Rotary niobium oxide target material as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of rotary niobium oxide target materials, and discloses a rotary niobium oxide target material which comprises a niobium oxide main body layer and a lining tube, the niobium oxide main body layer comprises a niobium oxide working surface layer and a metal transition bottom layer, and the niobium oxide main body layer is provided with a functional gradient middle 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 Nb2O5 content of the end, making contact with the metal transition bottom layer, of the functional gradient intermediate layer is larger than or equal to 45 wt% and smaller than or equal to 55 wt%, the Nb2O5 content of the end, making contact with the niobium oxide working surface layer, of the functional gradient intermediate layer is larger than or equal to 95 wt% and smaller than or equal to 100 wt%, and the Nb2O5 content is gradually increased from the end making contact with the metal transition bottom layer to the end making contact with the niobium oxide working surface layer. The components of the functional gradient intermediate layer are gradually changed, the thermal expansion coefficient is continuously transited, the generated thermal stress is small, the combined interface of the niobium oxide working surface layer and the functional gradient intermediate layer is not prone to being damaged, and the combined interface of the functional gradient intermediate layer and the metal transition bottom layer is also not prone to being damaged, so that the niobium oxide main body layer is not prone to being stripped from the lining pipe.

Description

Technical Field

[0001] This invention relates to the field of rotating niobium oxide target technology, and more specifically, to a rotating niobium oxide target, its preparation method, and its application. Background Technology

[0002] Spinning niobium oxide targets possess excellent high-temperature resistance, electrical insulation, and optical transparency. Thin films obtained through sputtering are widely used in semiconductors, optoelectronics, coatings, and flat panel displays. The basic structure of existing spinning niobium oxide targets includes a niobium oxide substrate layer and an inner liner tube. The niobium oxide substrate layer mainly consists of a niobium oxide working surface layer and a metal transition substrate. A current drawback of spinning niobium oxide targets is that the niobium oxide working surface layer is easily peeled off from the metal transition substrate. This is because the niobium oxide working surface layer in the niobium oxide substrate layer is a ceramic phase with a low coefficient of thermal expansion, approximately 7.1 × 10⁻⁶. -6 / K, while the metal transition layer and inner liner are metallic phases with a high coefficient of thermal expansion, approximately 12.5 × 10⁻⁶. -6 / K, the difference in thermal expansion coefficients between the niobium oxide working surface layer and the metal transition layer is as high as 5 to 6. With such a high difference in thermal expansion coefficients, direct contact between the two generates large thermal stress. As a result, the interface between the niobium oxide working surface layer and the metal transition layer is easily damaged. Therefore, the niobium oxide working surface layer of the rotating niobium oxide target is easily peeled off from the metal transition layer, which in turn causes the niobium oxide main body layer to peel off from the inner liner tube. Summary of the Invention

[0003] This invention provides a rotating niobium oxide target material, wherein the coefficient of thermal expansion of the niobium oxide main layer is close to that of the inner liner tube, and the bonding strength is superior to that of the prior art, or the niobium oxide main layer is not easily decomposed at high temperature and has uniform composition.

[0004] Another object of the present invention is to provide a method for preparing the rotating niobium oxide target.

[0005] To solve the above-mentioned technical problems, the technical solution provided by the present invention is as follows:

[0006] A rotating niobium oxide target includes a niobium oxide main layer and an inner liner. The niobium oxide main layer includes a niobium oxide working surface layer and a metal transition bottom layer. A functionally graded intermediate layer is provided between the niobium oxide working surface layer and the metal transition bottom layer. The functionally graded intermediate layer is composed of Nb2O5 and TiO2. The Nb2O5 content at the contact end with the metal transition bottom layer is ≥45wt% and ≤55wt%, while the Nb2O5 content at the contact end with the niobium oxide working surface layer is ≥95wt% and ≤100wt%. The Nb2O5 content gradually increases from the contact end with the metal transition bottom layer to the contact end with the niobium oxide working surface layer.

[0007] This invention adds a functionally graded intermediate layer to the existing niobium oxide host layer, wherein the Nb₂O₅ content gradually changes from 45wt% to 50wt% to 95wt% to 100wt%, and the Nb₂O₅ surface is coated with a SiO₂ nanolayer, which has the following technical effects:

[0008] The niobium oxide main layer has a high bonding strength with the inner liner tube and is not easily peeled off from the inner liner tube.

