CN1900352A - Enhanced sputter target manufacturing method - Google Patents
Enhanced sputter target manufacturing method Download PDFInfo
- Publication number
- CN1900352A CN1900352A CN 200610075466 CN200610075466A CN1900352A CN 1900352 A CN1900352 A CN 1900352A CN 200610075466 CN200610075466 CN 200610075466 CN 200610075466 A CN200610075466 A CN 200610075466A CN 1900352 A CN1900352 A CN 1900352A
- Authority
- CN
- China
- Prior art keywords
- alloy
- homogeneous
- powder
- complete fine
- molten alloy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
A method of manufacturing a sputter target the method including the step of preparing a plurality of raw materials into a composition corresponding to alloy system, the plurality of raw materials comprising pure elements or master alloys. The method also includes the step of heating the plurality of raw materials under vacuum or under a partial pressure of argon (Ar) to a fully liquid state to form a molten alloy corresponding to the alloy system, solidifying the molten alloy to form an ingot, and reheating the ingot to a fully liquid state to form a diffuse molten alloy. The method further includes the steps of rapidly solidifying the diffuse molten alloy into a homogeneous pre-alloyed powder material, admixing pure elemental powders to the homogeneous pre-alloyed powder material, consolidating the homogeneous pre-alloyed powder material into a fully dense homogeneous material, hot rolling the fully dense homogeneous material. Moreover, the method includes the steps of cold rolling the fully dense homogeneous material, and machining the fully dense homogenous material to form a sputter target.
Description
Mutual CROSS-REFERENCE TO RELATED APPLICATION
That the application requires to submit on July 22nd, 2005, exercise question is the U.S. Provisional Application the 60/701st of " Enhanced SputterTarget Manufacturing Method " (" strengthening the manufacture method of sputtering target "), No. 546 right of priority is introduced into as a reference at this.
Technical field
The present patent application relate generally to sputtering target, more specifically, the present patent application relates to the clotting method of producing intact blank (sound billet stocks), has the zero defect that strengthens by flux (pass through flux) (" PTF "), chemical sputtering target uniformly to be used for making.
Technical background
The DC magnetron sputtering technique is widely used in various fields, in order to the thin-film material deposition in thickness with accurate control and the narrow atomic level error (atomic fraction tolerances) to be provided in substrate, coating semiconductor and/or form rete for example on the surface of magnetic recording medium.In a kind of common structure, apply run-track shaped magnetic field to sputtering target by placing magnet on the back of the body surface of target.Electronics is captured near sputtering target, increases the argon ion generation and increases sputter rate.The surface of the intravital ionic bombardment sputtering target of plasma makes the sputtering target surface radiate atom.Voltage difference between cathode sputtering target and the anode substrate to be coated makes the atom that is radiated form the rete of expection at substrate surface.
Typically, by the sputtering target of traditional ingot metallurgy (ingot metallurgy) technology manufacturing based on cobalt (Co) alloy, chromium (Cr) alloy, iron (Fe) alloy and nickel (Ni) alloy.The side effect that these technologies had not been expected is, the solute of solidifying front (frout) distribute again and liquid phase in convection current can in casting (as-cast) product, cause serious chemical segregation.In addition, because gas hold-up takes place in foundry technology process, and do not have available heat processing technique to come sealed porosity, thus another consequence that causes is the pore (gas porosity) from ingot casting.
Because have only by from the ingot process of setting evenly and apace heat extraction just might make the uniform crystal particles growth, so typical ingot casting microstructure is heterogeneous.Do not having described fast and under the situation of heat extraction equably, the typical microstructures of ingot casting have by cylindrical (Columnar) on the surface grain structure surrounded, at the equi-axed crystal tissue at ingot center.
For the sputtering target of making based on cobalt (Co) alloy, traditional technology comprises the following steps: the starting material of vacuum induction melting (" VIM ") medium purity (99.9%) to high purity (〉=99.99%), and under vacuum or at the branch of rare gas element, depress the molten alloy of in copper (Cu), graphite or ceramic die, casting, thickness that wherein must default ingot casting is so that pre-determined number obtains required target thickness after by rolling mill (rolling mill).Tend to the alloy of chemical segregation for some in process of setting, the long-time homogenize annealing that need reach 72 hours is to reduce defective.
In manufacturing processed, utilize hot rolling to make grain refining, make the microstructure homogenizing and eliminate hole.Hot-rolled process often needs several compressions (reduction) step, and more than sustainable ten hours.Be lower than the alloy of 18at.% for chromium (Cr) content, also use cold rolling increasing target PTF, but workpiece often ftractures in cold-rolled process, thereby had a strong impact on productive rate.
As detailed above, aspect the ratio of material input and material output, the sputtering target manufacture method seems time-consuming and poor efficiency.High or contain the alloy of refractory element for some boron (B), phosphorus (P) content, for example Fe-Co-B, Ni-P and Co-Ta-Zr are even the intrinsic fragility of alloy makes that it all is difficult at high temperature carrying out any metal process operation.
When relating to the alloy that contains unmixing or insoluble composition, traditional ingot metallurgy method can not provide reliable ingot casting, and what wherein ' unmixing ' referred to take place in the liquid phase does not mix.Shown in the phasor among Fig. 1, for example, the Ag-Co alloy system shows by two liquidus line L that are higher than 1489 ℃
1And L
2The miscible district that defines (miscibility gap), therefore the liquid solubility of silver (Ag) is essentially 0 in 1489 ℃ of following cobalts (Co), and only is about 1at.% under 1700 ℃.For the fusion Ag-Co alloy in this temperature range, silver (Ag) composition tends to segregation (separate) and form isolated fine silver (Ag) district (pool) in liquid cobalt (Co).Depend on silver (Ag) content, these districts can form in as-cast structure and reach 1 centimetre big solid particulate.
In another phase separation, owing to silver (Ag) leaks on the aforesaid ingot surface, thereby proof remaining silver (Ag) when the cobalt that solidifies (Co) skeleton shrinks is extruded from most of ingot.The Au-Co phasor of Fig. 2 and the Co-Cu phasor of Fig. 3 illustrate that all gold (Au) and the solid solubility of copper (Cu) in cobalt (Co) are very limited.In both cases, in fact the equilibrium phase of rich cobalt (Co) alloy comprises pure cobalt (ε Co) and the two-phase sosoloid of gold (Au) or the two-phase sosoloid of cobalt (ε Co) and copper (Cu).
The sosoloid of gold (Au) or copper (Cu) segregation usually is independent crystal grain, or tends to the crystal boundary place growth of (ε Co) phase just in cobalt (Co) alloy.Because the fusing point of silver (Ag) (962 ℃), gold (Au) (1064 ℃) and copper (Cu) (1085 ℃) is low, their unmixability and limited solubleness in cobalt (Co) has limited the heat-mechanical workout temperature and the HIP processing temperature of ingot in the practice again.
Because their intrinsic fragility, the high and hot-rolled process that contain cobalt (Co) alloy of refractory element of boron (B) content carries out in 1050 ℃ to 1100 ℃ temperature range, to avoid cracking and other rolling inefficacy (rolling failures).Therefore, when the ingot reheat is added man-hour to carry out heat-mechanical workout and HIP, must change alloy phase and constitute to avoid the incipient melting of silver (Ag), gold (Au) or copper (Cu).
Therefore, be desirable to provide the defective that a kind of sputtering target manufacture method overcomes classical production process.Especially, be desirable to provide a kind of improved sputtering target manufacture method, be used to make the uniform sputtering target of zero defect, chemistry with improved PTF characteristic to produce intact blank.
Summary of the invention
The present patent application relate generally to sputtering target, more specifically, the present patent application relates to the sputter material of clotting method and gained.Manufacturing method according to the invention has been produced very intact blank, has the uniform sputtering target of zero defect, chemistry that strengthens by flux (" PTF ") to be used for making.
