CN102877033A - Manganese alloy target material and its manufacturing method - Google Patents
Manganese alloy target material and its manufacturing method Download PDFInfo
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Abstract
The invention relates to a manganese alloy sputtering target material and its manufacturing method. The target material is made of one or more of Pd, Pt, Ir, Au, Ru, Os, Rh and Re, and Mn, the mass content of Mn in the alloy is 2-80%, the deviation between the content of Mn in the alloy and a nominal composition is -0.2%-0.2% by mass, the content of O in the target material is below 200ppm, the purity of the target material is 99.9%-99.999%, the lowest surface roughness Ra is 0.8mum, the warp is below 0.1mm, and the target material has a fine and uniform structure. The target material has the advantages of accurate and uniform components, high compactness, accurate dimension and high surface quality; and the manganese alloy sputtering target material having excellent performances is prepared through adopting a melting technology and a machining process to prepare target materials of the alloy system in a low-cost and large-scale manner in a shortest possible flow, and overcoming a material preparation difficulty easily appearing in the preparation process of the alloy and a processing difficulty brought by high alloy crispness.
Description
Technical field
The present invention relates to a kind of manganese alloy target and manufacture method thereof, be particularly related to a kind of low-gas content, high-purity, high-compactness, size accurately, manganese alloy sputtering target material and the manufacture method thereof of great surface quality, can form the manganese alloy sputtering target material of high-quality thin film.
Background technology
Along with the development of informationized society, it is more and more important that information recording/becomes, and trend towards large capacity, high-density, small volume, the future development of high stability.The main flow information record carrier is hard disc of computer at present, and the hard disk magnetic recording is also thought more high record density and more small volume development at present, and the store content of the single hard disk of state-of-the-art business computer has reached the Tb order of magnitude.Material require as reproduce head is more and more advanced, because conventional induction magnetic head has reached operating limit, advanced anisotropic magnetic magnetoresistive head (AMR) is used more and more widely.Expansion along with computer market, the employing of anisotropic magnetic magnetoresistive head is just with geometric growth, high-density large reluctance magnetic head (GMR) is just in develop rapidly, the formed manganese alloy of manganese and platinum family element is used as the antiferromagnetism film of stopcock (spin valve) film that uses in the GMR magnetic head recently, and for further raising the efficiency research and development rapidly.This antiferromagnetism film is widely used in TMR and MRAM in addition.And this class film generally all is to form with magnetron sputtering deposition.
The method of magnetic control spattering target preparation generally has smelting process and powder metallurgic method.When above-mentioned alloy adopted general smelting process to prepare, composition was difficult to control, and the defective of alloy both macro and micro is all comparatively serious, and the very crisp cracking that is easy to of alloy is difficult to moulding, also is difficult to carry out plastic working and mechanical workout.(such as techniques such as hot pressed sintering, hot isostatic pressings) is because Specific Surface Area Measurement is large when the method that adopts powder metallurgy prepares, the oxygen level of absorption is obviously higher, and in powder mixing process, there be easily other impurity and the inhomogeneous problem of mixed powder of sneaking into, target exists and to contain oxygen, sulphur content is high, purity is low, density is low problem, have a strong impact on the magnetic property of film, be difficult to satisfy the service requirements of target.
The mode that patent CN 1503855A adopts common founding then to carry out viscous deformation prepares the manganese alloy target, the method still is difficult to avoid the easily tendency of cracking of this alloy when melting, to the elimination of casting flaw also Shortcomings, viscous deformation is subsequently often just carried out, and alloy is cracking, and alloy is cracked very serious, yield rate is lower simultaneously, operation is unusual difficulty also, and platinum metal alloy is generally all very valuable, and so the precious metal loss that brings of operation also can make composition rise rapidly.There is similar problem too in Japanese Patent Publication communique 2000-160332.
For the method for this manganese alloy target of preparation that adopts in the world at present, in fact do not propose to solve the scheme of this target fragility, breaking tenacity manganese alloy target low, that be easy to ftracture is difficult in batches preparation, also can cause high cost on the one hand in addition.
