate layer and the metal transition bottom layer is not easy to be damaged, the niobium oxide working surface layer of the rotating niobium oxide target is not easy to peel off from the metal transition bottom layer, and the niobium oxide main layer is not easy to peel off from the inner lining pipe.

[0010] Preferably, the surface of the niobium oxide working surface layer and the functional gradient intermediate layer is coated with a SiO2 nano layer.

[0011] The niobium oxide main layer is uniform in composition. The SiO2 nano layer coated on the surface of Nb2O5 can form a dense NbSiO with Nb2O5, block the oxygen diffusion channel, inhibit the high-temperature decomposition and volatilization of Nb2O5, so that the Nb / O atomic ratio on the surface of the target can approach the theoretical value, the composition on the surface of the target is uniform, on the one hand, the obtained target is not easy to locally crack during rotation sputtering, the service life of the target is long, and on the other hand, the sputtered thin film obtained by sputtering the target is uniform in thickness and good in electrical performance consistency.

[0012] Preferably, the metal transition bottom layer is a NiCrAlY alloy layer.

[0013] Preferably, the content of Ni in the NiCrAlY alloy layer is 70wt% to 80wt%, the content of Cr is 15wt% to 25wt%, the content of Al is 4wt% to 6wt%, and the content of Y is 0.5wt% to 1.5wt%.

[0014] Preferably, the thickness of the metal transition bottom layer is 100μm to 300μm, the thickness of the functional gradient intermediate layer is 200μm to 500μm, and the thickness of the niobium oxide working surface layer is 1mm to 2mm.

[0015] The application also provides a preparation method of the rotating niobium oxide target.

[0016] S1. Plasma spraying a metal transition layer on the inner lining pipe;

[0017] S2. Plasma spraying a functional gradient layer on the metal transition layer;

[0018] S3. supersonic flame spraying niobium oxide working surface layer on the functional gradient layer to obtain a rotating niobium oxide target precursor, and after treatment, a rotating niobium oxide target is obtained.

[0019] Preferably, the Nb2O5 in S3 is subjected to hydrogen reduction-passivation treatment, and a SiO2 nanolayer is coated on the surface.

[0020] Preferably, the Nb2O5 in S2 and S3 is subjected to hydrogen reduction-passivation treatment, and a SiO2 nanolayer is coated on the surface.

[0021] Preferably, the Nb2O5 is subjected to hydrogen reduction-passivation treatment, and a SiO2 nanolayer is coated on the surface, specifically: first, the hydrogen reduction treatment is to reduce the Nb2O5 in a pure H2 atmosphere at 400-500°C for 2-4h; then, the passivation treatment is to expose the hydrogen-reduced Nb2O5 in a N2 atmosphere containing 1-3vol% O2 at room temperature for 22-26h; finally, the passivated Nb2O5 is immersed in a 1-3wt% silane coupling agent ethanol solution, ultrasonic treated for 10-40min, and then calcined at 550-650°C for 50-80min to obtain the Nb2O5 coated with a SiO2 nanolayer on the surface.

[0022] The inner liner tube in S1 needs to be pretreated, specifically: the inner liner tube is sandblasted and roughened, and preheated at 300-320°C.

[0023] Preferably, the step S3 is subjected to post-treatment, specifically: the rotating niobium oxide target precursor is subjected to vacuum annealing and surface fine grinding to obtain a rotating niobium oxide target; the vacuum annealing temperature is 750-850°C, and the time is 1.5-2.5h. BRIEF DESCRIPTION OF DRAWINGS

[0024] Figure 1 It is a cross-sectional structure diagram of the rotating niobium oxide target of the present application, wherein 1 is a niobium oxide working surface layer, 2 is a functional gradient intermediate layer, 3 is a metal transition bottom layer, and 4 is an inner liner tube.

[0025] Figure 2 It is an SEM image of the surface of the rotating niobium oxide target obtained in Example 1.

[0026] Figure 3 It is an SEM image of the surface of the rotating niobium oxide target obtained in Comparative Example 2. DETAILED DESCRIPTION

[0027] The present application will be further described in detail in combination with the specific embodiments.