Manufacturing method according to the invention comprises sintered alloy prescription, rapid solidification processing scheme option and powder consolidation and fixed post-treatment step, has the sputtering target that improves performance with production.Shorten process period greatly, and the chemical uniformity of target, the volume constancy of product (productbulk soundness) or PTF characteristic do not reduce.The manufacture method of described sputter material and gained performance are applicable to many low magnetic moments (moment) (chromium (Cr) content＞18at.%) and high magnetic moment (cobalt (Co) alloy of chromium (Cr) content＜18at.%), and chromium (Cr) base, iron (Fe) base or the basic alloy of nickel (Ni).
According to first scheme, the present invention is a method of making cobalt (Co) based sputtering targets, and this cobalt (Co) based sputtering targets is formulated as Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2, X
1Represent copper (Cu), silver (Ag) or gold (Au), and X
2Represent titanium (Ti), vanadium (V), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), lanthanum (La), hafnium (Hf), tantalum (Ta), tungsten (W) or iridium (Ir).Described method comprises the steps: multiple raw material preparing is become and Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy, and it is liquid extremely fully to depress the described multiple starting material of heating at the branch of vacuum or argon (Ar), to form and Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The corresponding molten alloy of alloy system.Described method also comprises the steps: to solidify this molten alloy to form ingot, and is liquid extremely fully with formation diffusion molten alloy the ingot reheat, and this diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material.In addition, described method comprises the steps: that fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material, hot rolling not necessarily and cold rolling this complete fine and close homogeneous material, and this complete fine and close homogeneous material of mechanical workout is to form sputtering target.
Rapid solidification provides the method that is used to produce downsizing microstructure characteristic, because crystallite size that reduces and particulate (finely) dispersive time looks helps optimizing sputtering technology and alpha emission is minimized.At microscopic scale, rapid solidification forms the highly uniform microstructure of chemistry, makes corresponding target material become outstanding source to be used for forming the deposition medium film according to its name.
Rapid solidification has produced nonequilibrium microstructure, its can bear that high temperature solidifies and heat-mechanical processing process in most of thermal cycling.For gas atomization, depend on the thermal conductivity and the specific heat of alloy, for the little powder that most of mean particle sizes reach 350 μ m, very high rate of cooling is possible.
For Co-(5-40at.%) Fe-(5-20at.%) B alloy system, described method also is included in the step than the described complete fine and close homogeneous material of hot rolling under the low temperature of the solidus temperature of Co-(5-40at.%) Fe-(5-20at.%) B alloy system.
Described consolidation step also is included in encapsulation homogeneous prealloy powder powder material in the jar, under the temperature between about 300 ℃ and about 600 ℃ jar is evacuated to vacuum tightness 10
-2Holder (torr) and 10
-3Between the holder, seal this jar, and jar is stood in 10 kips per square inch and the pressure of 45 kips between per square inch.
A kind of pure simple substance silver (Ag) that is included between 0.2at.% and the 2.0at.% in the described multiple starting material wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 962 ℃ the temperature.In addition, a kind of pure simple substance gold (Au) that comprises in the described multiple starting material wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1065 ℃ the temperature.In addition, a kind of pure elemental copper (Cu) that comprises in the described multiple starting material wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1085 ℃ the temperature.
Preparation process also comprises the following steps: to mix Ag-Pt mother alloy (master alloy) pre-alloyed powder, Co-Cr-B and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance platinum (Pt) form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The alloy system corresponding compositions.Be lower than under 1186 ℃ the temperature, or be lower than the described complete fine and close homogeneous material of hot rolling under 1030 ℃ the temperature.
Preparation process also comprises the following steps: to mix Au-Cr mother alloy pre-alloyed powder, Co-B-Pt and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance chromium (Cr) or Co-Cr mother alloy pre-alloyed powder form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(1.5-7.5at.%) X
1With nonessential (1.5-7.5at.%) X
2The alloy system corresponding compositions.Be lower than under 1160 ℃ the temperature, or be lower than the described complete fine and close homogeneous material of hot rolling under 1070 ℃ the temperature.
Preparation process also comprises the following steps: to mix Cu-Pt mother alloy pre-alloyed powder, Co-Cr-B and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance platinum (Pt) form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The alloy system corresponding compositions.Be lower than under 1186 ℃ the temperature, or under than the low temperature of the solidus temperature of Co-Cr-B mother alloy the described complete fine and close homogeneous material of hot rolling.
Described multiple starting material comprise pure simple substance cobalt (Co), chromium (Cr), platinum (Pt), boron (B), X
1And/or X
2, and/or Co-Cr, Co-B, Co-Cr-B, Ag-Pt, Au-Cr and/or Cu-Pt mother alloy.
To reach 10
4℃/s or reach 10
7℃/speed of s and by atomizing, melt rotation or spraying plating be shaped (spray forming) rapid solidification of diffusion molten alloy takes place, spreading wherein that molten alloy is rapidly solidificated into to mean particle size range is the homogeneous prealloy powder powder material of 25 μ m to 350 μ m.Form at least the first boride phase in homogeneous prealloy powder powder material, wherein first boride comprises Co mutually
3B or boride Co
3B and Co
2The mixture of B, and wherein the boride granularity less than 2 μ m.
For Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2Alloy system forms primary phase in homogeneous prealloy powder powder material, wherein primary phase is for comprising Co-Cr-X
1-Pt or Co-Cr-X
1-X
2The expansion of-Pt (extended) sosoloid.Primary phase is to comprise the Co-Cr-X that contains the highest 2at.% silver (Ag), the highest 7.5at.% gold (Au) or the highest 7.5at.% copper (Cu)
1-Pt or Co-Cr-X
1-X
2The sosoloid of the expansion of-Pt.
According to alternative plan, the present invention is a method of making chromium (Cr) based sputtering targets, and this chromium (Cr) based sputtering targets is formulated as Cr-(2-20at.%) B or Cr-(2-20at.%) C.Described method comprises the steps: multiple raw material preparing is become and Cr-(7-20at.%) B or Cr-(5-25at.%) C alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy, and it is liquid extremely fully to depress the described multiple starting material of heating at the branch of vacuum or argon (Ar), to form and Cr-(7-20at.%) B or the corresponding molten alloy of Cr-(5-25at.%) C alloy system.Described method also comprises the steps: to solidify this molten alloy to form ingot, and is liquid extremely fully with formation diffusion molten alloy the ingot reheat, and this diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material.Described method comprises the steps: that also fixed described homogeneous prealloy powder powder material becomes and forms corresponding complete fine and close homogeneous material mixing of Cr-(2-20at.%) B or Cr-(2-20at.%) C, and mechanical workout this complete fine and close homogeneous material is with the formation sputtering target.
Described method also comprises the step of blending pure simple substance chromium (Cr) powder in homogeneous prealloy powder powder material.Homogeneous Cr-(2-20at.%) B prealloy powder powder material has microstructure, and this microstructure comprises over-saturation chromium (Cr) sosoloid and/or has submicron boride Cr
2Over-saturation chromium (Cr) sosoloid of B; Or having microstructure, this microstructure comprises having submicron carbide Cr
23C
6Over-saturation chromium (Cr) sosoloid.
According to third party's case, the present invention is a method of making iron (Fe) based sputtering targets, and this iron (Fe) based sputtering targets is formulated as Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) Pd.Described method comprises the steps: multiple raw material preparing is become and Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) Pd alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy, and it is liquid extremely fully to depress the described multiple starting material of heating at the branch of vacuum or argon (Ar), to form and Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or the corresponding molten alloy of Fe-(30-55at.%) Pd alloy system.Described method also comprises the steps: to solidify this molten alloy to form ingot, and is liquid extremely fully with formation diffusion molten alloy the ingot reheat, and this diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material.In addition, described method comprises the steps: that fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material, this complete fine and close homogeneous material of hot rolling, and this complete fine and close homogeneous material of mechanical workout is to form sputtering target.
