CN103797153A - Mo-W target and method for manufacturing same - Google Patents
Mo-W target and method for manufacturing same Download PDFInfo
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- CN103797153A CN103797153A CN201280044707.1A CN201280044707A CN103797153A CN 103797153 A CN103797153 A CN 103797153A CN 201280044707 A CN201280044707 A CN 201280044707A CN 103797153 A CN103797153 A CN 103797153A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
- B22F3/15—Hot isostatic pressing
Abstract
The invention provides a Mo-W target capable of improving relative density without performing a rolling process, and a method for manufacturing the Mo-W target. A molybdenum powder is subjected to a deoxidation process at a temperature of 1100 to 1300 DEG C inclusive, tungsten powder is mixed with the deoxidized molybdenum powder, and the mixture of the molybdenum powder and the tungsten powder is sintered under pressure at a predetermined temperature. Accordingly, fewer voids are generated during sintering, and the density of sintered bodies is increased. Therefore, higher densities without performing a rolling process can be achieved by the manufacturing method, thus achieving the uniform film thickness when sputtering is used to form a film.
Description
Technical field
The present invention relates to a kind of sputter Mo(molybdenum being formed by molybdenum-tungsten class sintered compact)-W(tungsten) target and manufacture method thereof.
Background technology
In recent years, electrode or the distribution materials'use using molybdenum-tungsten (Mo-W) alloy as flat-panel monitor (FPD), solar cell, semiconductor element etc.This alloy can form by sputtering method, and as sputtering target material, molybdenum-tungsten class sintered compact is widely used.The sputtering target material being formed by sintered compact, needs relative density higher, and crystal grain is small evenly.
For example, in following patent documentation 1, record the manufacture method of tungsten containing 30～70% Mo-W alloy target material of the proportional amount of attaching most importance to.Here by after the mixed powder extrusion molding of molybdenum powder and tungsten powder and sintering, implement calendering process to improve its relative density with the temperature of defined.
Patent documentation 1: No. 9-3635, Japanese patent of invention Publication Unexamined Patent
But, although being carried out to calendering process, sintered compact can improve its relative density, can cause presenting the distinctive crystal orientation that comes from rolling direction on sintered compact.Therefore, in the time of sputter, make the direction of dispersing of target can isotropy, thereby cause on substrate the film thickness distribution of sputtered film inhomogeneous, to such an extent as to produce the low problem of yield rate.
In view of this, the object of the present invention is to provide a kind of Mo-W target and manufacture method thereof that does not need to carry out calendering process and just can improve relative density.
Summary of the invention
In order to achieve the above object, the manufacture method of the Mo-W target of an embodiment of the invention comprises and molybdenum powder is carried out more than 1100 ℃ to deoxidation treatment at the temperature below 1300 ℃.Mixing tungsten powder through in the described molybdenum powder of deoxidation treatment.The mixed powder of described molybdenum powder and described tungsten powder is carried out to pressure sintering with the temperature of defined.
The Mo-W target of an embodiment of the invention is formed by the sintered compact of the mixed powder that contains molybdenum powder and tungsten powder.
By average weighted above-mentioned the orientation of proportion of composing of this molybdenum and tungsten respectively containing proportional, with respect to the summation of the X-ray diffraction intensity in each orientation of (110), (200) of molybdenum and tungsten, (211), (220), (310), (321), all below 25%.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the manufacture method of the Mo-W target of explanation one embodiment of the present invention;
Fig. 2 is the XRD(X-ray diffraction that represents the Mo-W target of one embodiment of the present invention, X-ray diffraction) the chart of test-results;
Fig. 3 is the SEM(Scanning Electron Microscope that represents the Mo-W target of one embodiment of the present invention, scanning electronic microscope) imaging and WDX(Wavelength Dispersive X-ray spectroscopy, X ray spectrometer) figure of imaging.
[description of reference numerals]
ST1:Mo powder granulating working procedure; ST2:Mo powder deoxidation treatment operation; ST3:Mo pelletizing broken process; ST4:W powder mixed processes; ST5: pressure sintering operation; ST6: mechanical workout operation.
Embodiment
The manufacture method of the Mo-W target of an embodiment of the invention comprises carries out molybdenum powder deoxidation treatment more than 1100 ℃ at the temperature below 1300 ℃.
Mixing tungsten powder through in the described molybdenum powder of deoxidation treatment.
The mixed powder of described molybdenum powder and described tungsten powder is carried out to pressure sintering with the temperature of defined.
In above-mentioned manufacture method, by molybdenum powder being carried out under said temperature to deoxidation treatment, can reduce the oxygen level in molybdenum powder.Thus, the generation in the cavity (pore) can suppress sintering time, thereby the densification of acceleration of sintering body.Therefore, according to above-mentioned manufacture method, owing to can just can not realize the densification of sintered compact by implementing calendering process, thus the homogeneity of the thickness can realize spatter film forming time.
The deoxidation treatment of molybdenum powder typically, is carried out under decompression or hydrogen environment.Treatment temp, the in the situation that of 1100 ℃ of less thaies, can not obtain sufficient deoxidation effect.On the other hand, when treatment temp exceeds 1300 ℃, molybdenum crystalline growth, makes crystallization particle diameter become large tendency and present.Paradoxical discharge can bring out sputter while becoming large due to crystallization particle diameter time, therefore also bad.Therefore, the deoxidation treatment temperature of molybdenum powder be 1100 ℃ above below 1300 ℃.
Above-mentioned molybdenum powder can be before deoxidation treatment, with the size granulation of defined.In this case, the pelletizing of this molybdenum powder is by deoxidation treatment.
Thus, the cavity between primary particle is diminished, thereby can improve the relative density after sintering.
Above-mentioned pelletizing also can be after deoxidation treatment, with the size fragmentation of defined.
Under said temperature, through the pelletizing of deoxidation treatment, in the time of local sintering, size of particles can become greatly, thereby direct sintering can not obtain desired relative density.Therefore,, by the pelletizing of broken deoxidation treatment, can stably make the sintered compact with desired relative density.
The mixed powder of above-mentioned molybdenum powder and above-mentioned tungsten powder, for example, by HIP(hot isostatic pressing) the pressure sintering method sintering of method or vacuum hot-pressing etc.
Thus, can produce highdensity sintered compact.
Sintering temperature by above-mentioned mixed powder when the HIP method sintering, be for example 1200 ℃ above below 1500 ℃.
Sintering temperature, the in the situation that of 1200 ℃ of less thaies, can make the relative density of sintered compact lower, and can form paradoxical discharge or produce particle.In addition, when sintering temperature exceeds 1500 ℃, molybdenum and tungstenalloy can be made, to such an extent as to forming of the main orientation that caused by its alloying can not be stoped.
The Mo-W target of being made by aforesaid method, by average weighted above-mentioned the orientation of proportion of composing of this molybdenum and tungsten respectively containing proportional, with respect to the summation of the X-ray diffraction intensity in each orientation of (110), (200) of molybdenum and tungsten, (211), (220), (310), (321), all below 25%.Thus, the homogenizing of thickness can reach sputter time.
Below, with reference to drawing, embodiments of the present invention are described.
Fig. 1 is the process flow sheet of the manufacture method of the Mo-W target of explanation one embodiment of the present invention.In the present embodiment, tungsten is described containing the manufacture method of proportional 5～20% the Mo-W target for atomic quantity.
The manufacture method of the Mo-W target of present embodiment has: the granulating working procedure (ST1) of molybdenum (Mo) powder, deoxidation step (ST2), broken process (ST3), with mixed processes (ST4), the pressure sintering operation (ST5) of mixed powder and the mechanical workout operation (ST6) of sintered compact of tungsten (W) powder.
The granulation of Mo powder
Raw material powder for example uses that purity is more than 99.95, the Mo powder of median size less than 10 μ m.In the present embodiment, Mo powder is according to the size granulation (ST1) of defined.The object of granulation processing is, the cavity between primary particle is reduced, thereby improves the relative density after sintering.
Size or the shape of prilling process, granulation are not particularly limited.In the present embodiment, raw material powder, in a pair of roller intercropping press-powder processing, and is manufactured to the pelletizing of several centimetres of large sheets.
The deoxidation treatment of Mo powder
Next, carry out the deoxidation treatment (ST2) through the Mo of granulation powder.The method of deoxidation treatment is not particularly limited, and in the present embodiment, uses hydrogen reduction furnace, Mo powder is heated with defined temperature under the atmosphere environment at hydrogen.Thus, on pelletizing, the amount of the oxygen of sorption or chemical combination (for example, 600～800ppm) can be lowered to below 100ppm.
Above-mentioned Mo powder more than 1100 ℃ 1300 ℃ carry out below deoxidation treatment.Treatment temp, the in the situation that of 1100 ℃ of less thaies, can not obtain deoxidation effect fully.On the other hand, if treatment temp exceeds 1300 ℃, Mo crystalline growth, makes crystallization particle diameter become large tendency and present.Paradoxical discharge can bring out sputter while becoming large due to crystallization particle diameter time, therefore also bad.Therefore, by make the deoxidation treatment temperature of Mo powder be 1100 ℃ above below 1300 ℃, reduce the oxygen level of Mo powder, can stably make the sintered compact with tiny crystal structure.
The fragmentation of Mo pelletizing
Next, carry out the broken process (ST4) through the Mo of deoxidation treatment powder.The object of this operation is, fragmentation is accompanied by the heating of deoxidation treatment and the local sintering that forms between powder, and obtains highdensity sintered compact by sintering circuit below.Breaking method is not particularly limited, and in the present embodiment, by hammer mill, by pelletizing fragmentation, and to adjust its maximum diameter be for example below 700 μ m.
With mixing of W powder
Next the Mo powder, being broken mixes (ST5) with the W powder that the ratio of components according to above-mentioned weighs.W raw material powder, it is more than 99.99% for example using purity, median size less than 10 μ m, the powder of the not enough 500ppm of oxygen concn.Blending means is not particularly limited, for example, use V-mixer to stir.
In addition, as required, W raw material powder can carry out deoxidation treatment before mixing in hydrogen reduction furnace etc.Thus, due to the oxygen of having removed in W raw material powder, and can further reduce the oxygen concn in sintered compact.
Pressure sintering
Next, carry out the mixed powder of Mo powder and W powder by the operation of defined form sintering (ST5).Sintering method can adopt HIP(hot isostatic pressing) method, in addition also can adopt HP(hot pressing) etc. other pressure sintering method.
Sintering temperature is not particularly limited, be for example 1200 ℃ above below 1500 ℃.Pressure is now for example 120～150MPa, and the hold-time under top temperature is for example 4 hours.Sintering temperature, the in the situation that of 1200 ℃ of less thaies, can make the relative density of sintered compact lower, and can form paradoxical discharge or produce particle.In addition, in the time that sintering temperature exceeds 1500 ℃, Mo and W alloy can be made, to such an extent as to forming of the main orientation that caused by its alloying can not be stoped.By sintering temperature is set as 1200 ℃ above below 1500 ℃, can stably make more than 97% relative density and the anisotropic less sintered compact of crystal orientation.
Below represent an example of the making method of the sintered compact that passes through HIP.First, the mixed powder of the broken powder of Mo granulation plate and W raw material powder, in the tank of the stainless steel of defined shape, is formed as to the tap density (bulk density) of more than 50% filling to apply the mode of vibration.Then,, after above-mentioned tank is arranged on and is vacuumized in heating under vacuum degasification furnace and by its inside, pass through welded seal.Then, this tank is arranged on HIP device, and passes through above-mentioned sintering condition by above-mentioned mixed powder sintering.
Mechanical workout
The sintered compact of making is machined the target size (ST6) into defined.Thus, the Mo-W target of cost of manufacture embodiment.The shape of target can be circular, can be also rectangle.Mechanical workout is mainly undertaken by machining, attrition process.As required, can be before mechanical workout, carrying out removing internal stress etc. is the thermal treatment of the sintered compact of object.Be processed as the sintered compact of defined shape by being combined on not shown liner plate, be configured to target assembling.
Mo-W target
The Mo-W target of making by above method has: the oxygen concn below 100ppm, more than 97% relative density and the average crystallite particle diameter below 20 μ m.Thus, the generation of paradoxical discharge and particle can be suppressed, thereby the Mo-W target that can guarantee stable sputtering can be obtained.
According to present embodiment, owing to carrying out the deoxidation treatment of Mo powder before sintering, thereby can stably manufacture the less highly purified Mo-W target of oxygen level.Especially as present embodiment, in the Mo-W class at the proportion of composing of Mo higher than W, by carrying out the deoxidation treatment of Mo powder, can effectively control the oxygen concn of sintered compact.
In addition, by reducing the oxygen concn of sintered compact, can stop the generation in the cavity (pore) of sintered compact inside, and can stably generate thus the Mo-W target of the relative density having more than 97%.
Have again, owing to not needing calendering process just can obtain more than 97% relative density, thereby can suppress the generation in the main orientation that comes from calendering process after sintering.Thus, in the time of sputter, the direction of dispersing of target is formed as isotropy, thereby makes the uniform film thickness of the sputtered film of film forming on substrate, and can improve yield rate.
Especially the crystallization phases of the Mo-W target of present embodiment, is not the alloy phase of the MoW of Mo and the mutual solid solution of W, but take the coexisting phase of Mo phase and W phase as main body.Therefore, by average weighted above-mentioned the orientation of proportion of composing of this molybdenum and tungsten respectively containing proportional, with respect to by the X-ray diffraction intensity of each crystal plane (110) of this Mo and W, (200), (211), (220), (310), (321) containing proportional, the ratio in each orientation during take the proportion of composing weighted mean of Mo and W is all as below 25%.Its result is, the crystalline orientation of target material surface is gone up in any direction all has isotropy, and when sputter by with plasma in the target that is sputtered of the shock of ion form that micropartical isotropy is dispersed and on substrate film forming.Thus, can make Mo-W film on substrate with the film thickness distribution film forming below ± 5%, thereby can improve the homogeneity of thickness.
In addition, in the Mo-W of present embodiment target, proportional for 5%～20% of atomic quantity by W is contained, the resistivity of the Mo-W film forming on substrate can be reduced in, and the wearing quality with respect to etching solution can be improved.
Embodiment
Below, embodiments of the invention are described, but the present invention is not limited to following embodiment.
Embodiment 1
By purity more than 99.95%, the Mo raw material powder of median size less than 10 μ m carries out several centimetres of large granulations, then this pelletizing after deoxidation treatment, is broken for to maximum particle diameter less than 700 μ m by this pelletizing in hydrogen reduction furnace.Deoxidation treatment temperature is 1200 ℃.Next, by purity more than 99.99%, the W raw material powder of median size less than 10 μ m, the not enough 500ppm of oxygen concn is blended in the broken powder of this Mo containing proportional 15% the mode as atomic quantity take W.Then, the mixed powder of Mo and W is enclosed in the tank of stainless steel, carried out HIP processing (pressure sintering).HIP treatment temp (sintering temperature) is that 1300 ℃, pressure are 125MPa, hold-time under top temperature is 4 hours.
The target shape (circular plate shape of diameter 25.4cm, thickness 6mm) that is defined by the Mo-15at%W sintered compact mechanical workout according to above-mentioned making, and evaluate the characteristic (X-ray diffraction characteristic, average crystallite particle diameter, relative density, oxygen concn) of this target.
Have again, above-mentioned target is combined on liner plate, and is arranged on target device.Then, vacuum chamber is adjusted into Ar(argon) environment of gas 0.3Pa, and to the DC electric power of the additional 1kW of target, then the sputter characteristic to form Mo-W film on the glass substrate of diameter 6 inches (inch) time (film thickness distribution, have or not paradoxical discharge) is evaluated.Its result represents in table 1.
Evaluate as the main orientation that has that it's too late of the diffraction peak of the MoW phase of the X-ray diffraction characteristic of target material surface containing proportional.X-ray diffraction determinator uses the リ ガ of Co., Ltd. Network (Rigaku) (Japanese firm's name) system " RINT X-Ray Diffractmeter ".
Proportional for containing of main orientation, evaluate respectively with respect to the summation of the X-ray diffraction intensity of each the orientation (110) of Mo and W, (200), (211), (220), (310), (321), by average weighted above-mentioned the orientation of proportion of composing of this Mo and W containing proportional.
Fig. 2 is the XRD figure table of the Mo-W sintered compact of making in embodiment 1, and represents respectively, is (A) that target material surface, (B) are that cross section, (C) are that molybdenum phase, (D) are tungsten phase.Confirm that by (A), (B) this sintered compact entirety has uniform crystal structure.In addition, confirm all there is clear and definite diffraction peak on the face of any one (110), (200), (211), (220), (310), (321) of Mo and W by (C), (D).In addition, be there is no the existence of the alloy phase of finding MoW by this XRD figure table.
The SEM(scanning electron microscope that Fig. 3 (A)～(D) is the Mo-W sintered compact made in embodiment 1) image the image while being expressed as 100 times, 300 times, 500 times and 1000 times.Fig. 3 (E), (F) they are the WDX(wavelength dispersive X-ray spectrometry of above-mentioned Mo-W sintered compact) image, and wherein (E) is the mapping Images of the Mo of the image of (D), is (F) mapping Images of the W in the image of (D).As shown in (D)～(F), Mo is the shape that separates of definition mutually with W, and confirms not exist MoW phase.
Table 2 is illustrated in embodiment 1 the measured value Is(project 2,7 of face orientation (110), (200), (211), (220), (310), the Mo of (321) and the X-ray diffraction intensity of W of the sintered compact of making), the standard pattern intensity I o(project 1,6 in above-mentioned each the orientation of Mo and W), above-mentioned each orientation of sintered compact containing proportional (project 11) etc.Here, the diffracted intensity of each of (200), (211), (220), (310) and (321) is expressed as, and the diffracted intensity of (110) face is set as the relative value of 100 o'clock.
For example, (110) crystal plane of Mo contain ratio, calculate by following calculating formula.
(110)={Is(110)/Io(110)}/{Σ(Is/Io)}
Here, Σ (Is/Io)={ Is (110)/Io (110) }+{ Is (200)/Io (200) }+... + { Is (321)/Io (321) },, even if relate to other the containing than calculating equally (project 3,4) of crystal plane.The value { Σ (Is/Io) } of the denominator in above formula is about 5.69(with reference to project 2).
Containing than also calculating (project 8) by above formula of each crystal orientation face of W.The value of the denominator of calculating formula is now about 2.43(with reference to project 7).
The X-ray diffraction intensity of the Mo calculating in the manner described above, each crystal orientation of W contains ratio, by the proportion of composing weighted mean of Mo, W., containing than containing ratio by calculating formula (Mo contains ratio) × 0.85+(W respectively of the Mo of each crystal plane and W) × 0.15 calculating.This result represents in project 10,11.In the present embodiment, (110) face contain the ratio that contains than the face higher than other, should form main orientation by (110) face.Containing than being about 21% of (110) face of being somebody's turn to do.
Average crystallite particle diameter
The mensuration of median size, by using the section S EM photo of sintered compact, and based on " ASTM(American Society for Testing and Materials) E112 " (JIS(Japanese Industrial Standards) G0551) granularity table carry out visual judgement.In the present embodiment, the average crystallite particle diameter less than 20 μ m of sintered compact.
Relative density
The relative density of sintered compact is by calculating apparent density and the theoretical density (11.58g/cm of sintered compact
3) ratio try to achieve.The method of calculation of apparent density are as follows,, first obtained sintered compact is carried out to mechanical workout and use vernier callipers, milscale or 3 dimension testers are measured the size of periphery and thickness and tried to achieve its volume, then gravimetry on electronic scale, and use the calculating formula of (weight/volume) to try to achieve this apparent density.In the present embodiment, the relative density of sintered compact is 97.50%.
Oxygen concn
The mensuration of the oxygen concn of sintered compact is used ICP spectroscopy apparatus (Shimadzu Scisakusho Ltd's system " ICPS-8100 ").The result of measuring, the oxygen concn of the sintered compact of the present embodiment is below 60ppm.
Film thickness distribution is measured
In the time carrying out the mensuration of film thickness distribution, with
for target film thickness, measure glass substrate Shang center 1 o'clock and the thickness that is positioned at minute other 4 point that radius is the position of 30mm, 50mm and 75mm (13 points altogether) on the vertical diaxon in this center.Then, using poor (d) of wherein maximum value and minimum value divided by the income value of the mean value (D) of the thickness of above-mentioned 13 ± 1/2 as film thickness distribution., film thickness distribution value is tried to achieve by calculation formula (d/D) × (± 1/2) %.According to present embodiment, film thickness distribution is ± 4%.
Paradoxical discharge
For being evaluated as of paradoxical discharge, in the sputter cumulative time of 10kWHr, the situation that produces seriously sparking on target is "×", and not having to produce the situation of seriously striking sparks is "○".According to the present embodiment, electric discharge does not note abnormalities.
Embodiment 2
Except W containing proportional for atomic quantity 5%, HIP treatment temp (sintering temperature) is 1400 ℃, by method evaluation target characteristic and sputter characteristic similarly to Example 1.Its result, as shown in table 1, the X-ray diffraction peak value of MoW " substantially without ", main orientation containing being proportionally 20%, average crystallite particle diameter less than 20 μ m, relative density are 98%, oxygen concn is below 50ppm, film thickness distribution is ± 4%, paradoxical discharge " nothing ".
Except W containing proportional for atomic quantity 20%, HIP treatment temp (sintering temperature) is 1200 ℃, by method evaluation target characteristic and sputter characteristic similarly to Example 1.Its result, as shown in table 1, the X-ray diffraction peak value of MoW " substantially without ", main orientation containing being proportionally 22%, average crystallite particle diameter less than 20 μ m, relative density are 97.3%, oxygen concn is below 60ppm, film thickness distribution is ± 5%, paradoxical discharge " nothing ".
Embodiment 4
Except the deoxidation treatment temperature of Mo pelletizing is 1100 ℃, by method evaluation target characteristic and sputter characteristic similarly to Example 1.Its result, as shown in table 1, the X-ray diffraction peak value of MoW " substantially without ", main orientation containing being proportionally 18%, average crystallite particle diameter less than 20 μ m, relative density are 98.5%, oxygen concn is below 50ppm, film thickness distribution is ± 4%, paradoxical discharge " nothing ".
Embodiment 5
Except the deoxidation treatment temperature of Mo pelletizing is 1300 ℃, HIP treatment temp (sintering temperature) is beyond 1500 ℃, by method evaluation target characteristic and sputter characteristic similarly to Example 1.Its result, as shown in table 1, the X-ray diffraction peak value of MoW " substantially without ", main orientation containing being proportionally 23%, average crystallite particle diameter less than 20 μ m, relative density are 99%, oxygen concn is below 60ppm, film thickness distribution is ± 5%, paradoxical discharge " nothing ".
Comparative example 1
Except the deoxidation treatment temperature of Mo pelletizing is 1000 ℃, HIP treatment temp (sintering temperature) is beyond 1400 ℃, by method evaluation target characteristic and sputter characteristic similarly to Example 1.Its result, as shown in table 1, the X-ray diffraction peak value of MoW " has ", main orientation containing being proportionally 35%, average crystallite particle diameter less than 40 μ m, relative density are 96.5%, oxygen concn is below 50ppm, film thickness distribution for ± 8%, paradoxical discharge " has ".
Comparative example 2
Except the deoxidation treatment temperature of Mo pelletizing is 1400 ℃, HIP treatment temp (sintering temperature) is beyond 1100 ℃, by method evaluation target characteristic and sputter characteristic similarly to Example 1.Its result, as shown in table 1, the X-ray diffraction peak value of MoW " substantially without ", main orientation containing being proportionally 18%, average crystallite particle diameter less than 20 μ m, relative density are 95.5%, oxygen concn is below 40ppm, film thickness distribution for ± 5%, paradoxical discharge " has ".
Comparative example 3
Except the deoxidation treatment temperature of Mo pelletizing is 1400 ℃, HIP treatment temp (sintering temperature) is beyond 1600 ℃, by method evaluation target characteristic and sputter characteristic similarly to Example 1.Its result, as shown in table 1, the X-ray diffraction peak value of MoW " has ", main orientation containing being proportionally 40%, average crystallite particle diameter less than 50 μ m, relative density are 99%, oxygen concn is below 60ppm, film thickness distribution for ± 10%, paradoxical discharge " has ".
Comparative example 4
Except the deoxidation treatment temperature of Mo pelletizing is 1000 ℃, HIP treatment temp (sintering temperature) is beyond 1100 ℃, by method evaluation target characteristic and sputter characteristic similarly to Example 1.Its result, as shown in table 1, the X-ray diffraction peak value of MoW " substantially without ", main orientation containing being proportionally 19%, average crystallite particle diameter less than 20 μ m, relative density are 95%, oxygen concn is below 50ppm, film thickness distribution for ± 5%, paradoxical discharge " has ".
According to the result of table 1, the deoxidation treatment temperature of Mo powder (pelletizing) is the Mo-W sintered compact (target) of 1000 ℃ of above 1300 ℃ of following embodiment 1～5 if, can effectively reduce the oxygen level in molybdenum powder.The generation in the cavity (pore) while suppressing sintering thus, thus the relative density of sintered compact can be improved.In addition, owing to having prevented the coarsening of crystal grain, thereby can obtain having the Mo-W sintered compact of tiny uniform formation.Have again, just can make sintered compact densification owing to not needing to implement calendering process, thus the homogenizing of the thickness can realize spatter film forming time.
In addition, HIP treatment temp (sintering temperature) is the Mo-W sintered compact (target) of 1200 ℃ of above 1500 ℃ of following embodiment 1～5 if, can obtain stable more than 97% relative density, and stoped the alloying reaction of Mo and W, thereby can suppress main orientation X-ray diffraction intensity containing proportional be below 25%.Can make thus sputtering particle be isotropy by target material surface and disperse, thereby can improve the homogeneity of thickness.
Above, be the explanation to embodiments of the present invention, but the present invention is not limited thereto, not departing from the scope of purport of the present invention, can make various changes to it.
For example, in the above-described embodiment, be the explanation that W is carried out containing the manufacture method of proportional 5～20% the Mo-W target for atomic quantity, but W amount is not limited to this, the present invention is also suitable for the manufacture of W containing proportional 5～95% the Mo-W target for atomic quantity.
In addition, in the above-described embodiment, the explanation that only object using Mo powder (pelletizing) as deoxidation treatment carries out, but be not limited to this, also can be on above-mentioned basis, the also object using W powder as deoxidation treatment.Thus, can further improve the relative density of sintered compact.
Claims (7)
1. a manufacture method for Mo-W target, is characterized in that,
Molybdenum powder is carried out more than 1100 ℃ to deoxidation treatment at the temperature below 1300 ℃,
Then, mixing tungsten powder through in the described molybdenum powder of deoxidation treatment,
Next, the mixed powder of described molybdenum powder and described tungsten powder is carried out to pressure sintering with the temperature of defined.
2. the manufacture method of Mo-W target according to claim 1, is characterized in that,
Described molybdenum powder is carried out before deoxidation treatment, the size granulation by described molybdenum powder with defined,
Then, by the pelletizing deoxidation treatment of described molybdenum powder.
3. the manufacture method of Mo-W target according to claim 2, is characterized in that,
By after described pelletizing deoxidation treatment, by described pelletizing fragmentation.
4. the manufacture method of Mo-W target according to claim 1, is characterized in that,
Described mixed powder is passed through to HIP(hot isostatic pressing) method sintering.
5. the manufacture method of Mo-W target according to claim 4, is characterized in that,
Described defined temperature be 1200 ℃ above below 1500 ℃.
6. a Mo-W target, its sintered compact by the mixed powder that contains molybdenum powder and tungsten powder forms, it is characterized in that,
By average weighted above-mentioned the orientation of proportion of composing of molybdenum and tungsten respectively containing proportional, with respect to the summation of the X-ray diffraction intensity in each orientation of (110), (200) of described molybdenum and tungsten, (211), (220), (310), (321), all below 25%.
