CN115874155B - Rare earth rotary target material and preparation method and application thereof - Google Patents
Rare earth rotary target material and preparation method and application thereof Download PDFInfo
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- CN115874155B CN115874155B CN202111151674.8A CN202111151674A CN115874155B CN 115874155 B CN115874155 B CN 115874155B CN 202111151674 A CN202111151674 A CN 202111151674A CN 115874155 B CN115874155 B CN 115874155B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 52
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000013077 target material Substances 0.000 title abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 215
- 238000005245 sintering Methods 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 64
- 238000001816 cooling Methods 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 238000001513 hot isostatic pressing Methods 0.000 claims abstract description 26
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 25
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 238000005324 grain boundary diffusion Methods 0.000 claims description 4
- 239000000696 magnetic material Substances 0.000 claims description 4
- 238000001272 pressureless sintering Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000003466 welding Methods 0.000 abstract description 56
- 229910052738 indium Inorganic materials 0.000 abstract description 6
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 6
- 230000004907 flux Effects 0.000 abstract description 4
- 238000000465 moulding Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 96
- 239000000843 powder Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000498 cooling water Substances 0.000 description 12
- 230000001276 controlling effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 239000010963 304 stainless steel Substances 0.000 description 6
- 241000357293 Leptobrama muelleri Species 0.000 description 6
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000007872 degassing Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 238000001755 magnetron sputter deposition Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Abstract
A rare earth rotary target material, a preparation method and application thereof, wherein the method comprises the following steps: placing a back pipe and powdery raw materials into a die to form a composite structure with a center of the back pipe and raw material layers around the back pipe, wherein the raw materials comprise rare earth metal simple substances and/or rare earth alloys, the raw material layers comprise a first raw material layer and a second raw material layer, the first raw material layer is positioned between the back pipe and the second raw material layer, and the particle size of the raw materials in the first raw material layer is smaller than that of the raw materials in the second raw material layer; and performing cold/hot isostatic pressing molding on the composite structure, and controlling the temperature difference between the back pipe and the raw material layer in the sintering cooling process to obtain the rare earth rotary target. The method combines two steps of target tube preparation and welding, realizes the welding of the target tube and the back tube in the process of preparing the rare earth rotary target tube, shortens the preparation flow of the rare earth metal and alloy rotary target material, improves the preparation efficiency, saves the welding flux such as indium and the like, and solves the problems of low welding rate and later opening welding of the target material.
Description
Technical Field
The invention relates to the technical field of rotary targets, in particular to a rare earth metal or rare earth alloy rotary target, and an integrated forming preparation method and application thereof.
Background
Magnetron sputtering technology utilizes the collision of incident particles and a target material for coating, wherein the target material can be classified into a planar target, a tubular target, a rotary target or the like. At present, the utilization rate of the rare earth metal and rare earth alloy planar target is generally 30-50 wt%, and the utilization rate of the tubular target or the rotary target is as high as more than 80wt%, so that the method is more suitable for the fields of magnetic material coating grain boundary diffusion, storage, electronic information and the like, and the market demand in the future is huge.
The rotary target must combine the target tube and the backing tube before being used for magnetron sputtering, and at present, the target tube and the backing tube are combined by adopting a welding mode. The rotary target obtained by welding needs to be free from welding in the use process, and has good heat conduction performance so as to timely take away the heat generated in the magnetron sputtering process. In order to meet the use requirements, the welding rate of the rotary target material is more than 95%. In order to meet the use requirements as much as possible, the existing preparation method of the rare earth metal or alloy rotary target comprises the following steps: the first step is to prepare a blank by a fusion casting or powder metallurgy method and process the blank into a target tube, and the second step is to connect the target tube and a back tube together by welding flux to obtain the target material. However, the existing preparation method cannot realize simultaneous preparation and welding of the target tube, so that more welding materials such as indium are consumed in welding, the preparation efficiency of the rotary target is low, the process is long, and the welding rate is still not high enough.