For Fe-(5-40at.%) Co-(5-20at.%) B alloy system, the described complete fine and close homogeneous material of hot rolling under the temperature lower than solidus temperature.Form at least the first boride phase in homogeneous prealloy powder powder material, wherein first boride comprises metastable boride Fe mutually
3B or metastable boride Fe
3B and balance boride Fe
2The mixture of B.
According to cubic case, the present invention is a method of making nickel (Ni) based sputtering targets that is formulated as Ni-(10-50at.%) P.Described method comprises the steps: multiple raw material preparing is become and Ni-(10-50at.%) P alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy, and it is liquid extremely fully to depress the described multiple starting material of heating at the branch of vacuum or argon (Ar), to form and the corresponding molten alloy of Ni-(10-50at.%) P alloy system.Described method also comprises the steps: to solidify this molten alloy to form ingot, and is liquid extremely fully with formation diffusion molten alloy the ingot reheat, and this diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material.In addition, described method comprises the steps: that fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material, and this complete fine and close homogeneous material of mechanical workout is to form sputtering target.
Described homogeneous prealloy powder powder material has microstructure, and this microstructure comprises the Ni that has less than 10 μ m
3Over-saturation nickel (Ni) sosoloid of P phosphide.
Below preferred embodiment describe with reference to the accompanying drawings, these description of drawings particular of the invention process.Should understand and under the situation that does not depart from scope of the present invention, also can adopt other embodiment, and can change.
Brief Description Of Drawings
Accompanying drawing to the application describes now, and wherein same reference numerals is represented identical parts:
Fig. 1 is the Ag-Co phasor;
Fig. 2 is the Au-Co phasor;
Fig. 3 is the Co-Cu phasor;
Fig. 4 is a schema, and an expression scheme according to the present invention is made the method for cobalt (Co) based sputtering targets;
Fig. 5 is a schema, and expression is according to the preparation process (step S402) of an embodiment;
Fig. 6 is the Ag-Pt phasor;
Fig. 7 is the Au-Cr phasor;
Fig. 8 is the Cu-Pt phasor;
Fig. 9 is a schema, and expression is according to the consolidation step (step S408) of an embodiment;
Figure 10 is scanning electron microscope (" SEM ") the back scattering figure of as cast condition Co-(8at.%) Cr-(7at.%) Pt-(8at.%) B alloy;
Figure 11 is the SEM back scattering figure of Co-(8at.%) Cr-(7at.%) Pt-(8at.%) the B alloy of rapid solidification;
Figure 12 represents X-ray diffractogram as cast condition and Co-rapid solidification (8at.%) Cr-(7at.%) Pt-(8at.%) B alloy;
Figure 13 is a schema, and expression second scheme according to the present invention made the method for chromium (Cr) based sputtering targets;
Figure 14 A and 14B are respectively under low ratio of enlargement and high power, the SEM back scattering figure of the Cr-of gas atomization (13.5at.%) B alloy;
Figure 15 is the SEM back scattering figure of Cr-(14at.%) the C alloy of gas atomization;
Figure 16 is a schema, and expression the 3rd scheme according to the present invention made the method for iron (Fe) based sputtering targets;
Figure 17 is the SEM secondary electron figure (secondary electron diagram) of as cast condition Fe-(30.6at.%) Co-(12.8at.%) B alloy;
Figure 18 is the SEM secondary electron figure of Fe-(30.6at.%) Co-(12.8at.%) the B alloy of rapid solidification;
Figure 19 is as cast condition and the X-ray diffractogram of Fe-rapid solidification (30.6at.%) Co-(12.8at.%) B alloy;
Figure 20 is a schema, and expression the 4th scheme according to the present invention made the method for nickel (Ni) based sputtering targets;
Figure 21 is the SEM secondary electron figure of Ni-(20at.%) the P alloy of gas atomization.
Detailed Description Of The Invention
The invention provides the sputtering target manufacture method, it has overcome the defective of classical production process.Particularly, the invention provides improved sputtering target manufacture method, it produces very intact blank to be used to have the uniform sputtering target of zero defect, chemistry that strengthens the PTF characteristic.
Fig. 4 is a schema, the method of cobalt (Co) based sputtering targets is made in expression, and this cobalt (Co) based sputtering targets is formulated as Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2, X
1Represent copper (Cu), silver (Ag) or gold (Au), and X
2Represent titanium (Ti), vanadium (V), yttrium (Y), zirconium (Zr), niobium (Nb), aluminium (Mo), ruthenium (Ru), rhodium (Rh), lanthanum (La), hafnium (Hf), tantalum (Ta), tungsten (W) or iridium (Ir).In brief, described method comprises the steps: multiple raw material preparing is become and Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy, and it is liquid extremely fully to depress the described multiple starting material of heating at the branch of vacuum or argon (Ar), to form and Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The corresponding molten alloy of alloy system.Described method also comprises the steps: to solidify this molten alloy to form ingot, and is liquid extremely fully with formation diffusion molten alloy the ingot reheat, and this diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material.In addition, described method comprises the steps: that fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material, hot rolling not necessarily and cold rolling this complete fine and close homogeneous material, and this complete fine and close homogeneous material of mechanical workout is to form sputtering target.Thereby described manufacture method is to be used to produce the alternative alloy preparation method of sputtering target of strengthening the property, and it provides solution for the problem that conventional cast technology is run into.
More specifically, the method of making cobalt (Co) based sputtering targets begins (step S401), and this cobalt (Co) based sputtering targets is formulated as Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2, X
1Represent copper (Cu), silver (Ag) or gold (Au), and X
2Represent titanium (Ti), vanadium (V), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), lanthanum (La), hafnium (Hf), tantalum (Ta), tungsten (W) or iridium (Ir).
Multiple raw material preparing is become and Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2Alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy (step S402).For the basic alloy of cobalt (Co), add silver (Ag), gold (Au) or copper (Cu) as signal-to-noise enhancer (booster).Because these elements are unmixing in cobalt (Co), when using the traditional method casting, they tend to segregation and formation fine silver (Ag), gold (Au) or copper (Cu) district from cobalt (Co) liquor, these districts are frozen into tangible group (cluster) subsequently, or seepage (leak) is to ingot surface.
Fig. 5 is a schema, and its expression is according to the more detailed preparation process in embodiment aspect (step S402) of first scheme of the present invention.Usually, preparation process also comprises mother alloy pre-alloyed powder and the alloying element that mixes the regulation weight fraction, forms and required alloy system corresponding compositions.
More specifically, and according to an aspect, process begins (step S501), mixes Ag-Pt mother alloy pre-alloyed powder, Co-Cr-B and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance platinum (Pt) form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2Alloy system corresponding compositions (step S502A), end of processing (step S504).According to this aspect, be lower than under 1186 ℃ the temperature, or be lower than the complete fine and close homogeneous material of hot rolling (seeing below step S409) under 1030 ℃ the temperature, though not necessarily, this hot-rolled step can omit.
According to this concrete aspect, use to comprise that the multiple starting material of pure substantially silver (Ag) and platinum (Pt) melt (melt stocks) prepare the Ag-Pt alloy, wherein Gui Ding platinum (Pt) content is about 10at.% to 90at.%, preferred 40at.% to 42at.%.Heat described multiple starting material to liquid fully, have the molten alloy of essentially identical regulation platinum (Pt) content, and solidify this molten alloy to form ingot with formation.Ag-Pt ingot reheat to liquid fully and rapid solidification become Ag-Pt prealloy powder powder material.
Fig. 6 is the Ag-Pt phasor, and it has shown at the peritectic reaction of about 1186 ℃ of Fu Yin (Ag) liquid (" L ") that take place down with platinum (Pt) sosoloid.For the alloy that contains about 40.6at.% platinum (Pt), silver (Ag) sosoloid of preparation same composition.When heating, contain other silver (Ag) alloy that is lower than 40.6at.% platinum (Pt) and will show incipient melting, wherein solidus curve is determined point of beginning by a dotted line.
