CN109778126A - A kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material - Google Patents
A kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material, molybdenum target material is prepared by isostatic cool pressing die mould-sintering-hot isostatic pressing die mould-mach process flow of hot rolling-annealing-, after molybdenum target material first passes through hip treatment, first time densification has been carried out to molybdenum target material blank, then the blank is subjected to hot rolling treatment, second of densification has been carried out to molybdenum target material blank, finally pass through 950-1100 DEG C, keeps the temperature the molybdenum target material of performance needed for the processes such as annealing and the machining of 60-90min obtain.Preparation method of the invention can produce high-purity (purity reaches 99.9% or more)), Quan Zhimi (density reaches 99.9% or more), Ultra-fine Grained (grain size is less than 20 μm) molybdenum target material, higher and higher sputtering technology can be met the requirements, improve thin film sputtering speed, improve the quality of molybdenum sputtered film, improves film performance.
Description
Technical field
The invention belongs to sputtering target material preparation technical fields, and in particular to a kind of high-densit Ultra-fine Grained large scale molybdenum target material
Preparation method.
Background technique
In recent years, as the fields such as solar battery, flat-panel monitor, semiconductor integrated circuit technology constantly develops,
The film as made from sputtering sedimentation is since with consistency height, adhesion is good between basis material, therefore obtains in these fields
To being widely applied.Molybdenum sputtered film due to low-resistivity, stronger thermal stability, preferable corrosion resistance and
Good environmental-protecting performance, so that this film is before the fields market such as solar battery, flat-panel monitor, semiconductor integrated circuit
Scape is wide.
Currently, there are many ways to preparing sputter coating molybdenum target material, such as sintering process, electron-beam smelting, hot isostatic pressing method
Deng, but all respectively have advantage and disadvantage for the above method, cannot all meet the needs of large-area coating film practical application well.Wherein
Electron-beam smelting is at high cost, complicated for operation, and the molybdenum base metal grain after melting is coarse, and following process is difficult, it is difficult to ensure that product
The grain structure for the fine uniform that target requires；The target hole defect produced using sintering process is more, and consistency is insufficient, production
Target be easy to happen in use particle splash the problems such as；Larger size target can not be produced using hot isostatic pressing method
Material shows not can exceed that 2m using the target length of this method preparation according to related data.
In sputtering process, if the quantity of field trash is excessive in target or is unevenly distributed, often formed on wafer
Particle, it is lower to lead to sputter in uneven thickness or sputtering yield, seriously affects film performance.In addition, the rate of thin film sputtering
Related with the crystalline results of molybdenum target material and crystallite dimension, molybdenum atom is easiest to along six side of atom most close-packed arrays direction preferential sputtering
Out, while the sputter rate of the crystal grain target of fine size is also compared with coarse grain target block, thus promoted molybdenum target material sputter rate and
Improving its quality can be realized by changing the grain structure of target, promoting the approach such as target purity and refinement crystal grain, but for
Prior art preparation have preferred orientation molybdenum target material it is very difficult, therefore prepare high-purity, fine grain molybdenum target material at
The important directions that everybody studies.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material, this method is used
Hot isostatic pressing combines the mode of rolling to implement, and can be used for the manufacture of molybdenum target material in thin film sputtering, and molybdenum target material obtained has high-purity
Spend (purity reaches 99.9% or more), high-compactness (density reaches 99.9% or more), Ultra-fine Grained (grain size is less than 20 μm) etc.
Feature can meet the needs of high request sputter coating.
To achieve the goals above, the invention provides the following technical scheme:
A kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material, the preparation method of the molybdenum target material includes following step
It is rapid:
(1) isostatic cool pressing die mould
Molybdenum powder is chosen, ready molybdenum powder is encased in mold, is then placed in cold static pressure equipment and carries out isostatic cool pressing
Die mould processing, obtains isostatic cool pressing green body after release；
(2) it is sintered
Isostatic cool pressing green body is sintered in sintering furnace using induction sintering mode, reproducibility gas is passed through in sintering furnace
Body obtains sintered body after cooling；
(3) hot isostatic pressing die mould
The sintered body that sintering is completed is subjected to machining shaping, hot isostatic pressing die mould is used to carry out first after shaping
Secondary densification carries out hot isostatic pressing die mould in hot isostatic apparatus, and is passed through inert gas, prevents green body from aoxidizing and miscellaneous
Matter is mixed into, cooling after heat preservation, then takes out green body, obtains densifying green body for the first time；
(4) hot rolling
First time densification green body after hot isostatic pressing die mould is subjected to hot rolling treatment, obtains second of densification green body；
(5) it anneals
Second of densification green body after hot rolling is subjected to recrystallization annealing processing, forms molybdenum target material plate；
(6) it is machined
Molybdenum target material plate is machined, required size is cut into, and be ground to required thickness, obtains molybdenum target material.