Summary of the invention
One of purpose of the present invention be to provide a kind of reliable and stable, can be mass the manganese alloy sputtering target material, guarantee the chemical ingredients of target, density, high purity and homogeneity form high-quality target.
For achieving the above object, the present invention takes following technical scheme:
A kind of manganese alloy sputtering target material is characterized in that: be comprised of a kind of and two or more metals and manganese among Pd, Pt, Ir, Au, Ru, Os, Rh and the Re, be preferably two yuan or ternary or quad alloy.The manganese content of alloy is 2% ~ 80%(mass ratio), alloy manganese content and nominal composition deviation are ± the 0.2%(mass ratio), the oxygen level of target is below the 200ppm, purity is 99.9% ~ 99.999%, surfaceness is minimum to be Ra=0.8um, warpage is below the 0.1mm, has tiny uniform weave construction.
A kind of preferred technical scheme is characterized in that: described manganese alloy sputtering target material is comprised of a kind of and two or more metals and the manganese among Pd, Pt, Ir, Au, Ru and the Rh.
A kind of preferred technical scheme is characterized in that: the manganese content of described alloy is preferably 10% ~ 75%(mass ratio).
A kind of preferred technical scheme is characterized in that: the manganese content of described alloy is 25% ~ 70%(mass ratio more preferably).
Another object of the present invention provides the manufacture method of above-mentioned manganese alloy sputtering target material, solves this puzzlement of alloy fragility problem in preparation process.Present method adopts special founding to obtain accurately controlled, homogeneity is high, density is high, air content is low target blank of chemical ingredients, subsequently blank is carried out the line cutting and abrasive machine is processed, and can obtain the good target of the accurate surface quality of size.
For achieving the above object, the present invention takes following technical scheme:
A kind of manufacture method of manganese alloy sputtering target material is characterized in that: adopt the method preparation of melting technology and mechanical workout.
A kind of preferred technical scheme is characterized in that: described melting technology may further comprise the steps:
(1) is that 99.9% ~ 99.999% manganese sheet is no less than 1 time electron beam melting, arc melting or vacuum induction melting with purity under vacuum or inert gas environment, obtains the manganese ingot, the manganese ingot is preserved under inert gas environment;
(2) the manganese ingot of step (1) gained and a kind of and two or more metals among Pd, Pt, Ir, Au, Ru, Os, Rh and the Re are made into master alloy, make the manganese content of master alloy be higher than the manganese content of finished product, under vacuum or inert gas environment, make the manganese master alloy by vacuum induction melting or electron beam melting etc.;
(3) adopt the ICP(inductively coupled plasma) test master alloy manganese content, according to master alloy manganese content and finished product requirement, suitably add a kind of and two or more metals among Pd, Pt, Ir, Au, Ru, Os, Rh and the Re, make that the content of manganese reaches the finished product requirement in the alloying ingredient, manganese content is 2% ~ 80%(mass ratio in the finished product), be preferably 10% ~ 75%(mass ratio), more preferably be 25% ~ 70%(mass ratio);
(4) under vacuum or protection of inert gas, the ready alloy melting of step (3) is become alloy pig with vacuum induction melting; Casting mould is water cooled copper mould, and mould circumferentially is incubated, temperature 〉=alloy melting point; Circumferentially heating source is closed, cast; When alloy graining is finished, temperature is preferably 500 ~ 1000 ℃ at 100 ~ 1000 ℃, more preferably 500 ~ 650 ℃, with its rapid taking-up, puts into a protection of inert gas annealing furnace and anneals.
A kind of preferred technical scheme is characterized in that: in the described water cooled copper mould, hydraulic pressure is 0.1 ~ 5Mpa, is preferably 0.3 ~ 5Mpa, and flow is 0.1 ~ 10kg/cm
2S is preferably 0.1 ~ 3.0kg/cm
2S, water temperature is 1 ℃ ~ 50 ℃, is preferably 1 ℃ ~ 10 ℃.
A kind of preferred technical scheme is characterized in that: to the scope of alloy melting point+200 ℃, pouring speed is 10 ~ 1500g/s to described teeming temperature, is preferably 500 ~ 1500g/s at alloy melting point.