Depend on the requirement of atomizing post-treatment temperature, be used to make CoCrPtBX
1Or CoCrPtBX
1-X
2The starting raw material of alloy can be divided into and comprise Ag-Pt alloy and CoCrB (Pt) or CoCrB (Pt) X
1Two kinds of pre-alloyed powders of alloy are wherein for keeping balance can add platinum (Pt) powder.This prescription is that argentiferous (Ag) alloy provides the highest 1186 ℃ hot processing temperature window (window), and has improved silver (Ag) distribution in entire target.Use prealloy Au-Cr or Cu-Pt powder, can attempt same method to the alloy that contains gold (Au) or copper (Cu), so that the highest 1160 ℃ and for the wider processing temperature window mouth of cupric (Cu) alloy higher temperature as shown in the phasor of Fig. 7 and 8 to be provided.
According to second alternative aspect, process begins (step S501), mixes Au-Cr mother alloy pre-alloyed powder, Co-B-Pt and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance chromium (Cr) or Co-Cr mother alloy pre-alloyed powder form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(1.5-7.5at.%) X
1With nonessential (1.5-7.5at.%) X
2Alloy system corresponding compositions (step S502B), end of processing (step S504).Though this hot-rolled step is nonessential and can omits, can be lower than under 1160 ℃ the temperature, or be lower than the complete fine and close homogeneous material of hot rolling (seeing below step S409) under 1070 ℃ the temperature.
According to this concrete aspect, use to comprise that the multiple starting material of pure substantially gold (Au) and chromium (Cr) melt prepare the Au-Cr alloy, wherein Gui Ding chromium (Cr) content is about 10at.% to 80at.%, preferred 47at.% to 49at.%.Heat described multiple starting material to liquid fully, have the molten alloy of essentially identical regulation chromium (Cr) content, and solidify this molten alloy to form ingot with formation.Au-Cr ingot reheat to liquid fully and rapid solidification become Au-Cr prealloy powder powder material.
According to the 3rd alternative aspect, process begins (step S501), mixes Cu-Pt mother alloy pre-alloyed powder, Co-Cr-B and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance platinum (Pt) form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2Alloy system corresponding compositions (step S502C), end of processing (step S504).Though hot-rolled step is nonessential and can omits, can be lower than under 1186 ℃ the temperature, or under than the low temperature of the solidus temperature of Co-Cr-B mother alloy the complete fine and close homogeneous material of hot rolling (seeing below step S409).
According to this concrete aspect, use multiple starting material and/or mother alloy to prepare Co-Cr-B and nonessential X
2Alloy, for given Cu-Pt alloy, selecting described multiple starting material and/or mother alloy is Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B and nonessential (0.5-7.5at.%) X
2Alloy system provides suitable former quantum balancing.Heat described multiple starting material to complete liquid, and solidify this molten alloy to form ingot with the formation molten alloy.Described ingot reheat to liquid fully and rapid solidification become the pre-alloyed powder material.
As mentioned above, be used to make CoCrPtBX
1Or CoCrPtBX
1-X
2The starting raw material of alloy can be divided into and comprise Ag-Pt alloy and CoCrB (Pt) or CoCrB (Pt) X
1Two kinds of pre-alloyed powders of alloy are wherein for keeping balance can add platinum (Pt) powder.Use prealloy Au-Cr or Cu-Pt powder, can attempt same method to the alloy that contains gold (Au) or copper (Cu), so that the highest 1160 ℃ and for the wider processing temperature window mouth of cupric (Cu) alloy higher temperature as shown in the phasor of Fig. 7 and 8 to be provided.
As the replacement scheme of not describing to above-mentioned prescription, a kind of pure simple substance silver (Ag) that comprises between 0.2at.% and the 2.0at.% in the described multiple starting material wherein is being lower than the complete fine and close homogeneous material of hot rolling (step S409 hereinafter) under 962 ℃ the temperature.Perhaps, a kind of pure simple substance gold (Au) that comprises in the described multiple starting material wherein is being lower than the complete fine and close homogeneous material of hot rolling (step S409 hereinafter) under 1065 ℃ the temperature.Or a kind of pure elemental copper (Cu) that comprises in the described multiple starting material wherein is being lower than the complete fine and close homogeneous material of hot rolling (step S409 hereinafter) under 1085 ℃ the temperature.In addition, these multiple starting material can comprise pure simple substance cobalt (Co), chromium (Cr), platinum (Pt), boron (B), X
1And/or X
2, and/or Co-Cr, Co-B, Co-Cr-B, Ag-Pt, Au-Cr and/or Cu-Pt mother alloy.
Get back to Fig. 4, depress the described multiple starting material of heating to liquid fully, to form and Co-(5-40at.%) Fe-(5-20at.%) B or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X at the branch of vacuum or argon (Ar)
1With nonessential (0.5-7.5at.%) X
2The corresponding molten alloy of alloy system (step S404).Solidify this molten alloy to form ingot (step S405), liquid extremely fully the ingot reheat to form diffusion molten alloy (step S406).
This diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material (step S407).Rapid solidification provides the method for the microstructure characteristic that is used for the production very small dimensions, because crystallite size that reduces and particulate dispersive time looks helps optimizing sputtering technology and alpha emission is minimized.At microscopic scale, rapid solidification forms the highly uniform microstructure of chemistry, and corresponding target material becomes outstanding source to be used for forming the deposition medium film by its name.Microstructure thinning has great effect to the fragility that reduces alloy (intermetallic containing alloys) between containing metal.Usually, when the sedimentary size of intermetallic phase was big, fragility was more remarkable.
Rapid solidification produces nonequilibrium microstructure, its can bear high temperature solidify with heat-mechanical processing process in most of thermal cycling.For gas atomization, depend on the thermal conductivity and the specific heat of alloy, reach the little powder of 350 μ m for most of mean particle sizes, very high rate of cooling is possible.
With the highest by 10
4℃/s or the highest by 10
7℃/speed of s spreads the rapid solidification of molten alloy.Be shaped by atomizing, melt rotation (melt spining) or spraying plating rapid solidification takes place, spreading wherein that molten alloy is rapidly solidificated into to mean particle size range is the homogeneous prealloy powder powder material of 25 μ m to 350 μ m.
From the thermodynamics angle because in the thermal conduction limitations slowly at mould-ingot interface heat extraction, follow the balance shown in the corresponding phasor usually so ingot solidifies.In many cases, the operation that has been construed as limiting sputtering technology of cast alloy phase, for example the stoichiometry of time looks will determine the PTF of target, and then influence the gross properties of the film of institute's sputter.
The present invention uses flash set technology to prepare sputter target alloy, and wherein the rapid quenching by molten state makes any sputter material solidify, and obtains being used for microstructure homogeneity, fineness and the globality of further processing simultaneously.Known rapid solidification can obtain high rate of cooling, therefore helps nonequilibrium liquid one solid the conversion.The product of this rapid quenching comprises the alloy that contains metastable phase and/or expansion or the super-saturated sosoloid that does not predict in complete unbodied solid alloy, the phasor.
Flash set technology, for example atomizing, melt rotation or spraying plating are shaped, be used to the various application in the aerospace industry, and other special applications, because atomization process can produce the pre-alloyed material of segregation-free (segregation-free) of the microstructure with very refinement.Usually, determine the size-grade distribution of powder by the character of technical parameter itself and alloy liquid by atomization process, and for given atomization process.For example, the known gas atomizing produces thinner powder than centrifugal atomizing.
Fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material (step S408).Form at least the first boride phase in homogeneous prealloy powder powder material, wherein first boride comprises boride Co mutually
3B or boride Co
3B and Co
2The mixture of B or other boride, wherein the boride granularity is less than 2 μ m.For Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2Alloy system forms primary phase in homogeneous prealloy powder powder material, wherein primary phase is the sosoloid of expansion, and it comprises the Co-Cr-X that contains the highest 2at.% silver (Ag) or the highest 7.5at.% gold (Au) or the highest 7.5at.% copper (Cu) or other component
1-Pt or Co-Cr-X
1-X
2-Pt.