[0028] Example 1

[0029] A rotating niobium oxide target comprises a niobium oxide main body layer and an inner lining tube, the niobium oxide main body layer comprises a niobium oxide working surface layer, a metal transition bottom layer and a functional gradient intermediate layer between the niobium oxide working surface layer and the metal transition bottom layer, the functional gradient intermediate layer is composed of Nb2O5 and TiO2, wherein the content of Nb2O5 gradually changes from 50wt% to 100wt%, the Nb2O5 surface of the niobium oxide working surface layer and the functional gradient intermediate layer is coated with a SiO2 nanolayer; the metal transition bottom layer is a NiCrAlY alloy layer, the content of Ni in the NiCrAlY alloy layer is 75wt%, the content of Cr is 20wt%, the content of Al is 5wt%, and the content of Y is 1wt%; the thickness of the niobium oxide working surface layer is 1.5mm, the thickness of the functional gradient intermediate layer is 300μm, and the thickness of the metal transition bottom layer is 200μm;

[0030] The preparation method of the rotating niobium oxide target comprises the following steps:

[0031] S1. Plasma spraying a metal transition bottom layer on the inner lining tube, specifically:

[0032] S11. Inner lining tube pretreatment: first, remove oil stains, rust and impurities on the surface of the inner lining tube to ensure surface cleanliness; then adjust the spray gun parameters, fix the inner lining tube in a suitable position, start the sandblasting machine, and move the spray gun at a uniform speed to perform sandblasting treatment on the surface of the inner lining tube; finally, remove the residual sand on the surface of the inner lining tube after sandblasting to obtain a sandblasted inner lining tube, and preheat the sandblasted inner lining tube at 310℃; the material of the inner lining tube is 304 stainless steel; after sandblasting and roughening, Ra=5μm;

[0033] S12. Nb2O5 pretreatment: first, hydrogen reduction treatment is to reduce Nb2O5 in a pure H2 atmosphere at 450℃ for 3h; then, passivation treatment is to expose the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 2vol% O2 at room temperature for 24h; finally, immerse the passivated Nb2O5 in a 2wt% silane coupling agent ethanol solution, ultrasonically treat for 30min, and then calcine at 600℃ for 60min to obtain Nb2O5 coated with a SiO2 nanolayer, the thickness of the SiO2 nanolayer is 80nm detected by TEM; the particle size D50 of the Nb2O5 is 30μm;

[0034] S13. Plasma spraying a metal transition layer on the inner liner tube: The plasma spraying metal transition layer process is as follows: first, select an F4-MB spray gun and debug the spraying system, the main parameters are as follows: current 500 A, main gas: argon (purity ≥ 99.99%), flow rate 40 SLPM; auxiliary gas: hydrogen (purity ≥ 99.99%), flow rate 8-10 SLPM; then, load the NiCrAlY alloy powder into the powder feeder, the powder feeding rate is 20 g / min, and the carrier gas is argon (flow rate 3-5 SLPM); finally, spray the NiCrAlY alloy metal transition layer on the inner liner tube;

[0035] S2. Plasma spraying a functional gradient intermediate layer on the metal transition layer: Specifically, select an F4-MB spray gun and debug the spraying system, the main parameters are as follows: current 500 A, main gas: argon (purity ≥ 99.99%), flow rate 40 SLPM; auxiliary gas: hydrogen (purity ≥ 99.99%), flow rate 8-10 SLPM; then, load the pre-processed Nb2O5 powder and TiO2 into a double-disc powder feeder, the powder feeding rate is 20 g / min, and the carrier gas is argon (flow rate 3-5 SLPM); finally, adjust the Nb2O5 / TiO2 mixing ratio (50%→100% Nb2O5) in real time to spray the functional gradient layer on the metal transition layer, with a layer thickness gradient control precision of ±5%;

[0036] S3. Supersonic flame spraying a niobia working surface layer on the functional gradient intermediate layer to obtain a rotating niobia target precursor, and after processing, a rotating niobia target is obtained, the specific steps are as follows:

[0037] S31. Adopting a high-velocity oxygen flame (HVOF) process to spray a niobia working surface layer, the process parameters are as follows: powder feeder: double-disc powder feeder, carrier gas: nitrogen (purity ≥ 99.99%), flow rate 8-10 SLPM, powder feeding rate 25-30 g / min, kerosene flow rate 0.3 L / min, oxygen flow rate 800 SLPM, spraying distance 200 mm, and the spraying ignition sequence is first oxygen inlet→kerosene pump start→ignition→adjustment to stable combustion state, the coating deposition rate ≥ 95%, and a rotating niobia target precursor is obtained;

[0038] S32. Post-processing: vacuum annealing and surface fine grinding the rotating niobia target precursor to obtain a rotating niobia target; wherein: the vacuum annealing process parameters are as follows: heating to 800℃ at a rate of 5℃ / min, holding for 2 h, and taking out of the furnace after cooling to 300℃ in the furnace; in the surface fine grinding process, the outer cylindrical grinding machine is processed to a roundness error ≤ 0.03 mm.

[0039] The structure of the rotating niobia target obtained in Example 1 is shown in the schematic diagram Figure 1In the figure, 1 is the niobium oxide working surface layer, 2 is the functional gradient intermediate layer, 3 is the metal transition bottom layer, and 4 is the inner liner tube.

[0040] Example 2

[0041] This embodiment is the second embodiment of the present invention. Unlike embodiment 1, the niobium oxide working surface layer of the rotating niobium oxide target has a thickness of 1 mm, the functional gradient intermediate layer has a thickness of 200 μm, and the metal transition bottom layer has a thickness of 300 μm.

[0042] Example 3

[0043] This embodiment is the third embodiment of the present invention. Unlike embodiment 1, the niobium oxide working surface layer of the rotating niobium oxide target has a thickness of 2 mm, the functional gradient intermediate layer has a thickness of 500 μm, and the metal transition bottom layer has a thickness of 100 μm.

[0044] Example 4

[0045] This embodiment is the fourth embodiment of the present invention. The difference from Embodiment 1 is that the S12.Nb2O5 pretreatment in the rotating niobium oxide target preparation method involves: firstly, hydrogen reduction treatment of Nb2O5 at 400℃ using pure H2.

[0046] The Nb2O5 was reduced in an atmosphere for 4 hours; then, the passivation treatment involved exposing the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 1 vol% O2 at room temperature for 22 hours; finally, the passivated Nb2O5 was immersed in a 3 wt% silane coupling agent ethanol solution, ultrasonicated for 10 minutes, and then calcined at 550°C for 80 minutes to obtain Nb2O5 with a SiO2 nanolayer on the surface. TEM analysis showed that the thickness of the SiO2 nanolayer was 60 nm; the particle size of the Nb2O5 was D50 = 15 μm.

[0047] Example 5

[0048] This embodiment is the fifth embodiment of the present invention. The difference from Embodiment 1 is that the rotating niobium oxide target material...

[0049] The preparation method for S12.Nb2O5 pretreatment involves: first, hydrogen reduction treatment, in which Nb2O5 is reduced in a pure H2 atmosphere at 500℃ for 2 hours; then, passivation treatment, in which the hydrogen-reduced Nb2O5 is exposed at room temperature for 26 hours in an N2 atmosphere containing 3 vol% O2; finally, the passivated Nb2O5 is immersed in a 1 wt% silane coupling agent ethanol solution, ultrasonically treated for 40 minutes, and then calcined at 650℃ for 50 minutes to obtain Nb2O5 with a SiO2 nanolayer on the surface. TEM analysis shows that the thickness of the SiO2 nanolayer is 100 nm; the particle size of the Nb2O5 is D50 = 45 μm.

[0050] Example 6

[0051] This embodiment is the 6th embodiment of the present application, which is different from the embodiment 1 in that the functional gradient intermediate layer in the rotating niobia target material is composed of Nb2O5 and TiO2, wherein the content of Nb2O5 gradually changes from 45wt% to 95wt%, and the Nb2O5 surface of the niobia working surface layer and the functional gradient intermediate layer is coated with a SiO2 nanolayer; the metal transition bottom layer is a NiCrAlY alloy layer, wherein the content of Ni is 70wt%, the content of Cr is 15wt%, the content of Al is 4wt%, and the content of Y is 0.5wt%.