A kind of preferred technical scheme is characterized in that: described annealing temperature is 100 ~ 1000 ℃, is preferably 500 ~ 650 ℃, and the time is 0.5 ~ 50h, is preferably 1.0 ~ 5.0h.
A kind of preferred technical scheme is characterized in that: will be machined to finished product through the ingot casting of melting technology gained, described mechanical workout is the line cutting processing, carries out subsequently turning or ground finish again.Preferred ground finish, wherein machining apparatus is only processed precious metal, is convenient to the processing-waste purification that contains precious metal is reclaimed.
Advantage of the present invention is:
1, the manganese elemental gas such as oxygen uptake very easily at first carries out repeatedly electron beam melting, arc melting or induction melting to starting material manganese under vacuum or inert gas environment.Can eliminate like this volatile matter and low melting point impurity, make the purity of manganese become higher, simultaneously repeatedly remelting can make gas content lower, thereby satisfies the requirement of target, makes that spatter film forming is more even, performance is better.Should under the environment of rare gas element, preserve after the manganese ingot is melted, prevent the aerial oxidation of manganese.
2, with electron beam melting or induction melting manganese and platinum metals are smelted into intermediate alloy ingot, the content of master alloy manganese can be 5% ~ 95%, and master alloy is convenient to preserve and is also preserved with inert gas seal.If the alloy of the direct required composition of melting in fusion process, under the normal temperature and pressure, about 1244 ℃ of the fusing point of manganese, 1962 ℃ of boiling points are 1.33 * 10
2The rough vacuum environment is lower, and the boiling point of manganese is 1522 ℃, and vacuum more high boiling point is lower.And the fusing point of platinum metals is generally all higher, all more than 1500 ℃, if direct molten alloy can cause a large amount of volatilizations of manganese under vacuum environment, composition is difficult to control, the composition precision also is difficult to reach, as under at inert gas environment directly molten alloy then be difficult to get rid of gas in the alloy.Therefore further degasification of melting master alloy also provides the basis for next step preparation alloy.
3, on the basis of gained master alloy, suitably prepare burden, alloy is configured to needed composition, under protection of inert gas, be smelted into alloy pig with induction melting.The mould that adopts is water cooled copper mould, circumferentially insulation.This class alloy is easy to produce grain-boundary crack when solidifying, cause alloy not fine and close, and intensity is low, and macroscopic view is loose serious, and rapid solidification can reduce these defectives as much as possible, makes dendrite arm more tiny, and composition is more even.Make alloy fine and close, eliminate loose and pore.Alloy when cast suitably control water temperature and water speed, circumferentially insulation has comparatively high temps, makes alloy from the bottom consecutive solidification, the defective such as loose and be mingled with is concentrated on the port part that emits of final set.Dendrite arm is along the direction growth of thermograde, form the fine and close tiny column crystal perpendicular to the target surface growth, eliminate the defectives such as loose and shrinkage cavity of grain-boundary crack and macroscopic view, it is upper without casting flaw to obtain macroscopic view, on the microcosmic crystal grain all perpendicular to target surface tiny evenly, the consistent structure of composition.When machining, can reduce as much as possible the cracked tendency of target base along the direction processing perpendicular to dendrite arm.
4, when alloy is cooled to 100 ℃ ~ 1000 ℃, alloy is taken out rapidly, the annealing furnace of putting under the protection of inert gas is annealed.Alloy directly cools off in stove, is easy to exist macrocrack in various degree.This class alloy has formed complicated fragility phase when solidifying, also have phase transformation to occur in the process of solid-state cooling, simultaneous casting stress, visible macroscopic view cracking often during to room temperature.The alloy unrelieved stress is larger in addition, also can have larger distortion in the machining process, and the release of stress has also increased the trend of alloy cracking.Therefore finish to solidify to be transformed at alloy and it is carried out protection of inert gas when solid-state and with furnace annealing its phase transformation is carried out slowly, eliminate stress simultaneously.
5, ingot casting is carried out the line cutting, carry out subsequently ground finish, make alloy reach desired accurate dimension and surface quality, simultaneously machining liquid is reclaimed purification.