Fig. 9 is a schema, and expression is according to the consolidation step (step S408) of an embodiment aspect of this programme, though also can use other consolidation technique.Particularly, consolidation step (step S408) beginning (step S901), encapsulation homogeneous prealloy powder powder material (step S902) in jar.Under the temperature between 300 ℃ and 600 ℃, jar is evacuated to vacuum tightness (vacuum level) 10
-2Holder and 10
-3Between the holder (step S904), seal this jar (step S905).In the hot isostatic pressing container of pressurization, make jar stand 10 kips per square inch and the pressure (step S906) of 45 kips between per square inch, end of processing (step 907) under the temperature between 300 ℃ and 1300 ℃.
Get back to Fig. 4, for Co-(5-40at.%) Fe-(5-20at.%) B alloy system, described method also is included in than the complete fine and close homogeneous material of hot rolling (step S409) under the low temperature of the solidus temperature of Co-(5-40at.%) Fe-(5-20at.%) B alloy system, certainly if necessary, this hot-rolled step can omit.Cold rolling complete fine and close homogeneous material (step S410), and mechanical workout is to form sputtering target (step S411), method end (step S412).
For gas atomization, the powder that uses helium (He) and Duo than to use argon (Ar) generation thin is because the viscosity of helium (He) is lower and the velocity of sound is higher.The rotations per minute (" RPM ") or the RPM of electrode by increase dish in centrifugal or rotating electrode atomization process reduce mean particle size.Under many atomizing situations, higher liquid alloy viscosity and/or surface tension cause bigger particle.In rapid solidification, rate of cooling and granularity are inversely proportional to.Though the complete amorphization of solid alloy is not easy to realize with regard to final target product, rapid solidification produces nonequilibrium microstructure, its can bear that high temperature solidifies and heat-mechanical processing process in most of thermal cycling.
The use quick setting method has obtained the expansion solid solubility as maximum 18at.% gold (Au) of being found in the Co-Au alloy of some thin slice chillings (splat cooling), and has obtained the sosoloid of the expansion of copper (Cu) in the cobalt (Co) that contains maximum 15at.% copper (Cu) in the Co-Cu liquid alloy of quenching.For the silver that contains cobalt (Co) (Ag) alloy, might in cobalt (Co) sosoloid, keep silver (Ag) atom seldom, still, for the high alloy of silver (Ag) content (2at.% and more than), because the existence at liquid miscible interval, when atomizing, silver (Ag) may will be frozen into tangible particle.Therefore, preferably by introducing silver (Ag) with the mother alloy of silver (Ag) complete miscibility and/or formation intermediate phase.
SEM and microprobe analysis show that the typical as-cast microstructure of CoCrPtB alloy is made of no boron dendroid CoPtCr primary phase, and this dendroid CoPtCr primary phase is comprised CoPtCr primary phase and boride Co
2The aggregate of the less thin layer of the eutectic phase of B surrounds.Figure 10 has shown the representational microstructure of as cast condition Co-(8at.%) Cr-(7at.%) Pt-(8at.%) B alloy.By comparison, as shown in Figure 11, the rapid solidification of the basic alloy of cobalt (Co) causes forming very thin microstructure, and wherein the size of boronation cobalt (Co) phase is significantly reduced.Compare with the distribution mutually of boride in as-cast microstructure, the distribution of these boride phases is also than very even.
Determined formation mutually as cast condition and Co-rapid solidification (8at.%) Cr-(7at.%) Pt-(8at.%) B alloy by X-ray diffraction, wherein the diffractogram among Figure 12 has been summarized analytical results.In cast alloy, balance boride Co
2B and Fe
2B forms with corresponding matrix (matrix), but the alloy of rapid solidification has formed metastable boride Co
3B.Shown that this non-equilibrium boride has goodish thermostability, even and in the hot consolidation process, be exposed under 1250 ℃ the high temperature and also can not be transformed (transformed).
In the increase of gained PTF aspect homogeneity and boride population distribution mutually, Co
3The stoichiometry of B should be ideal much.With the alloy composition is benchmark, and the atomic fraction that is preserved for forming the cobalt (Co) of boride phase in cast alloy is 0.16, and is 0.24 for the corresponding atomic fraction of the alloy of rapid solidification.Therefore, compare with cast alloy, for the alloy of rapid solidification, the volume fraction that constitutes cobalt (Co) the alloy mesostroma phase of ferromagnetic phase greatly reduces.The increase of the minimizing of matrix volume fraction and boride phase volume fraction has significant contribution to increase and the homogeneity of PTF.In addition, the increase of boride phase volume fraction is unusual ideal to the uniform distribution of realizing boron (B) in the material of rapid solidification.In cast alloy, the second balance boride Co
2B forms with corresponding matrix, but forms the first balance boride Co in the alloy of rapid solidification
3B.
Figure 13 is a schema, and expression second scheme according to the present invention made the method for chromium (Cr) based sputtering targets, and this chromium (Cr) based sputtering targets is formulated as Cr-(2-20at.%) B or Cr-(2-20at.%) C.In brief, described method comprises the steps: multiple raw material preparing is become and Cr-(7-20at.%) B or Cr-(5-25at.%) C alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy, and it is liquid extremely fully to depress the described multiple starting material of heating at the branch of vacuum or argon (Ar), to form and Cr-(7-20at.%) B or the corresponding molten alloy of Cr-(5-25at.%) C alloy system.Described method also comprises the steps: to solidify this molten alloy to form ingot, and is liquid extremely fully with formation diffusion molten alloy the ingot reheat, and this diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material.Described method comprises the steps: that also fixed described homogeneous prealloy powder powder material becomes and forms corresponding complete fine and close homogeneous material mixing of Cr-(2-20at.%) B or Cr-(2-20at.%) C, and mechanical workout this complete fine and close homogeneous material is with the formation sputtering target.
More specifically, the method of making chromium (Cr) based sputtering targets begins (step S1301), this chromium (Cr) based sputtering targets is formulated as Cr-(2-20at.%) B or Cr-(2-20at.%) C, multiple raw material preparing is become and Cr-(7-20at.%) B or Cr-(5-25at.%) C alloy system corresponding compositions, and described multiple starting material comprise pure simple substance or mother alloy (step S1302).
Depress the described multiple starting material of heating to liquid fully, to form and Cr-(7-20at.%) B or Cr-(5-25at.%) the corresponding molten alloy of C alloy system (step S1304) at the branch of vacuum or argon (Ar).Solidify this molten alloy to form ingot (step S1305), liquid extremely fully the ingot reheat to form diffusion molten alloy (step S1306).This diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material (step S1307).
Blending pure simple substance chromium (Cr) powder (step S1308) in homogeneous prealloy powder powder material.Homogeneous Cr-(2-20at.%) B prealloy powder powder material has microstructure, and this microstructure comprises solution (solution) or sosoloid, for example over-saturation chromium (Cr) sosoloid and/or have submicron boride Cr
2Over-saturation chromium (Cr) sosoloid of B or other boride; Or having microstructure, this microstructure comprises having submicron carbide Cr
23C
6Or over-saturation chromium (Cr) sosoloid of other carbide.Aspect interchangeable, omit blending step (step S1308).
Fixed described homogeneous prealloy powder powder material became with mixing of Cr-(2-20at.%) B or Cr-(2-20at.%) C forms corresponding complete fine and close homogeneous material (step S1309).Described consolidation step (step S1309) also is included in encapsulation homogeneous prealloy powder powder material in the jar, under the temperature between 300 ℃ and 600 ℃ jar is evacuated to vacuum tightness 10
-2Holder and 10
-3Between the holder, seal this jar, and jar is stood in 10 kips per square inch and the pressure of 45 kips between per square inch.Also can use other method to carry out described consolidation step (step S1309).