Disclosure of Invention
Object of the invention
The invention aims to provide a rare earth rotary target material and a preparation method and application thereof, and the method combines two steps of target material preparation and welding, and by controlling material layering, particle size difference of each layer and temperature difference of a backing tube and a raw material layer in a cooling process, the problems of low welding rate of the rotary target material and open welding in a using process are solved, the welding of the target tube and the backing tube is realized in the rare earth rotary target material preparation process, the preparation flow of rare earth metal and alloy rotary target material is shortened, the preparation efficiency is improved, and the welding flux such as indium is saved.
(II) technical scheme
In order to solve the above problems, a first aspect of the present application provides a method for preparing a rare earth rotary target, including:
Placing a back pipe and powdery raw materials into a die to form a composite structure with a center of the back pipe and raw material layers around the back pipe, wherein the raw materials comprise rare earth metal simple substances and/or rare earth alloys, the raw material layers comprise a first raw material layer and a second raw material layer, the first raw material layer is positioned between the back pipe and the second raw material layer, and the particle size of the raw materials in the first raw material layer is smaller than that of the raw materials in the second raw material layer;
and carrying out cold isostatic pressing or hot isostatic pressing on the composite structure to obtain the rare earth rotary target, wherein the cold isostatic pressing comprises the steps of cold isostatic pressing to obtain a blank and sintering the blank, and controlling a back tube and a raw material layer to keep a certain temperature difference in the cooling process of the cold isostatic pressing and the hot isostatic pressing to obtain the rare earth rotary target. The method combines two steps of target tube preparation and welding into one, realizes the efficient preparation of the rare earth rotary target tube and back tube welding integrated formation, shortens the preparation flow of rare earth metal and alloy rotary target materials, saves welding materials such as indium and the like, and solves the problems of low welding rate of the rotary target and open welding in the using process.
Specifically, the thickness of the first raw material layer is 0.1-1 mm, the particle size of the raw material in the first raw material layer is 1-100 mu m, and the particle size of the raw material in the second raw material layer is 10-150 mu m;
The particle size of the raw materials in the second raw material layer is 2-3 times of that of the raw materials in the first raw material layer.
In a specific embodiment, the specific conditions for cold isostatic pressing include:
The pressure is 50-500 MPa, and the pressure maintaining time is 80-200 min.
In an alternative embodiment, the specific conditions for sintering the blank include:
Pressureless sintering is carried out in vacuum or inactive atmosphere;
the sintering temperature T 1 satisfies the following conditions:
when T raw materials ≤T Back pipe , T 1＝0.5～0.95T raw materials ;
t 1＝0.5～0.95T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
The sintering time is 30-250 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
Further, in the cooling process after sintering, the temperature difference between the back pipe and the raw material layer is controlled to be 50-300 ℃, namely, the temperature difference between the back pipe and the raw material layer is controlled to be T X-Td = 50-300 ℃, wherein T x is the temperature of the lower expansion coefficient of the back pipe and the raw material layer, and T d is the temperature of the higher expansion coefficient of the back pipe and the raw material layer.
In another alternative embodiment, the specific conditions for sintering the blank include:
performing hot isostatic pressing sintering;
The sintering pressure is 5-50 MPa;
the sintering temperature T 1 satisfies the following conditions:
when T raw materials ≤T Back pipe , T 1＝0.5～0.9T raw materials ;
T 1＝0.5～0.9T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
the sintering time is 30-240 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
Further, in the cooling process after sintering, the temperature difference between the back pipe and the raw material layer is controlled to be 50-300 ℃, namely, the temperature difference between the back pipe and the raw material layer is controlled to be T X-Td = 50-300 ℃, wherein T x is the temperature of the lower expansion coefficient of the back pipe and the raw material layer, and T d is the temperature of the higher expansion coefficient of the back pipe and the raw material layer.
In another specific embodiment, the hot isostatic pressing of the composite structure specifically comprises:
Performing hot isostatic pressing sintering on the composite structure;
the sintering pressure is 10-60 MPa;
the sintering temperature T1 satisfies:
when T raw materials ≤T Back pipe , T 1＝0.5～0.9T raw materials ;
T 1＝0.5～0.9T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
The sintering time is 30-270 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
Further, in the cooling process after the hot isostatic pressing sintering is completed, the temperature difference T X-Td =50-300 ℃ between the back pipe and the raw material layer is controlled, wherein T x is the temperature of the lower expansion coefficient of the back pipe and the raw material layer, and T d is the temperature of the higher expansion coefficient of the back pipe and the raw material layer.