[0009] The composition of the additional functionally graded intermediate layer changes gradually, and the coefficient of thermal expansion transitions continuously. Therefore, the difference in the coefficient of thermal expansion in the niobium oxide main layer is low, resulting in small thermal stress. As a result, the interface between the niobium oxide working surface layer and the functionally graded intermediate layer is not easily damaged, and the interface between the functionally graded intermediate layer and the metal transition layer is also not easily damaged. Therefore, the niobium oxide working surface layer of the rotating niobium oxide target is not easily peeled off from the metal transition layer, and consequently, the niobium oxide main layer is not easily peeled off from the inner liner tube.

[0010] Preferably, the Nb₂O₅ surface of the niobium oxide working layer and the functionally graded intermediate layer is coated with a SiO₂ nanolayer. This provides the following technical advantages:

[0011] The niobium oxide host layer has a uniform composition. The SiO2 nanolayer coating on the Nb2O5 surface can form a dense NbSiO with Nb2O5, blocking oxygen diffusion channels and thus inhibiting the high-temperature decomposition and volatilization of Nb2O5. This allows the Nb / O atomic ratio on the target surface to be close to the theoretical value, and the target surface has a uniform composition. As a result, the target is less prone to local breakage during spin sputtering, has a long service life, and the sputtered film obtained by sputtering the target has a uniform thickness and good electrical properties.

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

[0013] Preferably, the NiCrAlY alloy layer contains 70-80 wt% Ni, 15-25 wt% Cr, 4-6 wt% Al, and 0.5-1.5 wt% Y.

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

[0015] The present invention also provides a method for preparing the rotating niobium oxide target as described in any one of the above claims, comprising the following steps:

[0016] S1. Plasma spraying a metal transition layer onto the inner liner tube;

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

[0018] S3. A niobium oxide working surface layer is sprayed onto the functionally graded layer with a supersonic flame to obtain a rotating niobium oxide target precursor, which is then post-processed to obtain the rotating niobium oxide target.

[0019] Preferably, the Nb2O5 in S3 undergoes hydrogen reduction-passivation treatment and is coated with a SiO2 nanolayer.

[0020] Preferably, in S2 and S3, Nb2O5 undergoes hydrogen reduction-passivation treatment and is coated with a SiO2 nanolayer.

[0021] Preferably, the Nb2O5 undergoes hydrogen reduction-passivation treatment to coat its surface with a SiO2 nanolayer. Specifically, the hydrogen reduction treatment involves reducing the Nb2O5 in a pure H2 atmosphere at 400–500°C for 2–4 hours; then, the passivation treatment involves exposing the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 1–3 vol% O2 at room temperature for 22–26 hours; finally, the passivated Nb2O5 is immersed in a 1–3 wt% silane coupling agent ethanol solution, ultrasonically treated for 10–40 minutes, and then calcined at 550–650°C for 50–80 minutes to obtain Nb2O5 with a SiO2 nanolayer coating on its surface.

[0022] In step S1 of the present invention, the inner lining tube needs to be pretreated, specifically: the inner lining tube is roughened by sandblasting and preheated at 300℃~320℃.

[0023] Preferably, the post-processing in step S3 specifically involves: vacuum annealing and surface finishing of the rotating niobium oxide target precursor to obtain the rotating niobium oxide target; the vacuum annealing temperature is 750–850°C, and the time is 1.5–2.5 h. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the cross-sectional structure of the rotating niobium oxide target of the present invention. In the figure, 1 is the working surface layer of niobium oxide, 2 is the functionally graded intermediate layer, 3 is the metal transition bottom layer, and 4 is the inner liner tube.

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

[0026] Figure 3 The image shows a SEM image of the surface of the rotating niobium oxide target obtained in Comparative Example 2. Detailed Implementation

[0027] The present invention will be further described in detail below with reference to specific embodiments.