The described complete fine and close homogeneous material of mechanical workout is to form sputtering target (step S1310), end of processing (step S1311).As cast condition Cr-(13.5at.%) B shows coarse eutectic microstructure, and it comprises Cr and Cr
2The alternating thin layers of B.Known coarse chromium boride (Cr) causes producing a large amount of particles in sputtering technology, unless therefore the boride granularity is reduced, otherwise should avoid forming these borides.Figure 14 A and 14B represent the microstructure of Cr-(13.5at.%) B of gas atomization, have wherein shown the sosoloid of the abundant extension that does not have shaping boride phase.
The Cr-C cast alloy tends to form coarse carbide, and it causes mechanical workout polishing (machining finish) weak effect and produces grain defect in sputtering technology.For example, Figure 15 has represented the internal microstructure of Cr-(14at.%) C of gas atomization, and wherein to cause the particle size reduction of chromium carbide (Cr) be about 5 μ m to rapid solidification.
Figure 16 is a schema, expression the 3rd scheme according to the present invention made the method for iron (Fe) based sputtering targets, and this iron (Fe) based sputtering targets is formulated as Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) Pd.In brief, described method comprises the steps: multiple raw material preparing is become and Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) Pd alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy, and it is liquid extremely fully to depress the described multiple starting material of heating at the branch of vacuum or argon (Ar), to form and Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or the corresponding molten alloy of Fe-(30-55at.%) Pd alloy system.Described method also comprises the steps: to solidify this molten alloy to form ingot, and is liquid extremely fully with formation diffusion molten alloy the ingot reheat, and this diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material.Described method comprises the steps: that also the described homogeneous prealloy powder powder material of circle knot becomes complete fine and close homogeneous material, and this complete fine and close homogeneous material of mechanical workout is to form sputtering target.
More specifically, the method of making iron (Fe) based sputtering targets begins (step S1601), this iron (Fe) based sputtering targets is formulated as Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) Pd, multiple raw material preparing is become and Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) Pd alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy (step S1602).
Depress the described multiple starting material of heating to liquid fully at the branch of vacuum or argon (Ar), to form and Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) the corresponding molten alloy of Pd alloy system (step S1604).Solidify this molten alloy to form ingot (step S1605), liquid extremely fully the ingot reheat to form diffusion molten alloy (step S1606).
This diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material (step S1607).Form at least the first boride phase in homogeneous prealloy powder powder material, wherein first boride comprises metastable boride Fe mutually
3B or metastable boride Fe
3B and balance boride Fe
2The mixture of B, or other boride component.
Fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material (step S1609).Described consolidation step (step S1609) also is included in encapsulation homogeneous prealloy powder powder material in the jar, under the temperature between 300 ℃ and 600 ℃ jar is evacuated to vacuum tightness 10
-2Holder and 10
-3Between the holder, seal this jar, and this jar stood in 10 kips per square inch and the pressure of 45 kips between per square inch.Also can use other method to carry out described consolidation step (step S1609).
The described complete fine and close homogeneous material of hot rolling (step S1610).For Fe-(5-40at.%) Co-(5-20at.%) B alloy system, the complete fine and close homogeneous material of hot rolling under the temperature lower than solidus temperature.The complete fine and close homogeneous material of mechanical workout is to form sputtering target (step S1612), end of processing (step S1614).
As shown in figure 17, the microstructure of as cast condition Fe-(30.6at.%) Co-(12.8at.%) B comprises periplast and the boride Fe that α ' is orderly
2B.By comparison, as shown in figure 18, the rapid solidification of the basic alloy of iron (Fe) causes forming very thin microstructure, and wherein the size of the boride phase of Fe is significantly reduced.Compare with the distribution mutually of boride in as-cast microstructure, the distribution of these boride phases is also very even.
Figure 19 represents the X-ray diffraction analysis that constitutes mutually of as cast condition and Fe-rapid solidification (30.6at.%) Co-(12.8at.%) B alloy.In cast alloy, balance boride Fe
2B forms with corresponding matrix, but the alloy of rapid solidification has formed metastable boride Fe
3B, wherein this non-equilibrium boride shows goodish thermostability, also can not transformed even it is exposed in the hot consolidation process under 1100 ℃ the high temperature.
In the increase of gained PTF aspect homogeneity and boride population distribution mutually, obvious Fe
3The stoichiometry of B is unusual ideal.With the alloy composition is benchmark, and the atomic fraction that is preserved for forming the iron (Fe) of boride phase in cast alloy is 0.256, and is 0.384 for the corresponding atomic fraction of the alloy of rapid solidification.Therefore, compare with cast alloy, for the alloy of rapid solidification, the volume fraction that constitutes iron (Fe) the alloy mesostroma phase of ferromagnetic phase greatly reduces.The increase of the minimizing of matrix volume fraction and boride phase volume fraction has significant contribution to increase and the homogeneity of PTF.In addition, the increase of boride phase volume fraction is unusual ideal to the uniform distribution of realizing boron (B) in the material of rapid solidification.
Figure 20 is the method that expression the 4th scheme according to the present invention made nickel (Ni) based sputtering targets, and this nickel (Ni) based sputtering targets is formulated as Ni-(10-50at.%) P.In brief, described method comprises the steps: multiple raw material preparing is become and Ni-(10-50at.%) P alloy system corresponding compositions, described multiple starting material comprise pure simple substance or mother alloy, and it is liquid extremely fully to depress the described multiple starting material of heating at the branch of vacuum or argon (Ar), to form and the corresponding molten alloy of Ni-(10-50at.%) P alloy system.Described method also comprises the steps: to solidify this molten alloy to form ingot, and is liquid extremely fully with formation diffusion molten alloy the ingot reheat, and this diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material.Described method comprises the steps: that also fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material, and this complete fine and close homogeneous material of mechanical workout is to form sputtering target.
More specifically, the method of making nickel (Ni) based sputtering targets begins (step S2001), this nickel (Ni) based sputtering targets is formulated as Ni-(10-50at.%) P, multiple raw material preparing is become and Ni-(10-50at.%) P alloy system corresponding compositions, and described multiple starting material comprise pure simple substance or mother alloy (step S2002).
Depress the described multiple starting material of heating to liquid fully, to form and Ni-(10-50at.%) the corresponding molten alloy of P alloy system (step S2004) at the branch of vacuum or argon (Ar).Solidify this molten alloy to form ingot (step S2005), liquid extremely fully the ingot reheat to form diffusion molten alloy (step S2006).
This diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material (step S2007).Described homogeneous prealloy powder powder material has microstructure, and this microstructure comprises the Ni that has less than 10 μ m
3Over-saturation nickel (Ni) sosoloid of P phosphide also may form other phosphide certainly.
Fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material (step S2009).Described consolidation step (step S2009) also is included in encapsulation homogeneous prealloy powder powder material in the jar, under the temperature between 300 ℃ and 600 ℃ jar is evacuated to vacuum tightness 10
-2Holder and 10
-3Between the holder, seal this jar, and in the hot isostatic pressing container of pressurization, make under the temperature between 300 ℃ and 1300 ℃ and jar stand per square inch and the pressure of 45 kips between per square inch in 10 kips.Also can use other method to carry out described consolidation step (step S2009).
The described complete fine and close homogeneous material of mechanical workout (step S2010), end of processing (step S2012).
Owing to formed various nickel phosphides (Ni), so the Ni-P alloy is highly brittle.The size of phosphide time looks is the brittle deciding factor of control.The cast alloy that contains more than 10at.%P generally is highly brittle, and is easy to ftracture under any load in mechanical processing process.Figure 21 has shown the internal microstructure of Ni-(20at.%) P of gas atomization, illustrates that rapid solidification makes the size of nickel phosphide (Ni) intermetallic phase be reduced to about 10 μ m.