[0052] Example 7

[0053] This embodiment is the 7th embodiment of the present application, which is different from the embodiment 1 in that the functional gradient intermediate layer in the rotating niobia target material is composed of Nb2O5 and TiO2, wherein the content of Nb2O5 gradually changes from 55wt% to 100wt%, and the Nb2O5 surface of the niobia working surface layer and the functional gradient intermediate layer is coated with a SiO2 nanolayer; the metal transition bottom layer is a NiCrAlY alloy layer, wherein the content of Ni is 80wt%, the content of Cr is 25wt%, the content of Al is 6wt%, and the content of Y is 1.5wt%.

[0054] Example 8

[0055] This embodiment is the 8th embodiment of the present application, which is different from the embodiment 1 in that the preheating temperature of the sandblasted inner lining tube in the inner lining tube pretreatment in the preparation method of the rotating niobia target material is 300℃; the vacuum annealing process parameters in the post-treatment are as follows: heating to 750℃ at a rate of 5℃ / min, holding for 1.5h, and furnace cooling to 300℃ before discharging, and the outer cylindrical grinding machine is processed to a roundness error of ≤0.03mm in the surface finishing process.

[0056] Example 9

[0057] This embodiment is the 9th embodiment of the present application, which is different from the embodiment 1 in that the preheating temperature of the sandblasted inner lining tube in the inner lining tube pretreatment in the preparation method of the rotating niobia target material is 320℃; the vacuum annealing process parameters in the post-treatment are as follows: heating to 850℃ at a rate of 5℃ / min, holding for 2.5h, and furnace cooling to 300℃ before discharging, and the outer cylindrical grinding machine is processed to a roundness error of ≤0.03mm in the surface finishing process.

[0058] Comparative Example 1

[0059] The comparative example is the first comparative example of the present application, and is different from example 1 in that the rotating niobium oxide target only includes a niobium oxide working surface layer and a metal transition bottom layer, without a functional gradient intermediate layer.

[0060] The method for preparing the rotating niobium oxide target comprises the following steps:

[0061] S1. Plasma spraying a metal transition layer on the inner liner pipe, specifically:

[0062] S11. Inner liner pipe pretreatment: first, remove oil stains, rust and impurities on the surface of the inner liner pipe to ensure the surface is clean; then adjust the spray gun parameters, fix the inner liner pipe in the appropriate position, start the sand blasting machine, and move the spray gun at a uniform speed to perform sand blasting treatment on the surface of the inner liner pipe; finally, remove the residual sand on the surface of the inner liner pipe after sand blasting, obtain the sand-blasted inner liner pipe, and preheat the sand-blasted inner liner pipe at 310°C; the material of the inner liner pipe is 304 stainless steel; the Ra of the sand-blasted inner liner pipe is 5 μm;

[0063] S12. Nb2O5 pretreatment: first, hydrogen reduction treatment is to reduce Nb2O5 at 450°C in a pure H2 atmosphere for 3 h; then, passivation treatment is to expose the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 2 vol% O2 at room temperature for 24 h; finally, immerse the passivated Nb2O5 in a 2 wt% silane coupling agent ethanol solution, ultrasonically treat for 30 min, and then calcine at 600°C for 60 min to obtain Nb2O5 coated with a SiO2 nanolayer on the surface; the particle size D50 of the Nb2O5 is 25 μm;

[0064] S13. Plasma spraying a metal transition bottom layer on the inner liner pipe: the process steps of plasma spraying a metal transition layer are as follows: first, select an F4-MB type spray gun and debug the spraying system, the main parameters are as follows: current 500 A, main gas: argon (purity ≥ 99.99%), flow rate 40 SLPM; auxiliary gas: hydrogen (purity ≥ 99.99%), flow rate 8-10 SLPM; then, fill the NiCrAlY alloy powder into the powder feeder, the powder feeding rate is 20 g / min, and the carrier gas is argon (flow rate 3-5 SLPM); finally, spray the NiCrAlY alloy metal transition layer on the inner liner pipe;