In a second aspect of the application, a rare earth rotary target prepared by any one of the preparation methods is provided.
In a third aspect, the application provides an application of the rare earth rotary target prepared by any one of the preparation methods in the fields of magnetic material film plating grain boundary diffusion, storage and electronic information.
(III) beneficial effects
The technical scheme of the invention has the following beneficial technical effects:
According to the preparation method of the rare earth rotary target material, the back tube and the powdery raw materials are placed into the die together to form the composite structure with the center of the back tube being the raw material layer around, the composite structure is subjected to cold isostatic pressing, sintering or direct isostatic pressing to realize the completion of the target tube forming and the binding of the target tube/the back tube together, the inner layer raw material particle size is controlled to be smaller than the outer layer raw material particle size to obtain good welding quality, and higher compactness and welding rate are ensured to be obtained in the target tube forming process; by controlling the temperature difference between the raw material layer and the back tube in the cooling process of sintering, the problem that the target material is welded in the later period due to the large expansion coefficient difference between the back tube and the rare earth target tube is effectively solved, and the rotary target is ensured not to be welded in the using process.
The method combines two steps of target tube preparation and welding, realizes the welding of the target tube and the back tube in the process of preparing the rare earth rotary target tube, shortens the preparation flow of the rare earth metal and alloy rotary target material, improves the preparation efficiency, saves the welding flux such as indium and the like, and solves the problems of low welding rate of the rotary target and open welding in the using process.
Drawings
Fig. 1 is a schematic diagram of a composite structure according to an embodiment of the present invention.
Detailed Description
The present invention will be further described in detail with reference to the following embodiments, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
The invention provides a preparation method of a rare earth rotary target, which comprises the following steps:
As shown in fig. 1, a back pipe and powdery raw materials are placed into a mold to form a composite structure with a center that a raw material layer is arranged around the back pipe A, wherein the raw materials comprise rare earth metal simple substances and/or rare earth alloys, the raw material layer comprises a first raw material layer B and a second raw material layer C, the first raw material layer B is positioned between the back pipe A and the second raw material layer C, and the particle size of the raw materials in the first raw material layer B is smaller than that of the raw materials in the second raw material layer C;
And carrying out cold isostatic pressing or hot isostatic pressing on the composite structure to obtain the rare earth rotary target, wherein the cold isostatic pressing comprises the steps of cold isostatic pressing to obtain a blank and sintering the blank, and controlling a back tube and a raw material layer to keep a certain temperature difference in the cooling process of the cold isostatic pressing and the hot isostatic pressing to obtain the rare earth rotary target.
Specifically, the invention can lead the back tube and the raw material layer to form temperature difference in the cooling process by controlling the cooling rate of the sintering furnace, leading the cooling medium into the center of the back tube, adding an auxiliary heating device and the like, and the specific method is not limited by the invention.
Specifically, the back tube in the invention can be selected from stainless steel tubes, copper tubes, alloy tubes, titanium tubes and the like as required, and the stainless steel tubes and the titanium tubes are preferable; at least one of rare earth metal simple substances is selected from Sc, Y, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm, yb, lu; the rare earth alloy is the single rare earth metal or the alloy of a plurality of rare earth metals and metals such as Al, cu, fe and the like.
Specifically, the raw materials can be degassed and the back tube can be cleaned before the preparation of the invention; the mould provided by the invention can be a conventional isostatic soft mould. In an alternative embodiment, to facilitate forming two raw material layers, the mold further comprises a thin-walled cylindrical auxiliary mold with an inner diameter slightly larger than the outer diameter of the back pipe, when the back pipe and the powdery raw material are put into the mold, the back pipe is firstly placed at the center of the mold, then the auxiliary mold and the back pipe are coaxially placed, a cavity between the auxiliary mold and the back pipe is filled with the raw material of the first raw material layer, an interlayer between the auxiliary mold and the mold is filled with the raw material of the second raw material layer, then the auxiliary mold is removed, and the raw material of the second raw material layer is continuously filled until the second raw material layer is compressed.