7. Mo-W target according to claim 6, is characterized in that,
There is the oxygen concn below 100ppm, more than 97% relative density and the average crystallite particle diameter below 20 μ m.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2011-199104 | 2011-09-13 | ||
| JP2011199104 | 2011-09-13 | ||
| PCT/JP2012/005812 WO2013038668A1 (en) | 2011-09-13 | 2012-09-13 | Mo-w target and method for manufacturing same |
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| CN103797153A true CN103797153A (en) | 2014-05-14 |
| CN103797153B CN103797153B (en) | 2016-11-23 |
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| JP (1) | JPWO2013038668A1 (en) |
| KR (1) | KR20140041869A (en) |
| CN (1) | CN103797153B (en) |
| TW (1) | TWI599668B (en) |
| WO (1) | WO2013038668A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106977202A (en) * | 2017-04-05 | 2017-07-25 | 北京冶科纳米科技有限公司 | The preparation technology and oxidation tungsten target material of a kind of High-purity low-density oxidation tungsten target material |
| CN107849689A (en) * | 2015-07-27 | 2018-03-27 | 日立金属株式会社 | target |
| CN109440065A (en) * | 2018-11-09 | 2019-03-08 | 南昌大学 | A kind of preparation method of Mg alloy surface tungsten molybdenum nanoscale anticorrosion film |
| CN111254396A (en) * | 2020-01-21 | 2020-06-09 | 洛阳高新四丰电子材料有限公司 | Preparation method of molybdenum-tungsten alloy sputtering target material |
| CN111621753A (en) * | 2020-07-29 | 2020-09-04 | 江苏集萃先进金属材料研究所有限公司 | Target blank and manufacturing method thereof |
| CN111763862A (en) * | 2020-06-29 | 2020-10-13 | 自贡硬质合金有限责任公司 | Tungsten-molybdenum alloy and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103255379A (en) * | 2013-04-16 | 2013-08-21 | 洛阳高新四丰电子材料有限公司 | Molybdenum-tungsten alloy sputtering target material for flat panel display and preparation method thereof |
| KR101364607B1 (en) | 2013-09-11 | 2014-02-20 | 한국지질자원연구원 | Method for refining grain of sintered body by reducing oxygen content from metallic molybdenum powder |
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- 2012-09-13 CN CN201280044707.1A patent/CN103797153B/en active Active
- 2012-09-13 WO PCT/JP2012/005812 patent/WO2013038668A1/en active Application Filing
- 2012-09-13 KR KR1020147004533A patent/KR20140041869A/en active Search and Examination
- 2012-09-13 JP JP2013533504A patent/JPWO2013038668A1/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107849689A (en) * | 2015-07-27 | 2018-03-27 | 日立金属株式会社 | target |
| CN106977202A (en) * | 2017-04-05 | 2017-07-25 | 北京冶科纳米科技有限公司 | The preparation technology and oxidation tungsten target material of a kind of High-purity low-density oxidation tungsten target material |
| CN109440065A (en) * | 2018-11-09 | 2019-03-08 | 南昌大学 | A kind of preparation method of Mg alloy surface tungsten molybdenum nanoscale anticorrosion film |
| CN109440065B (en) * | 2018-11-09 | 2020-07-14 | 南昌大学 | Preparation method of nano-scale corrosion-resistant molybdenum-tungsten film on surface of magnesium alloy |
| CN111254396A (en) * | 2020-01-21 | 2020-06-09 | 洛阳高新四丰电子材料有限公司 | Preparation method of molybdenum-tungsten alloy sputtering target material |
| CN111763862A (en) * | 2020-06-29 | 2020-10-13 | 自贡硬质合金有限责任公司 | Tungsten-molybdenum alloy and preparation method thereof |
| CN111763862B (en) * | 2020-06-29 | 2022-03-29 | 自贡硬质合金有限责任公司 | Tungsten-molybdenum alloy and preparation method thereof |
| CN111621753A (en) * | 2020-07-29 | 2020-09-04 | 江苏集萃先进金属材料研究所有限公司 | Target blank and manufacturing method thereof |
| CN111621753B (en) * | 2020-07-29 | 2020-11-17 | 江苏集萃先进金属材料研究所有限公司 | Target blank and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140041869A (en) | 2014-04-04 |
| CN103797153B (en) | 2016-11-23 |
| JPWO2013038668A1 (en) | 2015-03-23 |
| TW201319291A (en) | 2013-05-16 |
| WO2013038668A1 (en) | 2013-03-21 |
| TWI599668B (en) | 2017-09-21 |
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