[0065] S2. Supersonic flame spraying a niobium oxide working surface layer on the plasma-sprayed metal transition bottom layer to obtain a rotating niobium oxide target precursor, and obtaining a rotating niobium oxide target after post-treatment, the specific steps are as follows:

[0066] S21. Spraying a niobium oxide working surface layer by a high-velocity oxygen fuel (HVOF) process, process parameters are as follows: powder feeder: double-disc powder feeder, carrier gas is nitrogen (purity ≥ 99.99%), flow rate is 8-10 SLPM, powder feeding rate is 25-30 g / min, kerosene flow rate is 0.3 L / min, oxygen flow rate is 800 SLPM, spraying distance is 200 mm, spraying ignition sequence is first passing in oxygen → starting kerosene pump → ignition → adjusting to stable combustion state, coating deposition rate ≥ 95%, and a rotating niobium oxide target precursor is obtained;

[0067] S22. Post-processing: vacuum annealing and surface fine grinding the rotating niobium oxide target precursor, and a rotating niobium oxide target is obtained; wherein: the vacuum annealing process parameters are as follows: heating to 800 ℃ at a rate of 5 ℃ / min, keeping for 2 h, and taking out of the furnace after cooling to 300 ℃ in the furnace, and the outer circle grinding machine is used for processing to a roundness error ≤ 0.03 mm in the surface fine grinding process.

[0068] Comparative Example 2

[0069] This example is the 10th example of the present application, and the difference from Example 1 is that the Nb2O5 surface of the niobium oxide working surface layer and the functional gradient intermediate layer in the rotating niobium oxide target is not coated with a SiO2 nanolayer.

[0070] The method for preparing the rotating niobium oxide target comprises the following steps:

[0071] S1. Plasma spraying a metal transition layer on an inner liner tube, specifically:

[0072] S11. Inner liner tube pretreatment: first, removing oil stains, rust and impurities on the surface of the inner liner tube to ensure the surface is clean; then adjusting the spray gun parameters, fixing the inner liner tube at a suitable position, starting the sand blasting machine, and moving the spray gun at a uniform speed to perform sand blasting treatment on the surface of the inner liner tube; finally, removing the residual sand on the surface of the inner liner tube after sand blasting, obtaining a sand-blasted inner liner tube, and preheating the sand-blasted inner liner tube at 310 ℃; the material of the inner liner tube is 304 stainless steel; the Ra of the sand-blasted inner liner tube is 5 μm.

[0073] S12. Plasma spraying a metal transition layer on the inner liner tube: the process steps of plasma spraying a metal transition layer are as follows: first, selecting an F4-MB spray gun and debugging the spraying system, main parameters are as follows: current 500 A, main gas: argon (purity ≥ 99.99%), flow rate 40 SLPM; auxiliary gas: hydrogen (purity ≥ 99.99%), flow rate 8-10 SLPM; then, filling the NiCrAlY alloy powder into the powder feeder, powder feeding rate 20 g / min, carrier gas is argon (flow rate 3-5 SLPM); finally, spraying a NiCrAlY alloy metal transition layer on the inner liner tube.

[0074] Comparative Example 3

[0075] This comparative example is the 3rd comparative example of the present application, which is different from Example 1 in that the rotating niobium oxide target material only includes a niobium oxide working surface layer and a metal transition bottom layer without a functional gradient intermediate layer; and the Nb2O5 surface of the niobium oxide working surface layer in the rotating niobium oxide target material is not coated with a SiO2 nanolayer.

[0076] The method for preparing the rotating niobium oxide target material comprises the following steps:

[0077] S1. Plasma spraying a metal transition layer on the inner liner pipe, specifically:

[0078] S11. Inner liner pipe pretreatment: first, remove oil stains, rust and impurities on the surface of the inner liner pipe to ensure the surface is clean; then adjust the spray gun parameters, fix the inner liner pipe in the appropriate position, start the sandblasting machine, and move the spray gun at a uniform speed to perform sandblasting treatment on the surface of the inner liner pipe; finally, remove the residual sand on the surface of the inner liner pipe after sandblasting, obtain the sandblasted inner liner pipe, and preheat the sandblasted inner liner pipe at 310°C; the material of the inner liner pipe is 304 stainless steel; the sandblasted inner liner pipe has a Ra of 5 μm.