According to the preparation method of the rare earth rotary target material, the back tube and the powdery raw materials are placed into the die together to form the composite structure with the center of the back tube being the raw material layer around, the composite structure is subjected to cold isostatic pressing, sintering or direct hot isostatic pressing to realize the completion of the target tube forming and the binding of the target tube/the back tube together, the inner layer raw material particle size is controlled to be smaller than the outer layer raw material particle size to obtain good welding quality, and higher compactness and welding rate are ensured to be obtained in the target tube forming process; by controlling the temperature difference between the target tube and the raw material layer in the cooling process, the problem that the target material is welded in the later period due to the large expansion coefficient difference between the back tube and the rare earth target tube is effectively solved, and the rotary target is ensured not to be welded in the using process.
The method combines two steps of target tube preparation and welding into one, realizes the efficient preparation of the rare earth rotary target tube and back tube welding integrated formation, shortens the preparation flow of rare earth metal and alloy rotary target materials, saves welding materials such as indium and the like, and solves the problems of low welding rate of the rotary target and open welding in the using process.
Specifically, the thickness of the first raw material layer is 0.1-1 mm, the particle size of the raw material in the first raw material layer is 1-100 mu m, and the particle size of the raw material in the second raw material layer is 10-150 mu m;
specifically, in the present invention, the raw material particle diameter means an average particle diameter D50.
By controlling the particle size and thickness of the two layers of powder in the above range, the quality of the welding layer can be better controlled, not only can the formation of a diffusion layer between fine powder and the back tube be ensured, but also the formation of brittle intermetallic compounds caused by strong alloying of the first layer of powder and the back tube can be avoided, and the welding rate of the target material is further ensured.
Preferably, the particle size of the raw materials in the second raw material layer is 2-3 times of that of the raw materials in the first raw material layer, so that the density of the target material is ensured to be more than 96%, and the welding rate is ensured to be more than 96%.
In a specific embodiment, specific conditions for isostatic compaction include:
The pressure is 50-500 MPa, and the pressure maintaining time is 80-200 min.
In an alternative embodiment, the specific conditions for sintering the blank include:
Pressureless sintering is carried out in vacuum or inactive atmosphere;
the sintering temperature T 1 satisfies the following conditions:
when T raw materials ≤T Back pipe , T 1＝0.5～0.95T raw materials ;
t 1＝0.5～0.95T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
The sintering time is 30-250 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
Further, the temperature difference between the back tube and the raw material layer is controlled to be 50-300 ℃ in the cooling process after sintering.
In another alternative embodiment, the specific conditions for sintering the blank include:
performing hot isostatic pressing sintering;
The sintering pressure is 5-50 MPa;
the sintering temperature T 1 satisfies the following conditions:
when T raw materials ≤T Back pipe , T 1＝0.5～0.9T raw materials ;
T 1＝0.5～0.9T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
the sintering time is 30-240 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
Further, the temperature difference between the back tube and the raw material layer is controlled to be 50-300 ℃ in the cooling process after sintering.
Compared with cold isostatic pressing and sintering, the cold isostatic pressing and hot isostatic pressing sintering is beneficial to further improving the density, the welding strength and the welding rate and reducing the sintering temperature.
In another specific embodiment, the hot isostatic pressing of the composite structure specifically includes:
Performing hot isostatic pressing sintering on the composite structure;
the sintering pressure is 10-60 MPa;
the sintering temperature T 1 satisfies the following conditions:
when T raw materials ≤T Back pipe , T 1＝0.5～0.9T raw materials ;
T 1＝0.5～0.9T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
The sintering time is 30-270 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
Further, the temperature difference between the back tube and the raw material layer is controlled to be 50-300 ℃ in the cooling process after sintering.
Compared with cold isostatic pressing and sintering, the direct hot isostatic pressing sintering can shorten the preparation flow, save time and reduce energy consumption, and meanwhile, the rotary target material with the quality equivalent to that of the cold isostatic pressing and sintering can be prepared.
The following are specific embodiments of the present invention:
The raw materials used in each example are all commercial products.