Rapid solidification provides the method for the microstructure characteristic that is used for the production very small dimensions.Crystallite size that reduces and particulate dispersive time looks helps optimizing sputtering technology and alpha emission is minimized.In addition, at microscopic scale, rapid solidification forms the highly uniform microstructure of chemistry, and makes corresponding target material become outstanding source to be used for each justice composition deposition medium film by it.Microstructure thinning has great effect to the fragility that reduces alloy between containing metal.Usually, when the sedimentary size of intermetallic phase was big, fragility strengthened.
At last, aspect the increase and homogeneity of the inherent nature of the influence of secondary relative distribution and target such as PTF, the liquid one solid favourable inferior looks of the potential formation stoichiometry of nonequilibrium behavior that transforms in the rapid solidification.
Manufacture method of the present invention comprises the selection of casting approach (casting route), die design and moulding stock, provides practical and had the sputtering target that improves performance with production with work program fast.Significantly shorten process period, and do not damage important performance, as the chemical uniformity of target, the volume constancy and the PTF of product.
The present invention is illustrated by specific embodiment.Be to be understood that the present invention is not limited to above-mentioned embodiment, the variations and modifications that the one of ordinary skill in the art may carry out also without departing from the spirit and scope of the present invention.
Claims (39)
1. method of making cobalt (Co) based sputtering targets, this cobalt (Co) based sputtering targets is formulated as Co-(5-40at.%) Fe-(5-20at.%) B, or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at-%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2, X
1Represent copper (Cu), silver (Ag) or gold (Au), and X
2Represent titanium (Ti), vanadium (V), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), lanthanum (La), hafnium (Hf), tantalum (Ta), tungsten (W) or iridium (Ir), described method comprises the steps:
Multiple raw material preparing is become and Co-(5-40at.%) Fe-(5-20at.%) B, or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The alloy system corresponding compositions, described multiple starting material comprise pure element or mother alloy;
Depress the described multiple starting material of heating to liquid fully at the branch of vacuum or argon (Ar), with formation and Co-(5-40at.%) Fe-(5-20at.%) B, or Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The corresponding molten alloy of alloy system;
Solidify described molten alloy to form ingot;
Described ingot reheat is spread molten alloy to liquid fully to form;
The described diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material;
Fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material;
Cold rolling described complete fine and close homogeneous material; And
The described complete fine and close homogeneous material of mechanical workout is to form sputtering target.
2. the method for claim 1, wherein for Co-(5-40at.%) Fe-(5-20at.%) B alloy system, described method also is included in the step than the described complete fine and close homogeneous material of hot rolling under the low temperature of the solidus temperature of Co-(5-40at.%) Fe-(5-20at.%) B alloy system.
3. the method for claim 1, wherein said consolidation step also comprises the following steps:
The described homogeneous prealloy powder powder material of encapsulation in jar;
Temperature between 300 ℃ and 600 ℃ is evacuated to 10 for following described jar
-2Holder and 10
-3Vacuum tightness between the holder;
Seal described jar; With
In the hot isostatic pressing container of pressurization, under the temperature between 300 ℃ and 1300 ℃, make described jar to stand 10 kips per square inch to 45 kips pressure per square inch.
4. the method for claim 1, a kind of pure simple substance silver (Ag) that comprises in the wherein said multiple starting material.
5. method as claimed in claim 4, a kind of pure simple substance silver (Ag) that comprises 0.2at.% to 2.0at.% in the wherein said multiple starting material.
6. method as claimed in claim 2 wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 962 ℃ the temperature.
7. the method for claim 1, a kind of pure simple substance gold (Au) that comprises in the wherein said multiple starting material.
8. method as claimed in claim 2 wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1065 ℃ the temperature.
9. the method for claim 1, a kind of pure elemental copper (Cu) that comprises in the wherein said multiple starting material.
10. method as claimed in claim 2 wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1085 ℃ the temperature.
11. the method for claim 1, wherein said preparation process also comprise the following steps: to mix Ag-Pt mother alloy pre-alloyed powder, Co-Cr-B and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance platinum (Pt) form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The alloy system corresponding compositions.
12. method as claimed in claim 2 wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1186 ℃ the temperature.
13. method as claimed in claim 2 wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1030 ℃ the temperature.
14. the method for claim 1, wherein said preparation process also comprise the following steps: to mix Au-Cr mother alloy pre-alloyed powder, Co-B-Pt and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance chromium (Cr) or Co-Cr mother alloy pre-alloyed powder form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(1.5-7.5at.%) X
1With nonessential (1.5-7.5at.%) X
2The alloy system corresponding compositions.
15. method as claimed in claim 2 wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1160 ℃ the temperature.
16. method as claimed in claim 2 wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1070 ℃ the temperature.
17. the method for claim 1, wherein said preparation process also comprise the following steps: to mix Cu-Pt mother alloy pre-alloyed powder, Co-Cr-B and the nonessential X of regulation weight fraction
2Mother alloy pre-alloyed powder and simple substance platinum (Pt) form and Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2The alloy system corresponding compositions.
18. method as claimed in claim 2 wherein is being lower than the described complete fine and close homogeneous material of hot rolling under 1186 ℃ the temperature.
19. method as claimed in claim 2, the wherein described complete fine and close homogeneous material of hot rolling under than the low temperature of the solidus temperature of Co-Cr-B mother alloy.
20. the method for claim 1, wherein said multiple starting material comprise pure simple substance cobalt (Co), chromium (Cr), platinum (Pt), boron (B), X
1And/or X
2, and/or Co-Cr, Co-B, Co-Cr-B, Ag-Pt, Au-Cr and/or Cu-Pt mother alloy.
21. the method for claim 1 is wherein with the highest by 10
4℃/rapid solidification of described diffusion molten alloy takes place in the speed of s.
22. the method for claim 1 is wherein with the highest by 10
7℃/rapid solidification of described diffusion molten alloy takes place in the speed of s.
23. the method for claim 1 is wherein carried out rapid solidification by atomizing.
24. it is the homogeneous prealloy powder powder material of 25 μ m to 350 μ m that method as claimed in claim 23, wherein said diffusion molten alloy are rapidly solidificated into to mean particle size range.
25. rapid solidification wherein takes place by the melt rotation in the method for claim 1.
26. the method for claim 1 wherein is shaped by spraying plating rapid solidification takes place.
27. the method for claim 1 wherein form at least the first boride phase in described homogeneous prealloy powder powder material, and wherein said first boride comprises boride Co mutually
3B or boride Co
3B and Co
2The mixture of B.
28. the method for claim 1, the granularity of wherein said boride is less than 2 μ m.
29. the method for claim 1 is wherein for Co-(5-25at.%) Cr-(5-25at.%) Pt-(5-20at.%) B-(0.2-7.5at.%) X
1With nonessential (0.5-7.5at.%) X
2Alloy system forms primary phase in described homogeneous prealloy powder powder material, wherein this primary phase is for comprising Co-Cr-X
1-Pt or Co-Cr-X
1-X
2The sosoloid of the expansion of-Pt.
30. method as claimed in claim 29, wherein said primary phase are to comprise containing maximum 2at.% silver (Ag) or the 7.5at.% gold (Au) or the Co-Cr-X of 7.5at.% copper (Cu) at most at most
1-Pt or Co-Cr-X
1-X
2The sosoloid of the expansion of-Pt.
31. a method of making chromium (Cr) based sputtering targets, this chromium (Cr) based sputtering targets is formulated as Cr-(2-20at.%) B or Cr-(2-20at.%) C, and described method comprises the steps:
Multiple raw material preparing is become and Cr-(7-20at.%) B or Cr-(5-25at.%) C alloy system corresponding compositions, and described multiple starting material comprise pure element or mother alloy;
Depress the described multiple starting material of heating to liquid fully, to form and Cr-(7-20at.%) B or the corresponding molten alloy of Cr-(5-25at.%) C alloy system at the branch of vacuum or argon (Ar);
Solidify described molten alloy to form ingot;
Described ingot reheat is spread molten alloy to liquid fully to form;
The described diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material;
Fixed described homogeneous prealloy powder powder material became with mixing of Cr-(2-20at.%) B or Cr-(2-20at.%) C forms corresponding complete fine and close homogeneous material; And
The described complete fine and close homogeneous material of mechanical workout is to form sputtering target.