[0079] S12. Plasma spraying a metal transition layer on the inner liner pipe: the process steps of plasma spraying a metal transition layer are as follows: first, select an F4-MB type spray gun and debug the spraying system, the main parameters are as follows: current 500 A, main gas: argon (purity ≥ 99.99%), flow rate 40 SLPM; auxiliary gas: hydrogen (purity ≥ 99.99%), flow rate 8-10 SLPM; then, fill the NiCrAlY alloy powder into the powder feeder, the powder feeding rate is 20 g / min, and the carrier gas is argon (flow rate 3-5 SLPM); finally, spray the NiCrAlY alloy metal transition layer on the inner liner pipe;

[0080] S2. Supersonic flame spraying a niobium oxide working surface layer on the metal transition layer to obtain a rotating niobium oxide target material precursor, and obtaining a rotating niobium oxide target material after post-processing, the specific steps are as follows:

[0081] S11. Spraying a niobium oxide working surface layer by using a high-velocity oxygen flame (HVOF) process, the process parameters are as follows: powder feeder: double-disk powder feeder, carrier gas: nitrogen (purity ≥ 99.99%), flow rate 8-10 SLPM, powder feeding rate 25-30 g / min, kerosene flow rate 0.3 L / min, oxygen flow rate 800 SLPM, spraying distance 200 mm, and the spraying ignition sequence is first passing in oxygen → starting the kerosene pump → ignition → adjusting to a stable combustion state, the coating deposition rate ≥ 95%, and a rotating niobium oxide target material precursor is obtained;

[0082] S12. Post-processing: the rotating niobium oxide target precursor is vacuum annealed and surface finely ground to obtain the rotating niobium oxide target; wherein: the vacuum annealing process parameters are: the annealing temperature is 800℃, the annealing time is 2h, and the outer cylindrical grinding machine is processed to a roundness error ≤0.03mm in the surface fine grinding process.

[0083] Comparative Example 4

[0084] This comparative example is the 4th comparative example of the present application, which is different from Example 1 in that the rotating niobium oxide target

[0085] In the preparation method, S12. Nb2O5 pretreatment: first, hydrogen reduction treatment is to reduce Nb2O5 in a pure H2 atmosphere at 350℃ for 1.5h; then, passivation treatment is to expose the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 4vol% O2 at room temperature for 21h; finally, the passivated Nb2O5 is immersed in a 0.5wt% silane coupling agent ethanol solution, treated by ultrasonic for 45min, and then calcined at 500℃ for 90min to obtain Nb2O5 coated with a SiO2 nanolayer on the surface; the particle size D50 of the Nb2O5 is 10μm.

[0086] Comparative Example 5

[0087] This comparative example is the 5th comparative example of the present application, which is different from Example 1 in that the rotating niobium oxide target

[0088] In the preparation method, S12. Nb2O5 pretreatment: first, hydrogen reduction treatment is to reduce Nb2O5 in a pure H2 atmosphere at 550℃ for 5h; then, passivation treatment is to expose the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 0.5vol% O2 at room temperature for 28h; finally, the passivated Nb2O5 is immersed in a 4wt% silane coupling agent ethanol solution, treated by ultrasonic for 5min, and then calcined at 700℃ for 40min to obtain Nb2O5 coated with a SiO2 nanolayer on the surface; the particle size D50 of the Nb2O5 is 55μm.

[0089] Comparative Example 6

[0090] This comparative example is the 6th example of the present application, which is different from Example 1 in that the rotating niobium oxide target, the working surface layer of niobium oxide is 0.5mm thick, the functional gradient intermediate layer is 550μm thick, and the metal transition bottom layer is 350μm thick.

[0091] Comparative Example 7

[0092] This comparative example is the 7th example of the present application, which is different from Example 1 in that the rotating niobium oxide target, the working surface layer of niobium oxide is 2.5mm thick, the functional gradient intermediate layer is 150μm thick, and the metal transition bottom layer is 70μm thick.