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that the hot isostatic pressing die mould
The pressure chosen in the process is 150-200MPa, and heating temperature is 1450-1500 DEG C, heat-insulation pressure keeping 3-4h.
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that in the sintering furnace into
The temperature of row sintering is 1950-2050 DEG C, and heating rate is 3-5 DEG C/min, and keeps the temperature 1-10h at such a temperature.
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that hot rolling in the step (4)
Hot-rolled temperature when processing is 1000-1100 DEG C.
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that hot rolling in the step (4)
The rolling mode used is the rolling mode of fiery two passages.
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that rolling side described in hot rolling
The one-pass roller deflection of formula is 20-25%, and the total deformation for rolling processing is 60-70%.
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that hot rolling in the step (4)
The milling train used is wide cut 2100mm four-high reversing mill.
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that by the molybdenum target material plate
Material carries out before step (6) machining further include:
Nondestructive flaw detection examination detects a flaw to molybdenum target material plate by ultrasonic equipment, checks that its internal whether there is is split
The defects of line, layering.
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that the molybdenum content of the molybdenum powder
>=99.95%, Fisher particle size is 3.0-3.8 μm, apparent density 4.0-8.0g/cm3。
In the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described above, it is preferable that by described the after hot rolling
The annealing temperature that secondary densification green body is made annealing treatment is 950-1100 DEG C, soaking time 60-90min.
Compared with the immediate prior art, technical solution provided by the invention has following excellent effect:
Molybdenum target material of the invention passes through isostatic cool pressing-sintering-hot isostatic pressing-mach process flow of hot rolling-annealing-
Prepare molybdenum target material, molybdenum target material first passes through 1450-1500 DEG C, 150-200MPa, right after heat-insulation pressure keeping 3-4h hip treatment
Molybdenum target material blank has carried out first time densification, and the blank is then carried out 1000-1100 DEG C using hot rolling technology and is rolled
System processing, has carried out second of densification to molybdenum target material blank, finally passes through 950-1100 DEG C, keeps the temperature moving back for 60-90min
The molybdenum target material of performance needed for the processes such as fire processing and machining obtain.
Using molybdenum target material production method provided by the invention, high-purity (purity reaches 99.9% or more) can be produced),
The molybdenum target material of complete fine and close (density reaches 99.9% or more), Ultra-fine Grained (grain size is less than 20 μm), can meet the requirements higher and higher
Sputtering technology, improve thin film sputtering speed, improve molybdenum sputtered film quality, improve film performance.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.Wherein:
Fig. 1 is the preparation technology flow chart of the molybdenum target material of the embodiment of the present invention；
Fig. 2 is the micro-organization chart of the molybdenum target material of the embodiment of the present invention 1；
Fig. 3 is the micro-organization chart of the molybdenum target material of the embodiment of the present invention 2；
Fig. 4 is the micro-organization chart of the molybdenum target material of reference examples 1 of the present invention；
Fig. 5 is the micro-organization chart of the molybdenum target material of reference examples 2 of the present invention.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is general
Logical technical staff's every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings and embodiments.It should be noted that in the feelings not conflicted
Under condition, the feature in embodiment and embodiment in the present invention be can be combined with each other.
A kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material provided by the invention, passes through isostatic cool pressing die mould-
Sintering-hot isostatic pressing-mach process flow of hot rolling-annealing-prepares large scale molybdenum target material, and molybdenum target material first passes through heat etc.
After static pressure processing, first time densification is carried out to molybdenum target material blank, to obtain the grain size of fine uniform at 7 grades or more
Grain structure, while for the first time densification green body consistency reach 90% or more；Then connected using big compression ratio reversible
The blank is carried out hot rolling treatment by roll process, has been carried out second of densification to molybdenum target material blank, has been rolled total change of processing
Shape amount is big, is suitble to prepare large-sized target, then using 950-1100 DEG C, keep the temperature at the recrystallization annealing of 60-90min
Reason, eliminating metaplasia stress recrystallizes tissue, while refining crystal grain, dimensional thickness required for being finally machined into and table
The molybdenum target material of face smoothness.