[0028] Example 1

[0029] A rotating niobium oxide target includes a niobium oxide main layer and an inner liner. The niobium oxide main layer comprises a niobium oxide working surface layer, a metal transition bottom layer, and a functionally graded intermediate layer located between the niobium oxide working surface layer and the metal transition bottom layer. The functionally graded intermediate layer is composed of Nb₂O₅ and TiO₂, wherein the Nb₂O₅ content gradually increases from 50 wt% to 100 wt%. The Nb₂O₅ surfaces of the niobium oxide working surface layer and the functionally graded intermediate layer are coated with SiO₂ nanolayers. The metal transition bottom layer is a NiCrAlY alloy layer, wherein the Ni content is 75 wt%, the Cr content is 20 wt%, the Al content is 5 wt%, and the Y content is 1 wt%. The thickness of the niobium oxide working surface layer is 1.5 mm, the thickness of the functionally graded intermediate layer is 300 μm, and the thickness of the metal transition bottom layer is 200 μm.

[0030] The method for preparing the rotating niobium oxide target includes the following steps:

[0031] S1. Plasma spraying a metal transition underlayer onto the inner liner tube, specifically:

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

[0033] S12. Nb2O5 Pretreatment: First, hydrogen reduction treatment involves reducing Nb2O5 in a pure H atmosphere at 450℃ for 3 hours; then, passivation treatment involves exposing the hydrogen-reduced Nb2O5 to a N atmosphere containing 2 vol% O at room temperature for 24 hours; finally, the passivated Nb2O5 is immersed in a 2 wt% silane coupling agent ethanol solution, ultrasonically treated for 30 minutes, and then calcined at 600℃ for 60 minutes to obtain Nb2O5 with a SiO2 nanolayer coated on the surface. TEM analysis shows that the SiO2 nanolayer thickness is 80 nm; the particle size D50 of the Nb2O5 is 30 μm.

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

[0035] S2. Plasma spraying of a functionally graded intermediate layer onto the metal transition layer, specifically: using an F4-MB spray gun and adjusting the spraying system with the following main parameters: current 500A, main gas: argon (purity ≥99.99%), flow rate 40 SLPM; auxiliary gas: hydrogen (purity ≥99.99%), flow rate 8-10 SLPM; then, loading pretreated Nb2O5 powder and TiO2 into a dual-disc powder feeder at a feed rate of 20 g / min, with argon as the carrier gas (flow rate 3-5 SLPM); finally, adjusting the Nb2O5 / TiO2 mixing ratio in real time (50% → 100% Nb2O5) to spray the functionally graded layer onto the metal transition layer, with a layer thickness gradient control accuracy of ±5%;

[0036] S3. A niobium oxide working layer is supersonic flame-sprayed onto a functionally graded intermediate layer to obtain a rotating niobium oxide target precursor. The precursor is then post-processed to obtain the rotating niobium oxide target. The specific steps are as follows:

[0037] S31. The working surface of niobium oxide is sprayed using high-velocity flame spraying (HVOF) technology. The 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, and the spraying ignition sequence is to first introduce oxygen → start the kerosene pump → ignite → adjust to a stable combustion state. The coating deposition rate is ≥95%, and a rotating niobium oxide target precursor is obtained.

[0038] S32. Post-processing: The niobium oxide target precursor is vacuum annealed and surface-finished to obtain the niobium oxide target. The vacuum annealing process parameters are: heating to 800℃ at 5℃ / min, holding for 2 hours, cooling to 300℃ in the furnace, and then removing from the furnace. In the surface-finishing process, the outer cylindrical grinding machine is used to process the roundness error to ≤0.03mm.

[0039] A schematic diagram of the rotating niobium oxide target obtained in Example 1 is shown below. Figure 1 In 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 pretreatment of S12.Nb2O5 in the method for preparing the rotating niobium oxide target is as follows: First, hydrogen reduction treatment involves reducing Nb2O5 in a pure H atmosphere at 400°C for 4 hours; then, passivation treatment involves exposing the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 1 vol% O2 at room temperature for 22 hours; finally, the passivated Nb2O5 is immersed in a 3 wt% silane coupling agent ethanol solution, ultrasonically treated for 10 minutes, and then calcined at 550°C for 80 minutes to obtain Nb2O5 with a SiO2 nanolayer on its surface. TEM analysis shows that the SiO2 nanolayer thickness is 60 nm; the Nb2O5 particle size D50 = 15 μm.

