CN105308002A - Ito sputtering target material and method for producing same - Google Patents

Ito sputtering target material and method for producing same Download PDF

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Publication number
CN105308002A
CN105308002A CN201580000974.2A CN201580000974A CN105308002A CN 105308002 A CN105308002 A CN 105308002A CN 201580000974 A CN201580000974 A CN 201580000974A CN 105308002 A CN105308002 A CN 105308002A
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China
Prior art keywords
ito
sintered compact
indium oxide
tin indium
powder
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CN201580000974.2A
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寺村享祐
武内朋哉
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Mitsui Mining and Smelting Co Ltd
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Mitsui Mining and Smelting Co Ltd
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Priority to CN201710623904.3A priority Critical patent/CN107253855A/en
Publication of CN105308002A publication Critical patent/CN105308002A/en
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    • 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
    • C04B35/453—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 zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract

The present invention provides: an ITO sintered body which has an Sn content of 2.5-10.0% by mass in terms of SnO2, while comprising an In2O3 matrix and an In4Sn3O12 phase that is present at the grain boundary of the In2O3 matrix, and which has a relative density of 98.0% or more, an average grain size of the In2O3 matrix of 17 um or less, and an area ratio of the In4Sn3O12 phase in a cross-section of the ITO sintered body of 0.4% or more; and an ITO sputtering target material which is formed of this ITO sintered body. An ITO sintered body according to the present invention is not susceptible to the occurrence of cracks or deformation during a processing step. An ITO sputtering target material according to the present invention is not susceptible to the occurrence of cracks or deformation during a step for bonding to a base. Consequently, the ITO sintered body and the ITO sputtering target material according to the present invention are able to improve production yield.

Description

ITO sputtering target material and manufacture method thereof
Technical field
The present invention relates to a kind of ITO sputtering target material and manufacture method thereof.
Background technology
Rotary magnetic keyholed back plate cathode sputtering device is have magnetic field generation device in the inner side of cylindrical target, while carrying out cooling from the inner side of target, target is rotated and implement sputter device, it makes the whole surface of target by acid etching thus is cut equably.Therefore, in plate-type magnetron sputter equipment, the service efficiency of target is generally 20 ~ 30%, relative to this, in rotary magnetic keyholed back plate cathode sputtering device, the service efficiency of target can be made to become more than 70%, thus very high service efficiency can be obtained.And, in rotary magnetic keyholed back plate cathode sputtering device, by making target rotate, thus compared with existing plate-type magnetron sputter equipment, because per unit area can input larger power, therefore, it is possible to obtain higher film forming speed.
This rotating cathode sputtering mode is being easy to be processed into drum and is extensively popularizing in the stronger metal targets of physical strength.But the intensity due to pottery is lower and more crisp, therefore easily to crack in the fabrication process or when engaging with base material etc. when being processed into drum, distortion etc.Therefore, for ceramic sputter targets, to universal in fact not yet fully realization of rotating cathode sputtering mode.
Because ITO (Indium-Tin-Oxide: tin indium oxide) film has higher penetrance and electroconductibility, therefore as flat-panel monitor transparency electrode and be widely used.Ito film is formed by sputtering ITO sputtering target usually.Ito film uses the SnO containing mass percent about 10% usually 2iTO sputtering target and by film forming, but in the purposes of touch panel etc., the SnO containing mass percent about 3% when the various substrates of film substrate etc. carry out film forming to ito film, can be used 2iTO sputtering target.
Known SnO 2less ITO material, the such as SnO of content 2content be that the ITO material of mass percent less than 7% is more crisp and easily crack.Especially SnO 2content be that the ITO material of mass percent less than 5% is more crisp and easily crack.In order to by this SnO 2content less ITO material when being used for the target of rotating cathode sputtering mode and being set to drum, be more prone to crack.In addition, at SnO as above 2content less ITO tubular sputtering target material also easily crack when engaging with base material.
Therefore, relative to SnO 2the less ITO tubular sputtering target material of content, when the manufacture of to process etc. and the time of joint, the Anti-cracking technology that needs are higher compared with common ceramic sputtering target material.
Patent Document 1 discloses a kind of following technology, that is, be set to below 0.2mm by the core shift of the ceramic cylindrical target by density being more than 98%, thus make thermal expansion evenly and then suppress crackle when engaging with cylindrical base material.But, in the art, as described in example 1 above, even if density is more than 98% and the core shift of round shape target is below 0.2mm also can crack.Can think, this is because at the thickness of the low melting point scolding tin for engaging and occur difference in implementing between the well heater that heats distance and make coefficient of thermal expansion change.
In patent documentation 2, describe following situation, that is, work as SnO 2concentration is grown by the grain of the exception caused because burning till and intensity is reduced when being less than 10%, and then cracks, and discloses a kind of following technology, that is, at SnO 2content be in the ITO sputtering target of mass percent 2.5 ~ 5.2%, by density is set to 7.1g/cm 3above, thus the crackle that minimizing sintered body produces, and the generation of crackle or caking is suppressed.But, there is following situation in the art, that is, cannot prevent density from being 7.1g/cm 3following ITO target cracks, even and if density be 7.1g/cm 3above, the ITO target of the higher drum of service efficiency also cracks sometimes.
At first technical literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2005-281862 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2012-126937 publication
Summary of the invention
Invent problem to be solved
The object of the invention is to, even a kind of drum easily to crack etc. is provided but be also not easy to crack in manufacturing procedure, the ITO sintered compact of distortion etc., be not easy to crack in bonding process, the manufacture method of the ITO sputtering target material of distortion etc., ITO sputtering target and described ITO sintered compact and ITO sputtering target material.
For solving the method for problem
ITO sintered compact of the present invention is that the content of Sn is with SnO 2amount is scaled mass percent 2.5 ~ 10.0%, and has In 2o 3parent phase be present in this In 2o 3the In at the grain boundary place of parent phase 4sn 3o 12the ITO sintered compact of phase,
The relative density of described ITO sintered compact is more than 98.0%, described In 2o 3the median size of parent phase is less than 17 μm, the described In in the cross section of this ITO sintered compact 4sn 3o 12the area occupation ratio of phase is more than 0.4%.
ITO sintered compact of the present invention can be set to round shape.
ITO sputtering target material of the present invention is made up of described ITO sintered compact.
ITO sputtering target of the present invention is formed by utilizing grafting material to be bonded on base material by tin indium oxide sputtering target material according to claim 3.