Example 1
(1) Degassing Tb powder with the particle size of 30 mu m and Tb powder with the particle size of 80 mu m for later use;
(2) Cleaning and drying a 304 stainless steel back pipe with the outer diameter of 90mm for later use;
(3) Placing the raw material powder treated in the step (1) and the back pipe treated in the step (2) into a mold under vacuum, sealing, and forming a composite structure with a center of the back pipe and raw material layers around, wherein the raw material layers are respectively 30 mu m powder, 80 mu m powder and 9.5mm thick;
(4) After the step (3) is completed, the raw material and back pipe composite structure is subjected to cold isostatic pressing to obtain a blank, wherein the pressure is 250MPa, and the pressure maintaining time is 120min;
(5) And (3) performing vacuum sintering on the blank obtained in the step (4) to obtain a rotary target material, wherein the temperature is 0.8T m(Tm = 1356 ℃, the melting point of the raw material is equal to 150 minutes, the cooling rate in a sintering furnace is controlled to be 5 ℃/min (the cooling rate of the raw material layer) in the cooling process, cooling water is introduced into a back pipe, the cooling rate of the back pipe is controlled by dynamically regulating the cooling water flow through an automatic temperature control device, and the back pipe is controlled to be 100 ℃ lower than the temperature of the raw material layer (the target pipe) and is recorded as the target material A1.
Comparative examples 1 to 5
The preparation process was essentially the same as in example 1, except that see Table 1, and the resulting rotary targets were designated as targets A1 'to A5' in sequence.
Table 1 process parameter tables for example 1 and comparative examples 1 to 5
Example 2
(1) Degassing DyFe alloy powder with the grain diameter of 30 mu m (Dy mass ratio is 80%) and DyFe alloy powder with the grain diameter of 80 mu m for later use;
(2) Cleaning and drying a 304 stainless steel back pipe with the outer diameter of 90mm for later use;
(3) Placing the raw material powder treated in the step (1) and the back pipe treated in the step (2) into a mold under vacuum, sealing, and forming a composite structure with a center of the back pipe and raw material layers around, wherein the raw material layers are respectively 30 mu m powder, 80 mu m powder and 9.5mm thick;
(4) After the step (3) is completed, the raw material and back pipe composite structure is subjected to cold isostatic pressing to obtain a blank, wherein the pressure is 210MPa, and the pressure maintaining time is 120min;
(5) And (3) performing vacuum sintering on the blank obtained in the step (4) to obtain a rotary target material, wherein the temperature is 0.8T m(Tm =890 ℃, the heat preservation time is 150min, the cooling rate in a sintering furnace is controlled to be 5 ℃/min (the cooling rate of a raw material layer) in the cooling process, cooling water is introduced into a back pipe, the cooling rate of the back pipe is controlled by dynamically regulating the cooling water flow through an automatic temperature control device, and the back pipe is controlled to be 200 ℃ lower than the temperature of the raw material layer and is recorded as a target material B1.
Comparative examples 6 to 10
The preparation process was essentially the same as in example 2, except that see Table 2, and the resulting rotary targets were designated as targets B1 'to B5' in sequence.
Table 2 process parameter tables for example 2 and comparative examples 6 to 10
Example 3
(1) Degassing Tb powder with the particle size of 30 mu m and Tb powder with the particle size of 80 mu m for later use;
(2) Cleaning and drying a 304 stainless steel back pipe with the outer diameter of 90mm for later use;
(3) Placing the raw material powder treated in the step (1) and the back pipe treated in the step (2) into a mold under vacuum, sealing, and forming a composite structure with a center of the back pipe and raw material layers around, wherein the raw material layers are respectively 30 mu m powder, 80 mu m powder and 9.5mm thick;
(4) After the step (3) is completed, the raw material and back pipe composite structure is subjected to cold isostatic pressing to obtain a blank, wherein the pressure is 250MPa, and the pressure maintaining time is 120min;
(5) And (3) performing hot isostatic pressing sintering on the blank obtained in the step (4) to obtain a rotary target material, wherein the temperature is 0.8T m(Tm =1356 ℃, the pressure is 30MPa, the heat preservation and pressure maintaining time is 150min, the cooling rate in a sintering furnace is controlled to be 5 ℃/min (the cooling rate of a raw material layer) in the cooling process, cooling water is introduced into a back pipe, the cooling rate of the back pipe is controlled by dynamically regulating the cooling water flow through an automatic temperature control device, and the back pipe is controlled to be 100 ℃ lower than the raw material temperature and is recorded as a target material A2.