In a word, the present invention can provide a kind of manganese alloy sputtering target material, and its oxygen level is below 200ppm, and purity is 99.9% ~ 99.999%, and composition is accurate, even, and density is high, and the target size is accurate, and surface quality is high, has fine tissue.By manufacture method of the present invention, can under short as far as possible flow process, prepare low-costly and in high volume this alloy system target, and overcome material preparation difficulty and the very crisp processing difficulties of bringing of alloy that this alloy is prone in preparation process, obtain having the manganese alloy sputtering target material of excellent properties.
The present invention will be further described below by the drawings and specific embodiments, but and do not mean that limiting the scope of the invention.
Description of drawings
Fig. 1 is the process flow sheet of manganese alloy sputtering target material manufacture method of the present invention.
Fig. 2 is manganese alloy sputtering target material metallograph of the present invention.
Fig. 3 is manganese alloy sputtering target material finished product synoptic diagram of the present invention.
Embodiment
As shown in Figure 1, be the process flow sheet of manganese alloy sputtering target material manufacture method of the present invention, its preparation method comprises melting technology and mechanical workout, i.e. manganese refining, master alloy preparation, alloy casting, line cutting and ground finish.
Embodiment 1
Preparation MnPt72.2 manganese alloy sputtering target material may further comprise the steps:
(1) be that 99.99% manganese sheet 3kg carries out 3 electron beam meltings repeatedly with domestic purity under inert gas atmosphere.The manganese ingot 850g that obtains preserves under inert gas environment;
(2) with manganese ingot and purity be the 99.99%Pt piece to be made into manganese content be 60%(quality %, following alloy content is mass ratio) master alloy, by the vacuum induction melting method melting, casting mold is copper mold under inert gas environment;
(3) with master alloy surface car light, all get the about 0.5g of bits from the ingot casting upper, middle and lower segment and carry out the ICP-OES(inductive coupling plasma emission spectrograph) analyze its manganese content, its result is as shown in table 1 below.The 53.7% manganese content as master alloy of averaging adds the Pt metal piece, makes the Pt content after the batching reach the finished product requirement;
Table 1, master alloy different sites manganese content
| The alloy position | Top (%) | Middle part (%) | Bottom (%) | On average (%) |
| Manganese content | 53.8 | 53.7 | 53.6 | 53.7 |
(4) under protection of inert gas, (3) ready alloy melting is become alloy pig with vacuum induction melting.The mould that adopts is water cooled copper mould, hydraulic pressure 0.35Mpa, flow 0.5kg/cm
2S, 5 ℃ of water temperatures circumferentially are heated to 1670 ℃, close heating source, cast.About 1650 ℃ of teeming temperature, pouring speed 0.85kg/s when alloy is cooled to 550 ℃, is transferred to rapidly furnace temperature and is in 550 ℃ the protection of inert gas annealing furnace and carry out 2h annealing furnace cooling;
(5) ingot casting with (4) gained carries out the line cutting, carries out subsequently ground finish, obtains the target that size and smooth finish all meet the demands;
(6) the residue alloy after the line cutting is taken a sample 3, it is as shown in table 2 below to analyze its manganese content with ICP-OES, and obtaining average manganese content is 27.8%.Machining liquid is reclaimed purification.
Table 2, ICP-OES analyze manganese content
| Sample | 1 | 2 | 3 | On average |
| Manganese content (%) | 27.7 | 27.8 | 27.9 | 27.8 |
In the manganese alloy sputtering target material of embodiment 1 preparation, MnPt72.2 ± 0.2 (mass ratio), purity is not less than 99.99%, and oxygen level is not higher than 200ppm, size 110 * 4mm, tolerance+0.1mm, surface smoothness Ra=0.8um is below the warpage 0.1mm.
As shown in Figure 2, be the metallographic synoptic diagram of embodiment 1 manganese alloy sputtering target material, can see having tiny uniform weave construction.
Fig. 3 is embodiment 1 manganese alloy sputtering target material finished product synoptic diagram photo.
