CN1218843A - Indium oxide/tin oxide sputtering target material and its preparing method - Google Patents
Indium oxide/tin oxide sputtering target material and its preparing method Download PDFInfo
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- CN1218843A CN1218843A CN 97108322 CN97108322A CN1218843A CN 1218843 A CN1218843 A CN 1218843A CN 97108322 CN97108322 CN 97108322 CN 97108322 A CN97108322 A CN 97108322A CN 1218843 A CN1218843 A CN 1218843A
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Abstract
The production of indium oxide/tin oxide (ITO) sputtering target material features the mass ratio of indium oxide to tin oxide in material being 9 : 1, average grain size 30-200 nm, purity 99.99%; cold isostatic pressure 200-280 MPa, constant-pressure period 10 min; hot isostatic temperature 1100-1300 deg.c, thermostatic period 0.5-6 hr; atmosphere pressure 100-120 MPa, and specially designed jacket and container. The ITO target material produced has high density, high purity and large size. The production method has high efficiency and low cost.
Description
The present invention relates to a kind of metal oxide target and manufacture method thereof that is used for sputter coating, particularly a kind of Indium sesquioxide/stannic oxide (ITO) target and manufacture method thereof that is applied to liquid crystal indicator.
With magnetron sputtering method is made indium tin metal oxide compound (ITO) target as sputter to glass surface transparent conductive film, require the high-quality ITO target of its process using.Yet, because Indium sesquioxide/stannic oxide limitation of characteristic such as decomposition easily at high temperature, so ITO target and manufacture method thereof are still being done unremitting research.Common manufacture method has sintering process, pressure sintering and hot isostatic pressing method, and just still there is defective in various degree in these methods:
Sintering process needs 2～10 atmospheric oxygen atmospheres, and the yielding cracking of product;
Graphite jig in the pressure sintering makes the indium metal/tin in the oxide compound be reduced into the lower valency material easily, and easily introduces contaminating impurity.
Though hot isostatic pressing method can overcome the shortcoming of above-mentioned sintering process, pressure sintering, used container in the heat and other static pressuring processes, what its material adopted is stainless steel, and a stainless steel vessel can only place a plate-like product, the shortcoming of existence also has:
1. need to remove stainless steel vessel with mechanical means in postprocessing working procedures, this often makes the interior product of container crack even ruptures;
2. sheet material of a container output, its production efficiency is low, and the loss that the grinding interlayer material brings all born by a sheet material, thus production cost increases.
The objective of the invention is to: overcome the weak point of prior art, not only produce high-density, high purity, large-sized Indium sesquioxide/stannic oxide (ITO) target, and its production cost reduces the production efficiency raising.
Technical scheme of the present invention is: Indium sesquioxide and tin oxider composite powder are packed into behind cold isostatic compaction in the special container, make the column target with hot isostatic pressing method, be cut into the product of polylith desired size then with wire cutting method, it is characterized in that:
A kind of metal oxide target that is used for sputter coating, its raw material adopts indium, tin metal oxide composite end, and the mass ratio of Indium sesquioxide and stannic oxide is 9: 1 in this composite powder, spherical in shape or the torispherical of powder, median size 30～200nm, purity 99.99%, hard aggregation-free.
A kind of method of making above-mentioned Indium sesquioxide/stannic oxide sputtering target material, with the powder of combined oxidation indium/stannic oxide deoxidation treatment in 1350 ℃, oxygen atmosphere, the jacket of packing into then, then isostatic cool pressing, cold isostatic pressure is 200～280MPa, 10 minutes dwell times, the isostatic cool pressing medium is an oil, and crude green body density is 45～55% of theoretical density after the isostatic cool pressing;
The jacket that isostatic cool pressing is used is designed to cylindrical or square column type, makes with rubber, and square body 1 transits to cylindrical by transition face 3 or elliptical cylinder-shape port 4, forms an integral body, so that tighten in the port;
Crude green body is packed in the carbon steel container of correspondingly-sized, between container and crude green body every with metal tantalum foil or nickel foil or niobium paper tinsel or platinum foil;
The preceding vacuumize degassing of container sealing of crude green body is housed;
Hip temperature is 1100～1300 ℃, soaking time 0.5～6 hour, and atmosphere pressures is 100～120MPa, the hot isostatic pressing medium is an argon;
With the molten carbon elimination steel container of rare nitric acid, stripping metal paper tinsel interlayer.
A kind of aforesaid method is made the special container of Indium sesquioxide/stannic oxide sputtering target material, is square column type or cylindrical, and this container is made by carbon steel, and container welds through argon arc, and port and end caps adopt arc transition, to avoid stress concentration.