The manufacture method of ITO sintered compact of the present invention is,
Comprise the firing process that the ITO formed body be made up of ITO raw material powder is burnt till and the refrigerating work procedure that the burned material obtained in described firing process is cooled,
In described refrigerating work procedure, with the speed of cooling rate 25 DEG C/below h, the cooling in the temperature range below the firing temperature burnt till in the scope implementing 1200 ~ 1350 DEG C and to described tin indium oxide formed body.
The manufacture method of another kind of ITO sintered compact of the present invention is,
Comprise the firing process that the ITO formed body be made up of ITO raw material powder is burnt till and the refrigerating work procedure that the burned material obtained in described firing process is cooled,
In described refrigerating work procedure, with the speed of cooling rate 25 DEG C/below h, the cooling in the temperature range below the firing temperature burnt till in the scope implementing 1200 ~ 1500 DEG C and to described tin indium oxide formed body.
In the manufacture method of described ITO sintered compact, described ITO formed body and ITO sintered compact can be set to round shape.
The manufacture method of ITO target of the present invention is produced ITO sintered compact by described manufacture method, and processes obtained ITO sintered compact thus produce target.
Invention effect
Even if ITO sintered compact of the present invention is the drum easily to crack etc., be also not easy to crack in manufacturing procedure, distortion etc.Even if ITO sputtering target material of the present invention is the drum easily to crack etc., be also not easy to crack in the bonding process engaged with base material, distortion etc.Therefore, ITO sintered compact of the present invention and ITO sputtering target material can promote fabrication yield.
The manufacture method of ITO sintered compact of the present invention can produce described ITO sintered compact effectively.
Accompanying drawing explanation
Fig. 1 be ITO sintered compact of the present invention and ITO sputtering target material organize synoptic diagram.
Embodiment
Below, the manufacture method of ITO sintered compact involved in the present invention, ITO sputtering target material, ITO sputtering target, ITO sintered compact and ITO sputtering target material is described in detail.Although the ITO sintered compact that the present invention comprises and the shape of ITO sputtering target material are plate shaped or round shape etc. does not limit especially, especially larger effect can be obtained for the round shape easily cracking, be out of shape.
ITO sintered compact
ITO sintered compact of the present invention is that the content of Sn is with SnO 2amount is scaled mass percent 2.5 ~ 10.0%, and has In 2o 3parent phase be present in In 2o 3the In at the grain boundary place of parent phase 4sn 3o 12iTO sintered compact, relative density is more than 98.0%, described In 2o 3the median size of parent phase is less than 17 μm, the described In on the cross section of this ITO sintered compact 4sn 3o 12the area occupation ratio of phase is more than 0.4%.
Fig. 1 be represent ITO sintered compact of the present invention and ITO sputtering target material organize synoptic diagram.The figure of tissue image of Fig. 1 for obtaining when observing the cross section of ITO sintered compact of the present invention and ITO sputtering target material under being shown schematically in scanning electron microscope.In FIG, symbol 1 is In 2o 3parent phase, symbol 2 is In 4sn 3o 12phase.In 4sn 3o 122 are present in In mutually 2o 3the grain boundary place of parent phase 1.So-called In in the present invention 2o 3parent phase refers to, SnO 2a part is at In 2o 3upper solid solution and the In formed 2o 3phase.
In ITO sintered compact of the present invention, In 2o 3the median size of parent phase is less than 17 μm, is preferably 3 ~ 15 μm, is more preferably 5 ~ 15 μm.In herein 2o 3the particle diameter of parent phase can be tried to achieve as horizontal Feret's diameter on described tissue image.Horizontal Feret's diameter is that the particle observed by above-mentioned scanning electron microscope is resolved and by the value of trying to achieve.In 2o 3the median size of parent phase is, utilizes scanning electron microscope and carries out observation 10 visual field to the visual field of 100 μm × 130 μm at random in the mode of multiplying power 1000 times, and by for the whole In in each visual field contained by this visual field 2o 3parent phase and the value of the horizontal Feret's diameter of trying to achieve are averaged, thus calculate the mean level (ML) Feret's diameter of each visual field, and the value being averaged to the mean level (ML) Feret's diameter obtained in whole visual field further and obtaining.As described In 2o 3when the median size of parent phase is below 17 μm, ITO sintered compact is not easy to crack in manufacturing procedure, and the ITO sputtering target material obtained by this ITO sintered compact with the bonding process of base material in be not easy to crack or distortion etc.On the other hand, there is the situation that resistance rising is increased in grain boundary when median size is less, be therefore preferably In 2o 3the median size of parent phase is more than 3 μm.
In ITO sintered compact of the present invention, the In in this cross section 4sn 3o 12the area occupation ratio of phase is more than 0.4%, is preferably 0.5 ~ 5%, is more preferably 0.5 ~ 2.5%.In herein 4sn 3o 12the area occupation ratio of phase is, in the cross section of this ITO sintered compact, utilizes scanning electron microscope and carries out observation 10 visual field to the visual field of 33 μm × 43 μm at random in the mode of multiplying power 3000 times, and obtaining the In in each visual field 4sn 3o 12the total area of phase relative to visual field area (33 × 43 μm 2) percentile value, and the numerical value further described percentile value obtained in whole visual fields being averaged and obtaining.
As described In 2o 3the median size of parent phase be less than 17 μm and described area occupation ratio is more than 0.4% time, In 4sn 3o 12be present in grain boundary place in large area mutually, thus toughness is uprised and then cracking enhancing, therefore make ITO sintered compact become in manufacturing procedure and be more not easy to crack, and make the ITO sputtering target material that obtained by this ITO sintered compact with the bonding process of base material in be not easy to crack, distortion etc.On the other hand, from In 4sn 3o 12the viewpoint becoming the possibility of the Producing reason of electric arc in sputtering or caking mutually lower is set out, and described area occupation ratio is preferably less than 5%.
ITO sintered compact of the present invention is that the content of Sn is with SnO 2amount is scaled mass percent 2.5 ~ 10.0%.When the content of Sn is in described scope, can effectively utilize as sputtering target material, and processing, with the joint of base material in be not easy to crack or distortion etc.Especially when the content of Sn is with SnO 2amount is when being scaled mass percent 2.5 ~ 6.0%, can be produced the ITO sputtering target material of the transparency electrode etc. for the manufacture of flat-panel monitor or touch panel by ITO sintered compact of the present invention.In addition, as previously mentioned, the content of Sn is with SnO 2it is more crisp and easily crack that amount is scaled the existing ITO sintered compact of mass percent 2.5 ~ 6.0%, even if but the content of ITO sintered compact Sn of the present invention be also not easy to crack in described scope.And, when the content of Sn is with SnO 2amount when being scaled mass percent 3.0 ~ 5.0%, can produce useful described ITO sputtering target material, can effectively prevent in addition processing, with the crackle in the joint of base material or distortion etc.