[0046] Example 5

[0047] This embodiment is the fifth embodiment of the present invention. The difference from Embodiment 1 is that the pretreatment of S12.Nb2O5 in the method for preparing the rotating niobium oxide target is as follows: First, hydrogen reduction treatment involves reducing Nb2O5 in a pure H atmosphere at 500°C for 2 hours; then, passivation treatment involves exposing the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 3 vol% O2 at room temperature for 26 hours; 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°C for 50 minutes to obtain Nb2O5 with a SiO2 nanolayer on its surface. TEM analysis shows that the SiO2 nanolayer thickness is 100 nm; the Nb2O5 particle size D50 = 45 μm.

[0048] Example 6

[0049] This embodiment is the sixth embodiment of the present invention. Unlike embodiment 1, the functionally graded intermediate layer in the niobium oxide main body layer of the rotating niobium oxide target is composed of Nb2O5 and TiO2, wherein the NbO content gradually changes from 45wt% to 95wt%. The Nb2O5 surface of the niobium oxide working surface layer and the functionally graded intermediate layer is coated with a SiO2 nanolayer. The metal transition bottom layer is a NiCrAlY alloy layer, in which the Ni content is 70wt%, the Cr content is 15wt%, the Al content is 4wt%, and the Y content is 0.5wt%.

[0050] Example 7

[0051] This embodiment is the 7th embodiment of the present invention. Unlike embodiment 1, the functionally graded intermediate layer in the niobium oxide main body layer of the rotating niobium oxide target is composed of Nb2O5 and TiO2, wherein the Nb2O5 content gradually changes from 55wt% to 100wt%. The Nb2O5 surface of the niobium oxide working surface layer and the functionally graded intermediate layer is coated with a SiO2 nanolayer. The metal transition bottom layer is a NiCrAlY alloy layer, in which the Ni content is 80wt%, the Cr content is 25wt%, the Al content is 6wt%, and the Y content is 1.5wt%.

[0052] Example 8

[0053] This embodiment is the 8th embodiment of the present invention. The difference from embodiment 1 is that in the method for preparing the rotating niobium oxide target, the preheating temperature of the sandblasted inner liner tube in S11. pretreatment is 300℃; and in S32. posttreatment, the vacuum annealing process parameters are: heating to 750℃ at 5℃ / min, holding for 1.5h, cooling to 300℃ in the furnace and then taking it out of the furnace. In the surface finishing process, the outer cylindrical grinding machine is used to process the roundness error to ≤0.03mm.

[0054] Example 9

[0055] This embodiment is the 9th embodiment of the present invention. The difference from embodiment 1 is that in the method for preparing the rotating niobium oxide target, the preheating temperature of the sandblasted inner liner tube in S11. pretreatment is 320℃; and in S32. posttreatment, the vacuum annealing process parameters are: heating to 850℃ at 5℃ / min, holding for 2.5h, cooling to 300℃ in the furnace and then taking it out of the furnace. In the surface finishing process, the outer cylindrical grinding machine is used to process the roundness error to ≤0.03mm.

[0056] Comparative Example 1

[0057] This comparative example is the first comparative example of the present invention. Unlike Example 1, the niobium oxide main layer in the rotating niobium oxide target only includes the niobium oxide working surface layer and the metal transition bottom layer, without the functional gradient intermediate layer.

[0058] The method for preparing the rotating niobium oxide target includes the following steps:

[0059] S1. Plasma spraying a metal transition layer onto the inner lining tube, specifically:

[0060] S11. Pretreatment of the inner liner tube: First, remove oil, rust, and impurities from the surface of the inner liner tube to ensure cleanliness; then adjust the spray gun parameters, fix the inner liner tube in a suitable position, start the sandblasting machine, and move the spray gun at a uniform speed to sandblast the surface of the inner liner tube; finally, after sandblasting, remove the residual sand from the surface of the inner liner tube to obtain a sandblasted inner liner tube, and preheat the sandblasted inner liner tube at 310℃; the material of the inner liner tube is 304 stainless steel; after sandblasting and roughening, Ra = 5μm;

[0061] S12. Nb2O5 Pretreatment: First, hydrogen reduction treatment involves reducing Nb2O5 in a pure H2 atmosphere at 450℃ for 3 hours; then, passivation treatment involves exposing the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 2 vol% O2 at room temperature for 24 hours; finally, the passivated Nb2O5 is immersed in a 2 wt% silane coupling agent ethanol solution, ultrasonically treated for 30 minutes, and then calcined at 600℃ for 60 minutes to obtain Nb2O5 with a SiO2 nanolayer coated on the surface; the particle size D50 of the Nb2O5 is 25 μm.