Advantage of the present invention and positively effect:
1) compare sintering process and pressure sintering, strict control process parameters of the present invention and technological process produce high-density, high purity, large-sized ITO sputtering target material.Because Indium sesquioxide and stannic oxide uniform distribution and density height in this target, when with magnetron sputtering method it being sputtered onto glass surface, the transparent conductive film of making has uniform physicals and electrical property.
2) adopt cylindrical container to replace traditional plate to describe device, can once obtain the polylith plate-like product, and can reduce the metallic spacer layer stock removal of monolithic plate-like product, thereby enhance productivity, reduce production costs.
3) replace traditional stainless steel to make container material with carbon steel, thereby can use the container after chemical process rather than mechanical means are removed hot isostatic pressing.Can avoid the product crackle even the fracture that produce because of mechanical effect like this.
Be further described below in conjunction with accompanying drawing:
Fig. 1: the process flow sheet of making Indium sesquioxide/stannic oxide sputtering target material;
Fig. 2: rectangular cylindricality wrapping structure synoptic diagram; The 1-cylinder, the 2-wall, the 3-transition face,
The 4-port
The vertical view of Fig. 3: Fig. 2;
Fig. 4: square cylindricality wrapping structure synoptic diagram; 1 cylinder, the 2-wall, the 3-transition face,
The 4-port
The vertical view of Fig. 5: Fig. 4;
Fig. 6: cylindrical carbon steel container structural representation; The 1-cylinder, 2-end cap, 3-transition
Circular arc
The vertical view of Fig. 7: Fig. 6;
Fig. 8: square column type carbon steel container structural representation; The 1-cylinder, 2-end cap, 3-transition
Circular arc
The vertical view of Fig. 9: Fig. 8;
Fig. 1 has described technical process of the present invention:
At first make the chemically composited powder of indium tin oxide with chemical method or with free oxygen Change indium powder and monomer stannic oxide powder and be mixed and made into by a certain percentage the mechanical compound of them Powder. The mass ratio of indium oxide and tin oxide is 9: 1 in the composite powder, powder spherical in shape or Torispherical, the about 30～200nm of average grain diameter, purity 99.99%, hard aggregation-free. Then multiple Close powder and in 1350 ℃, oxygen atmosphere, make the deoxidation treatment of appropriateness. Then pack into cylindrical or Carry out isostatic cool pressing in the jacket of square column type, cold isostatic pressure is 200～280MPa, pressurize 10 minutes time, the isostatic cool pressing medium is oil, and crude green body density is solid density after the isostatic cool pressing 45～55%. The crude green body of isostatic cool pressing is packed in the special container in the corresponding size. Carbon steel Between container and the crude green body every with metal tantalum foil or nickel foil or niobium paper tinsel or platinum foil, with stop them it Between chemical reaction under HTHP. The container of crude green body is housed through vacuumizing sealing. Again will Airtight container is put into the high temperature insostatic pressing (HIP) stove and is carried out hip treatment. Hip temperature is 1100～1300 ℃, temperature retention time 0.5～6 hour, atmosphere pressures is 100～120MPa, The high temperature insostatic pressing (HIP) medium is argon. Dissolve carbon steel container with nitric acid behind the high temperature insostatic pressing (HIP), peel off the target table The interlayer of face obtains target. Target is cut into the product of required size with wire cutting method.
The jacket that isostatic cool pressing technology is used is square column type, makes with rubber, and square body 1 is by mistake Cross face 3 and transit to cylindrical or elliptical cylinder-shape port 4, form an integral body, in order to tighten.
The special container of hot isostatic pressing method is square column type or cylindrical, through argon arc welding. Cylinder 1 port section adopts transition arc 3 to connect with end cap 2, concentrates to avoid stress.
Embodiment:
Claims (8)
1. metal oxide target that is used for sputter coating, it is characterized in that: its raw material adopts indium, tin metal oxide composite end, the mass ratio of Indium sesquioxide and stannic oxide is 9: 1 in this composite powder, spherical in shape or the torispherical of powder, median size is 30～200nm, purity 99.99%, hard aggregation-free; Design specialized isostatic cool pressing jacket and hot isostatic pressing container, isostatic cool pressing---hot isostatic pressing method is made column Indium sesquioxide/stannic oxide target in employing, and cuts into the product of multi-disc desired size with wire cutting method.