Comparative examples 11 to 15
The preparation process was substantially the same as in example 3, except that the obtained rotary targets were designated as targets a11 'to a15' in this order, see table 3.
TABLE 3 Process parameter tables for example 3 and comparative examples 11-15
Example 4
(1) Degassing DyFe alloy powder with the grain diameter of 30 mu m (Dy mass ratio is 80%) and DyFe alloy powder with the grain diameter of 80 mu m for later use;
(2) Cleaning and drying a 304 stainless steel back pipe with the outer diameter of 90mm for later use;
(3) Placing the raw material powder treated in the step (1) and the back pipe treated in the step (2) into a mold under vacuum, sealing to form a composite structure with a center of the back pipe and a raw material layer around, wherein the raw material layer has a particle size of 30 mu m, the outer layer has a particle size of 80 mu m, the inner layer has a thickness of 0.5mm and the outer layer has a thickness of 9.5mm;
(4) After the step (3) is completed, the raw material and back pipe composite structure is subjected to cold isostatic pressing to obtain a blank, wherein the pressure is 210MPa, and the pressure maintaining time is 120min;
(5) And (3) performing hot isostatic pressing sintering on the blank obtained in the step (4) to obtain a rotary target material, wherein the temperature is 0.8T m(Tm =890 ℃, the pressure is 30MPa, the heat preservation and pressure maintaining time is 150min, the cooling rate in a sintering furnace is controlled to be 5 ℃/min (the cooling rate of a raw material layer) in the cooling process, cooling water is introduced into a back pipe, the cooling rate of the back pipe is controlled by dynamically regulating the cooling water flow through an automatic temperature control device, and the back pipe is controlled to be 200 ℃ lower than the temperature of the raw material layer and is recorded as a target material B2.
Comparative examples 16 to 20
The preparation process was essentially the same as in example 4, except that see Table 4, and the resulting rotary targets were designated as targets B6 'to B10' in sequence.
Table 4 process parameter tables for example 2 and comparative examples 16 to 20
Example 5
(1) Degassing Tb powder with the particle size of 30 mu m and Tb powder with the particle size of 80 mu m for later use;
(2) Cleaning and drying a 304 stainless steel back pipe with the outer diameter of 90mm for later use;
(3) Placing the raw material powder treated in the step (1) and the back pipe treated in the step (2) into a mold under vacuum, sealing, and forming a composite structure with a center of the back pipe and raw material layers around, wherein the raw material layers are respectively 30 mu m powder, 80 mu m powder and 9.5mm thick;
(4) After the step (3) is completed, the target material is obtained by hot isostatic pressing of the composite structure of the raw material and the back tube, the temperature is 0.8T m(Tm =1356 ℃, the pressure is 28MPa, the dwell time is 150min, the cooling rate in the sintering furnace is controlled to be 5 ℃/min (the cooling rate of the raw material layer) in the cooling process, cooling water is introduced into the back tube, the cooling rate of the back tube is controlled by dynamically adjusting the cooling water flow through an automatic temperature control device, and the back tube is controlled to be 100 ℃ lower than the temperature of the raw material layer and is recorded as the target material A3.
Comparative examples 21 to 25
The preparation process was substantially the same as in example 5, except that the obtained rotary targets were designated as targets a11 'to a15' in this order, see table 5.