[0062] S13. Plasma spraying of metal transition layer on inner liner: The plasma spraying process for the metal transition layer is as follows: First, select an F4-MB spray gun and adjust the spraying system. The main parameters are as follows: current 500A, main gas: argon (purity ≥99.99%), flow rate 40SLPM; auxiliary gas: hydrogen (purity ≥99.99%), flow rate 8-10SLPM; then, load NiCrAlY alloy powder into the powder feeder, with a powder feeding rate of 20g / min, and argon as the carrier gas (flow rate 3-5SLPM); finally, spray the NiCrAlY alloy metal transition layer onto the inner liner.

[0063] S2. A niobium oxide working layer is supersonic flame-sprayed onto a plasma-sprayed metal transition substrate to obtain a rotating niobium oxide target precursor. After post-processing, the rotating niobium oxide target is obtained. The specific steps are as follows:

[0064] S21. The working surface of niobium oxide is sprayed using a high-velocity flaming (HVOF) process. The 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, and the spraying ignition sequence is to first introduce oxygen → start the kerosene pump → ignite → adjust to a stable combustion state. The coating deposition rate is ≥95%, and a rotating niobium oxide target precursor is obtained.

[0065] S22. Post-processing: The niobium oxide target precursor is vacuum annealed and surface-finished to obtain the niobium oxide target. The vacuum annealing process parameters are: heating to 800℃ at 5℃ / min, holding for 2 hours, cooling to 300℃ in the furnace, and then removing from the furnace. In the surface-finishing process, the outer cylindrical grinding machine is used to process the roundness error to ≤0.03mm.

[0066] Comparative Example 2

[0067] This embodiment is the 10th embodiment of the present invention. Unlike embodiment 1, the Nb2O5 surface of the niobium oxide working surface layer and the functional gradient intermediate layer in the rotating niobium oxide target is not covered with a SiO2 nanolayer.

[0068] The method for preparing the rotating niobium oxide target includes the following steps:

[0069] S1. Plasma spraying a metal transition layer onto the inner liner tube, specifically:

[0070] S11. Pretreatment of the inner liner tube: First, remove oil, rust, and impurities from the surface of the inner liner tube to ensure cleanliness; then adjust the spray gun parameters, fix the inner liner tube in a suitable position, start the sandblasting machine, and move the spray gun at a uniform speed to sandblast the surface of the inner liner tube; finally, after sandblasting, remove the residual sand from the surface of the inner liner tube to obtain a sandblasted inner liner tube, and preheat the sandblasted inner liner tube at 310℃; the material of the inner liner tube is 304 stainless steel; after sandblasting and roughening, Ra = 5μm;

[0071] S12. Plasma spraying of metal transition layer on inner liner: The process steps for plasma spraying of metal transition layer are as follows: First, select F4-MB type spray gun and adjust the spraying system. The main parameters are as follows: current 500A, main gas: argon (purity ≥99.99%), flow rate 40SLPM; auxiliary gas: hydrogen (purity ≥99.99%), flow rate 8-10SLPM; then, load NiCrAlY alloy powder into the powder feeder, powder feeding rate 20g / min, carrier gas is argon (flow rate 3-5SLPM); finally, spray NiCrAlY alloy metal transition layer on inner liner.

[0072] Comparative Example 3

[0073] This comparative example is the third comparative example of the present invention. Unlike Example 1, the niobium oxide main layer in 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; the Nb2O5 surface of the niobium oxide working surface layer in the rotating niobium oxide target is not covered with a SiO2 nanolayer.