[0093] Comparative Example 8

[0094] This comparative example is the 8th embodiment of the present application, which is different from Example 1 in that the rotating niobium oxide target has a SiO2nanolayer with a thickness of 50 nm coated on the surface of the Nb2O5of the working surface layer and the functional gradient intermediate layer of the niobium oxide.

[0095] Comparative Example 9

[0096] This comparative example is the 9th embodiment of the present application, which is different from Example 1 in that the rotating niobium oxide target has a SiO2nanolayer with a thickness of 110 nm coated on the surface of the Nb2O5of the working surface layer and the functional gradient intermediate layer of the niobium oxide.

[0097] Performance detection:

[0098] Bonding strength detection between the niobium oxide main layer and the substrate: ASTM C633 method is used for bonding strength test, and the test equipment is a universal material testing machine (range ≥ 50 kN). The test steps include the following steps:

[0099] 1. Sample preparation:

[0100] - Cutting size: φ30x10mm samples (including inner liner tube + coating) are taken from the rotating niobium oxide target obtained from each of the above examples and comparative examples

[0101] - Adhesion: the two ends of the sample are roughened with sandpaper (Ra=3μm), and then adhered to the loading column after coating with epoxy resin glue

[0102] - Curing: 80℃x2h + room temperature x24h

[0103] 2. Test procedure:

[0104] - Loading rate: 0.75mm / min (constant displacement control)

[0105] - Termination condition: coating peeling or load drop ≥20%

[0106] - Data recording: take the maximum load value `F_max`

[0107] 3. Calculate the bonding strength (take 5 groups of samples and take the average value)

[0108] The bonding strength detection results of the niobium oxide main layer and the inner liner tube in the rotating niobium oxide target obtained from each of the examples and comparative examples are shown in Table 1.

[0109] Nb2O5 stability of the NbOx bulk layer: the Nb2O5 stability of the NbOx bulk layer of the rotating NbOx target obtained in Example 1 was judged by observing the target morphology from the SEM image, and the SEM of the Nb2O5 of the NbOx bulk layer of the rotating NbOx target obtained in Example 1 is shown in FIG. 1. Figure 2 It can be seen that the Nb2O5 grain boundary is clear, not decomposed, and the target component is uniform, and the SEM morphology of the rotating NbOx target obtained in each of the other examples is similar Figure 2 . Figure 3 The Nb2O5 grain boundary is blurred, decomposed, and the target component is not uniform, and the SEM morphology of the rotating NbOx target obtained in Comparative Example 3 is similar Figure 3 .

[0110] Application of the rotating NbOx target

[0111] Equipment: rotating magnetron sputtering system (substrate size 2m x 2.5m);

[0112] The rotating NbOx targets obtained in each of the examples and comparative examples were subjected to magnetron sputtering film application test, and the service life of the target and the uniformity of the sputtered film were detected, wherein:

[0113] Sputtering application parameters: Ar flow rate 150sccm, working pressure 0.5Pa, target rotation speed 40rpm, DC power 8kW;

[0114] The film thickness deviation test method is as follows: film thickness deviation test (SEMI MF1528 9-point method), test equipment: non-contact film thickness meter. Film thickness deviation test 9-point position: 1 point at the center of the substrate + 8 points at the edge (uniformly distributed 50mm from the edge). The test results of the rotating NbOx targets obtained in each of the examples and comparative examples are shown in Table 1.

[0115] The service life test method of the rotating NbOx target is as follows: SEMI F1392 (failure standard), flaking area > 5% or crack length > 2mm

[0116] Test equipment: rotating magnetron sputtering system (equipped with particle counter)

[0117] Test steps:

[0118] 1. Continuous sputtering:

[0119] - Stop for detection every 25 hours, record:

[0120] - Surface state of the target (photograph record)

[0121] - Number of particle contamination on the substrate

[0122] - Cooling water temperature: constant 15±1°C (to prevent thermal stress accumulation)

[0123] 2. Termination conditions (any one of the following is satisfied, the life is terminated)

[0124] - Total peeling area ≥ 5% of the target surface

[0125] - Main crack length ≥ 2mm

[0126] - Sputtering rate drop > 15% (compared to the initial value), the sputtering rate is tested by the film thickness monitor method.