The molybdenum target material that through the invention prepared by preparation process can reach complete fine and close (density reaches 99.9% or more), target
The molybdenum target material of material purity is high (purity reaches 99.9% or more), Ultra-fine Grained (grain size is less than 20 μm), meets stringent sputtering work
Skill requirement, prepares the sputtered film of high-quality.
A kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material provided by the invention, comprising the following steps:
(1) isostatic cool pressing die mould
Choose molybdenum powder, ready molybdenum powder is encased in mold, be then placed in cold static pressure equipment carry out it is cold etc.
The processing of static pressure die mould, obtains isostatic cool pressing green body after release；
Preferably, molybdenum content >=99.95% of molybdenum powder, meeting GB/T3461-2006 national standard Fisher particle size is 3.0-
3.8 μm, apparent density 4.0-8.0g/cm3, and the molybdenum of bulky grain partial size is filtered out before molybdenum powder use using standard screen
Powder.
Preferably, the density of the isostatic cool pressing green body after isostatic cool pressing die mould is not less than 40%.
(2) it is sintered
Isostatic cool pressing green body is sintered using induction sintering mode, reducibility gas is passed through in sintering furnace, after cooling
Obtain sintered body；
Preferably, isostatic cool pressing green body is put into Medium frequency induction sintering furnace and is sintered, sintering temperature 1950-
2050 DEG C (such as 1950 DEG C, 1960 DEG C, 1970 DEG C, 1980 DEG C, 1990 DEG C, 2000 DEG C, 2010 DEG C, 2020 DEG C, 2030 DEG C,
2040 DEG C, 2050 DEG C), soaking time 1-10h (such as 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h), heating rate be 3-5 DEG C/
Min (such as 3 DEG C/min, 4 DEG C/min, 5 DEG C/min).
The crystallite dimension and impurities removal situation that sintering temperature and heating rate mainly influence target sintered body are (for target base
Body impurities affect is larger), in general sintering temperature is high, and slab crystal grain is partially thick, and what heating rate influenced is entire sintering time,
The final purity of target is influenced whether if sintering time is insufficient, keeps impurity content higher, and target material blank body of the invention is being burnt
Under the comprehensive function of two parameters of junction temperature and heating rate, small grains tissue and high-purity are obtained.
Preferably, the density of sintered sintered body is not less than 90%.
(3) hot isostatic pressing die mould
The sintered body that sintering is completed is subjected to machining shaping, hot isostatic pressing die mould is used to carry out first after shaping
Secondary densification carries out hot isostatic pressing die mould in hot isostatic apparatus, is passed through in equipment during hot isostatic pressing die mould
Inert gas prevents green body oxidation and impurity to be mixed into, cooling after heat preservation, then takes out green body, obtains densifying base for the first time
Body；
Preferably, the inert gas being passed through in hot isostatic apparatus is argon gas.
Preferably, the pressure chosen during hot isostatic pressing die mould be 150-200MPa (such as 152MPa, 154MPa,
155MPa, 160MPa, 165MPa, 170MPa, 175MPa, 180MPa, 185MPa, 190MPa, 195MPa), heating temperature is
1450-1500 DEG C (such as 1452 DEG C, 1454 DEG C, 1456 DEG C, 1458 DEG C, 1500 DEG C), heat-insulation pressure keeping 3-4h (such as 3.2h,
3.4h、3.6h、3.8h)。
(4) hot rolling
First time densification green body after hot isostatic pressing die mould is put into milling train and carries out hot rolling, is carried out at second of densification
Reason, obtains second of densification green body；
Preferably, first time densification green body is put into milling train to carry out the temperature of hot rolling is 1000-1100 DEG C (such as 1010
℃、1020℃、1030℃、1040℃、1050℃、1060℃、1070℃、1080℃、1090℃、1100℃)。
Preferably, road is rolled according to the size adjusting of first time densification green body and finished product after hip treatment
It is secondary.
Preferably, the rolling mode that hot rolling uses is the rolling mode of fiery two passages.Using it is unidirectional along by the way of rolling into
Row rolling.