2. make the described Indium sesquioxide of claim 1/stannic oxide sputtering target material for one kind, its manufacturing step comprises:
A. make composite metal oxide powder;
B. with the composite powder deoxidation treatment;
C. composite powder is packed into and carry out isostatic cool pressing in the jacket;
D. crude green body is packed in the container of corresponding size;
E. vacuumize sealing the container of crude green body is housed;
F. said vesse is put into the hot isostatic pressing stove and carried out hip treatment;
G. container is removed in pickling behind the hot isostatic pressing, and the stripping metal interlayer obtains target;
H. cut target with wire cutting method, obtain the product of desired size;
It is characterized in that:
1. the mass ratio of Indium sesquioxide and stannic oxide is 9: 1 in the composite powder described in a, and the spherical in shape or torispherical of powder, median size are 30～200nm, purity 99.99%, hard aggregation-free;
2. the deoxidation treatment described in the b, its Indium sesquioxide/tin oxider composite powder is handled in 1350 ℃ of oxygen atmospheres;
3. the cold isostatic pressure described in the c is 200～280MPa, and 10 minutes dwell times, the isostatic cool pressing medium is an oil, and crude green body density is 45～55% of theoretical density after the isostatic cool pressing;
4. the crude green body described in the d is packed in the container, between its container and the crude green body every with metal tantalum foil or nickel foil or niobium paper tinsel or platinum foil;
5. the hot isostatic pressing top temperature described in the f is 1100～1300 ℃, soaking time 0.5～6 hour, and argon atmospher pressure is 100～120MPa;
6. the rare nitric acid acidwashing of removal container described in the g.
3. method that realizes the described manufacturing Indium sesquioxide of claim 2/stannic oxide sputtering target material, it is characterized in that: the special-purpose jacket that described isostatic cool pressing is used, to make with rubber, square body 1 transits to cylindrical by transition face 3 or elliptical cylinder-shape port 4, form an integral body, be convenient to the port and tighten.
4. method that realizes the described manufacturing Indium sesquioxide of claim 2/stannic oxide sputtering target material, it is characterized in that: the special container that described hot isostatic pressing is used, be square column type or cylindrical, make by carbon steel, container welds through argon arc, and the port section of cylinder 1 adopts transition arc 3 to connect with end cap 2.
5. the method for manufacturing Indium sesquioxide according to claim 2/stannic oxide sputtering target material, it is characterized in that: make indium tin composite oxide power with chemical process, powder is torispherical, median size 30nm, with this kind composite powder isostatic cool pressing in the rubber package set of packing into, cold isostatic pressure 280MPa, 10 minutes dwell times, crude green body is of a size of φ 21 * 20mm, this base substrate is packed in the carbon steel container of corresponding size, interlayer material is the metal platinum foil, 1150 ℃ of hip temperatures, soaking time 0.5 hour, Ar Pressure 120MPa, the platinum interlayer is peelled off with the molten carbon elimination steel container of nitric acid in quiet back such as heat, obtains the target that density is 94.6% theoretical density.
6. the method for manufacturing Indium sesquioxide according to claim 2/stannic oxide sputtering target material, it is characterized in that: make composite oxide power with Indium sesquioxide and stannic oxide monomer powder, powder is torispherical, median size 80nm, the isostatic cool pressing in the rubber package set of in 1350 ℃ of oxygen atmospheres, packing into after the deoxidation treatment, isostatic cool pressing pressure 280MPa, 10 minutes dwell times, the back base substrate of colding pressing is packed into and is carried out hot isostatic pressing in the carbon steel container of corresponding size, interlayer material adopts the metal nickel foil, 1150 ℃ of hip temperatures, soaking time 3 hours, air pressure 128MPa, container is removed in pickling behind the hot isostatic pressing, target density reaches 96% of theoretical density, and right cylinder target line is cut into the disk shape product that five chip sizes are φ 90 * 8mm.
7. the method for manufacturing Indium sesquioxide according to claim 2/stannic oxide sputtering target material, it is characterized in that: make composite oxide power with Indium sesquioxide and stannic oxide monomer powder, powder is torispherical, median size 100nm, the isostatic cool pressing in the square column type rubber package set of in 1350 ℃ of oxygen atmospheres, packing into after the deoxidation treatment, isostatic cool pressing pressure 250MPa, 10 minutes dwell times, the isostatic cool pressing medium is an oil, and the base of colding pressing is packed into and carried out hot isostatic pressing in the square column type carbon steel container of corresponding size, and interlayer material adopts metal tantalum foil, 1200 ℃ of hip temperatures, soaking time 3 hours, Ar Pressure 120MPa, behind the hot isostatic pressing with the molten steel carbon vessel that goes of nitric acid, remove the target material surface interlayer, the square column type target is of a size of 180 * 60 * 50mm, and target density reaches 95% of theoretical density, cuts into the columnar product of 180 * 60 * 8mm with the line patterning method.