[0127] The rotating niobium oxide target materials obtained in each of the examples and the comparative example are tested, and the test results are shown in Table 1.

[0128] The sputtering film layer of the rotating niobium oxide target material obtained in Example 1 has a refractive index n = 2.30@550nm and an extinction coefficient k < 0.001; the sputtering film layers of the rotating niobium oxide target materials obtained in the remaining examples have similar refractive index and extinction coefficient to those of Example 1.

[0129] Table 1: Performance test of the rotating niobium oxide obtained in each of the examples and the comparative example

[0130]

[0131] The above description is only an embodiment of the present application, and does not limit the scope of patent protection. Those skilled in the art can make non-essential changes or substitutions on the basis of the present application, and still fall within the scope of patent protection.

Claims

1. A rotating niobium oxide target comprising a niobium oxide bulk layer and an inner liner tube, the niobium oxide bulk layer comprising a niobium oxide working surface layer and a metallic transition underlayer, characterized in that, The functional gradient intermediate layer is composed of Nb2O5 and TiO2, the content of Nb2O5 at the contact end with the metal transition bottom layer is ≥45wt% and ≤55wt%, and the content of Nb2O5 at the contact end with the niobium oxide working surface layer is ≥95wt% and ≤100wt%, and the content of Nb2O5 gradually increases from the contact end with the metal transition bottom layer to the contact end with the niobium oxide working surface layer; The Nb2O5 surface of the niobium oxide working surface layer and the functional gradient intermediate layer is coated with a SiO2 nanolayer; The thickness of the metal transition bottom layer is 100-300μm, the thickness of the functional gradient intermediate layer is 200-500μm, and the thickness of the niobium oxide working surface layer is 1-2mm; The Nb2O5 is subjected to hydrogen reduction-passivation treatment and coated with a SiO2 nanolayer, specifically: first, the hydrogen reduction treatment is to reduce the Nb2O5 in a pure H2 atmosphere at 400-500℃ for 2-4h; then, the passivation treatment is to expose the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 1-3vol% O2 at room temperature for 22-26h; finally, the passivated Nb2O5 is immersed in a 1-3wt% silane coupling agent ethanol solution, subjected to ultrasonic treatment for 10-40min, and then calcined at 550-650℃ for 50-80min to obtain the Nb2O5 coated with the SiO2 nanolayer; The thickness of the SiO2 nanolayer is 60nm, 80nm or 100nm.

2. The rotating niobium oxide target according to claim 1, wherein The metal transition bottom layer is a NiCrAlY alloy layer.

3. The rotating niobium oxide target according to claim 2, wherein The content of Ni in the NiCrAlY alloy layer is 70-80wt%, the content of Cr is 15-25wt%, the content of Al is 4-6wt%, and the content of Y is 0.5-1.5wt%.

4. The method of any one of claims 1 to 3, wherein the target is rotated at a speed of 0.1 to 10 rpm. The method comprises the following steps: S1. Plasma spraying a metal transition bottom layer on an inner liner tube; S2. Plasma spraying a functional gradient intermediate layer on the metal transition bottom layer; S3. Supersonic flame spraying a niobium oxide working surface layer on the functional gradient intermediate layer to obtain a rotating niobium oxide target precursor, and obtaining a rotating niobium oxide target through post-processing.

5. The method of claim 4, wherein the target is rotated at a speed of 0.1 to 10 rpm. The Nb2O5 in S3 is subjected to hydrogen reduction-passivation treatment and coated with a SiO2 nanolayer.

6. The method of claim 4, wherein the target is rotated at a speed of 0.1 to 10 rpm. The Nb2O5 in S2 and S3 is subjected to hydrogen reduction-passivation treatment and coated with a SiO2 nanolayer.

7. The method of claim 4, wherein the target is rotated at a speed of 0.1 to 10 rpm. The post-processing after step S3 is specifically: vacuum annealing and surface grinding the rotating niobium oxide target precursor to obtain a rotating niobium oxide target; the vacuum annealing temperature is 750-850℃, and the time is 1.5-2.5h.

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