The relative density of ITO sintered compact of the present invention is more than 98.0%, is preferably more than 98.5%, is more preferably more than 99.0%.When relative density is less than 98.0%, intensity is insufficient and easily crack.
That is, by meeting described In 2o 3the underlying condition of the median size of parent phase, described area occupation ratio and relative density, thus make ITO sintered compact of the present invention in manufacturing procedure, occur that the possibility of crackle is adequately suppressed, and then make the ITO sputtering target material obtained by this ITO sintered compact in the bonding process engaged with base material, occur that the possibility of crackle or distortion etc. is adequately suppressed.
Although the ITO sintered compact existing with drum easily cracks as previously mentioned, is out of shape, though ITO sintered compact of the present invention for drum be also not easy to crack in manufacturing procedure, distortion etc.Therefore, the ITO product of drum can suitably be produced by this ITO sintered compact of drum, such as ITO tubular sputtering target material etc.
The size of ITO sintered compact of the present invention does not limit especially.When ITO round shape sintered compact is processed into sputtering target material, its size is roughly external diameter 140 ~ 170mm, internal diameter 110 ~ 140mm, more than length 50mm.Length can be appropriately decided according to purposes.
ITO sputtering target material
ITO sputtering target material of the present invention is made up of described ITO sintered compact.ITO sputtering target material of the present invention by implementing suitable processing on described ITO sintered compact, such as machining etc. and being made into.
Therefore, ITO sputtering target material of the present invention meet with described ITO sintered compact content, relative density, the In of Sn that meet 2o 3the median size of parent phase and In 4sn 3o 12the full terms that the area occupation ratio of phase is relevant.About the explanation of these conditions of ITO sputtering target material of the present invention, with about in described ITO sintered compact the explanation of these conditions that describes identical.
Because ITO sputtering target material of the present invention meets above-mentioned condition, therefore intensity is higher and then be not easy to crack, be out of shape, even if thus be also not easy to crack or be out of shape for round shape.
When ITO sputtering target material is used to sputtering, utilizes scolding tin and be engaged with and be generally on the base material of titanium etc.When being set to ITO tubular sputtering target material, this joint is implemented usually in the following way, namely, target and cylindrical base material are heated, and scolding tin is applied in the inner peripheral surface of target and the outer surface of cylindrical base material, and in the cavity of target, insert cylindrical base material, and after both soldering-tin layers are bonded together, it is cooled.When carrying out this cooling, can make target produces stress because of the difference of the thermal expansivity between target and base material.Existing ITO tubular sputtering target material cannot overcome this stress completely, thus can make more to crack in bonding process.On the other hand, due to ITO sputtering target material of the present invention, intensity is higher as previously mentioned, even if be therefore round shape and produce described stress in bonding process to be also not easy to cause crackle, distortion.
ITO sputtering target
ITO sputtering target of the present invention is, is formed by utilizing grafting material to be engaged with base material by described ITO sputtering target material.
Described base material has the tabular or drum that sputtering target material can be engaged usually.The kind of base material does not limit especially, suitably can be carried out selecting and using from existing by the base material that uses.Material as base material include, for example out stainless steel, titanium etc.
The kind of described joint material does not also limit especially, suitably can be carried out selecting and using from existing by the joint material that uses.The scolding tin etc. of indium is include, for example out as grafting material.
Also multiple sputtering target material can be engaged on a base material.Such as, at outer side engagement ITO tubular sputtering target material of a base material, also two or more ITO tubular sputtering target material can be engaged on the same axis side by side.Under engaging plural situation side by side, the gap between each ITO tubular sputtering target material, namely the length of cutting part is generally 0.05 ~ 0.5mm.Although be more not easy during the shorter sputtering of the length of cutting part to produce electric arc, the target caused by bonding process or the thermal expansion in sputtering when being less than 0.05mm is impinging one another, thus cracks.
Method of joining does not also limit especially, can adopt the method identical with existing ITO sputtering target.
The manufacture method of ITO sintered compact
The manufacture method of described ITO sintered compact of the present invention comprises the firing process burnt till ITO formed body, and to the operation that the burned material obtained in described firing process cools, first method is, in described refrigerating work procedure, with the speed of cooling rate 25 DEG C/below h, implement in the scope of 1200 ~ 1500 DEG C, and the cooling in temperature range below the temperature that described ITO formed body is burnt till, second method is, in described refrigerating work procedure, with the speed of cooling rate 25 DEG C/below h, implement in the scope of 1200 ~ 1350 DEG C, and the cooling in temperature range below the temperature that described ITO formed body is burnt till, .
Specifically, by following manufacture method, thus under the condition not making crackle, distortion etc. produce, effectively can produce described ITO sintered compact of the present invention, but the manufacture method of ITO sintered compact of the present invention is not limited except above-mentioned manufacturing condition, and is not restricted to following manufacture method.
The preferred mode of the manufacture method of ITO sintered compact of the present invention comprises: operation 1, prepares particle by the slurries containing raw material powder and organic additive; Operation 2, carries out CIP to described particle shaping thus produce formed body; Operation 3, carries out degreasing to described formed body; Operation 4, burns till the formed body of described degreasing; Operation 5, cools the burned material obtained in described firing process.
(operation 1)
In operation 1, prepare particle by the slurries containing raw material powder and organic additive.
By preparing particle by raw material powder and organic additive, and the CIP this particle being supplied to operation 2 is shaping, thus can obtain the fillibility of raw material is promoted and highdensity formed body.In addition, be less likely to occur fill irregular and can fill equably.Punching press inequality is also less likely to occur.
As raw material powder, both In can be used 2o 3powder and SnO 2the mixed powder of powder, also can be used alone ito powder, or by ito powder and In 2o 3powder and SnO 2powder is used in combination.In the present invention, be used to the mixed powder of these raw material powders of the preparation of particle and ito powder when being used alone, this ito powder is called ITO raw material powder.Utilize BET (Brunauer-Emmett-Teller) method and the In determined 2o 3powder, SnO 2the specific surface area of powder and ito powder is respectively 1 ~ 40m usually 2/ g.In 2o 3powder, SnO 2the mixture ratio of powder and ito powder is appropriately decided in the mode of the content of the constitution element of this sintered compact in aforesaid scope.Such as, in final obtained sintered compact with SnO 2when the content of Sn that amount converts is mass percent 5.0%, with make in sintered compact with SnO 2the content of the Sn that amount converts becomes the mode of mass percent 5.0%, decides the ratio of each raw material powder comprised in ITO raw material powder.
In this manufacture method, by In 2o 3powder and SnO 2following situation can be confirmed, that is, the SnO in ITO raw material powder when the mixed powder of powder uses as ITO raw material powder 2the content (mass percent) of powder can be regarded as, in final obtained sintered compact and target with SnO 2the content (mass percent %) of the Sn that amount converts.In addition, following situation can be confirmed when ITO raw material powder comprises ito powder, that is, the SnO in ITO raw material powder 2the content (mass percent %) of powder with in ito powder with SnO 2the total of content (mass percent %) of the Sn that amount converts can be regarded as, in final obtained sintered compact and target with SnO 2the content (mass percent %) of the Sn that amount converts.
The blending means of powder is not limited especially, such as, each powder and zirconium white spheroid can be inserted in tank, and carry out ball milling mixing.
Described organic additive is, the material be added for suitably regulating the characteristic of slurries, formed body.As organic additive, tackiness agent, dispersion agent and softening agent etc. can be listed.
In operation 1, the amount of organic additive is preferably mass percent 0.3 ~ 2.0% relative to the amount of ITO raw material powder.When the described combined amount of organic additive is greater than mass percent 2.0%, occur that the intensity of the formed body in skimming processes reduces amplitude and will become large and become the situation easily producing degreasing cracking sometimes, or appear at degreasing aftershaping body hollow hole and increase and be difficult to the situation of densification.When the described combined amount of organic additive is less than mass percent 0.3%, the abundant effect of each composition cannot be obtained sometimes.When the combined amount of organic additive being set in described scope, the ITO sintered compact that relative density is more than 98.0% can be produced.
Tackiness agent is in order to be undertaken bonding by the ITO raw material powder in formed body thus the intensity improving formed body is added.As tackiness agent, usual used tackiness agent when obtaining formed body can be used in known powder sintering.
Dispersion agent is, in order to the dispersiveness improving raw material powder in slurries and tackiness agent is added.As dispersion agent, include, for example out poly carboxylic acid ammonium, ammonium polyacrylate etc.
Softening agent is, is added for the plasticity-improving formed body.As softening agent, include, for example out polyoxyethylene glycol (PEG), ethylene glycol (EG) etc.
The dispersion medium used when preparing the slurries containing raw material powder and organic additive does not limit especially, can suitably select from water, alcohol etc. according to object and use.
Contain in preparation in the method for the slurries of raw material powder and organic additive and do not limit especially, such as, can use and raw material powder, organic additive and dispersion medium are inserted in tank, and carry out the method for ball milling mixing.
Do not limit especially in the method being prepared particle by slurries, such as, can use spray-drying process, rotate comminution granulation, extruder grain method etc.Wherein, higher in the mobility of particle, easily produce the aspect of easily deformable particle time shaping, be preferably spray-drying process.Condition for spray-drying process does not limit especially, can suitably select usual used condition in the granulation of ITO raw material powder to implement.
(operation 2)
In operation 2, CIP shaping (ColdIsostaticPressing (cold isostatic compaction)) is carried out to the particle prepared by operation 1, thus produces formed body.The plate shaped sintered compact of ITO can being obtained when being set as plate shaped by the shape of formed body, ITO round shape sintered compact can be obtained when the shape of formed body being set as round shape.
Pressure when CIP is shaping is generally 800kgf/cm 2above.Pressure is larger, particle more can be made shaping densely, thus can make formed body densification and high strength.
(operation 3)
In operation 3, degreasing is carried out to the formed body produced by operation 2.Degreasing is implemented by heating formed body.
Skimming temp is generally 600 ~ 800 DEG C, is preferably 700 ~ 800 DEG C, is more preferably 750 ~ 800 DEG C.Although the intensity of the higher formed body of skimming temp is higher, due to when more than 800 DEG C, the contraction of formed body can be caused, therefore preferably below 800 DEG C, carry out degreasing.
(operation 4)
Burnt till by the formed body of degreasing in operation 3 in operation 4 i.e. firing process.
Calcining furnace is not limited especially, existing used calcining furnace in the manufacture of ITO sintered compact can be used in.
Firing temperature is generally 1450 ~ 1700 DEG C, is preferably 1500 ~ 1650 DEG C, is more preferably 1500 ~ 1600 DEG C.Although firing temperature is more high more can obtain highdensity sintered compact, will the sintering structure hypertrophyization of sintered compact be made and become easily to break when too high.Firing time is generally 3 ~ 30 hours, is preferably 5 ~ 20 hours, is more preferably 8 ~ 16 hours.The easier densification of the longer sintered compact of firing time, but when long, will the sintering structure hypertrophyization of sintered compact be made and become easily to break.
Heat-up rate is generally 100 ~ 500 DEG C/h.
The environment burnt till is generally oxygen atmosphere.
(operation 5)
In operation 5, the burned material obtained in operation 4 is cooled.In operation 5 i.e. refrigerating work procedure, make temperature reduce or be maintained fixing.
In the first method of the manufacture method of ITO sintered compact of the present invention, in temperature range (hereinafter also referred to specific range of temperatures) the scopes of 1200 DEG C ~ 1500 DEG C and below described firing temperature, cooling rate when cooling obtained burned material is set to 25 DEG C/below h, be preferably 20 DEG C/below h, be more preferably 15 DEG C/below h, more preferably 10 DEG C/below h.That is, when the firing temperature of formed body is more than 1500 DEG C, the cooling rate in the temperature range of 1200 DEG C ~ 1500 DEG C is set to 25 DEG C/below h.When the firing temperature of formed body is lower than 1500 DEG C, be set to 25 DEG C/below h by from the cooling rate in 1200 DEG C of temperature ranges to this firing temperature.Such as, when the firing temperature of formed body is 1450 DEG C, the cooling rate in the temperature range of 1200 ~ 1450 DEG C is set to 25 DEG C/below h.
When cooling the burned material obtained by burning till, at certain temperature, be solid-solubilized in In 2o 3the SnO of parent phase 2as In 4sn 3o 12separate out mutually.By at In 4sn 3o 12cool lentamente near the temperature separated out, thus can In be made 4sn 3o 12the area of phase becomes large, and can obtain described area occupation ratio.In addition its result is, can to In 2o 3the situation of particle diameter excessiveization of parent phase suppresses, and can obtain described In 2o 3the median size of parent phase.In 4sn 3o 12the temperature separated out is comprised in described specific range of temperatures usually.That is, in described specific range of temperatures, In is solid-solubilized in 2o 3the SnO of parent phase 2as In 4sn 3o 12separate out mutually.Therefore, by making the cooling rate of described specific range of temperatures be set to 25 DEG C/below h, can to In 4sn 3o 12the area occupation ratio of phase and In 2o 3the particle diameter of parent phase controls.Cooling rate in described specific range of temperatures is less, more can make In 4sn 3o 12the area of phase increases, thus can to In 2o 3excessiveization of the particle diameter of parent phase suppresses, thus comparatively preferred, and does not limit this lower value.
Cooling rate in specific range of temperatures, without the need to fixing, can change in the scope of 25 DEG C/below h, or also can there is cooling rate in specific range of temperatures and become the moment of 0 DEG C/h.
Temperature range beyond described specific range of temperatures, namely when the firing temperature of formed body is higher than 1500 DEG C, and when from the temperature range of this firing temperature to 1500 DEG C, be below 1500 DEG C lower than the firing temperature of the temperature ranges of 1200 DEG C, formed body, lower than in the temperature range of 1200 DEG C, cooling rate is generally 10 ~ 100 DEG C/h, be preferably 20 ~ 70 DEG C/h, be more preferably 20 ~ 50 DEG C/h.Although more little being more not easy of cooling rate produces because of the crackle caused by thermal stresses difference, usually also can not change lower than 10 DEG C/h thermal differential even if be set to.
In the second method of the manufacture method of ITO sintered compact of the present invention, in temperature range in the scope of 1200 DEG C ~ 1350 DEG C and below described firing temperature, cooling rate when cooling obtained burned material is set to 25 DEG C/below h, be preferably 20 DEG C/below h, be more preferably 15 DEG C/below h, more preferably 10 DEG C/below h.Second method is more effectively implement the mode of described first method.That is, second method can shorten the necessary time that operation spends more, or especially more critically controls the speed of cooling in the temperature range of 1200 DEG C important in organization formation ~ 1350 DEG C, thus can obtain required tissue.The implementation condition of second method is except the temperature range specified cooling rate, identical with described first method.
The environment of cooling is generally oxygen atmosphere.
By cooling described burned material thus obtaining ITO sintered compact.
By the manufacture method of above-mentioned ITO sintered compact, thus effectively can produce above-mentioned ITO sintered compact of the present invention.
The manufacture method of ITO round shape target
The manufacture method of ITO target of the present invention is, produces ITO sintered compact by the manufacture method of above-mentioned ITO sintered compact, and processes the ITO sintered compact obtained thus produce ITO target.Under normal circumstances, the plate shaped target of ITO can be produced when the shape of sintered compact is plate shaped, when for ITO round shape target can be produced during round shape.
The working method of ITO sintered compact suitably can be selected according to the ITO target as object.As described working method, include, for example out machining etc.
Embodiment
Based on embodiment, the present invention is specifically described further below.
The ITO sintered compact obtained in embodiment and comparative example and the evaluation method of ITO sputtering target material as described below.
1. relative density
The relative density of ITO sintered compact measures based on Archimedes method.Specifically, by the aerial weight of ITO sintered compact divided by volume (the water proportion in the water of ITO sintered compact in weight/measuring tempeature), and relative to the theoretical density ρ (g/cm based on following mathematical expression (X) 3) percentile value be set to relative density.(unit: %)
[mathematical expression 1]
ρ ≡ ( C i / 100 ρ 1 + C 2 / 100 ρ 2 + ... + C i / 100 ρ i ) - 1 ... ( x )
In mathematical expression (X), C 1~ C irepresent the content (weight percent %) of the structural material of sintered compact respectively, ρ 1~ ρ irepresent and C 1~ C idensity (the g/cm of each corresponding structural material 3).
The crackle of 2.ITO sintered compact and ITO sputtering target material
By visual observation ITO sintered compact and ITO sputtering target material, and confirm the presence or absence of the crackle (hereinafter also referred to engaging crackle) of this target when ITO sintered compact is added the crackle (hereinafter also referred to processing crackle) of this sintered compact in man-hour and engaged ITO sputtering target material.
3.In 2o 3the median size of parent phase
In 2o 3the median size of parent phase and the mean value of horizontal Feret's diameter can be tried to achieve in the following ways.Utilize sand paper #170, #320, #800, #1500, #2000, the cross section obtained being cut off ITO sintered compact by diamond cutter is periodically ground, finally carry out polishing and after being finish-machined to minute surface, (nitric acid (60 ~ 61% aqueous solution, Northeast chemistry (strain) system, nitric acid 1.38 deer 1 grade of production code member 28161-03), hydrochloric acid (35.0 ~ 37.0% aqueous solution, Northeast chemistry (strain) system, hydrochloric acid deer 1 grade of production code member 18078-01) and pure water are with volume ratio HCl:H at the etching solutions of 40 DEG C 2o:HNO 3the ratio mixing of=1:1:0.08) in dipping 9 minutes and etch, and utilize scanning electron microscope (JXA-8800-R, JEOL society system) to observe the surface of exposing.Doubly take pictures with multiplying power 1000 in optional 10 visual fields, thus obtain the tissue image of 100 μm × 130 μm.
Utilize particle analysis software (particle analysis Version3.0, technology Co., Ltd. of Sumitomo Metal Industries system), first the SEM picture of each phase followed the trail of and utilize scanner to carry out pattern recognition, and binaryzation is carried out to this image.Now, scaled value is set by the mode of μm unit representation with 1 pixel.Next, by selecting the horizontal Feret's diameter as measure the item, thus In is passed through 2o 3whole pixel counts of the horizontal direction of parent phase calculate horizontal Feret's diameter (μm).The mean value of the horizontal Feret's diameter be calculated in 10 visual fields is as In of the present invention 2o 3the median size of parent phase.
4.In 4sn 3o 12the area occupation ratio of phase
ITO sintered compact is implemented and above-mentioned " 3.In 2o 3the median size of parent phase " identical process, and utilize scanning electron microscope (JXA-8800-R, JEOL Inc.) to observe square section.Take pictures with multiplying power 3000 times of enforcements in optional 10 visual fields, thus obtain the tissue image of 33 μm × 43 μm.
Utilize particle analysis software (particle analysis Version3.0, technology Co., Ltd. of Sumitomo Metal Industries system), first the SEM picture of crystal grain followed the trail of and utilize scanner to carry out pattern recognition, and this image is carried out binaryzation.Now, in the mode of 1 pixel by μm unit representation, scaled value is set.Try to achieve In 4sn 3o 12the area of phase, and will relative to visual field area (33 × 43 μm 2) percentile value try to achieve as area occupation ratio.Using the mean value of area occupation ratio that obtains in 10 visual fields as the In in ITO sintered compact 4sn 3o 12the area occupation ratio of phase.
Embodiment 1
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 2.5% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
In this tank, as tackiness agent, adding relative to ITO raw material powder is the polyvinyl alcohol of mass percent 0.3%, and as dispersion agent, adding relative to ITO raw material powder is the poly carboxylic acid ammonium of mass percent 0.2%, as softening agent, adding relative to ITO raw material powder is the polyoxyethylene glycol of mass percent 0.5%, and as dispersion medium, and adding relative to ITO raw material powder is the water of mass percent 50%, and carry out ball milling mixing, thus prepare slurries.
These slurries are supplied in spray drying unit, and implement spraying dry under the condition of atomization rotating speed 14,000rpm, temperature in 200 DEG C, temperature out 80 DEG C, thus prepare particle.
By described particles filled in the mould of 300mm × 500mm, and at 200kgf/cm 2pressure under to utilize coldmoulding method to carry out shaping, thus produce flat interim formed body.
Vacuum-sealing is carried out to described interim formed body, and at 800kgf/cm 2pressure under to carry out CIP shaping, thus produce flat formed body.
Thermal debinding is added to this formed body.Skimming temp is set to 600 DEG C, and degreasing time is set to 10 hours, and heat-up rate is set to 20 DEG C/h in the temperature range to 400 DEG C, and is set to 50 DEG C/h in higher than the temperature range of 400 DEG C.
By by the formed body after degreasing in oxygen atmosphere, burn till with the condition of firing temperature 1500 DEG C, firing time 12 hours, heat-up rate 300 DEG C/h.Cooling rate in the temperature range of 1500 DEG C ~ 1200 DEG C is set to 10 DEG C/h, and the cooling rate beyond described temperature range is set to 50 DEG C/h, and obtained burned material is cooled.The relative density of the sintered compact obtained is 98.6%, In 2o 3the median size of parent phase is 7.0 μm, In 4sn 3o 12the area occupation ratio of phase is 0.8%.
Machining is carried out to the sintered compact obtained, thus produces the dull and stereotyped sputtering target material 30 of ITO of minor face 200mm, long limit 350mm, thickness 9mm.By above-mentioned processing, in 30,1 does not all crack.
On copper backboard, by In scolding tin, 9 described targets are combined into 1 row to make the opposite mode of the long leg of adjacent target, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.Engage and implement in the following manner, that is, under the condition of 150 DEG C, target and backboard are heated, and indium scolding tin is coated on the junction surface of target and backboard, and after both soldering-tin layers are bonded together, cool.
When confirming the target after joint, 1 does not all crack.
By the relative density of manufacturing condition, sintered compact, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase, processing crackle and the result engaging crackle are shown in Table 1.
About following embodiment 2 ~ 12, comparative example 1 ~ 5, also by the relative density of manufacturing condition, sintered compact, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase, processing crackle and the result engaging crackle are shown in Table 1.In addition, in Table 1, about processing crackle and engage in test body Y that " X/Y " this label table of crackle is shown in for being tested on X to create crackle.Such as, 1 in being shown in for testing sintered compact 30 about the label table of " 1/30 " of processing crackle creates crackle.
Embodiment 2
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 3% mixes, and carries out ball mill mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and adopt the method identical with embodiment 1, thus producing by the formed body of degreasing.
To being burnt till by the formed body of degreasing thus producing sintered compact.Burn till and be set as, in oxygen environment, firing temperature 1500 DEG C, firing time 12 hours, heat-up rate 300 DEG C/h.Cooling is set as, and be 20 DEG C/h, and the cooling rate beyond described temperature range is 50 DEG C/h from 1500 DEG C of cooling rates to 1200 DEG C.The density of the sintered body obtained is 98.8%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 9.5 μm, 0.5%.
Machining is carried out to obtained sintered compact, thus produces the dull and stereotyped sputtering target material 30 of ITO of minor face 200mm, long limit 350mm, thickness 9mm.By above-mentioned processing, in 30,1 does not all crack.
Similarly to Example 1, by In scolding tin, 9 described targets are bonded on copper backboard, thus produce ITO target.When confirming the target after joint, 1 does not all crack.
Embodiment 3
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 5% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use ITO raw material powder by the method identical with embodiment 1, thus produce by the formed body of degreasing.
Burn till by the formed body of degreasing, thus produce sintered compact.Burn till and be set as, under an oxygen atmosphere firing temperature 1500 DEG C, firing time 12 hours, heat-up rate 300 DEG C/h.Cooling is set as, and be 15 DEG C/h, and the cooling rate beyond described temperature range is 50 DEG C/h from 1500 DEG C of cooling rates to 1200 DEG C.The density of the sintered body obtained is 99.2%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 11.5 μm, 0.7%.
Machining is carried out to obtained sintered compact, thus produces the dull and stereotyped sputtering target material 30 of ITO of minor face 200mm, long limit 350mm, thickness 9mm.By above-mentioned processing, in 30,1 does not all crack.
Similarly to Example 1, by In scolding tin, 9 described targets are bonded on copper backboard, thus produce ITO target.When confirming the target after joint, 1 does not all crack.
Embodiment 4
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is with SnO 2the mode that the content of powder becomes mass percent 2.5% mixes, and carries out ball milling mixing with zirconium white spheroid in tank, thus prepares ITO raw material powder.
In this tank, as tackiness agent, adding relative to ITO raw material powder is the polyethylene alcohol of mass percent 0.3%, as dispersion agent, adding relative to ITO raw material powder is the poly carboxylic acid ammonium of mass percent 0.2%, as softening agent, adding relative to ITO raw material powder is the polyoxyethylene glycol of mass percent 0.5%, and as dispersion medium, adding relative to ITO raw material powder is the water of mass percent 50%, and carries out ball milling mixing thus prepare slurries.
These slurries are supplied to spray drying unit, and carry out spraying dry under the condition of atomization rotating speed 14000rpm, temperature in 200 DEG C, temperature out 80 DEG C, thus prepare particle.
Described particle is rapped while be filled in the urethanes type of the internal diameter 220mm (wall thickness 10mm) of the columned core (axle) with external diameter 150mm, the drum of length 450mm, and rubber-type is airtight after, with 800kgf/cm 2pressure to carry out CIP shaping, thus produce columnar formed body.
Thermal debinding is added to this formed body.Skimming temp is set to 600 DEG C, and degreasing time is set as 10 hours, and heat-up rate is set as 20 DEG C/h in the temperature range to 400 DEG C, in higher than the temperature range of 400 DEG C, be set as 50 DEG C/h.
To burn till by the formed body of degreasing under the condition of firing temperature 1500 DEG C, firing time 12 hours, heat-up rate 300 DEG C/h in oxygen atmosphere.Cooling rate in the temperature range of 1500 DEG C ~ 1200 DEG C is set to 10 DEG C/h, and the cooling rate beyond described temperature range is set to 50 DEG C/h, thus the burned material obtained is cooled.
The relative density of the sintered compact obtained is 98.8%, In 2o 3the median size of parent phase is 6.6 μm, In 4sn 3o 12the area occupation ratio of phase is 0.9%.
Machining is carried out to obtained sintered compact, thus produces the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.Machining is implemented in the following way, that is, utilize whetstone to process external diameter, and to be kept external diameter by fixture and after processing internal diameter, to be kept thus carry out the precision work of external diameter by fixture to internal diameter.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, in 30,1 does not all crack.
By In scolding tin, 9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.Engage and implement in the following manner, namely, under the condition of 150 DEG C, target and cylindrical base material are heated, and indium scolding tin is coated on the inner peripheral surface of target and the outer surface of cylindrical base material, and cylindrical base material is inserted in the cavity of target, and after both soldering-tin layers are bonded together, cool.
When confirming the target after joint, 1 does not all crack.
Embodiment 5
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is with SnO 2the mode that the content of powder becomes mass percent 3% mixes, and carries out ball milling mixing with zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and produced by the formed body of degreasing by the method identical with embodiment 4.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1470 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling is set as, and be 10 DEG C/h from 1470 DEG C of cooling rates to 1200 DEG C, the cooling rate beyond described temperature range is 50 DEG C/h.The density of the sintered body obtained is 98.1%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 4.2 μm, 0.8%.
Machining is carried out to obtained sintered compact, thus produces the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, in 30,1 creates crackle.
9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When confirming the target after joint, 1 does not all crack.
Embodiment 6
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the content of powder is that the mode of mass percent 3% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1520 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling is set as, and be 10 DEG C/h from 1500 DEG C of cooling rates to 1200 DEG C, the cooling rate beyond described temperature range is 50 DEG C/h.The density of the sintered body obtained is 98.5%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 10.8 μm, 0.9%.
By the method identical with embodiment 4, machining is carried out to obtained sintered compact, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, in 30, one does not all crack.
Similarly to Example 4,9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When confirming the target after joint, one does not all crack.
Embodiment 7
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the content of powder is that the mode of mass percent 3% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1500 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling is set as, and be 20 DEG C/h from 1500 DEG C of cooling rates to 1200 DEG C, the cooling rate beyond described temperature range is 50 DEG C/h.The density of the sintered body obtained is 98.4%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 9.2 μm, 0.4%.
By the method identical with embodiment 4, machining is carried out to obtained sintered compact, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, two in 30 create crackle.
Similarly to Example 4,9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, 1 creates crackle.
Embodiment 8
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 3% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4.Thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1550 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling is set as, and be 10 DEG C/h from 1500 DEG C of cooling rates to 1200 DEG C, the cooling rate beyond described temperature range is 50 DEG C/h.The density of the sintered body obtained is 99.2%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 13.1 μm, 1.0%.
By the method identical with embodiment 4, machining is carried out to the sintered compact obtained, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, in 30, one does not all crack.
Similarly to Example 4,9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When confirming the target after joint, one does not all crack.
Embodiment 9
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 5% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1470 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling is set as, and be 10 DEG C/h from 1470 DEG C of cooling rates to 1200 DEG C, the cooling rate beyond described temperature range is 50 DEG C/h.The density of the sintered body obtained is 98.2%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 5.3 μm, 2.2%.
By the method identical with embodiment 4, machining is carried out to the sintered compact obtained, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, in 30, one does not all crack.
Similarly to Example 4,9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When confirming the target after joint, one does not all crack.
Embodiment 10
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 5% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1520 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling is set as, and be 10 DEG C/h from 1500 DEG C of cooling rates to 1200 DEG C, the cooling rate beyond described temperature range is 50 DEG C/h.The density of the sintered body obtained is 99.2%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 11.3 μm, 1.8%.
By the method identical with embodiment 4, machining is carried out to the sintered compact obtained, thus produces the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, thus in 30 one all do not crack.
Similarly to Example 4,9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, there is no generation crackle.
Embodiment 11
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 5% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body of degreasing, thus produce sintered compact.Burn till and be set as, in oxygen environment, firing temperature is 1500 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling is set as, and be 15 DEG C/h from 1500 DEG C of cooling rates to 1200 DEG C, the cooling rate beyond described temperature range is 50 DEG C/h.The density of the sintered body obtained is 99.0%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 12.1 μm, 0.5%.
By the method identical with embodiment 4, machining is carried out to obtained sintered compact, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, in 30, one does not all crack.
Identical with embodiment 4,9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, there is no generation crackle.
Embodiment 12
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 5% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1600 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling is set as, and be 10 DEG C/h from 1500 DEG C of cooling rates to 1200 DEG C, the cooling rate beyond described temperature range is 50 DEG C/h.The density of the sintered body obtained is 99.5%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 14.9 μm, 1.3%.
By the method identical with embodiment 4, machining is carried out to the sintered compact obtained, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of the ITO tubular sputtering target material of 30.By above-mentioned processing, in 30, one does not all crack.
Identical with embodiment 4, by In scolding tin, 9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, there is no generation crackle.
Comparative example 1
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the content of powder is that the mode of mass percent 3% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 1, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1500 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling rate is set as, and in whole temperature ranges, cooling rate is 50 DEG C/h.The density of the sintered body obtained is 98.5%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 15.1 μm, 0.1%.
Machining is carried out to obtained sintered compact, thus produces the dull and stereotyped sputtering target material of ITO of 30 minor face 200mm, long limit 350mm, thickness 9mm.By above-mentioned processing, 9 in 30 create crackle.
Similarly to Example 1, by In scolding tin, 9 described targets are combined on copper backboard, thus produce ITO target.When target after joint is confirmed, 3 create crackle.
Comparative example 2
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 3% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares former ITO and expect powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1550 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling rate is set as, and in whole temperature range, cooling rate is 50 DEG C/h.The density of the sintered body obtained is 98.6%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 17.7 μm, 0.1%.
By the method identical with embodiment 4, machining is carried out to obtained sintered compact, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, thus in 30 12 create crackle.
Similarly to Example 4,9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, 4 create crackle.
Comparative example 3
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 3% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body of degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1400 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling rate is set as, and in whole temperature ranges, cooling rate is 50 DEG C/h.The density of the sintered body obtained is 97.6%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 11.6 μm, 0.2%.
By the method identical with embodiment 4, machining is carried out to obtained sintered compact, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, 8 in 30 create crackle.
Similarly to Example 4, by In scolding tin, 9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, two create crackle.
Comparative example 4
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 3% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares former ITO and expect powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1400 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling rate is set as, and in whole temperature ranges, cooling rate is 20 DEG C/h.The density of the sintered body obtained is 97.7%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 6.3 μm, 0.5%.
By the method identical with embodiment 4, machining is carried out to obtained sintered compact, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, 4 in 30 create crackle.
Similarly to Example 4,9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm by In scolding tin, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, 1 creates crackle.
Comparative example 5
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 3% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1520 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling rate is set as, and in whole temperature ranges, cooling rate is 30 DEG C/h.The density of the sintered body obtained is 98.6%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 18.1 μm, 0.3%.
By the method identical with embodiment 4, machining is carried out to obtained sintered compact, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, 6 in 30 create crackle.
Similarly to Example 4, by In scolding tin, 9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, 2 create crackle.
Comparative example 6
Be 5m by the specific surface area measured by BET method 2the SnO of/g 2powder is 5m with the specific surface area measured by BET method 2the In of/g 2o 3powder is to make SnO 2the mode that the content of powder becomes mass percent 5% mixes, and carries out ball milling mixing by zirconium white spheroid in tank, thus prepares ITO raw material powder.
Use this ITO raw material powder and by the method identical with embodiment 4, thus produce by the formed body of degreasing.
Burn till by the formed body after degreasing, thus produce sintered compact.Burn till and be set as, in oxygen atmosphere, firing temperature is 1550 DEG C, and firing time is 12 hours, and heat-up rate is 300 DEG C/h.Cooling rate is set to, and in whole temperature ranges, cooling rate is 50 DEG C/h.The density of the sintered body obtained is 98.6%, In 2o 3the median size of parent phase, In 4sn 3o 12the area occupation ratio of phase is respectively 18.3 μm, 0.3%.
By the method identical with embodiment 4, machining is carried out to obtained sintered compact, thus produce the ITO tubular sputtering target material of external diameter 153mm, internal diameter 135mm, length 300mm.By identical operation, implement the manufacture of 30 ITO tubular sputtering target materials.By above-mentioned processing, 9 in 30 create crackle.
Similarly to Example 4, by In scolding tin by and 9 described targets are bonded on the titanium backing pipe of external diameter 133mm, internal diameter 123mm, length 3200mm, thus produce ITO target.Interval (length of cutting part) between each target is set to 0.5mm.When target after joint is confirmed, 3 create crackle.
[table 1]
Nomenclature
1In 2o 3parent phase;
2In 4sn 3o 12phase.

Claims (8)

1. a tin indium oxide sintered compact, the content of its Sn is with SnO 2amount is scaled mass percent 2.5 ~ 10.0%, and has In 2o 3parent phase be present in this In 2o 3the In at the grain boundary place of parent phase 4sn 3o 12phase,
The relative density of described tin indium oxide sintered compact is more than 98.0%, described In 2o 3the median size of parent phase is less than 17 μm, and the described In on the cross section of this tin indium oxide sintered compact 4sn 3o 12the area occupation ratio of phase is more than 0.4%.
2. tin indium oxide sintered compact as claimed in claim 1, wherein,
Described tin indium oxide sintered compact is round shape.
3. a tin indium oxide sputtering target material, it is made up of the tin indium oxide sintered compact described in claim 1 or 2.
4. a tin indium oxide sputtering target, it is formed by utilizing grafting material to be bonded on base material by tin indium oxide sputtering target material according to claim 3.
5. a manufacture method for tin indium oxide sintered compact according to claim 1, comprising:
Firing process, burns till the tin indium oxide formed body be made up of tin indium oxide raw material powder;
Refrigerating work procedure, cools the burned material obtained in described firing process,
In described refrigerating work procedure, with the speed of cooling rate 25 DEG C/below h, the cooling in the temperature range below the firing temperature burnt till in the scope implementing 1200 ~ 1350 DEG C and to described tin indium oxide formed body.
6. a manufacture method for tin indium oxide sintered compact according to claim 1, comprising:
Firing process, burns till the tin indium oxide formed body be made up of tin indium oxide raw material powder;
Refrigerating work procedure, cools the burned material obtained in described firing process,
In described refrigerating work procedure, with the speed of cooling rate 25 DEG C/below h, the cooling in the temperature range below the firing temperature burnt till in the scope implementing 1200 ~ 1500 DEG C and to described tin indium oxide formed body.
7. the manufacture method of the tin indium oxide sintered compact as described in claim 5 or 6, wherein,
Described tin indium oxide formed body and tin indium oxide sintered compact are round shape.
8. a manufacture method for tin indium oxide target material, it manufactures tin indium oxide sintered compact by the manufacture method described in any one in claim 5 ~ 7, and processes obtained tin indium oxide sintered compact thus produce target.
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CN110257782A (en) * 2016-03-28 2019-09-20 Ｊｘ金属株式会社 Cylinder type sputtering target and its manufacturing method
CN110337507A (en) * 2017-04-07 2019-10-15 三菱综合材料株式会社 Cylinder type sputtering target and its manufacturing method
CN113149614A (en) * 2021-05-28 2021-07-23 通威太阳能（合肥）有限公司 Sintered body, target material and preparation method thereof

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