TABLE 5 Process parameters Table for example 5 and comparative examples 21-25
Example 6
(1) Degassing DyFe alloy powder with the grain diameter of 30 mu m (Dy mass ratio is 80%) and DyFe alloy powder with the grain diameter of 80 mu m for later use;
(2) Cleaning and drying a 304 stainless steel back pipe with the outer diameter of 90mm for later use;
(3) Placing the raw material powder treated in the step (1) and the back pipe treated in the step (2) into a mold under vacuum, sealing to form a composite structure with a center of the back pipe and a raw material layer around, wherein the raw material layer has a particle size of 30 mu m, the outer layer has a particle size of 80 mu m, the inner layer has a thickness of 0.5mm and the outer layer has a thickness of 9.5mm;
(4) After the step (3) is completed, the target material is obtained by hot isostatic pressing of the composite structure of the raw material and the back pipe, the temperature is 0.8T m(Tm =890 ℃, the pressure is 26MPa, the dwell time is 150min, the cooling rate in the sintering furnace is controlled to be 5 ℃/min (the cooling rate of the raw material layer) in the cooling process, cooling water is introduced into the back pipe, the cooling rate of the back pipe is controlled by dynamically adjusting the cooling water flow through an automatic temperature control device, and the back pipe is controlled to be 200 ℃ lower than the temperature of the raw material layer and is recorded as the target material B3.
Comparative examples 26 to 30
The preparation process was substantially the same as in example 6, except that the obtained rotary targets were designated as targets B11 'to B15' in this order, see table 6.
TABLE 6 Process parameter tables for example 6 and comparative examples 26-30
Examples 7 to 12
Substantially the same as in example 3, except for referring to Table 7, the obtained rotary targets were A4, A5, B4, B5, C1, C2 in this order.
TABLE 7 comparison of parameters for examples 7-12
Examples 13 to 18
Substantially the same as in example 5, except for the differences, see table 8.
TABLE 8 comparison of parameters for examples 13-18
Performing performance test on the target:
1. Welding rate test
The testing method comprises the following steps: and detecting the welding rate of the target material by adopting ultrasonic flaw detection equipment.
The test results are shown in Table 9.
2. And (3) compactness test:
the testing method comprises the following steps: and testing the compactness of the target by adopting a drainage method.
The test results are shown in Table 8.
3. Method for testing whether open welding is performed in using process
And verifying by means of magnetron sputtering, wherein the target utilization rate reaches 70-80% and the target is not welded as a criterion for judging whether the target is welded.
TABLE 9 Performance parameter tables for examples and comparative examples
As can be seen from Table 9, the rotary target provided by the embodiment of the invention has better comprehensive performance under the conditions of adopting different granularity material layers and controlling the temperature difference between the back pipe and the target pipe in the cooling process:
(1) The density of the alloy material can reach more than 96 percent, the highest density can reach 99 percent, and the sputtering target material requirement is met, but the welding rate of the target material can reach more than 95 percent and the welding problem does not exist under the conditions that the particle sizes of the first layer and the second layer of raw materials are different and the temperature difference exists between the back tube and the raw materials (target tube) in the cooling process, and the sputtering requirement of the target material is met, the highest welding rate of Tb rotary targets can reach 99.5 percent, the highest welding rate of DyFe alloy targets can reach 98.5 percent, the highest welding rate of Dy targets is 99.5 percent, and the highest welding rate of AlSc alloy targets is 98 percent.
(2) Under the conditions of controlling the granularity of the raw materials of the first layer and the second layer and controlling the temperature difference between the back tube and the target tube, the rare earth rotary target material with the welding rate of more than 95%, the compactness of more than 96% and no welding in the using process can be prepared by cold pressing and pressureless sintering, cold pressing and hot isostatic pressing sintering or direct hot isostatic pressing sintering.
In summary, when the target provided by the embodiment of the invention is applied to magnetron sputtering, the density of the target is 96% -99%, the welding rate is 95% -99.5%, and the application requirements of the fields of magnetic material coating grain boundary diffusion, storage, electronic information and the like are met without open welding in the using process.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: modifications and equivalents may be made to the specific embodiments of the invention without departing from the spirit and scope of the invention, which is intended to be covered by the claims.
