A rotating zinc target material, a method for manufacturing the same, and an application thereof

Abstract

This invention belongs to the field of rotating zinc target technology, and discloses a rotating zinc target, its preparation method and application. The rotating zinc target includes a zinc main body layer (1) and an inner liner tube (2) disposed inside the zinc main body layer (1). The zinc main body layer (1) is provided with a zinc working surface layer (12) and a Ni-Cu alloy transition bottom layer (11). The zinc working surface layer (12) is an ultrafine-grained pure zinc surface layer (12), and a Zn-Ti alloy intermediate layer (13) is provided between it and the Ni-Cu alloy transition bottom layer (11). The Zn-Ti alloy intermediate layer (13) can effectively prevent the downward diffusion of surface Zn atoms. Zn-Ti can form a dense intermetallic compound (such as TiZn2, TiZn3, Ti2Zn). 11 The Zn-Ti alloy intermediate layer (13) is metallurgically bonded to the interface without voids or porosity defects, effectively preventing the diffusion of Zn atoms from the surface layer. The ultrafine-grained pure zinc surface layer (12) has small grain size, and the interface grains formed by the Zn-Ti alloy intermediate layer (13) with the surface layer and with the bottom layer are also small in size, which can effectively disperse stress. The resulting deposited film has a uniform and dense composition and a long service life.

Description

Technical Field

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

[0002] Rotating zinc sputtering targets are cylindrical and used in magnetron sputtering coating processes. They possess excellent electrical and thermal conductivity, as well as continuous sputtering uniformity, ensuring better thickness consistency and material properties in the thin film. They offer significant advantages in large-area thin film deposition and are widely used in flat panel displays, solar cells, electronic components, and decorative and protective coatings. The basic structure of existing rotating zinc sputtering targets includes a zinc main layer 1 and an inner liner tube 2. The zinc main layer 1 primarily consists of a zinc working surface layer 12 and a Ni-Cu alloy transition underlayer 11.

[0003] The main technical problems currently existing are as follows:

[0004] (1) A large number of Zn atoms diffuse into the zinc working surface layer 12, with a diffusion depth >50μm into the bottom layer. On the one hand, after the Zn atoms diffuse into the Ni-Cu alloy transition bottom layer, they react chemically with Cu atoms in the bottom layer, generating brittle Zn-Cu intermetallic compounds (such as CuZn, CuZn2, Cu5Zn8, etc.) at the interface between the surface layer and the bottom layer, resulting in low interfacial bonding. On the other hand, when a large number of Zn atoms diffuse from the surface layer to the bottom layer, since the surface layer is a coarse-grained structure with large grain size and few grain boundaries, Zn atoms will preferentially diffuse in a few grain boundaries or dislocation-rich areas inside the grains, resulting in different diffusion rates in different regions. This leads to uneven overall composition distribution of the zinc working surface layer, fluctuations in the target sputtering rate, and poor uniformity of the thickness of the deposited film.

[0005] (2) The grains of the zinc working surface layer 12 and the grains at the interface between the zinc working surface layer 12 and the Ni-Cu alloy transition substrate 11 are relatively large, making the target material prone to cracking and detachment. Moreover, the interfacial bonding force is low, resulting in a short service life of the target material. On the one hand, the grain size of the zinc working surface layer of the existing target material is too large, reaching 15~50μm, which has limited stress dispersion effect, resulting in stress concentration on the surface layer, making it prone to cracking and detachment. The detached zinc particles embed into the deposited film, causing foreign impurity defects in the film. On the other hand, the grain size of the interface between the zinc working surface layer and the Ni-Cu alloy transition substrate 11 is large, and the interfacial bonding force is as low as 15MPa. Therefore, the interface is prone to peeling and delamination, resulting in a short service life of the target material. Summary of the Invention

[0006] This invention provides a rotating zinc target material, which, compared with the prior art, has a smaller Zn element diffusion depth or smaller interface and surface grain size.

[0007] Another object of the present invention is to provide a method for preparing the rotating zinc target.

[0008] To solve the above-mentioned technical problems, the technical solution provided by the present invention is as follows:

[0009] A rotating zinc target includes a zinc main layer 1 and an inner liner tube 2 disposed inside the zinc main layer 1. The zinc main layer 1 is provided with a zinc working surface layer 12 and a Ni-Cu alloy transition bottom layer 11. The zinc working surface layer 12 is an ultrafine crystal pure zinc surface layer 12, and a Zn-Ti alloy intermediate layer 13 is provided between it and the Ni-Cu alloy transition bottom layer 11.

[0010] The rotating zinc target provided by this invention has a zinc working surface layer 12 that is an ultrafine-grained pure zinc surface layer 12, and a Zn-Ti alloy intermediate layer 13 between the ultrafine-grained pure zinc surface layer 12 and the Ni-Cu alloy transition bottom layer 11, which has the following technical effects:

[0011] (1) The Zn-Ti alloy interlayer 13 can effectively prevent the downward diffusion of Zn atoms from the zinc working surface layer 12. Zn-Ti can form dense intermetallic compounds (such as TiZn2, TiZn3, Ti2Zn). 11 The interfaces between the Zn-Ti alloy intermediate layer 13 and the zinc working surface layer 12, and between the Zn-Ti alloy transition bottom layer 13 and the Ni-Cu alloy transition bottom layer 11, are all metallurgical bonds without voids or loose defects, effectively preventing the diffusion of Zn atoms on the surface. The shallow diffusion depth of Zn atoms on the surface of the rotating zinc target of this invention prevents the formation of brittle Zn-Cu intermetallic compounds at the interface, thus not affecting the interfacial bonding force. Furthermore, the small number of Zn atoms diffused on the surface and the extremely high grain boundary density of the ultrafine-grained pure zinc surface layer 12 result in a uniform network distribution. Because the Zn atom diffusion path mainly relies on grain boundary diffusion, the Zn atom diffusion rate of the zinc working surface layer 12 is basically consistent, resulting in a uniform overall composition distribution on the surface, consistent target sputtering rate, and excellent uniformity in the thickness of the deposited film.

[0012] (2) The ultrafine-grained pure zinc surface layer 12 has a small grain size, and the interface grains formed by the Zn-Ti alloy intermediate layer 13 with the surface layer and with the bottom layer are also small in size. The target material is not prone to cracking or peeling, resulting in a long service life and uniform composition of the deposited film without foreign impurities. The interface formed by the rotating zinc target Zn-Ti alloy intermediate layer 13 with the zinc working surface layer 12 and with the Ni-Cu alloy transition bottom layer 11 has relatively small grains, resulting in high interfacial bonding and making it less prone to delamination. The ultrafine-grained pure zinc surface layer 12 has a small surface grain size, which can effectively disperse stress and prevent stress concentration on the surface. It will not cause cracking or peeling during sputtering, resulting in a uniform and dense composition of the deposited film with good consistency and a long service life of the target material.

[0013] Preferably, the Cu content in the Ni-Cu alloy transition layer 11 is 8~12 wt%.

[0014] Preferably, the Ti content in the Zn-Ti alloy intermediate layer 13 is 3~7 wt%.

[0015] Preferably, the Ni-Cu alloy transition layer 11 has a thickness of 0.05~0.2mm, the Zn-Ti alloy intermediate layer 13 has a thickness of 0.3~0.8mm, and the ultrafine crystalline pure zinc surface layer 12 has a thickness of 0.4~0.8mm.

[0016] Preferably, the Ni-Cu alloy transition layer 11 has a grain size of 3~5μm, the Zn-Ti alloy intermediate layer 13 has a grain size of 2~3μm, and the ultrafine pure zinc surface layer 12 has a grain size of 0.5~1μm.

[0017] This invention also provides a method for preparing the rotating zinc target, comprising the following steps:

[0018] S1. Cold spray Ni-Cu alloy transition underlayer 11 onto the inner liner tube 2;

[0019] S2. Cold spray a Zn-Ti alloy intermediate layer 13 onto the Ni-Cu alloy transition base layer 11;

[0020] S3. Cold spray an ultrafine-grained pure zinc surface layer 12 onto the Zn-Ti alloy intermediate layer 13 to obtain a rotating zinc target precursor;

[0021] S4. Heat-treat the rotating zinc target precursor to obtain the rotating zinc target.

[0022] The preparation method provided by the present invention can produce the above-mentioned rotating zinc target. The ultrafine pure zinc surface layer 12 of the rotating zinc target has a shallow zinc atom diffusion depth and a small grain size. Furthermore, the grains formed by the Zn-Ti alloy intermediate layer 13 and the ultrafine pure zinc surface layer 12, as well as the grains formed at the interface with the Ni-Cu alloy transition bottom layer 11, are all small in size.

[0023] Preferably, the inner liner tube 2 in S1 is sandblasted.

[0024] Preferably, each of steps S1 to S3 involves ultrasonic rolling treatment simultaneously with cold spraying. Ultrasonic energy reduces the coefficient of friction at the interfaces between the surface, intermediate, and bottom layers of the target material, thus allowing the mechanical force of the rolling process to act uniformly on each interface, promoting atomic diffusion and uniform mixing at the interface, and enhancing the bonding strength between layers. The rolling mechanical force provides continuous pressure to the interface, compressing the material gaps and allowing the ultrasonic energy to act more concentratedly within the grains. This facilitates the acoustic energy-driven atomic movement, enabling the grains at the interface to undergo plastic deformation under the combined action of mechanical force and ultrasonic vibration, dividing large grains into smaller grains and achieving grain refinement at the interface.