Embodiment 2
Preparation MnPd25.6 manganese alloy sputtering target material may further comprise the steps:
(1) be that 99.999% manganese sheet 5kg carries out 3 electron beam meltings repeatedly with purity under vacuum atmosphere.The manganese ingot that obtains;
(2) with manganese ingot and purity be 99.999% Pd piece to be made into manganese content be 85% master alloy, under inert gas environment, pass through vacuum induction melting method;
(3) all get the about 0.5g of bits from the ingot casting upper, middle and lower segment and carry out ICP-OES and analyze its manganese content, its result is as shown in table 3 below.The 81.2% manganese content as master alloy of averaging adds the Pd piece, makes the Pd content after the batching reach the finished product requirement;
Table 3, master alloy different sites manganese content
| The alloy position | Top (%) | Middle part (%) | Bottom (%) | On average (%) |
| Manganese content | 81.1 | 81.2 | 81.3 | 81.2 |
(4) under protection of inert gas, (3) ready alloy melting is become alloy pig with vacuum induction melting.The mould that adopts is water cooled copper mould, hydraulic pressure 0.3Mpa, flow 0.6kg/cm
2S, 3 ℃ of water temperatures circumferentially are heated to 1670 ℃, close heating source, cast.About 1350 ℃ of teeming temperature, pouring speed 1200g/s, 1360 ℃ when alloy is cooled to 510 ℃, blow-on is taken out, and is transferred to rapidly furnace temperature and is in 510 ℃ the annealing furnace of protection of inert gas, annealing 1.5h;
(5) ingot casting with (4) gained carries out the line cutting, carries out subsequently ground finish, obtains the target that size and smooth finish all meet the demands;
(6) the residue alloy after the line cutting is taken a sample 3, it is as shown in table 4 below to analyze its manganese content with ICP-OES, and obtaining mean P d content is 25.5%.Machining liquid is reclaimed purification.
Table 4, ICP-OES analyze manganese content
| Sample | 1 | 2 | 3 | On average |
| Pd content (%) | 25.4 | 25.5 | 25.6 | 25.5 |
In the manganese alloy sputtering target material of embodiment 2 preparations, MnPd25.6 ± 0.2 (mass ratio), purity is not less than 99.999%, and oxygen level is not higher than 150ppm, size 160 * 5mm, tolerance+0.1mm, surface smoothness Ra=1.6um is below the warpage 0.1mm.
Embodiment 3
Preparation MnIr50 manganese alloy sputtering target material may further comprise the steps:
(1) be that 99.9% manganese sheet carries out 2 electron beam meltings repeatedly with purity under inert gas atmosphere.The manganese ingot that obtains is preserved under inert gas environment;
(2) with manganese ingot and purity be 99.9% Ir powder to be made into manganese content be 65% master alloy, under vacuum, become intermediate alloy ingot with the electron-beam process founding;
(3) the master alloy car is fallen crust, all get the about 0.5g of bits from the ingot casting upper, middle and lower segment and carry out ICP-OES and analyze its manganese content, its result is as shown in table 5 below.The 55.2% manganese content as master alloy of averaging adds the Ir piece, makes the Ir content after the batching reach the finished product requirement;
Table 5, master alloy different sites manganese content
| The alloy position | Top (%) | Middle part (%) | Bottom (%) | On average (%) |
| Manganese content | 55.1 | 55.2 | 55.3 | 55.2 |
(4) under protection of inert gas, (3) ready alloy melting is become alloy pig with vacuum induction melting.The mould that adopts is water cooled copper mould, hydraulic pressure 3.2Mpa, flow 0.2kg/cm
2S, 10 ℃ of water temperatures circumferentially are heated to 1670 ℃, close heating source, cast.About 1620 ℃ of teeming temperature, pouring speed 1.3kg/s.When alloy was cooled to 650 ℃, blow-on was taken out, and was transferred to rapidly furnace temperature and was in 650 ℃ the annealing furnace of protection of inert gas, annealing 5h;
(5) ingot casting with (4) gained carries out the line cutting, carries out subsequently ground finish, obtains the target that size and smooth finish all meet the demands;
(6) the residue alloy after the line cutting is taken a sample 3, it is as shown in table 6 below to analyze its manganese content with ICP-OES, and obtaining average Ir content is 50.2%.Machining liquid is reclaimed purification.