Preferably, in hot rolling rolling mode one-pass roller deflection be 20-25% (such as 21%, 22%, 23%,
24%, 25%), roll processing total deformation be 60-70% (such as 60%, 61%, 62%, 63%, 64%, 65%,
66%, 67%, 68%, 69%, 70%).The rolling of large scale molybdenum target material needs while rolling reduction big using single pass
More fire rollings are carried out, need to melt down between every fire, being equivalent to is also to anneal target to eliminate in the operation of rolling and generate
Stress, avoid cracking.
Preferably, the milling train that hot rolling uses for 2100mm wide four-high mill, the milling train be stiff mill, be capable of providing compared with
Big roll-force can obtain tiny grain structure using zerolling, while 2100mm wide can roll the target of more wide cut
Green body.High rigidity four-high mill occurs " rolling motionless " when can be to avoid target material blank body rolling and melts down phenomenon again, for obtaining target
Fine grain tool has very great help.
Preferably, second of densification green body after hot rolling also have passed through smoothing process, obtain convenient for target higher
Flatness.
(5) it anneals
Second of densification green body after hot rolling is subjected to recrystallization annealing processing, forms molybdenum target material plate；
Preferably, the annealing temperature second of densification green body after hot rolling made annealing treatment is 950-1100 DEG C
(such as 950 DEG C, 980 DEG C, 1000 DEG C, 1030 DEG C, 1050 DEG C, 1080 DEG C, 1100 DEG C), soaking time 60-90min (such as
62min、65min、70min、72min、75min、80min、85min、88min)。
(6) it is machined
Molybdenum target material plate is machined, is cut into required size, and be ground to required thickness.
Preferably, before being machined molybdenum target material plate further include: nondestructive flaw detection examination is set by ultrasonic wave
It is standby to detect a flaw to molybdenum target material plate, it checks its internal the defects of whether there is crackle, layering, carries out machinery again after detection is qualified
Processing.
Embodiment 1
The molybdenum target material trimmed size of preparation of the embodiment of the present invention are as follows: long 3430mm, wide 400mm, thick 18mm.
As shown in Figure 1, a kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material provided in an embodiment of the present invention, packet
Include following steps:
(1) preparation of molybdenum powder analysis and powder
Using the purity of the device analysis molybdenum powder such as ICP Atomic Absorption Spectrometer and carbon oxygen analyzer, it is desirable that Mo content >=
99.5%, the content for controlling impurity element is in following ranges:
C<0.003；O<0.1；N<0.001；S<0.001；Fe<0.003；Sn<0.0005；Ni<0.003；Sb<0.01；Si<
0.002；Cd<0.0005；Al<0.001；Ca<0.0015；Mg<0.002；Cu<0.001；W<0.02；Pb<0.0005；Bi<
0.0005。
Meet GB/T3461-2006 national standard on granulometry, Fisher particle size is 3.0-3.8 μm, and apparent density is
4.0-8.0g/cm3.It chooses and use intermediate value for 3 μm of molybdenum powder, purity >=99.95%, then using 200 the polished standard screens, to molybdenum
Powder is screened, and large-sized molybdenum powder is filtered out.
(2) isostatic cool pressing die mould
Ready molybdenum powder is fitted into plastic mould, is then placed in required for being pressed into isostatic cool pressing equipment
The density of size, the target material blank body after hydro-forming is not less than 40%.
(3) Medium frequency induction is sintered
Target material blank body after cold moudling is put into intermediate frequency furnace and is sintered, is heated up with the heating rate of 5 DEG C/min
To 2050 DEG C, and the H for keeping the temperature 5h at such a temperature, and being passed through2As reducing gas, it is ensured that target material blank body is during the sintering process not
It aoxidizes, the density of sintered target material blank body is not less than 90%.
(4) hot isostatic pressing die mould
The sintered body completed to sintering is machined, it is ensured that and green body has good flatness and plate shape, so as to
The progress of subsequent hot isostatic pressing pressure-type process；
Target material blank body through oversintering is put into progress first time densification in hot isostatic press, it is quiet to adjust heat etc.
Pressing press temperature is 1450 DEG C, pressure 200MPa, and the heat-insulation pressure keeping time is 4h, then cools to room temperature with the furnace and comes out of the stove, entire heat
Isostatic pressing carries out in argon atmosphere, the target material blank body size after hot isostatic pressing are as follows: long 1000-1100mm, wide 450-
500mm, thick 60-65mm.