32. method as claimed in claim 31 further comprises the step of mixing pure simple substance chromium (Cr) powder in described homogeneous prealloy powder powder material.
33. method as claimed in claim 31, wherein said homogeneous Cr-(2-20at.%) B prealloy powder powder material has microstructure, and this microstructure comprises over-saturation chromium (Cr) sosoloid and/or has submicron boride Cr
2Over-saturation chromium (Cr) sosoloid of B.
34. method as claimed in claim 31, wherein said homogeneous Cr-(2-20at.%) B prealloy powder powder material has microstructure, and this microstructure comprises having submicron carbide Cr
23C
6Over-saturation chromium (Cr) sosoloid.
35. method of making iron (Fe) based sputtering targets, this iron (Fe) based sputtering targets is formulated as Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) Pd, and described method comprises the steps:
Multiple raw material preparing is become and Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or Fe-(30-55at.%) Pd alloy system corresponding compositions, and described multiple starting material comprise pure element or mother alloy;
Depress the described multiple starting material of heating to liquid fully at the branch of vacuum or argon (Ar), to form and Fe-(5-40at.%) Co-(5-20at.%) B, Fe-(5-90at.%) Ni, Fe-(5-70at.%) Co, Fe-(30-50at.%) Pt or the corresponding molten alloy of Fe-(30-55at.%) Pd alloy system;
Solidify described molten alloy to form ingot;
Described ingot reheat is spread molten alloy to liquid fully to form;
The described diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material;
Fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material;
The described complete fine and close homogeneous material of hot rolling; And
The described complete fine and close homogeneous material of mechanical workout is to form sputtering target.
36. method as claimed in claim 35, wherein for Fe-(5-40at.%) Co-(5-20at.%) B alloy system, the described complete fine and close homogeneous material of hot rolling under the temperature lower than solidus temperature.
37. method as claimed in claim 35 wherein form at least the first boride phase in described homogeneous prealloy powder powder material, and wherein said first boride comprises metastable boride Fe mutually
3B or metastable boride Fe
3B and balance boride Fe
2The mixture of B.
38. a method of making nickel (Ni) based sputtering targets, this nickel (Ni) based sputtering targets is formulated as Ni-(10-50at.%) P, and described method comprises the steps:
Multiple raw material preparing is become and Ni-(10-50at.%) P alloy system corresponding compositions, and described multiple starting material comprise pure element or mother alloy;
Depress the described multiple starting material of heating to liquid fully, to form and the corresponding molten alloy of Ni-(10-50at.%) P alloy system at the branch of vacuum or argon (Ar);
Solidify described molten alloy to form ingot;
Described ingot reheat is spread molten alloy to liquid fully to form;
The described diffusion molten alloy of rapid solidification becomes homogeneous prealloy powder powder material;
Fixed described homogeneous prealloy powder powder material becomes complete fine and close homogeneous material; And
The described complete fine and close homogeneous material of mechanical workout is to form sputtering target.
39. method as claimed in claim 38, wherein said homogeneous prealloy powder powder material has microstructure, and this microstructure comprises the phosphide Ni that has less than 10 μ m
3Over-saturation nickel (Ni) sosoloid of P.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US70154605P | 2005-07-22 | 2005-07-22 | |
| US60/701,546 | 2005-07-22 | ||
| US11/284,911 | 2005-11-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1900352A true CN1900352A (en) | 2007-01-24 |
Family
ID=37656332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610075466 Pending CN1900352A (en) | 2005-07-22 | 2006-04-21 | Enhanced sputter target manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1900352A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100571966C (en) * | 2007-12-26 | 2009-12-23 | 安泰科技股份有限公司 | A kind of manufacture method of magnetron sputtering Fe-Co alloy target |
| CN102423802A (en) * | 2011-12-20 | 2012-04-25 | 宁波江丰电子材料有限公司 | Preparation method of high-purity cobalt target |
| CN103620083A (en) * | 2011-06-30 | 2014-03-05 | 吉坤日矿日石金属株式会社 | Co-cr-pt-b alloy sputtering target and method for producing same |
| CN107075668A (en) * | 2015-05-14 | 2017-08-18 | 美题隆公司 | Sputtering target |
| CN112106134A (en) * | 2018-07-31 | 2020-12-18 | 田中贵金属工业株式会社 | Sputtering target for magnetic recording medium |
-
2006
- 2006-04-21 CN CN 200610075466 patent/CN1900352A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100571966C (en) * | 2007-12-26 | 2009-12-23 | 安泰科技股份有限公司 | A kind of manufacture method of magnetron sputtering Fe-Co alloy target |
| CN103620083A (en) * | 2011-06-30 | 2014-03-05 | 吉坤日矿日石金属株式会社 | Co-cr-pt-b alloy sputtering target and method for producing same |
| CN102423802A (en) * | 2011-12-20 | 2012-04-25 | 宁波江丰电子材料有限公司 | Preparation method of high-purity cobalt target |
| CN107075668A (en) * | 2015-05-14 | 2017-08-18 | 美题隆公司 | Sputtering target |
| CN112106134A (en) * | 2018-07-31 | 2020-12-18 | 田中贵金属工业株式会社 | Sputtering target for magnetic recording medium |
| CN112106134B (en) * | 2018-07-31 | 2022-05-03 | 田中贵金属工业株式会社 | Sputtering target for magnetic recording medium |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1746173A2 (en) | Enhanced sputter target manufacturing method | |
| US11098403B2 (en) | High entropy alloy thin film coating and method for preparing the same | |
| US7229588B2 (en) | Mechanically alloyed precious metal magnetic sputtering targets fabricated using rapidly solidified alloy powders and elemental Pt metal | |
| CN104032270B (en) | A kind of large scale ruthenium-base alloy sputtering target material and preparation method thereof | |
| TWI390066B (en) | Ag base alloy sputtering target and method for manufacturing the same | |
| TWI622661B (en) | W-ni sputtering target as well as the production process and use thereof | |
| JP2005533182A (en) | Method for producing sputtering target doped with boron / carbon / nitrogen / oxygen / silicon | |
| US11101118B2 (en) | Cobalt, iron, boron, and/or nickel alloy-containing articles and methods for making same | |
| CN1900352A (en) | Enhanced sputter target manufacturing method | |
| US20130206591A1 (en) | Sputtering Target for Magnetic Recording Film and Method for Producing Same | |
| JP6393696B2 (en) | Cu-Ga-In-Na target | |
| CN105648407A (en) | High-density molybdenum-niobium alloy target and preparation process thereof | |
| CN1671881A (en) | High-PTF sputtering targets and method of manufacturing | |
| JPH08120445A (en) | Production of titanium-aluminum alloy target material | |
| TW201103999A (en) | Method for manufacturing nickel alloy target | |
| US10519538B2 (en) | Sputtering target comprising Al—Te—Cu—Zr alloy, and method for producing same | |
| CN107151755B (en) | A method of preparing the high-entropy alloy of close-packed hexagonal structure | |
| JP2007197811A (en) | Sputter target | |
| CN113145850B (en) | High-flux preparation method of metal material with gradient structure | |
| TW200404908A (en) | Fabrication of ductile intermetallic sputtering targets | |
| EP4006198A1 (en) | Sputtering target | |
| RU2707375C2 (en) | Coating source | |
| EP1923481A2 (en) | Enhanced sputter target manufacturing method | |
| JP2002332508A (en) | Method for producing thermoelectric material | |
| JP2001262325A (en) | Cr-W ALLOY BASED SPUTTERING TARGET MATERIAL AND ITS PRODUCING METHOD |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |