CN110352263A - The manufacturing method of oxide sputtering target and oxide sputtering target - Google Patents
The manufacturing method of oxide sputtering target and oxide sputtering target Download PDFInfo
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- CN110352263A CN110352263A CN201880004813.4A CN201880004813A CN110352263A CN 110352263 A CN110352263 A CN 110352263A CN 201880004813 A CN201880004813 A CN 201880004813A CN 110352263 A CN110352263 A CN 110352263A
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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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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- 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
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
- G11B7/26—Apparatus or processes specially adapted for the manufacture of record carriers
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6565—Cooling rate
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/658—Atmosphere during thermal treatment
- C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
- C04B2235/6585—Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage above that of air
Abstract
The present invention provides a kind of oxide sputtering target, it is made of the oxide for containing zirconium, silicon and indium as metal component, the oxide sputtering target is characterized in that the difference of the maxima and minima of the oxygen concentration in target surface is 15% or less relative to total ratio of the maxima and minima of the oxygen concentration.
Description
Technical field
The present invention relates to a kind of oxide sputtering targets comprising zirconium oxide, silica and indium oxide and oxide to sputter
The manufacturing method of target.
Background technique
As information recording carrier, it is known to the phase transition optical disks such as DVD, BD [Blu-ray (registered trademark) Disc].These
Phase transition optical disk is usually made the layer that multiple layers of dielectric layer, recording layer, dielectric layer and reflecting layer etc. is laminated on substrate
Stack.As the film build method of each layer, sputtering method is utilized extensively.Phase transition optical disk is by being irradiated to light note with laser beam for record
Recording medium come make recording layer generate phase transformation, to record information.
As the dielectric layer or protective layer of phase transition optical disk, the oxygen comprising zirconium oxide, silica and indium oxide is used
Compound film (patent document 1,2).
A kind of oxide sputtering target is disclosed in patent document 2, is formed as optical recording medium protection film with sputtering
Target, have by being formed as follows at what is be grouped as, that is, contain zirconium oxide in terms of mole %: 10~70%, silica: 50% with
Under (do not include 0%), remainder: indium oxide and inevitable impurity.The oxide is recorded in the patent document 2 to splash
The manufacturing method shot at the target, this method are as follows: weigh the ZrO of specified amount2Powder, noncrystalline SiO2Powder and In2O3Powder, and utilize
After Henschel mixer is uniformly mixed, which is burnt into formed body obtained in oxygen atmosphere
And make its sintering.
Patent document 1: No. 4567750 bulletins (B) of Japanese Patent No.
Patent document 2: No. 5088464 bulletins (B) of Japanese Patent No.
In phase transition optical disk, with the increase of packing density, the miniaturization development of pothole or gauge is recorded, it is mixed to foreign matter
The management entered becomes stringent.Therefore, in the oxide sputtering target for the manufacture of phase transition optical disk, it is desirable that particulate matter not Workflow
It dissipates.
However, being burnt sometimes when being burnt into formed body in the manufacturing method for the oxide sputtering target recorded in patent document 2
At the hypoxgia in atmosphere.If in the state of hypoxgia in firing atmosphere, being burnt into formed body, then oxide obtained splashes
Oxygen concentration in shooting at the target becomes uneven.Moreover, specifying following content: if oxygen concentration in the target surface of oxide sputtering target
Deviation becomes larger, then the resistivity in target surface becomes unevenly, can generate in sputtering due to current potential concentrates on privileged site abnormal
Electric discharge, and lead to the problem of particulate matter because of the paradoxical discharge and disperse.
Summary of the invention
The present invention completes in view of the foregoing, and its purpose is to provide a kind of paradoxical discharges being able to suppress in sputtering
The manufacturing method of oxide sputtering target and the oxide sputtering target that generation and particulate matter disperse.
In order to solve the above problems, oxide sputtering target of the invention is characterized in that, by as metal component contain zirconium,
The oxide of silicon and indium forms, maximum value of the difference of the maxima and minima of the oxygen concentration in target surface relative to the oxygen concentration
Total ratio with minimum value is 15% or less.
According to the oxide sputtering target of the invention for being set as this structure, due to the oxygen concentration in target surface maximum value with most
Small value meets above-mentioned relation, and the deviation of the oxygen concentration in target surface is inhibited.Therefore, the uniformity of the oxygen concentration in target surface is high,
Resistivity in target surface becomes uniformly, therefore the paradoxical discharge in sputtering is inhibited, and inhibits the generation of particulate matter therewith.
Wherein, in oxide sputtering target of the invention, the difference of the maxima and minima of the resistivity preferably in target surface
Total ratio of maxima and minima relative to the resistivity is 15% or less.
At this point, the deviation of the resistivity in target surface is controlled in above range, therefore further suppress different in sputtering
Often electric discharge, is reliably suppressed the generation of particulate matter therewith.
The manufacturing method of oxide sputtering target of the invention is characterized in that, for the side for manufacturing above-mentioned oxide sputtering target
Method, this method have following process: mixed oxidization zirconium powder, SiO 2 powder and indium oxide powder and obtain specific surface area and be
11.5m2/ g or more and 13.5m2/ g mixed-powder below；The mixed-powder is formed and obtains formed body；Oxygen is set to exist on one side
Circulation in burning apparatus, on one side by the formed body with 1300 DEG C or more and 1600 DEG C of temperature below are burnt into and generate burning
Knot body；And oxygen is made to circulate in the burning apparatus on one side, on one side with 200 DEG C/h of cooling velocities below by the sintering
Body, which is cooled to, at least becomes 600 DEG C of temperature below.
The manufacturing method of oxide sputtering target according to this structure will be mixed with Zirconium oxide powder, dioxy as raw material
The specific surface area of the mixed-powder of SiClx powder and indium oxide powder is set as 11.5m2/ g or more and 13.5m2/ g is hereinafter, therefore anti-
Answering property is higher.Also, so that oxygen is circulated in burning apparatus on one side, carry out the firing of formed body on one side, firing atmosphere will not occur
In hypoxgia the case where, therefore the sintering of formed body becomes can uniformly to obtain fine and close and high density sintered body.Moreover,
The sintered body is cooled down with 200 DEG C/h of cooling velocities below, therefore is not susceptible to temperature change sharply, is sintered
The oxygen concentration of body is stablized.Therefore, the small oxide sputtering target of the deviation of the oxygen concentration in target surface can steadily be manufactured.
In accordance with the invention it is possible to provide generation and the oxygen that disperses of particulate matter of a kind of paradoxical discharge being able to suppress in sputtering
The manufacturing method of compound sputtering target and the oxide sputtering target.
Detailed description of the invention
Fig. 1 is the survey for indicating oxygen concentration and resistivity in oxide sputtering target involved in one embodiment of the present invention
Position the explanatory diagram set.
Fig. 2 is the flow chart for indicating the manufacturing method of oxide sputtering target involved in one embodiment of the present invention.
Fig. 3 is the explanatory diagram that the position of the In concentration of the oxidation film formed in embodiment to measurement is illustrated.
Specific embodiment
Hereinafter, being illustrated referring to oxide sputtering target of the attached drawing to embodiments of the present invention.
Oxide sputtering target involved in present embodiment for example can be used as the phases such as DVD or BD being formed using sputtering method
It is used when the oxidation film of the dielectric layer of modification CD and protective layer.Also, the oxide sputtering target of present embodiment can also
It is enough formed using sputtering method the basal layer for being used as the magnetic recording media such as HDD (Hard-Disk Drive: hard disk drive) and
It is used when the oxidation film of protective layer.
The oxide sputtering target of present embodiment is made of the oxide for containing zirconium, silicon and indium as metal component.Zirconium, silicon
And there is no particular restriction for the content of indium, can be set as and the oxide as existing optical recording medium protection film formation sputtering target
It is identical.In the present embodiment, total content of metal component is set as 100 mass %, and the content of zirconium is set as 10 matter
% or more and 75% mass range below are measured, the content of silicon is set as 35 mass % or less (not including 0 mass % wherein), indium
Content be set as remainder.Zirconium, silicon and a part of of indium can be respectively formed composite oxides.As composite oxides
Example can enumerate In2Si2O7。
It is in the oxide sputtering target of present embodiment, the difference of the maxima and minima of the oxygen concentration in target surface is opposite
15% is set as in total ratio of the maxima and minima of oxygen concentration, i.e. by the deviation of the oxygen concentration of following formula (1) expression
Below.
Formula (1):
The deviation (%) of oxygen concentration=[(maximum value of oxygen concentration)-(minimum value of oxygen concentration)]/[(maximum of oxygen concentration
Value)+(minimum value of oxygen concentration)] × 100
Moreover, in the oxide sputtering target of present embodiment, by the maxima and minima of the resistivity in target surface it
The deviation of total ratio of the difference relative to the maxima and minima of resistivity, i.e., the resistivity indicated by following formula (2) is set
It is 15% or less.
Formula (2):
The deviation of resistivity=[(maximum value of resistivity)-(minimum value of resistivity)]/[(maximum value of resistivity)+
(minimum value of resistivity)] × 100
Hereinafter, the reasons why deviation of oxygen concentration and resistivity to the oxide sputtering target of regulation present embodiment as above into
Row explanation.
(deviation of oxygen concentration)
If the deviation of the oxygen concentration of oxide sputtering target becomes larger, paradoxical discharge and particulate matter are easy to produce in sputtering.Cause
This, in the oxide sputtering target of present embodiment, the deviation setting by the oxygen concentration in the target surface indicated by above-mentioned formula (1) is
15% or less.If the deviation of oxygen concentration is more than 15%, generates paradoxical discharge and particulate matter and be formed by oxidation film
Foreign matter is adhered on surface, and deviation is possible to become larger in the face of film composition.In addition, the oxygen concentration of oxide sputtering target according to zirconium,
The content of silicon and indium and it is different, preferably more than 15 mass % and 35 mass % ranges below.Oxygen concentration can pass through EPMA
Or gas analysis and measure.
Wherein, the deviation about the oxygen concentration in target surface, multiple Site Determination oxygen concentrations in target surface, and extract and measured
Oxygen concentration maxima and minima, thus pass through above-mentioned formula (1) calculate.The measurement site of oxygen concentration be preferably set at 5 with
On.Wherein, in the present embodiment, when oxide sputtering target is disk-shaped, as shown in Figure 1, in the central point of target surface (circle)
(1) and on two mutually orthogonal straight lines of the central point in target surface and 4 point (2)~(5) of the position away from outer rim 20mm
Oxygen concentration is measured at this total 5 point, and extracts the maxima and minima of measured oxygen concentration, so as to find out oxygen concentration
Deviation.
When oxide sputtering target is cylindrical shape, it is being located at the position away from outer rim 20mm and is being located at circumferential equally spaced position
Oxygen concentration is measured at total 5 points set, and extracts the maxima and minima of measured oxygen concentration, so as to find out oxygen
The deviation of concentration.
(deviation of resistivity)
If the deviation of the resistivity of oxide sputtering target becomes larger, paradoxical discharge and particulate matter are easy to produce in sputtering.Cause
This, in the oxide sputtering target of present embodiment, the deviation setting by the resistivity in the target surface indicated by above-mentioned formula (2) is
15% or less.If the deviation of resistivity is more than 15%, generates paradoxical discharge and particulate matter and be formed by oxidation film
Foreign matter is adhered on surface, and deviation is possible to become larger in the face of film composition.In addition, the resistivity of oxide sputtering target is preferably
0.1 Ω cm or less.
Wherein, the deviation about the resistivity in target surface, multiple Site Determination resistivity in target surface, and extract and measured
Resistivity maxima and minima, thus pass through above-mentioned formula (2) calculate.The measurement site of resistivity be preferably set at 5 with
On.Wherein, in the present embodiment, when oxide sputtering target is disk-shaped, as shown in Figure 1, in the central point of target surface (circle)
(1) and on two mutually orthogonal straight lines of the central point in target surface and 4 point (2)~(5) of the position away from outer rim 20mm
Resistivity is measured at this total 5 point, and extracts the maxima and minima of measured resistivity, so as to find out resistivity
Deviation.
When oxide sputtering target is cylindrical shape, it is being located at the position away from outer rim 20mm and is being located at circumferential equally spaced position
Resistivity is measured at total 5 points set, and extracts the maxima and minima of measured resistivity, so as to find out electricity
The deviation of resistance rate.
Then, referring to the flow chart of Fig. 2, the manufacturing method of oxide sputtering target involved in present embodiment is said
It is bright.
As shown in Fig. 2, the manufacturing method of oxide sputtering target involved in present embodiment has: being pulverized and mixed process
S01 is pulverized and mixed raw material powder；Mixed-powder through being pulverized and mixed is shaped to defined shape by molding procedure S02；Sintering
Process S03 makes the molding formed body sintering of institute；Cooling process S04, cooling sintered body obtained；Manufacturing procedure S05, processing
Through cooling sintered body.
As raw material powder, prepare ZrO2Powder, SiO2Powder, In2O3Powder.ZrO2The preferred purity of powder is 99.9 matter
% or more is measured, average grain diameter is 0.2 μm or more and 20 μm or less.SiO2The preferred purity of powder is 99.8 mass % or more, average
Partial size is 0.2 μm or more and 20 μm or less.In2O3The preferred purity of powder is 99.9 mass % or more, and average grain diameter is 0.1 μ or more
And 10 μm or less.
(being pulverized and mixed process S01)
When total content of metal component in mixed-powder obtained is set as 100 mass %, by above-mentioned raw materials powder
End with the content of zirconium more than 10 mass % and 75% mass range below, the content of silicon be 35 mass % or less (wherein not
Include 0 mass %), the mode that the content of indium is remainder weighs, and is pulverized and mixed.In the present embodiment, about
It is pulverized and mixed, carries out case of wet attrition mixing using using the zirconium pearl of diameter 0.5mm as the bead mill device of crushing medium.
It is pulverized and mixed in process S01 at this, is become with the specific surface area (BET specific surface area) of mixed-powder obtained
11.5m2/ g or more and 13.5m2/ g mode below is pulverized and mixed.By using specific surface area above range mixing
Powder is easy to get and gets higher with the reactivity of atmosphere oxygen and agglutinating property in aftermentioned sintering process, have uniform oxygen concentration,
The sputtering target of resistivity and high sintered densities.On the other hand, if being less than 11.5m using specific surface area2The mixed-powder of/g, then have
May in firing, reaction is uneven and the deviation of the oxygen concentration of sputtering target becomes larger.Also, it is ground into the specific surface of mixed-powder
Product is more than 13.5m2/ g, it is possible to cause to be pulverized and mixed the time elongated and uneconomical.
(molding procedure S02)
Then, the mixed-powder obtained in being pulverized and mixed process S01 is shaped to defined shape to obtain formed body.
In the present embodiment, it is formed using punch forming.
(sintering process S03)
Then, make the molding formed body sintering in molding procedure S02.In sintering process S03, led using having oxygen
The burning apparatus of entrance is burnt into formed body on one side and makes its sintering on one side to oxygen is imported inside it.By one side to burning apparatus
Interior importing oxygen carries out the firing of formed body on one side, can inhibit the In in mixed-powder2O3The distillation of powder, therefore it is easy to get tool
There is the sputtering target of uniform oxygen concentration, resistivity and high sintered densities.The optimum flow for importing the oxygen in burning apparatus can basis
The conditions such as the size or quantity of the formed body of the internal volume or sintering of burning apparatus and change, it is therefore desirable to appropriate selection.For example,
As standard, by 100~300mm of diameter, thickness 15mm formed body below in 15000~30000cm of internal volume3Firing dress
In setting while the required flow of firing 6 or less was in 3L/ minutes or more and 10L/ minute range below.More than 10L/ minutes
Flow is not usually preferred in economic aspect.In addition, the volume fraction of the preferred oxygen of the gas to circulate in burning apparatus is 100%, i.e.,
The gas with other gas mixings such as nitrogen or argon gas may be used if the volume fraction of oxygen is 80% or more in pure oxygen.
Holding temperature when firing is preferably in 1300 DEG C or more and 1600 DEG C of ranges below.It is being lower than 1300 DEG C of temperature
Under, it is possible to sintered body is difficult to become fine and close, and density is lower.Temperature more than 1600 DEG C is used for conventional production, in economy
Aspect is not preferred.Preferably 200 DEG C/h of heating rate when firing hereinafter, more preferably 10 DEG C/h or more and 200 DEG C/it is small
When range.If more than 200 DEG C/h, it is likely that due to generating the non-uniform reaction between raw material powder, sintering, shrinking
The reason of as warpage or rupture.On the other hand, if less than 10 DEG C/h, it is likely that spent for a long time and reduced production
Rate.
(cooling process S04)
Then, the cooling sintered body obtained in sintering process S03.In cooling process S04, on one side to burning apparatus
Interior importing oxygen cools down sintered body on one side, until at least becoming 600 DEG C of temperature below.Through one side into burning apparatus
Oxygen is imported, the cooling of body is sintered on one side, can inhibit the disengaging of the oxygen in cooling procedure in sintered body, and is easy to get and has
The sputtering target of uniform oxygen concentration and resistivity.The flow of the oxygen imported in burning apparatus is preferably set to and in sintering process S03
Flow in middle importing burning apparatus is identical.The circulation of oxygen is preferably implemented until taking out sintered body in cooling process S04, examines
Consider economy, can suitably stop at the time of becoming 600 DEG C of temperature below.
Preferably 200 DEG C/h of cooling velocity when being cooled to until becoming 600 DEG C of temperature below are hereinafter, more preferably 1
DEG C/h or more and 200 DEG C/h of ranges below.If more than 200 DEG C/h, the cooling of sintered body be not easy uniformly into
The uniformity of row, oxygen concentration is impaired, and sintered body is possible to become easy rupture because of thermal stress in addition to this.On the other hand, if
Less than 1 DEG C/h, it is likely that cooling time is too long and reduces productivity.Cooling velocity is preferably in entire cooling process S04
It is constant, but can be in 200 DEG C/h of ranges below in cooling change appropriate on the way.Also, it is being cooled to 600 DEG C or less
Later, it can be cooled down with the cooling velocity more than 200 DEG C/h, but the operation for taking out sintered body from burning apparatus is preferred
It is carried out in 100 DEG C of temperature below.
(manufacturing procedure S05)
In manufacturing procedure S05, by implementing machining or grinding to add to cooling sintered body in cooling process S05
Work and the sputtering target for being processed into regulation shape.
According to the oxide sputtering target of the present embodiment as structure as above, the deviation of the oxidation concentration in target surface is set
For 15% hereinafter, therefore the uniformity of the oxygen concentration in target surface is high, the resistivity in target surface becomes uniform.Therefore, different in sputtering
Often electric discharge is inhibited, and inhibits the generation of particulate matter therewith.
Also, the manufacturing method of oxide sputtering target according to the present embodiment will be in being pulverized and mixed process S01
For the ZrO of raw material2Powder, SiO2Powder and In2O3The specific surface area of mixed-powder for being pulverized and mixed and being obtained is set as
11.5m2/ g or more and 13.5m2/ g is hereinafter, therefore reactivity is higher.Also, in sintering process S03, on one side to burning apparatus
Interior importing oxygen carries out the firing of formed body on one side, will not be there is a situation where the hypoxgia in firing atmosphere, therefore the burning of formed body
Knot becomes uniformly obtain fine and close and high density sintered body.Moreover, in cooling process S04, by the sintered body with 200
DEG C/h cooling velocity below is cooled down, therefore is not susceptible to temperature change sharply, and the oxygen concentration of sintered body is stablized.
Therefore, the lesser oxide sputtering target of deviation of the oxygen concentration in target surface can steadily be manufactured.
More than, embodiments of the present invention are illustrated, but the present invention is not limited to this, is not departing from the present invention
Technical idea in the range of can suitably change.
For example, in the present embodiment, the shape of oxide sputtering target is illustrated for disk-shaped situation, but oxygen
There is no particular restriction for the shape of compound sputtering target.Oxide sputtering target can be square plate shape.The shape of oxide sputtering target is side
When plate, the measurement site of oxygen concentration and resistivity can be set as the adjacent corner on the intersection point and each diagonal line of diagonal line intersection
4 points this total 5 point at.
Also, oxide sputtering target may be cylindrical shape.When the shape of oxide sputtering target is cylindrical shape, oxygen is dense
The measurement site of degree and resistivity can be set as at circumferential equally spaced total 5 points.
Also, the oxide sputtering target of present embodiment can contain inevitable impurity.Wherein, inevitably miscellaneous
Matter indicates inevitably to include impurity in raw material powder and the inevitably mixed impurity in manufacturing process.
It, will be in being pulverized and mixed process S01 moreover, the manufacturing method of oxide sputtering target according to the present embodiment
For the ZrO of raw material2Powder, SiO2Powder and In2O3Powder is pulverized and mixed, but can also only be mixed.Wherein, it needs to mix
The specific surface area of the mixed-powder of conjunction and acquisition is set as 11.5m2/ g or more and 13.5m2/ g or less.
Embodiment
Hereinafter, the evaluation test knot evaluated the function and effect about oxide sputtering target according to the present invention
Fruit is illustrated.
[example 1~7 of the present invention]
As raw material powder, the ZrO that purity is 99.9 mass % or more, average grain diameter is 2 μm is prepared2Powder；Purity
For 99.8 mass % or more, the SiO that average grain diameter is 2 μm2Powder and purity are 99.9 mass % or more, average grain diameter is 1 μm
In2O3Powder.Each raw material powder prepared is weighed in a manner of respectively becoming molar ratio shown in table 1.
By weighed raw material powder put into together with solvent and used the zirconium pearl of diameter 0.5mm as crushing medium
Bead mill device simultaneously crush/mix.As solvent, Japan Alcohol Trading CO. has been used, LTD's
Solmix A-11.Crushing/mixing time is set as 1 hour.After terminating crushing/mixing, zirconium pearl is separated and recovered, and obtain
Obtained the slurry comprising raw material powder and solvent.Slurry obtained is heated, solvent is removed and obtains mixed-powder.
It determines and is obtained using specific area measuring device (MOUNTECH Co.Ltd. system, Macsorb model 1201)
The BET specific surface area of the mixed-powder obtained.It the results are shown in table 1.
Then, mixed-powder obtained is filled into the mold of diameter 200mm, with 150kg/cm2Pressure carry out
Punching press, to make the disk-shaped formed body of two panels diameter 200mm, thickness 10mm.
Two sheet molded article obtained is put into electric furnace (furnace volume 27000cm3), make oxygen with the stream of 4L per minute on one side
Amount circulates in electric furnace, on one side with the holding of firing temperature shown in table 17 hours, is thus burnt into and generates sintered body.It connects
, continue that oxygen is made to circulate in electric furnace on one side, sintered body is cooled to 600 DEG C with cooling velocity shown in table 1 on one side, later,
The circulation for stopping oxygen, cools down in through furnace after being cooled to room temperature, and takes out sintered body from electric furnace.
To sintered body obtained implement machining and obtain two panels diameter 152.4mm, thickness 6mm it is disk-shaped
Sputtering target.
[comparative example 1]
The weighed raw material powder of institute is mixed with Henschel mixer, in addition to this, is manufactured in the same manner as example 1 of the present invention
Two panels sputtering target.
[comparative example 2]
The cooling velocity of sintered body until 600 DEG C is set as 250 DEG C/h, in addition to this, with example 1 of the present invention
Two panels sputtering target is similarly manufactured.
[comparative example 3]
When being burnt into formed body, oxygen is not made to circulate in electric furnace, in addition to this, has manufactured two in the same manner as example 1 of the present invention
Piece sputtering target.
[comparative example 4]
The firing temperature of sintered body is set as 1250 DEG C, in addition to this, has manufactured two panels sputtering in the same manner as example 1 of the present invention
Target.
[evaluation]
Determine metal component composition, relative density, oxygen content and the resistivity of sputtering target.Also, sputtering target is carried out
Sputtering test.
1 in manufactured two panels sputtering target is used for the measurement of relative density, resistivity, oxygen content, and remaining 1
Piece is for sputtering test.In sputtering test, the generation number of the paradoxical discharge in sputtering is determined first.Then, pass through sputtering
It is formed after oxidation film, it is thus identified that whether there is or not the ruptures of target.Moreover, determining the indium concentration being formed by oxidation film.
It is each evaluation method is as follows.
(metal component of sputtering target forms)
A part of the end of the sintered body before being machined into sputtering target is acquired as sample.By examination collected
Sample is dissolved in acid, and utilizes the inductively coupled plasma atomic emission of Agilent Technologies Japan, Ltd.
(ICP-OES) device (Agilent 5100) analyzes the composition of solution obtained, and analyzes the metal component of Zr, Si, In
Composition.The measurement result is shown in table 2.
(relative density)
Relative density is calculated as actual density relative to the ratio (actual density/theoretical density × 100) of theoretical density
Out.Actual density is found out by the weight and size for surveying sputtering target.Theoretical density is by including each oxidation in sputtering target
The concentration and density of object calculate.Specifically, by ZrO2Quality % concentration be set as C1, density is set as ρ 1, SiO2Quality % it is dense
Degree is set as C2, and density is set as ρ 2, In2O3Quality % concentration be set as C3, density is set as ρ 3, and has calculated reason by formula below
By density p.
ρ=1/ [C1/100 ρ 1+C2/100 ρ 2+C3/100 ρ 3]
Wherein, ρ 1=5.60g/cm has been used3, ρ 2=2.20g/cm3, ρ 3=7.18g/cm3Value.In addition, C1, C2, C3
It is calculated by the use level of raw material powder.
(resistivity)
Resistivity is determined by four probe method.In order to measure the deviation of resistivity, as shown in Figure 1, in target surface (circle)
Central point (1) and on two mutually orthogonal straight lines of the central point in target surface and 4 points of the position away from outer rim 20mm
(2) it is determined at this total 5 point of~(5).The maxima and minima in measured resistivity is extracted, and passes through institute
State the deviation that formula (2) has calculated resistivity.It is shown in Table 2 the measured value and deviation in the resistivity of each measuring point.
(oxygen concentration)
As shown in Figure 1, straight from the central point (1) of target surface (circle) and positioned at the central point in target surface mutually orthogonal two
The small pieces that 10mm square is cut out at this total 5 point of 4 point (2)~(5) of on the line and position away from outer rim 20mm are dense as oxygen
Measurement sample piece is spent, and determines the oxygen concentration on the surface (target surface) of the oxygen concentration determination coupons as follows.
Firstly, oxygen concentration determination sample is embedded to resin, and the table of the oxygen concentration determination coupons of resin will be embedded to
Face (target surface) is mirror-finished using burnishing device.And after polishing, EPMA (JEOL Ltd. system, JXA- are utilized
Quantitative analysis 8500F) has been carried out to the oxygen concentration of burnishing surface.The condition of the quantitative analysis of oxygen based on EPMA is set as follows.
Acceleration voltage: 15kV
Irradiation electric current: 5 × 10-8A
Beam diameter: 100 μm
In addition, the analyzing crystal used in the quantitative analysis of oxygen is LDE1.
In the coupons of 10mm square at random to 10 at be measured, using its average value as a position shown in Fig. 1
Oxygen concentration measured value.
The maxima and minima in the oxygen concentration at 5 shown in measured Fig. 1 is extracted, and is calculated by the formula (1)
The deviation of oxygen concentration.It is shown in Table 2 the measured value and deviation of the oxygen concentration of each oxygen concentration determination sample.
(sputtering test)
Sputtering target is welded on anaerobic backboard made of copper, and be mounted on magnet controlled sputtering equipment (ULVAC, Inc. system,
SIH-450H in).Then, using vacuum pumping hardware to being exhausted in sputtering equipment to 5 × 10-5After Pa or less, import
Ar gas and O2Gas, and sputter gas pressure is adjusted to 0.67Pa, implement 1 hour pre-sputtering, thus eliminates target table
The machined layer in face.By Ar gas and O at this time2The flow-rate ratio of gas is set as 47:3, and power is set as pulse DC1000W, pulse item
Part is set as frequency 50kHz, and duty (duty) ratio is set as 0.08.
(paradoxical discharge number)
Under the same conditions, continuous sputtering in 1 hour is being carried out with above-mentioned pre-sputtering.Utilize used sputtering equipment
The electric arc tally function that has of DC power supply measure the paradoxical discharge number generated during this is 1 hour.By its result
It is shown in table 3.
(formation of oxidation film and the composition analysis of oxidation film)
After the measurement of above-mentioned paradoxical discharge number, prepare the poly- of 20mm square size on 6 inches of diameter of Si substrate
Carbonic ester substrate is pasted on 5 points shown in Fig. 3 (1 point of Si substrate center and positioned at the part 4 away from center radius 60mm
Point) made of component, which is seated in sputtering equipment and is still in it right above target, and utilizes vacuum pumping hardware pair
It is exhausted in sputtering equipment to 5 × 10-5After Pa or less, sputtered under the same conditions with above-mentioned pre-sputtering, thus
The oxidation film of thickness 200nm is formd on substrate.Substrate at this time is set as 70mm at a distance from target.Utilize Agilent
Inductively coupled plasma atomic emission (ICP-OES) device (Agilent 5100) of Technologies Japan, Ltd
Each oxidation film obtained is dissolved in the composition of the solution of acid by analysis, and measures the In concentration in each oxidation film, is utilized
Following formula (3) has calculated its deviation.Total content of metallic element (is set as 100 by the In concentration being shown in Table 3 in oxidation film
When quality %) measured value and deviation.
Formula (3):
The deviation (%) of the In concentration of oxidation film=[(maximum value of In concentration)-(minimum value of In concentration)]/[(In
The maximum value of concentration)+(minimum value of In concentration)] × 100
(the presence or absence of rupture)
After forming oxidation film, sputtering equipment is open into air.Then, sputtering target is taken out from sputtering equipment,
Its appearance is observed by visual observation and confirmed that whether there is or not rupture.It the results are shown in table 3.
[table 1]
[table 2]
[table 3]
The BET specific surface area of mixed-powder about raw material powder is less than 11.5m2The comparative example 1 of/g, until 600 DEG C be
The cooling velocity of sintered body only be more than 200 DEG C/h of comparative example 2, oxygen do not made to circulate in burning apparatus and be burnt at
Any one comparative example in the comparative example 3 of type body, comparative example 4 of the firing temperature lower than 1300 DEG C of formed body, it is obtained to splash
The deviation for the oxygen concentration in target surface shot at the target has been more than 15%.
The deviation of oxygen concentration in target surface is more than that the deviation of the resistivity of the sputtering target of 15% comparative example 1~4 is larger
It is 15% or more, and the paradoxical discharge number in sputtering becomes more.Also, pass through the inclined of the In concentration of the oxidation film of sputtering formation
Difference becomes larger.Especially, the sputtering target of comparative example 2 and 4 is ruptured after sputtering.
In contrast, the BET specific surface area of the mixed-powder of raw material powder is set as 11.5m2/ g or more and 13.5m2/ g with
Under range, the cooling velocity of the sintered body until 600 DEG C be set as 200 DEG C/h hereinafter, and make on one side oxygen firing fill
Interior circulation is set, on one side in the sputtering target of the example of the present invention 1~7 of 1300 DEG C or more and 1600 DEG C temperature firing formed bodys below
The deviation of oxygen concentration in target surface is 15% or less.
The deviation of oxygen concentration in target surface is that the deviation of the resistivity of the sputtering target of 15% example 1~7 of the present invention below is equal
It is lower be 15% hereinafter, and sputtering in paradoxical discharge number substantially reduce.Also, the In for passing through the oxidation film that sputtering is formed
The deviation of concentration tails off.Moreover, not ruptured after sputtering.
It is confirmed from the result of above evaluation test, in accordance with the invention it is possible to provide a kind of be able to suppress in sputtering
The manufacturing method of oxide sputtering target and the oxide sputtering target that the generation of paradoxical discharge and particulate matter disperse.
Claims (3)
1. a kind of oxide sputtering target is made of the oxide for containing zirconium, silicon and indium as metal component, the oxide splashes
It shoots at the target and is characterized in that,
The difference of the maxima and minima of oxygen concentration in target surface relative to the oxygen concentration maxima and minima it is total
Ratio be 15% or less.
2. oxide sputtering target according to claim 1, which is characterized in that
The difference of the maxima and minima of resistivity in target surface relative to the resistivity maxima and minima it is total
Ratio be 15% or less.
3. a kind of manufacturing method of oxide sputtering target, which is characterized in that for for oxidation described in manufacturing claims 1 or 2
The method of object sputtering target, the method have following process:
Mixed oxidization zirconium powder, SiO 2 powder, indium oxide powder and obtain specific surface area be 11.5m2/ g or more and
13.5m2/ g mixed-powder below；
The mixed-powder is formed and obtains formed body；
So that oxygen is circulated in burning apparatus on one side, on one side by the formed body with 1300 DEG C or more and 1600 DEG C of temperature below into
Row is burnt into and generates sintered body；And
Oxygen is set to circulate in the burning apparatus on one side, it is with 200 DEG C/h of cooling velocities below that the sintered body is cold on one side
But at least as 600 DEG C of temperature below.
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| CN114853447B (en) * | 2021-02-04 | 2023-09-26 | 光洋应用材料科技股份有限公司 | InZr-Si oxide target material, preparation method thereof and InZr-Si oxide film |
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- 2018-02-08 KR KR1020197014613A patent/KR102115126B1/en active IP Right Grant
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| KR20190096974A (en) | 2019-08-20 |
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