Carried out hip moulding in the present invention, molybdenum powder green body carried out during cold isostatic compaction green body at
Type, and cooling down molded is to carry out at normal temperature, wants further compressing and compacting when pressure reaches metal molybdenum powder to a certain degree
Can be relatively difficult, and after hip treatment, it is compressed under conditions of heating high temperature, is more advantageous to compressive deformation, target
Green body further densification under the effect of high moderate pressure, can achieve the higher green body of consistency, between green body particle
Gap is compressed, and crystal grain refinement when subsequent rolling process is conducive to, and crystal grain is not easy to grow up, it is not easy to form coarse-grain.
(5) four-high mill hot rolling
It is 1000 that first time densification green body after hot isostatic pressing die mould, which is put into, and carries out the rolling temperature of hot rolling in milling train
DEG C, it green body is then placed into 2100mm wide milling train and carries out hot rolling, carries out second of densification, using unidirectional along rolling
Mode, the rolling mode of fiery two passages (continuous rolling is taken out from heating furnace twice)；The compression ratio of single pass is 25%,
By the rolling of two fire time, the total deformation for rolling processing is 65-70%, obtains second of densification green body.
It is rolled in the present invention using 2100mm wide four-high mill, rolling power is big, and compression deformation ability is high, in low temperature
The compression ratio of big compression ratio reversible continuous rolling process down, single pass can reach 25%, and the total deformation for rolling processing reaches 65-
70%, it can reduce to melt down in this way using big compression ratio and number and melt down the time, it is less to melt down number and reach base
The size requirement of body, avoids crystal grain from being roughened when melting down and grows up.The milling train that the present invention uses is MESTA 2100mm milling train.
(6) recrystallization annealing
Second of densification green body after hot rolling is subjected to recrystallization annealing processing, annealing temperature is 1000 DEG C, heat preservation
60min forms molybdenum target material plate.
(7) smoothing process
Molybdenum target material after hot rolling is subjected to smoothing process by 11 roller levelling machines, smoothing temperature setting is 950-1000 DEG C,
Prevent target from generating internal injury, the purpose of smoothing process is to obtain higher target plane degree, easy to process and use.
(8) nondestructive flaw detection examination
Nondestructive flaw detection examination is carried out for the molybdenum target material plate after smoothing process, target is visited by ultrasonic equipment
Wound, check its it is internal with the presence or absence of crackle, layering the defects of, it is good to pick out target interior tissue crystal property, without being layered, split
The high-quality molybdenum target material sheet material portions of the defects of line, the molybdenum target material plate after smoothing process is substantially without layering, crack defect.
(9) it is machined
By water knife by size required for molybdenum target material sheet fabrication to finished product, while using grinding machine by target material surface plain grinding
To desired size and precision.Final preparation growth 3430mm, wide 400mm, the molybdenum target material of thick 18mm.Molybdenum target in embodiment 1 produces
Product are strip target, long for length direction the characteristics of the product, using unidirectional along by the way of rolling when hot rolling, i.e., along length side
It is rolled to suitable always, the final molybdenum target material obtained in the present embodiment.
It is sampled and observes the crystallite dimension of sputter face to the molybdenum target material of this example production, rated, this example production
The purity of molybdenum target material be 99.9%, relative density 99.9%, as shown in Fig. 2, to be obtained to molybdenum target material by microexamination
Crystal grain figure, average grain size be 17.8 μm.
The major impurity content of the molybdenum target material prepared in the present embodiment: C < 0.002；O<0.003；N<0.001；S<0.001；
Fe<0.002；Sn<0.0005；Ni<0.001；Sb<0.001；Si<0.001；Cd<0.0005；Al<0.001；Ca<0.001；Mg<
0.001；Cu<0.001；W<0.012；Pb<0.0005；Bi<0.0005；The purity of molybdenum target material is 99.9%.
Embodiment 2
The molybdenum target material trimmed size of preparation of the embodiment of the present invention are as follows: long 2300mm, wide 1800mm, thick 14mm.
A kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material provided in an embodiment of the present invention, including following step
It is rapid:
(1) preparation of molybdenum powder analysis and powder
Using the purity of the device analysis molybdenum powder such as ICP Atomic Absorption Spectrometer and carbon oxygen analyzer, it is desirable that Mo content >=
99.5%, the content for controlling impurity element is in following ranges:
C<0.003；O<0.1；N<0.001；S<0.001；Fe<0.003；Sn<0.0005；Ni<0.003；Sb<0.01；Si<
0.002；Cd<0.0005；Al<0.001；Ca<0.0015；Mg<0.002；Cu<0.001；W<0.02；Pb<0.0005；Bi<
0.0005。
Meet GB/T3461-2006 national standard on granulometry, Fisher particle size is 3.0-3.8 μm, and apparent density is
4.0-8.0g/cm3.It chooses and use intermediate value for 3 μm of molybdenum powder, purity >=99.95%, then using 200 the polished standard screens, to molybdenum
Powder is screened, and large-sized molybdenum powder is filtered out.
(2) isostatic cool pressing die mould
Ready molybdenum powder is fitted into plastic mould, is then placed in required for being pressed into isostatic cool pressing equipment
The density of size, the target material blank body after hydro-forming is not less than 40%.
(3) Medium frequency induction is sintered
Target material blank body after cold moudling is put into intermediate frequency furnace and is sintered, is heated up with the heating rate of 5 DEG C/min
To 1950 DEG C, and the H for keeping the temperature 8h at such a temperature, and being passed through2As reducing gas, it is ensured that target material blank body is during the sintering process not
It aoxidizes, the density of sintered target material blank body is not less than 90%.
(4) hot isostatic pressing die mould
The sintered body completed to sintering is machined, it is ensured that and green body has good flatness and plate shape, so as to
The progress of subsequent hot isostatic pressing pressure-type process；
Target material blank body through oversintering is put into progress first time densification in hot isostatic press, it is quiet to adjust heat etc.
Pressing press temperature is 1500 DEG C, pressure 200MPa, and the heat-insulation pressure keeping time is 3h, then cools to room temperature with the furnace and comes out of the stove, entire heat
Isostatic pressing carries out in argon atmosphere, the target material blank body size after hot isostatic pressing are as follows: long 1100-1200mm, wide 900-
1000mm, thick 50-55mm.
Hip moulding is carried out in the present invention, molybdenum powder green body has carried out fine and close chemical conversion during cold isostatic compaction
Type, and cooling down molded is to carry out at normal temperature, wants further compressing and compacting when pressure reaches metal molybdenum powder to a certain degree
Can be relatively difficult, and after hip treatment, it is compressed under conditions of heating high temperature, is more advantageous to compressive deformation, target
Green body further densification under the effect of high moderate pressure, can achieve the higher green body of consistency, between green body particle
Gap is compressed, and crystal grain refinement when subsequent rolling process is conducive to, and crystal grain is not easy to grow up, it is not easy to form coarse-grain.
(5) four-high mill hot rolling
It is 1100 DEG C that first time densification green body after hot isostatic pressing die mould, which is put into milling train to carry out the rolling temperature of hot rolling,
Then green body is placed into 2100mm wide milling train and carries out hot rolling, second of densification is carried out, using the side of tandem rolling
Formula (is rerolled, then adjust 90 ° to be rolled again) after blank is rotated by 90 °, fiery two passage of tandem rolling (i.e. from the heating furnace company of taking out
It is continuous rolling twice) rolling mode；The compression ratio of single pass is 25%, by the rolling of two fire time, rolls the total deformation of processing
Amount is 65-70%, obtains second of densification green body.
It is rolled in the present invention using 2100mm wide four-high mill, rolling power is big, and compression deformation ability is high, in low temperature
The compression ratio of big compression ratio reversible continuous rolling process down, single pass can reach 25%, and the total deformation for rolling processing reaches 65-
70%, it can reduce to melt down in this way using big compression ratio and number and melt down the time, it is less to melt down number and reach base
The size requirement of body, avoids crystal grain from being roughened when melting down and grows up.
(6) recrystallization annealing
Second of densification green body after hot rolling is subjected to recrystallization annealing processing, annealing temperature is 1300 DEG C, heat preservation
60min forms molybdenum target material plate.
(7) smoothing process
Molybdenum target material after hot rolling is subjected to smoothing process by 11 roller levelling machines, smoothing temperature setting is 950-1000 DEG C anti-
Only target generates internal injury, and the purpose of smoothing process is to obtain higher target plane degree, easy to process and use.
(8) nondestructive flaw detection examination
Nondestructive flaw detection examination is carried out for the molybdenum target material plate after smoothing process, target is visited by ultrasonic equipment
Wound, check its it is internal with the presence or absence of crackle, layering the defects of, it is good to pick out target interior tissue crystal property, without being layered, split
The high-quality molybdenum target material sheet material portions of the defects of line, the molybdenum target material plate after smoothing process is substantially without layering, crack defect.
(9) it is machined
By water knife by size required for molybdenum target material sheet fabrication to finished product, while using grinding machine by target material surface plain grinding
To desired size.Final preparation growth 2300mm, wide 1800mm, the molybdenum target material of thick 14mm.Molybdenum target product in embodiment 2 is side
The characteristics of target, the product is wide cut, and tandem rolling feature is used when hot rolling, i.e., has tuning (not along length in the operation of rolling
Roll always in direction), the final molybdenum target material obtained in the present embodiment.
It is sampled and observes the crystallite dimension of sputter face to the molybdenum target material of this example production, rated, this example production
The purity of molybdenum target material be 99.9%, relative density 99.9%, as shown in figure 3, to be obtained to molybdenum target material by microexamination
Crystal grain figure, average grain size be 17.4 μm.
The major impurity content of the molybdenum target material prepared in the present embodiment: C < 0.002；O<0.003；N<0.001；S<0.001；
Fe<0.002；Sn<0.0005；Ni<0.001；Sb<0.001；Si<0.001；Cd<0.0005；Al<0.001；Ca<0.001；Mg<
0.001；Cu<0.001；W<0.012；Pb<0.0005；Bi<0.0005；The purity of molybdenum target material is 99.9%.
Embodiment 3
Heating rate when being sintered 1 Medium frequency induction of embodiment in the present embodiment is changed to 4 DEG C/min, soaking time change
For 10h, other methods step is same as Example 1, and details are not described herein.
Growth 3430mm, wide 400mm, the molybdenum target material of thick 18mm are finally prepared in the present embodiment.To the molybdenum of this example production
Target is sampled and observes the crystallite dimension of sputter face, rated, and the purity of the molybdenum target material of this example production is 99.9%, phase
It is 99.9% to density, average grain size is 19.2 μm, and target interior tissue crystal property is good, no layering, crackle etc.
Defect.
Embodiment 4
The single pass compression ratio in embodiment 2 in four-high mill course of hot rolling is changed to 22% in the present embodiment, a fire
Two passage of tandem rolling need to roll 2 fire altogether, and the total deformation for rolling processing is 65-70%, other methods step and 2 phase of embodiment
Together, details are not described herein.
Growth 2300mm, wide 1800mm, the molybdenum target material of thick 14mm are finally prepared in the present embodiment.To the molybdenum of this example production
Target is sampled and observes the crystallite dimension of sputter face, rated, and the purity of the molybdenum target material of this example production is 99.9%, phase
It is 99.9% to density, average grain size is 19.8 μm, and target interior tissue crystal property is good, no layering, crackle etc.
Defect.
Reference examples 1
Step (4) the hot isostatic pressing die mould in embodiment 1 is omitted in this reference examples, i.e., without hot isostatic pressing die mould,
Other steps are same as Example 1, and details are not described herein.
Growth 3430mm, wide 400mm, the molybdenum target material of thick 18mm are finally prepared in this reference examples.To the molybdenum of this example production
Target is sampled and observes the crystallite dimension of sputter face, rated, and the purity of the molybdenum target material of this example production is 99.9%, phase
It is 99.86% to density, as shown in figure 4, for the crystal grain figure obtained to molybdenum target material by microexamination, average grain size is
64.7μm。
Reference examples 2
This reference examples controls the single pass compression ratio in step (5) four-high mill course of hot rolling in embodiment 2
18%, using fiery two passages, by the rolling mode of 3 fire time, the total deformation for rolling processing is 65-70%, other methods
Step is same as Example 2, and details are not described herein.
Growth 2300mm, wide 1800mm, the molybdenum target material of thick 14mm are finally prepared in the present embodiment.To the molybdenum of this example production
Target is sampled and observes the crystallite dimension of sputter face, rated, and the purity of the molybdenum target material of this example production is 99.9%, phase
It is 99.89% to density, as shown in figure 5, for the crystal grain figure obtained to molybdenum target material by microexamination, average grain size 36
μm, target interior tissue crystal property is good, it is no layering, crackle the defects of.
In summary: molybdenum target material prepared by the present invention is a kind of large-sized molybdenum target material, is provided simultaneously with high-compactness, ultra-fine
Brilliant and crystal property is good, can satisfy higher and higher sputter coating requirement.Using twice in preparation method in the present invention
Densification target blank uses hot isostatic pressing die mould first, presses metal molybdenum particle further
Contracting, improve the consistency of green body, secondly using four-high mill hot rolling technology carry out second of densification blank, and use compared with
Big compression ratio reduces blank and melts down number and melt down the time, avoid crystal grain from being roughened when melting down and grow up, finally by recrystallization
Annealing and machining can obtain consistency height, and crystal grain is tiny, the molybdenum target material of surfacing.
Preparation process in the present invention is simple, facilitates operation, can obtain high-purity (purity reaches 99.9% or more)),
The molybdenum target material of complete fine and close (density reaches 99.9% or more), Ultra-fine Grained (grain size is less than 20 μm), can satisfy high-precision plated film
It is required that improving the sputtering rate of molybdenum target material, the quality of sputter coating is improved.
The above description is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material, which is characterized in that the preparation method of the molybdenum target material
The following steps are included:
(1) isostatic cool pressing die mould
Molybdenum powder is chosen, ready molybdenum powder is encased in mold, is then placed in progress isostatic cool pressing die mould in cold static pressure equipment
Processing, obtains isostatic cool pressing green body after release；
(2) it is sintered
Isostatic cool pressing green body is sintered in sintering furnace using induction sintering mode, reducibility gas is passed through in sintering furnace,
Sintered body is obtained after cooling；
(3) hot isostatic pressing die mould
The sintered body that sintering is completed is subjected to machining shaping, hot isostatic pressing die mould is used to carry out first time cause after shaping
Densification process carries out hot isostatic pressing die mould in hot isostatic apparatus, and is passed through inert gas, prevents green body oxidation and impurity mixed
Enter, it is cooling after heat preservation, then green body is taken out, obtains densifying green body for the first time；
(4) hot rolling
First time densification green body after hot isostatic pressing die mould is subjected to hot rolling treatment, obtains second of densification green body；
(5) it anneals
Second of densification green body after hot rolling is subjected to recrystallization annealing processing, forms molybdenum target material plate；
(6) it is machined
Molybdenum target material plate is machined, required size is cut into, and be ground to required thickness, obtains molybdenum target material.
2. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described in claim 1, which is characterized in that described heat etc.
The pressure chosen during static pressure die mould is 150-200MPa, and heating temperature is 1450-1500 DEG C, heat-insulation pressure keeping 3-4h.
3. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described in claim 1, which is characterized in that in the burning
The temperature being sintered in freezing of a furnace is 1950-2050 DEG C, and heating rate is 3-5 DEG C/min, and keeps the temperature 1-10h at such a temperature.
4. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described in claim 1, which is characterized in that the step
(4) hot-rolled temperature in when hot rolling treatment is 1000-1100 DEG C.
5. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as claimed in claim 4, which is characterized in that the step
(4) rolling mode that hot rolling uses in is the rolling mode of fiery two passages.
6. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as claimed in claim 5, which is characterized in that institute in hot rolling
The one-pass roller deflection for stating rolling mode is 20-25%, and the total deformation for rolling processing is 60-70%.
7. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described in claim 1, which is characterized in that the step
(4) milling train that hot rolling uses in is wide cut 2100mm four-high reversing mill.
8. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described in claim 1, which is characterized in that will be described
Molybdenum target material plate carries out before step (6) machining further include:
Nondestructive flaw detection examination detects a flaw to molybdenum target material plate by ultrasonic equipment, checks that its inside whether there is crackle, divide
The defects of layer.
9. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described in claim 1, which is characterized in that the molybdenum powder
Molybdenum content >=99.95%, Fisher particle size be 3.0-3.8 μm, apparent density 4.0-8.0g/cm3。
10. the preparation method of high-densit Ultra-fine Grained large scale molybdenum target material as described in claim 1, which is characterized in that by hot rolling
The annealing temperature that second of densification green body afterwards is made annealing treatment is 950-1100 DEG C, soaking time 60-90min.
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