[0074] The method for preparing the rotating niobium oxide target includes the following steps:

[0075] S1. Plasma spraying a metal transition layer onto the inner lining tube, specifically:

[0076] S11. Pretreatment of the inner liner tube: First, remove oil, rust, and impurities from the surface of the inner liner tube to ensure cleanliness; then adjust the spray gun parameters, fix the inner liner tube in a suitable position, start the sandblasting machine, and move the spray gun at a uniform speed to sandblast the surface of the inner liner tube; finally, after sandblasting, remove the residual sand from the surface of the inner liner tube to obtain a sandblasted inner liner tube, and preheat the sandblasted inner liner tube at 310℃; the material of the inner liner tube is 304 stainless steel; after sandblasting and roughening, Ra = 5μm;

[0077] S12. Plasma spraying of metal transition layer on inner liner: The plasma spraying process for the metal transition layer is as follows: First, select an F4-MB spray gun and adjust the spraying system. The main parameters are as follows: current 500A, main gas: argon (purity ≥99.99%), flow rate 40SLPM; auxiliary gas: hydrogen (purity ≥99.99%), flow rate 8-10SLPM; then, load NiCrAlY alloy powder into the powder feeder at a powder feeding rate of 20g / min, with argon as the carrier gas (flow rate 3-5SLPM); finally, spray the NiCrAlY alloy metal transition layer onto the inner liner.

[0078] S2. A niobium oxide working surface layer is supersonic flame-sprayed onto the metal transition layer to obtain a rotating niobium oxide target precursor. After post-processing, the rotating niobium oxide target is obtained. The specific steps are as follows:

[0079] S11. The niobium oxide working surface layer is sprayed using high-velocity oxygen fuel (HVOF) spraying technology. 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; spraying ignition sequence: first introduce oxygen → start kerosene pump → ignite → adjust to stable combustion state; coating deposition rate: ≥95%; thus, a rotating niobium oxide target precursor is obtained. S12. Post-treatment: The rotating niobium oxide target precursor is subjected to vacuum annealing and surface finishing to obtain the rotating niobium oxide target. The vacuum annealing process parameters are as follows: annealing temperature: 800℃; annealing time: 2 h; surface finishing process: the external cylindrical grinder is used to process the roundness error to ≤0.03 mm.

[0080] Comparative Example 4

[0081] This comparative example is the fourth comparative example of the present invention. The difference between this example and Example 1 is that, in the method for preparing the rotating niobium oxide target,

[0082] S12. Nb2O5 Pretreatment: First, hydrogen reduction treatment involves reducing Nb2O5 in a pure H atmosphere at 350℃ for 1.5h; then, passivation treatment involves exposing the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 4 vol% O2 at room temperature for 21h; finally, the passivated Nb2O5 is immersed in a 0.5 wt% silane coupling agent ethanol solution, ultrasonically treated for 45 min, and then calcined at 500℃ for 90 min to obtain Nb2O5 with a SiO2 nanolayer coated on the surface; the particle size D50 of the Nb2O5 is 10 μm.

[0083] Comparative Example 5

[0084] This comparative example is the fifth comparative example of the present invention. The difference between this example and Example 1 is that, in the method for preparing the rotating niobium oxide target,

[0085] S12. Nb2O5 Pretreatment: First, hydrogen reduction treatment involves reducing Nb2O5 in a pure H atmosphere at 550℃ for 5 hours; then, passivation treatment involves exposing the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 0.5 vol% O2 at room temperature for 28 hours; finally, the passivated Nb2O5 is immersed in a 4 wt% silane coupling agent ethanol solution, ultrasonically treated for 5 minutes, and then calcined at 700℃ for 40 minutes to obtain Nb2O5 with a SiO2 nanolayer coated on the surface; the particle size D50 of the Nb2O5 is 55 μm.

[0086] Comparative Example 6

[0087] This comparative example is the sixth embodiment of the present invention. Unlike embodiment 1, the rotating niobium oxide target has a working surface layer thickness of 0.5 mm, a functionally graded intermediate layer thickness of 550 μm, and a metal transition underlayer thickness of 350 μm.

[0088] Comparative Example 7

[0089] This comparative example is the 7th embodiment of the present invention. Unlike embodiment 1, the rotating niobium oxide target has a working surface layer thickness of 2.5 mm, a functionally graded intermediate layer thickness of 150 μm, and a metal transition underlayer thickness of 70 μm.

[0090] Comparative Example 8

[0091] This comparative example is the 8th embodiment of the present invention. Unlike embodiment 1, the rotating niobium oxide target has a 50 nm thick SiO2 nanolayer coated on the Nb2O5 surface of the niobium oxide working surface layer and the functional gradient intermediate layer.