Table 6, ICP-OES analyze manganese content
| Sample | 1 | 2 | 3 | On average |
| Pd content (%) | 50.2 | 50.1 | 50.2 | 50.2 |
In the manganese alloy sputtering target material of embodiment 3 preparations, MnIr50 ± 0.2 (mass ratio), purity is not less than 99.9%, and oxygen level is not higher than 100ppm, size 50 * 3mm, tolerance+0.1mm, surface smoothness Ra=1.6um is below the warpage 0.1mm.
Embodiment 4
Preparation MnRu25.2 manganese alloy sputtering target material may further comprise the steps:
(1) be that 99.9% manganese sheet carries out 2 electron beam meltings repeatedly with purity under vacuum.The manganese ingot that obtains.Preserving under inert gas environment, is that 99.9% Ru powder is block with electron beam melting also with purity;
(2) manganese ingot and Ru being made into manganese content is 90% master alloy, becomes intermediate alloy ingot with the electron-beam process founding under inert gas environment;
(3) with the master alloy pickling, all get the about 0.5g of bits from the ingot casting upper, middle and lower segment and carry out ICP-OES and analyze its manganese content, its result is as shown in table 7 below.The 85.3% manganese content as master alloy of averaging adds the Ir piece, makes the Ru content after the batching reach the finished product requirement;
Table 7, master alloy different sites manganese content
| The alloy position | Top (%) | Middle part (%) | Bottom (%) | On average (%) |
| Manganese content | 85.2 | 85.2 | 85.4 | 85.3 |
(4) under protection of inert gas, (3) ready alloy melting is become alloy pig with vacuum induction melting.The mould that adopts is water cooled copper mould, hydraulic pressure 4Mpa, flow 10kg/cm
2S, 50 ℃ of water temperatures circumferentially are heated to 1670 ℃, close heating source, cast.About 1380 ℃ of teeming temperature, pouring speed 520g/s.When alloy was cooled to 620 ℃, blow-on was taken out, and was transferred to rapidly furnace temperature and was in 620 ℃ the annealing furnace of protection of inert gas, annealing 3h;
(5) ingot casting with (4) gained carries out the line cutting, carries out subsequently ground finish, obtains the target that size and smooth finish all meet the demands;
(6) the residue alloy after the line cutting is taken a sample 3, it is as shown in table 8 below to analyze its manganese content with ICP-OES, and obtaining average Ru content is 25.2%.Machining liquid is reclaimed purification.
Table 8, ICP-OES analyze manganese content
| Sample | 1 | 2 | 3 | On average |
| Ru content (%) | 25.2 | 25.1 | 25.2 | 25.2 |
In the manganese alloy sputtering target material of embodiment 4 preparations, MnRu25.2 ± 0.2 (mass ratio), purity is not less than 99.9%, and oxygen level is not higher than 200ppm, size 205 * 5mm, tolerance+0.1mm, surface smoothness Ra=1.6um is below the warpage 0.1mm.
Embodiment 5
Preparation MnAu30Rh9Re1 manganese alloy sputtering target material may further comprise the steps:
(1) be that 99.9% manganese sheet carries out 2 electron beam meltings repeatedly with purity under vacuum.The manganese ingot that obtains;
(2) manganese ingot and Au being made into manganese content is 90% master alloy, becomes intermediate alloy ingot with the electron-beam process founding under inert gas environment;
(3) with the master alloy pickling, all get the about 0.5g of bits from the ingot casting upper, middle and lower segment and carry out ICP-OES and analyze its manganese content, its result is as shown in table 9 below.The 85.3% manganese content as master alloy of averaging adds Rh, and the elements such as Re make Au, Mn content after the batching reach the finished product requirement;
Table 9, master alloy different sites manganese content
| The alloy position | Top (%) | Middle part (%) | Bottom (%) | On average (%) |
| Manganese content | 85.2 | 85.2 | 85.4 | 85.3 |
(4) under protection of inert gas, (3) ready alloy melting is become alloy pig with vacuum induction melting.The mould that adopts is water cooled copper mould, hydraulic pressure 5Mpa, flow 2.5kg/cm
2S, 2 ℃ of water temperatures circumferentially are heated to 1670 ℃, close heating source, cast.About 1480 ℃ of teeming temperature, pouring speed 520g/s.When alloy was cooled to 620 ℃, blow-on was taken out, and was transferred to rapidly furnace temperature and was in 620 ℃ the annealing furnace of protection of inert gas, annealing 3h;
(5) ingot casting with (4) gained carries out the line cutting, carries out subsequently ground finish, obtains the target that size and smooth finish all meet the demands;
(6) the residue alloy after the line cutting is taken a sample 3, it is as shown in table 10 below to analyze its manganese content with ICP-OES.Machining liquid is reclaimed purification.
Table 10, ICP-OES analyze manganese content
| Sample | 1 | 2 | 3 | On average |
| Au content (%) | 29.8 | 29.8 | 29.8 | 29.8 |
| Mn content (%) | 59.9 | 59.9 | 59.9 | 59.9 |
| Rh content (%) | 9.1 | 9.1 | 9.2 | 9.1 |
In the manganese alloy sputtering target material of embodiment 5 preparations, MnAu30Rh9Re1 ± 0.2 (mass ratio), purity is not less than 99.9%, and oxygen level is not higher than 200ppm, size 205 * 5mm, tolerance+0.1mm, surface smoothness Ra=1.6um is below the warpage 0.1mm.
Embodiment 6
Preparation MnPt30Rh39 manganese alloy sputtering target material may further comprise the steps:
(1) be that 99.9% manganese sheet carries out 2 electron beam meltings repeatedly with purity under vacuum.The manganese ingot that obtains;
(2) with manganese ingot and Pt, it is 90% master alloy that Rh is made into manganese content, becomes intermediate alloy ingot with the electron-beam process founding under inert gas environment;
(3) with the master alloy pickling, all get the about 0.5g of bits from the ingot casting upper, middle and lower segment and carry out ICP-OES and analyze its manganese content, its result is as shown in table 11 below.The 85.3% manganese content as master alloy of averaging adds Pt, and the elements such as Rh make the Mn content after the batching reach the finished product requirement;
Table 11, master alloy different sites manganese content
| The alloy position | Top (%) | Middle part (%) | Bottom (%) | On average (%) |
| Manganese content | 85.2 | 85.2 | 85.4 | 85.3 |
(4) under protection of inert gas, (3) ready alloy melting is become alloy pig with vacuum induction melting.The mould that adopts is water cooled copper mould, hydraulic pressure 5Mpa, flow 1kg/cm
2S, 1 ℃ of water temperature circumferentially is heated to 1670 ℃, closes heating source, cast.About 1480 ℃ of teeming temperature, pouring speed 1500g/s.When alloy was cooled to 620 ℃, blow-on was taken out, and was transferred to rapidly furnace temperature and was in 950 ℃ the annealing furnace of protection of inert gas, annealing 3h;
(5) ingot casting with (4) gained carries out the line cutting, carries out subsequently ground finish, obtains the target that size and smooth finish all meet the demands;
(6) the residue alloy after the line cutting is taken a sample 3, it is as shown in table 12 below to analyze its manganese content with ICP-OES, and machining liquid is reclaimed purification.
Table 12, ICP-OES analyze manganese content
| Sample | 1 | 2 | 3 | On average |
| Pt content (%) | 29.9 | 29.9 | 29.9 | 29.9 |
| Rh content (%) | 38.8 | 38.8 | 38.9 | 38.8 |
In the manganese alloy sputtering target material of embodiment 6 preparations, MnPt30Rh39 ± 0.2 (mass ratio), purity is not less than 99.9%, and oxygen level is not higher than 200ppm, size 205 * 5mm, tolerance+0.1mm, surface smoothness Ra=1.6um is below the warpage 0.1mm.
Claims (10)
1. manganese alloy sputtering target material, it is characterized in that: formed by a kind of and two or more metals and manganese among Pd, Pt, Ir, Au, Ru, Os, Rh and the Re, the mass content of manganese is 2% ~ 80% in the alloy, the oxygen level of target is below the 200ppm, purity is 99.9% ~ 99.999%, surfaceness is minimum to be Ra=0.8um, and warpage is below the 0.1mm, has tiny uniform weave construction.