[0025] The combined effect of ultrasonic energy and the mechanical force of roller pressing can refine the surface layer and interlayer grains of the target material, resulting in the following technical effects:

[0026] (1) The ultrafine pure zinc surface layer 12 and the interfaces of each layer of the rotating zinc target are all fine-grained, and the atomic diffusion and mixing at the interfaces of each layer are uniform, so the bonding strength between each layer is large.

[0027] (2) Ultrasonic rolling promotes the compactness of each layer structure and refines the grains. On the one hand, it makes the grain boundary density high and the grain boundary blocks the diffusion channel of Zn atoms. On the other hand, grain boundary twisting will occur during the grain refinement process, providing conditions for Ti to agglomerate and effectively increasing the diffusion resistance of Zn atoms in the surface layer. Therefore, the diffusion depth of Zn atoms in the ultrafine pure zinc surface layer 12 is shallow.

[0028] Preferably, the specific parameters of the ultrasonic roller pressing are: pressure 80~120N, frequency 30~40kHz.

[0029] Preferably, the heat treatment in S4 specifically involves: annealing temperature of 170~190℃, annealing time of 2~4h, and vacuum annealing.

[0030] The present invention also provides the application of the rotating zinc target in display panel sputtering.

[0031] Specifically, the application of the rotating zinc target in the sputtering of zinc oxide transparent conductive film in display panels. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of a rotating zinc target structure.

[0033] Figure 2 This is a flowchart for determining the validity of data in the bond strength test between the zinc body layer and the inner liner of a rotating zinc target.

[0034] Figure 3 This is a microstructure diagram of the rotating zinc target obtained in Example 1.

[0035] Figure 4 This is a microstructure diagram of the rotating zinc target obtained in Comparative Example 1.

[0036] Figure 5 The diagram shows the longitudinal structure and composition analysis of each layer of the rotating zinc target obtained in Example 1, where: (a) and (b) are the zinc working surface layer 12, (c) and (d) are the Zn-Ti alloy intermediate layer 13, (e) and (f) are the Ni-Cu alloy transition bottom layer 11, and (g) and (h) are the inner liner tube 2.

[0037] Figure 6 The diagrams show the longitudinal structure and composition of each layer of the rotating zinc target obtained in Comparative Example 1, where: (a) and (b) are the zinc working surface layer 12, (c) and (d) are the Ni-Cu alloy transition bottom layer 11, and (e) and (f) are the inner liner tube 2.

[0038] List of reference numerals in the attached diagram:

[0039] 1-Zinc main layer, 2-Inner liner, 11-Ni-Cu alloy transition layer, 12-Zinc working surface layer, 13-Zn-Ti alloy intermediate layer. Detailed Implementation

[0040] The present invention will be further described in detail below with reference to specific embodiments.

[0041] In the methods for preparing rotating zinc targets described in the various embodiments and comparative examples of the present invention:

[0042] The Ni-Cu alloy transition layer 11, Zn-Ti alloy intermediate layer 13, and ultrafine pure zinc surface layer 12 were cold-sprayed using the PCS-800 cold spraying system from Japan Plasma Technology Co., Ltd.

[0043] The ultrasonic roller pressing device uses the German Sonics URS-40.

[0044] The vacuum annealing furnace is a Thermo Scientific Lindberg furnace.

[0045] Example 1

[0046] A rotating zinc target includes a zinc main layer 1 and an inner liner tube 2 disposed inside the zinc main layer 1. The zinc main layer 1 has a zinc working surface layer 12 and a Ni-Cu alloy transition bottom layer 11. The zinc working surface layer 12 is an ultrafine-grained pure zinc surface layer 12, and a Zn-Ti alloy intermediate layer 13 is disposed between it and the Ni-Cu alloy transition bottom layer 11. The Ni-Cu alloy transition bottom layer 11 has a Cu content of 10wt%, a thickness of 0.1mm, and a grain size of 4μm; the Zn-Ti alloy intermediate layer 13 has a Ti content of 5wt%, a thickness of 0.5mm, and a grain size of 2.5μm; the ultrafine-grained pure zinc surface layer 12 has a thickness of 0.65mm and a grain size of 0.8μm.

[0047] The method for preparing the rotating zinc target includes the following steps:

[0048] S1. Cold spraying a Ni-Cu alloy transition underlayer 11 onto the inner liner tube 2, specifically:

[0049] First, 304 stainless steel was selected as the inner liner tube 2. The inner liner tube 2 was sandblasted with white corundum with a particle size of 80 mesh. After sandblasting, the surface roughness was measured by a white light interferometer and found to be Ra=2.5μm.

[0050] Then, Ni-Cu was cold-sprayed onto the inner liner tube 2 using an argon / helium mixture (70% He) at a pressure of 2.0 MPa, and ultrasonic rolling pressure (100 N pressure, 35 kHz frequency, and 100 mm roller curvature radius) was applied simultaneously during the cold spraying process. The specific parameters of the cold-sprayed Ni-Cu alloy transition underlayer 11 are as follows:

[0051] The powder is a Ni-10Cu pre-alloyed powder with a D50 of 25 μm and an O content of less than 500 ppm.

[0052] The gas is an Ar / He mixture (70% He).

[0053] pressure = 2.0 MPa;

[0054] Nozzle angle = 90°, meaning the nozzle angle is perpendicular to the mandrel surface;

[0055] Rotation speed = 30 rpm;

[0056] Traverse speed = 100 mm / s;

[0057] Layer thickness = 0.1 mm (achieved by two deposition passes).

[0058] S2. A Zn-Ti alloy intermediate layer 13 is cold-sprayed onto the Ni-Cu alloy transition base layer 11, specifically as follows:

[0059] Zn-Ti (Ti particle size 1μm) was cold-sprayed onto the Ni-Cu alloy transition substrate 11 under a nitrogen pressure of 2.5MPa, and ultrasonic rolling pressure (pressure 100N, frequency 35kHz, roller curvature radius 100 mm) was applied simultaneously during the cold spraying process. The specific parameters for the cold-sprayed Zn-Ti are as follows:

[0060] Mechanically mixed powder, comprising: zinc powder (4N, D50=20μm, 95wt%); titanium powder (99.9% purity, D50=1μm, 5wt%).

[0061] The gas is N2;

[0062] Pressure = 2.5 MPa;

[0063] Rotation speed = 25 rpm;

[0064] Layer thickness = 0.5 mm (achieved by depositing in 5 passes, each layer being 0.1 mm thick).

[0065] After cold spraying, interlayer cooling is performed by argon purging to reduce the temperature to <50℃, which can prevent Ti oxidation.

[0066] S3. An ultrafine-grained pure zinc surface layer 12 (zinc powder D50 = 15 μm) is cold-sprayed onto the Zn-Ti alloy intermediate layer 13 under a helium pressure of 3.0 MPa, and ultrasonic rolling pressure (pressure 120 N, frequency 35 kHz) is applied simultaneously during cold spraying to obtain a rotating zinc target precursor; the specific parameters of the cold-sprayed ultrafine-grained pure zinc surface layer 12 are as follows:

[0067] The powder is 4N zinc powder with a D50 of 15μm and an O content of less than 300ppm.

[0068] Gas is He (purity 99.999%).

[0069] Pressure = 3.0 MPa, at which high kinetic energy can be used to refine the grains;

[0070] Gas temperature = 150℃

[0071] Rotation speed = 20 rpm

[0072] Layer thickness = 0.65 mm (achieved in 7 passes).

[0073] S4. The rotating zinc sputtering precursor is subjected to vacuum annealing at 180°C for 3 hours to obtain the rotating zinc sputtering material; the specific vacuum annealing parameters are as follows:

[0074] The temperature is increased to 180℃ at a rate of 5℃ / min, held for 3 hours, and then cooled to 60℃ in the furnace; the vacuum degree during the vacuum annealing process is ≤5×10⁻⁶. -3 Pa, and apply an axial tension of 35 MPa using a hydraulic tie rod system.

[0075] Example 2

[0076] This embodiment is the second embodiment of the present invention. Unlike embodiment 1, the Cu content of the Ni-Cu alloy transition layer 11 is 8 wt%, and the thickness is 0.2 mm.

[0077] Example 3

[0078] This embodiment is the third embodiment of the present invention. Unlike embodiment 1, the Cu content of the Ni-Cu alloy transition layer 11 is 12 wt%, and the thickness is 0.05 mm.

[0079] Example 4

[0080] This embodiment is the fourth embodiment of the present invention. Unlike embodiment 1, the grain size of the Ni-Cu alloy transition bottom layer 11 is 3μm.

[0081] Example 5

[0082] This embodiment is the fifth embodiment of the present invention. Unlike embodiment 1, the grain size of the Ni-Cu alloy transition bottom layer 11 is 5μm.

[0083] Example 6

[0084] This embodiment is the fourth embodiment of the present invention. The difference from embodiment 1 is that the Ti content of the Zn-Ti alloy intermediate layer 13 is 3wt%.

[0085] Example 7

[0086] This embodiment is the fifth embodiment of the present invention. The difference from embodiment 1 is that the Ti content of the Zn-Ti alloy intermediate layer 13 is 7 wt%.

[0087] Example 8

[0088] This embodiment is the 8th embodiment of the present invention. Unlike embodiment 1, the Zn-Ti alloy intermediate layer 13 has a grain size of 2μm and a thickness of 0.8mm.

[0089] Example 9

[0090] This embodiment is the 9th embodiment of the present invention. Unlike embodiment 1, the Zn-Ti alloy intermediate layer 13 has a grain size of 3 μm and a thickness of 0.3 mm.

[0091] Example 10

[0092] This embodiment is the 10th embodiment of the present invention. Unlike embodiment 1, the ultrafine crystalline pure zinc surface layer 12 has a thickness of 0.4 mm and a grain size of 0.5 μm.

[0093] In the method for preparing the rotating zinc target:

[0094] S3. An ultrafine-grained pure zinc surface layer 12 (zinc powder D50 = 15 μm) is cold-sprayed onto the Zn-Ti alloy intermediate layer 13 under a helium pressure of 3.0 MPa, and ultrasonic rolling pressure (pressure 120 N, frequency 35 kHz) is applied simultaneously during cold spraying to obtain a rotating zinc target precursor; the specific parameters of the cold-sprayed ultrafine-grained pure zinc surface layer 12 are as follows:

[0095] The powder is 4N zinc powder with a D50 of 15μm and an O content of less than 300ppm.

[0096] The gas is He, with a purity of 99.999%.

[0097] Pressure = 3.0 MPa, at which high kinetic energy can be used to refine the grains;

[0098] Gas temperature = 150℃

[0099] Rotation speed = 20 rpm

[0100] Layer thickness = 0.4 mm (achieved by applying 4 layers of 0.1 mm each).

[0101] Example 11

[0102] This embodiment is the 11th embodiment of the present invention. Unlike embodiment 1, the ultrafine crystalline pure zinc surface layer 12 has a thickness of 0.8 mm and a grain size of 1 μm.

[0103] In the method for preparing the rotating zinc target:

[0104] S3. An ultrafine-grained pure zinc surface layer 12 (zinc powder D50 = 15μm) is cold-sprayed onto the Zn-Ti alloy intermediate layer 13 under a helium pressure of 3.0MPa. No ultrasonic rolling is applied simultaneously during the cold spraying process to obtain a rotating zinc target precursor. The specific parameters of the cold-sprayed ultrafine-grained pure zinc surface layer 12 are as follows:

[0105] The powder is 4N zinc powder with a D50 of 15μm and an O content of less than 300ppm.

[0106] The gas is He, with a purity of 99.999%.

[0107] Pressure = 3.0 MPa, at which high kinetic energy can be used to refine the grains;

[0108] Gas temperature = 150℃

[0109] Rotation speed = 20 rpm

[0110] Layer thickness = 0.8 mm (achieved by applying 8 layers of 0.1 mm each).

[0111] Example 12

[0112] This embodiment is the 12th embodiment of the present invention. The difference from embodiment 1 is that, in the process of preparing the rotating zinc target, the ultrasonic rolling pressure applied in S1 and S2 is 80N; and the ultrasonic rolling pressure applied in S3 is 100N.

[0113] S4 vacuum annealing treatment, temperature 170℃, time 4h.

[0114] Example 13

[0115] This embodiment is the 13th embodiment of the present invention. The difference from embodiment 1 is that the ultrasonic rolling frequency applied in S1 and S2 is 40KZ; and the ultrasonic rolling frequency applied in S3 is 30KHz.

[0116] S4 vacuum annealing treatment, temperature 190℃, time 2h.

[0117] Comparative Example 1

[0118] This comparative example is the first comparative example of the present invention. Unlike Example 1, the zinc main body layer 1 of the rotating zinc target does not have a Zn-Ti alloy intermediate layer 13, the zinc working surface layer 12 has a thickness of 0.72 mm, and the Ni-Cu alloy transition bottom layer 11 has a thickness of 0.09 mm.

[0119] Comparative Example 2

[0120] This comparative example is the second comparative example of the present invention. Unlike Example 1, the zinc working surface layer 12 of the zinc body layer 1 of the rotating zinc target has a grain size of 30 μm.

[0121] Regarding rotating zinc sputtering targets, among which:

[0122] S3. An ultrafine-grained pure zinc surface layer 12 (zinc powder D50 = 15 μm) is cold-sprayed onto the Zn-Ti alloy intermediate layer 13 under a helium pressure of 3.0 MPa. Simultaneous ultrasonic rolling (pressure 120 N, frequency 35 kHz) is applied during cold spraying. In cases where simultaneous ultrasonic rolling is not applied during cold spraying, a rotating zinc target precursor is obtained. The specific parameters of the cold-sprayed ultrafine-grained pure zinc surface layer 12 are as follows:

[0123] The powder is 4N zinc powder with a D50 of 15μm and an O content of less than 300ppm.

[0124] Gas is He (purity 99.999%).

[0125] Pressure = 1.5 MPa. This pressure is low, the kinetic energy is low, the grains cannot recrystallize dynamically, and a fine-grained structure cannot be obtained.

[0126] Gas temperature = 150℃

[0127] Rotation speed = 20 rpm

[0128] Layer thickness = 0.65 mm (achieved in 7 passes).

[0129] Comparative Example 3

[0130] This comparative example is the third comparative example of the present invention. Unlike Example 1, the Cu content of the Ni-Cu alloy transition bottom layer 11 is 5 wt%, and the thickness is 0.02 mm.

[0131] Comparative Example 4

[0132] This comparative example is the fourth comparative example of the present invention. Unlike Example 1, the Cu content of the Ni-Cu alloy transition layer 11 is 15 wt%, the grain size is 8 μm, and the thickness is 0.4 mm.

[0133] Comparative Example 5

[0134] This comparative example is the fourth comparative example of the present invention. Unlike Example 1, the Ti content of the Zn-Ti alloy intermediate layer 13 is 1 wt%, and the thickness is 0.1 mm.

[0135] Comparative Example 6

[0136] This comparative example is the sixth embodiment of the present invention. Unlike embodiment 1, the Ti content of the Zn-Ti alloy intermediate layer 13 is 10wt%, the grain size is 5μm, and the thickness is 1.5mm.

[0137] Performance testing

[0138] 1. Structure and composition analysis of rotating zinc sputtering target

[0139] (1) Rotating zinc target structure

[0140] Schematic diagrams of the rotating zinc target structures obtained in each embodiment are shown below. Figure 1 The target structure mainly includes a zinc main layer 1 and an inner liner tube 2. The zinc main layer 1 is located on the outside of the inner liner tube 2 and includes a Ni-Cu alloy transition bottom layer 11 and a zinc working surface layer 12. The zinc working surface layer 12 is an ultrafine crystal pure zinc surface layer 12. A Zn-Ti alloy intermediate layer 13 is provided between the ultrafine crystal pure zinc surface layer 12 and the Ni-Cu alloy transition bottom layer 11.

[0141] Microscopic images of the actual structure of the rotating zinc target obtained in Example 1 are shown below. Figure 3 As can be seen, the rotating zinc target obtained in Example 1 has a four-layer structure, which consists of the following layers from the inside out: inner liner tube 2, Ni-Cu alloy transition bottom layer 11, Zn-Ti alloy intermediate layer 13 and zinc working surface layer 12. The thickness of Ni-Cu alloy transition bottom layer 11 is 0.1 mm, the thickness of Zn-Ti alloy intermediate layer 13 is 0.5 mm, and the thickness of ultrafine pure zinc surface layer 12 is 0.65 mm. Figure 3 It can also be seen that the Zn-Ti alloy intermediate layer 13 is well bonded to the zinc working surface layer 12 and the Ni-Cu alloy transition layer 11, respectively, with strong adhesion. The actual structure of the rotating zinc target obtained in the other embodiments is similar. Figure 3 .

[0142] Microscopic images of the actual structure of the rotating zinc target obtained in Comparative Example 1 are shown below. Figure 4 As can be seen, the rotating zinc target obtained in Comparative Example 1 has only three layers, from the inside out: inner liner 2, Ni-Cu alloy transition layer 11, and zinc working surface layer 12. The zinc working surface layer 12 is 0.72 mm thick, and the Ni-Cu alloy transition layer 11 is 0.09 mm thick. Figure 4 It can also be seen that the zinc working surface layer 12 and the Ni-Cu alloy transition bottom layer 11 are poorly bonded and have weak adhesion.

[0143] (2) Composition analysis of each layer of the rotating zinc target

[0144] The composition of each layer of the rotating zinc target obtained in Example 1 is shown below. Figure 5 Among them: (a) and (b) are zinc working surface layer 12. In (b) the spectrum 15 shows that the actual composition of zinc working surface layer 12 is Zn. (c) and (d) are Zn-Ti alloy intermediate layer 13. In (d) the spectrum 14 shows that the actual composition of Zn-Ti alloy intermediate layer 13 is Zn and Ti. (e) and (f) are Ni-Cu alloy transition bottom layer 11. In (f) the spectrum 13 shows that the actual composition of Ni-Cu alloy transition bottom layer 11 is Ni and Cu. (g) and (h) are inner liner tube 2. In (h) the spectrum 12 shows that the main component of inner liner tube 2 is Fe.

[0145] The actual structure of the rotating zinc target obtained in Comparative Example 1 is shown in Figure 1. Figure 6 Among them: (a) and (b) are zinc working surface layer 12. In (b) the spectrum 16 shows that the actual composition of zinc working surface layer 12 is Zn. (c) and (d) are Ni-Cu alloy transition bottom layer 11. In (d) the spectrum 17 shows that the actual composition of Ni-Cu alloy transition bottom layer 11 is Ni and Cu. (e) and (f) are inner liner tube 2. In (f) the spectrum 18 shows that the main component of inner liner tube 2 is Fe.

[0146] 2. The bonding strength test between the zinc main body layer 1 and the inner liner tube 2 of the rotating zinc target is performed using the following method.

[0147] (1) Sample preparation:

[0148] Sampling: Multiple (at least 5) cylindrical specimens are cut from the prepared rotating zinc target using a wire cutting machine. The specimen diameter should be 30-50 mm, and must include the entire structure from the inner liner to the zinc surface layer.

[0149] End face treatment: Grind the two end faces of the sample flat on a grinding machine to ensure parallelism better than 0.03 mm, so as to eliminate additional bending stress;

[0150] Bonding: Use a high-strength, high-rigidity thermosetting adhesive (e.g., anaerobic adhesive specifically designed for high-strength tensile testing or high-temperature curing epoxy structural adhesive), with a nominal tensile strength greater than 70 MPa, significantly higher than the expected strength of the interface under test. Bond both ends of the specimen to a specially designed universal joint loading rod. Using a universal joint ensures that the tensile load is perpendicular to the bonding surface, avoiding shear forces.

[0151] Curing: Strictly follow the process requirements of the selected adhesive for curing (for example, some structural adhesives require heating and curing at 150°C for 2 hours).

[0152] (2) Testing Procedure:

[0153] Using a universal testing machine, install a universal coupling between the loading rod and the testing machine to ensure centered tension;

[0154] Loading rate: Using displacement control mode, the rate is set to 0.5 - 1.0 mm / min;

[0155] Continuously record the load-displacement curves.

[0156] (3) Data processing and validity determination (see the data validity determination process) Figure 2 ):

[0157] Record the maximum load value F_max;

[0158] Calculate the bond strength: σ = F_max / A (where A is the cross-sectional area of ​​the specimen);

[0159] Key: Failure Mode and Effects Analysis

[0160] After the test, the fracture surfaces at both ends of the sample must be observed with the naked eye or a microscope;

[0161] Valid data: Only when the fracture surface occurs 100% at the interface between the "Ni-Cu alloy transition layer 11 and the inner liner 2" (e.g.) Figure 2 (As shown in Part C), only that data point is considered valid.

[0162] Invalid data: If the fracture occurs inside the adhesive layer, at the interface between the adhesive layer and the loading rod, or inside the zinc substrate layer (e.g.) Figure 2 If the data point is shown in sections E and G, then that data point must be discarded and resampled for testing.

[0163] The final result is the average of at least 5 valid data points.

[0164] The bonding force test results between the zinc main layer 1 and the inner liner tube 2 in the rotating zinc target obtained in each embodiment and comparative example are shown in Table 1.

[0165] 3. Zn atomic diffusion depth test on the surface layer of rotating zinc target. Using a scanning electron microscope (SEM) equipped with an energy dispersive spectroscopy (EDS) instrument, elemental line scan analysis was performed on the cross-section of the target material to accurately measure the Zn element concentration as a function of depth, thereby determining its diffusion depth. The detection results of Zn atomic diffusion depth on the surface layer of the zinc main body in each embodiment and comparative example are shown in Table 1.

[0166] 4. Grain size test of the surface layer of rotating zinc target.

[0167] The determination was performed using scanning electron microscopy (SEM) image analysis, and the specific steps are as follows:

[0168] (1) Using resin cold-mounted samples: cut a sample containing an ultrafine crystalline pure zinc surface layer 12 from the target material, and polish the sample on a metallographic polishing machine in sequence using 1200 grit, 1500 grit and 2000 grit sandpaper, and then polish it with 0.5um diamond suspension polishing liquid.

[0169] (2) Prepare a chemical etching solution with a ratio of nitric acid to alcohol of 1:9;

[0170] (3) Wipe the polished sample with a cotton swab dipped in chemical etching solution for 5-10 seconds, then rinse with pure water immediately;

[0171] (4) Use a metallographic microscope to observe the crystal phase. If the crystal surface is not clear, repolish and etch it.

[0172] (7) Data Analysis: The intercept method was adopted, and the number of intersections between the test line and the grain boundary was calculated using image analysis software. According to the formula L = L T The formula (P * M) calculates the average intercept length, which is used as the average grain size. The final result is the average of multiple field-of-view measurements. Where: L is the average intercept length, i.e., the average grain size. T Where is the total cross-sectional length, P is the total number of intersections between the test line and the grain boundary, and M is the magnification of the microscopic image.

[0173] The surface layer grain size test results of the rotating zinc targets obtained in each embodiment and comparative example are shown in Table 1.

[0174] 5. Rotating zinc sputtering target life test

[0175] The rotating zinc targets obtained in each embodiment and comparative example were subjected to magnetron sputtering film application tests, and the service life of the targets and the uniformity of the sputtered film were tested.

[0176] Sputtering application parameters: Ar flow rate 150 sccm, working pressure 0.5 Pa, target rotation speed 40 rpm, DC power 8 kW;

[0177] (1) The film thickness deviation test method is as follows: The film thickness deviation test refers to SEMI MF 1528-2019 "Test Method for Film Thickness Uniformity", and the test equipment is a non-contact film thickness gauge. The film thickness deviation is measured at 9 points: 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 zinc target obtained in each embodiment and comparative example are shown in Table 1.

[0178] (2) Rotating zinc target life test: The failure judgment criteria for the rotating zinc target in this invention are customized based on the sputtering application scenario of large-size display panels, as follows: ① Total peeling area of ​​the target surface ≥ 5%; ② Main crack length ≥ 2mm; ③ Sputtering rate decreases by > 15% from the initial value. This test method refers to the actual working conditions of the rotating zinc target in sputtering on a 2m×2.5m substrate (DC power 8kW, target rotation speed 40rpm), ensuring that the judgment results are consistent with the actual failure mode of the target in industrial applications, and avoiding test deviations caused by excessive stringency or leniency.

[0179] Test equipment: Rotary magnetron sputtering system (equipped with a particle counter, substrate size 2m×2.5m).

[0180] The zinc sputtering sputtering life test procedure is as follows:

[0181] ① Continuous sputtering:

[0182] Continuous or semi-continuous sputtering, checked only during normal board replacement.

[0183] Target surface condition (photographed).

[0184] Substrate particle contamination count;

[0185] Cooling water temperature: constant 15±1℃ (to prevent thermal stress accumulation);

[0186] ② Termination conditions (the lifespan is determined to have ended if any one of them is met):

[0187] Total abrasion area ≥ 5% of the target surface

[0188] The length of the main crack is ≥2mm.

[0189] 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.

[0190] The test results of the rotating zinc targets obtained in each embodiment and comparative example are shown in Table 1.

[0191] Table 1. Rotary zinc target formation tests obtained in Examples 1-13 and Comparative Examples 1-6

[0192]

[0193] 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 zinc target, comprising a zinc body layer and an inner liner tube disposed inside the zinc body layer, wherein the zinc body layer has a zinc working surface layer and a Ni-Cu alloy transition underlayer, characterized in that, The zinc working surface layer is an ultrafine-grained pure zinc surface layer, and a Zn-Ti alloy intermediate layer is provided between the ultrafine-grained pure zinc surface layer and the Ni-Cu alloy transition bottom layer; the grain size of the ultrafine-grained pure zinc surface layer is 0.5~1μm.

2. The rotating zinc target according to claim 1, characterized in that, The Cu content in the Ni-Cu alloy transition layer is 8~12 wt%.

3. The rotating zinc target according to claim 1, characterized in that, The Ti content in the Zn-Ti alloy interlayer is 3~7wt%.

4. The rotating zinc target according to claim 1, characterized in that, The thickness of the Ni-Cu alloy transition layer is 0.05~0.2mm, the thickness of the Zn-Ti alloy intermediate layer is 0.3~0.8mm, and the thickness of the ultrafine crystalline pure zinc surface layer is 0.4~0.8mm.

5. The rotating zinc target according to claim 1, characterized in that, The grain size of the transition layer of the Ni-Cu alloy is 3~5μm, and the grain size of the intermediate layer of the Zn-Ti alloy is 2~3μm.

6. The method for preparing the rotating zinc target according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Cold spray Ni-Cu alloy transition underlayer onto the inner liner tube; S2. Cold spray a Zn-Ti alloy intermediate layer onto the Ni-Cu alloy transition base layer; S3. Cold spray an ultrafine-grained pure zinc surface layer onto the Zn-Ti alloy intermediate layer to obtain a rotating zinc target precursor; S4. Heat-treat the rotating zinc target precursor to obtain the rotating zinc target.

7. The method for preparing the rotating zinc target according to claim 6, characterized in that, The inner liner tube in S1 is sandblasted.

8. The method for preparing the rotating zinc target according to claim 6, characterized in that, In each of steps S1 to S3, ultrasonic rolling treatment is performed simultaneously during the cold spraying process.

9. The method for preparing the rotating zinc target according to claim 8, characterized in that, The specific parameters of the ultrasonic roller pressing are: pressure 80~120N, frequency 30~40kHz.

10. The method for preparing the rotating zinc target according to claim 6, characterized in that, The heat treatment in S4 specifically involves annealing at a temperature of 170~190℃ for 2~4 hours, followed by vacuum annealing.

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