Claims (9)
1. The preparation method of the rare earth rotary target is characterized by comprising the following steps:
Placing a back pipe and powdery raw materials into a die to form a composite structure with a center of the back pipe and raw material layers around the back pipe, wherein the raw materials comprise rare earth metal simple substances and/or rare earth alloys, the raw material layers comprise a first raw material layer and a second raw material layer, the first raw material layer is positioned between the back pipe and the second raw material layer, and the particle size of the raw materials in the first raw material layer is smaller than that of the raw materials in the second raw material layer;
Performing cold isostatic pressing or hot isostatic pressing on the composite structure to obtain a rare earth rotary target, wherein the cold isostatic pressing comprises the steps of performing cold isostatic pressing to obtain a blank and sintering the blank, and controlling a back tube and a raw material layer to keep a certain temperature difference in the cooling process of the cold isostatic pressing and the hot isostatic pressing to obtain the rare earth rotary target;
wherein, control the back pipe and raw materials layer keep certain temperature difference in the cooling process, specifically include:
In the cooling process, the temperature difference T X-Td =50-300 ℃ between the back pipe and the raw material layer is controlled, wherein T x is the temperature of the lower expansion coefficient of the back pipe and the raw material layer, and T d is the temperature of the higher expansion coefficient of the back pipe and the raw material layer.
2. The method for producing a rare earth rotary target according to claim 1, wherein the thickness of the first raw material layer is 0.1 to 1mm, the raw material particle size in the first raw material layer is 1 to 100 μm, and the raw material particle size in the second raw material layer is 10 to 150 μm.
3. The method for producing a rare earth rotary target according to claim 2, wherein the particle size of the raw material in the second raw material layer is 2 to 3 times the particle size of the raw material in the first raw material layer.
4. A method according to any one of claims 1 to 3, wherein the specific conditions of cold isostatic pressing include:
The pressure is 50-500 MPa, and the pressure maintaining time is 80-200 min.
5. A method according to any one of claims 1 to 3, wherein the specific conditions for sintering the blank comprise:
Pressureless sintering is carried out in vacuum or inactive atmosphere;
the sintering temperature T 1 satisfies the following conditions:
when T raw materials ≤T Back pipe , T 1＝0.5～0.95T raw materials ;
t 1＝0.5～0.95T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
The sintering time is 30-250 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
6. A method according to any one of claims 1 to 3, wherein the specific conditions for sintering the blank comprise:
performing hot isostatic pressing sintering;
The sintering pressure is 5-50 MPa;
the sintering temperature T 1 satisfies the following conditions:
when T raw materials ≤T Back pipe , T 1＝0.5～0.9T raw materials ;
T 1＝0.5～0.9T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
the sintering time is 30-240 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
7. A method according to any one of claims 1 to 3, characterized in that the hot isostatic pressing of the composite structure, in particular, comprises:
Performing hot isostatic pressing sintering on the composite structure;
the sintering pressure is 10-60 MPa;
the sintering temperature T 1 satisfies the following conditions:
when T raw materials ≤T Back pipe , T 1＝0.5～0.9T raw materials ;
T 1＝0.5～0.9T raw materials , and T 1＜0.8T Back pipe when T raw materials ＞T Back pipe ;
The sintering time is 30-270 min;
wherein T raw materials is the melting point of the raw material, and T Back pipe is the melting point of the back tube.
8. A rare earth rotary target prepared by the preparation method of any one of claims 1 to 7.
9. The application of the rare earth rotary target prepared by the preparation method of any one of claims 1 to 7 in the fields of magnetic material coating grain boundary diffusion, storage and electronic information.
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| CN105624619A (en) * | 2016-03-14 | 2016-06-01 | 无锡舒玛天科新能源技术有限公司 | Preparation method of rotary sputtering aluminum rare-earth alloy target for touch screen of flat panel display and target prepared by using preparation method |
| CN112743075A (en) * | 2020-12-29 | 2021-05-04 | 宁波江丰电子材料股份有限公司 | Binding method of tubular target |
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| CN104480437A (en) * | 2014-12-30 | 2015-04-01 | 山东昊轩电子陶瓷材料有限公司 | Production method for integrally formed cylindrical target |
| CN111384345A (en) * | 2020-03-20 | 2020-07-07 | 中航锂电技术研究院有限公司 | Diaphragm, preparation method and lithium ion battery comprising diaphragm |
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| CN105624619A (en) * | 2016-03-14 | 2016-06-01 | 无锡舒玛天科新能源技术有限公司 | Preparation method of rotary sputtering aluminum rare-earth alloy target for touch screen of flat panel display and target prepared by using preparation method |
| CN112743075A (en) * | 2020-12-29 | 2021-05-04 | 宁波江丰电子材料股份有限公司 | Binding method of tubular target |
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