[0092] Comparative Example 9

[0093] This comparative example is the 9th embodiment of the present invention. Unlike embodiment 1, the rotating niobium oxide target has a SiO2 nanolayer with a thickness of 110 nm on the Nb2O5 surface of the niobium oxide working surface layer and the functional gradient intermediate layer.

[0094] Performance testing:

[0095] Bond strength testing between the niobium oxide host layer and the substrate: The bonding strength was tested using the ASTM C633 method. The testing equipment was a universal testing machine (range ≥ 50 kN). The testing procedure included the following steps:

[0096] 1. Sample preparation:

[0097] - Cutting dimensions: Cut from the rotating niobium oxide target material obtained by comparing the proportions of the above embodiments. Sample (including inner liner + coating)

[0098] - Bonding: The two ends of the sample were roughened with sandpaper (Ra = 3μm), coated with epoxy resin, and then bonded to the loading column.

[0099] -Curing: 80℃×2h+room temperature×24h

[0100] 2. Testing process:

[0101] - Loading rate: 0.75 mm / min (constant displacement control)

[0102] - Termination condition: Coating peeling or load reduction ≥20%

[0103] -Data Recording: Retrieves the maximum load value ˋF_maxˋ

[0104] 3. Calculate the bonding strength (take 5 groups of samples and take the average value).

[0105] The bonding force test results between the niobium oxide main layer and the inner liner tube in the rotating niobium oxide target obtained in each embodiment and comparative example are shown in Table 1.

[0106] Stability of Nb₂O₅ in the Niobium Oxide Host Layer: The stability of Nb₂O₅ in the rotating niobium oxide targets obtained in the above examples was determined by observing the target morphology through SEM images. The SEM image of the Nb₂O₅ host layer of the rotating niobium oxide target obtained in Example 1 is shown below. Figure 2 It can be seen that the Nb2O5 grain boundaries are clear and undecomposed, and the target material composition is uniform. The SEM images of the rotated niobium oxide targets obtained in the other examples are similar. Figure 2 The SEM images of the niobium oxide host layer (Nb₂O₅) of the rotating niobium oxide target obtained in Comparative Example 2 are shown below. Figure 3 It is evident that the Nb2O5 grain boundaries are blurred, decomposition has occurred, and the target material composition is inhomogeneous. The SEM images of the rotated niobium oxide target obtained in Comparative Example 3 are similar. Figure 3 .

[0107] Applications of niobium oxide in rotating niobium oxide targets

[0108] Equipment: Rotary magnetron sputtering system (substrate size 2m × 2.5m);

[0109] The rotating niobium oxide targets obtained in each embodiment and comparative example were subjected to magnetron sputtering film application tests, and the target lifespan and sputtering film uniformity were tested.

[0110] Sputtering application parameters: Ar flow rate 150 sccm, working pressure 0.5 Pa, target rotation speed 40 rpm, DC power 8 kW;

[0111] The film thickness deviation test method is as follows: Film thickness deviation test (SEMI MF1528 9-point method), test equipment: non-contact film thickness gauge. The 9-point positions for measuring film thickness deviation are: 1 point at the center of the substrate + 8 points at the edge (uniformly distributed at a distance of 50 mm from the edge). The test results of the rotating niobium oxide target obtained in each embodiment and comparative example are shown in Table 1.

[0112] The life test method for rotating niobium oxide sputtering targets is as follows: SEMI F1392 (failure criterion), spalling area > 5% or crack length > 2mm.

[0113] Test equipment: Rotary magnetron sputtering system (equipped with a particle counter)

[0114] Test steps:

[0115] 1. Continuous sputtering:

[0116] -Stop the machine for inspection every 25 hours and record the results:

[0117] - Target surface condition (recorded by photograph)

[0118] - Substrate particle contamination number

[0119] - Cooling water temperature: constant 15±1℃ (to prevent thermal stress accumulation)

[0120] 2. Termination conditions (the lifespan is determined to end if any one of them is met):

[0121] - Total peeling area ≥ 5% of the target surface

[0122] -Main crack length ≥2mm

[0123] - The sputtering rate decreased by more than 15% (compared to the initial value), and the sputtering rate was measured using a thin film thickness monitoring method.