2. manganese alloy sputtering target material according to claim 1 is characterized in that: be comprised of a kind of and two or more metals and manganese among Pd, Pt, Ir, Au, Ru and the Rh.
3. manganese alloy sputtering target material according to claim 1, it is characterized in that: the mass content of manganese is 10% ~ 75% in the described alloy.
4. manganese alloy sputtering target material according to claim 3, it is characterized in that: the mass content of manganese is 25% ~ 70% in the described alloy.
5. the manufacture method of a manganese alloy sputtering target material is characterized in that: adopt the method preparation of melting technology and mechanical workout.
6. the manufacture method of manganese alloy sputtering target material according to claim 5, it is characterized in that: described melting technology may further comprise the steps:
(1) is that 99.9% ~ 99.999% manganese sheet is no less than 1 time electron beam melting, arc melting or vacuum induction melting with purity under vacuum or inert gas environment, obtains the manganese ingot, the manganese ingot is preserved under inert gas environment;
(2) the manganese ingot of step (1) gained and a kind of and two or more metals among Pd, Pt, Ir, Au, Ru, Os, Rh and the Re are made into master alloy, make the manganese content of master alloy be higher than the manganese content of finished product, under vacuum or inert gas environment, make the manganese master alloy by vacuum induction melting or electron beam melting;
(3) adopt ICP test master alloy manganese content, according to master alloy manganese content and finished product requirement, add a kind of and two or more metals among Pd, Pt, Ir, Au, Ru, Os, Rh and the Re, make that the content of manganese reaches the finished product requirement in the alloying ingredient, the mass content of manganese is 2% ~ 80% in the finished product;
(4) under vacuum or protection of inert gas, the ready alloy melting of step (3) is become alloy pig with vacuum induction melting; Casting mould is water cooled copper mould, and mould circumferentially is incubated, temperature 〉=alloy melting point; Circumferentially heating source is closed, cast; When alloy graining is finished, temperature, is put into a protection of inert gas annealing furnace and is annealed its rapid taking-up at 100 ~ 1000 ℃.
7. the manufacture method of manganese alloy sputtering target material according to claim 6, it is characterized in that: in the described water cooled copper mould, hydraulic pressure is 0.1 ~ 5Mpa, and flow is 0.1 ~ 10kg/cm
2S, water temperature is 1 ℃ ~ 50 ℃.
8. the manufacture method of manganese alloy sputtering target material according to claim 7 is characterized in that: to 200 ℃ scope more than the alloy melting point, pouring speed is 10 ~ 1500g/s to described teeming temperature at alloy melting point.
9. the manufacture method of manganese alloy sputtering target material according to claim 8, it is characterized in that: described annealing temperature is 100 ~ 1000 ℃, the time is 0.5 ~ 50h.
10. the manufacture method of manganese alloy sputtering target material according to claim 5, it is characterized in that: described mechanical workout is the line cutting processing, carries out subsequently turning or ground finish again.
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| CN104416325A (en) * | 2013-08-21 | 2015-03-18 | 宁波江丰电子材料股份有限公司 | Manufacturing method of tungsten target |
| CN104805406A (en) * | 2015-04-17 | 2015-07-29 | 无锡舒玛天科新能源技术有限公司 | Aluminium-scandium rotating target material and preparation method thereof |
| CN105241867A (en) * | 2014-07-07 | 2016-01-13 | 苏州电器科学研究院股份有限公司 | Detection method of content of ruthenium element in electronic materials |
| CN107955881A (en) * | 2017-11-17 | 2018-04-24 | 宁波创润新材料有限公司 | A kind of method of smelting for recycling sputtering target material |
| CN111195803A (en) * | 2018-11-17 | 2020-05-26 | 上海派尼科技实业股份有限公司 | Method for preparing target plate |
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| CN113737011A (en) * | 2021-09-08 | 2021-12-03 | 宁波江丰电子材料股份有限公司 | Preparation method of ultra-pure copper-manganese alloy |
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