[0124] The test results of the rotating niobium oxide targets obtained in each embodiment and comparative example are shown in Table 1.

[0125] The refractive index n = 2.30 @ 550 nm of the sputtered film obtained by the rotating niobium oxide target in Example 1 is less than 0.001; the refractive index and extinction coefficient of the sputtered film obtained by the rotating niobium oxide target in the other examples are similar to those in Example 1.

[0126] Table 1. Performance testing of rotary zinc oxide obtained from each example and comparative example.

[0127]

[0128]

[0129] The above description is merely an embodiment of the present invention and does not limit the scope of patent protection. Any non-substantial changes or substitutions made by those skilled in the art based on the present invention will still fall within the scope of patent protection.

Claims

1. A rotating niobium oxide target, comprising a niobium oxide main body layer and an inner liner tube, wherein the niobium oxide main body layer comprises a niobium oxide working surface layer and a metal transition underlayer, characterized in that, The niobium oxide host layer has a functionally graded intermediate layer between the niobium oxide working surface layer and the metal transition bottom layer. This functionally graded intermediate layer is composed of Nb2O5 and TiO2. The Nb2O5 content at the contact end with the metal transition bottom layer is ≥45wt% and ≤55wt%, while the Nb2O5 content at the contact end with the niobium oxide working surface layer is ≥95wt% and ≤100wt%. The Nb2O5 content gradually increases from the contact end with the metal transition bottom layer to the contact end with the niobium oxide working surface layer.

2. The rotating niobium oxide target according to claim 1, characterized in that, The Nb2O5 surface of the niobium oxide working surface layer and the functional gradient intermediate layer is coated with a SiO2 nanolayer.

3. The rotating niobium oxide target according to claim 1, characterized in that, The metal transition substrate is a NiCrAlY alloy layer.

4. The rotating niobium oxide target according to claim 3, characterized in that, The NiCrAlY alloy layer contains 70–80 wt% Ni, 15–25 wt% Cr, 4–6 wt% Al, and 0.5–1.5 wt% Y.

5. The rotating niobium oxide target according to claim 1, characterized in that, The thickness of the metal transition layer is 100–300 μm, the thickness of the functionally graded intermediate layer is 200–500 μm, and the thickness of the niobium oxide working surface layer is 1–2 mm.

6. A method for preparing a rotating niobium oxide target according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Plasma spraying a metal transition layer onto the inner liner tube; S2. Plasma spraying of a functional gradient layer onto the metal transition layer; S3. A niobium oxide working surface layer is sprayed onto the functionally graded layer with a supersonic flame to obtain a rotating niobium oxide target precursor, which is then post-processed to obtain the rotating niobium oxide target.

7. The method for preparing a rotating niobium oxide target according to claim 6, characterized in that, The Nb2O5 in S3 undergoes hydrogen reduction-passivation treatment and is coated with a SiO2 nanolayer.

8. The method for preparing a rotating niobium oxide target according to claim 6, characterized in that, In S2 and S3, Nb2O5 undergoes hydrogen reduction-passivation treatment and is coated with a SiO2 nanolayer.

9. The method for preparing a rotating niobium oxide target according to claim 7 or 8, characterized in that, The Nb2O5 undergoes hydrogen reduction-passivation treatment to coat its surface with a SiO2 nanolayer. Specifically, the hydrogen reduction treatment involves reducing the Nb2O5 in a pure H2 atmosphere at 400–500 °C for 2–4 hours. Then, the passivation treatment involves exposing the hydrogen-reduced Nb2O5 to a N2 atmosphere containing 1–3 vol% O2 at room temperature for 22–26 hours. Finally, the passivated Nb2O5 is immersed in a 1–3 wt% silane coupling agent ethanol solution, ultrasonically treated for 10–40 minutes, and then calcined at 550–650 °C for 50–80 minutes to obtain Nb2O5 with a SiO2 nanolayer coating on its surface.

10. The method for preparing a rotating niobium oxide target according to claim 6, characterized in that, The post-processing in step S3 specifically involves: vacuum annealing and surface finishing of the rotating niobium oxide target precursor to obtain the rotating niobium oxide target; the vacuum annealing temperature is 750–850℃ and the time is 1.5–2.5h.

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