8. the method for manufacturing Indium sesquioxide according to claim 2/stannic oxide sputtering target material, it is characterized in that: with the indium tin combined oxidation powder isostatic cool pressing in the square column type rubber package set of doing to pack into after the appropriate deoxidation treatment, isostatic cool pressing pressure 230MPa, 10 minutes dwell times, the square column type crude green body is packed into and is carried out hot isostatic pressing in the carbon steel container of corresponding size, crude green body and carbon steel container are at interval with the metal niobium paper tinsel, 1200 ℃ of hip temperatures, soaking time 4 hours, Ar Pressure 120MPa, behind the hot isostatic pressing with the molten steel carbon vessel that goes of nitric acid, remove target material surface niobium interlayer, target density reaches 96% of theoretical density, and line cuts this column target and obtains the target product that multi-disc is of a size of 330 * 100 * 6mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108322A CN1120899C (en) | 1997-11-27 | 1997-11-27 | Indium oxide/tin oxide sputtering target material and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97108322A CN1120899C (en) | 1997-11-27 | 1997-11-27 | Indium oxide/tin oxide sputtering target material and its preparing method |
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| CN1218843A true CN1218843A (en) | 1999-06-09 |
| CN1120899C CN1120899C (en) | 2003-09-10 |
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| CN97108322A Expired - Fee Related CN1120899C (en) | 1997-11-27 | 1997-11-27 | Indium oxide/tin oxide sputtering target material and its preparing method |
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| CN1333103C (en) * | 2003-10-10 | 2007-08-22 | 桂林电子工业学院 | High-density ITO targe material and preparing method thereof |
| CN102173817A (en) * | 2011-01-30 | 2011-09-07 | 河北鹏达新材料科技有限公司 | Method for preparing indium tin oxide (ITO) target |
| CN101111627B (en) * | 2005-02-01 | 2012-05-09 | 东曹株式会社 | Sinter, sputtering target and molding die, and production process of sintered compact |
| CN102498233A (en) * | 2009-09-18 | 2012-06-13 | 株式会社钢臂功科研 | Metal oxide-metal composite sputtering target |
| CN103787651A (en) * | 2012-10-30 | 2014-05-14 | 宁波江丰电子材料有限公司 | Manufacturing method of indium-tin oxide target material |
| CN105624612A (en) * | 2016-03-29 | 2016-06-01 | 苏州方昇光电装备技术有限公司 | Metal evaporation device applied to evaporation coatings |
| CN107459345A (en) * | 2017-07-31 | 2017-12-12 | 洛阳晶联光电材料有限责任公司 | A kind of sintering method of indium tin oxide rotary target material |
| CN108218419A (en) * | 2018-01-15 | 2018-06-29 | 宁波纳诺特新材料科技有限公司 | A kind of preparation method of indium tin oxide ceramic target |
| CN108950494A (en) * | 2018-07-30 | 2018-12-07 | 常州苏晶电子材料有限公司 | The production method of strip molybdenum target material |
| CN109721356A (en) * | 2017-10-27 | 2019-05-07 | 辽宁法库陶瓷工程技术研究中心 | The preparation method of thermal barrier coating large scale zirconia ceramics target |
| CN111763914A (en) * | 2020-06-12 | 2020-10-13 | 厦门虹鹭钨钼工业有限公司 | Method for controlling content of non-metal elements in tungsten-silicon target material |
| CN112592173A (en) * | 2020-12-15 | 2021-04-02 | 株洲火炬安泰新材料有限公司 | Preparation method of ITO (indium tin oxide) sintered target material |
| CN113999000A (en) * | 2021-10-21 | 2022-02-01 | 宁波江丰电子材料股份有限公司 | Method for recycling ITO waste target |
| CN114436642A (en) * | 2020-11-06 | 2022-05-06 | 湖南七点钟文化科技有限公司 | Preparation method of indium tin oxide alloy target material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4407774C1 (en) * | 1994-03-09 | 1995-04-20 | Leybold Materials Gmbh | Target for cathode sputtering to produce transparent, conductive layers, and method for the fabrication thereof |
| JPH08246140A (en) * | 1995-03-03 | 1996-09-24 | Sumitomo Metal Mining Co Ltd | Oxide sintered compact |
| JPH0931634A (en) * | 1995-07-13 | 1997-02-04 | Kobe Steel Ltd | Ito sputtering target and its production |
| EP0761838B1 (en) * | 1995-08-18 | 2001-08-08 | W.C. Heraeus GmbH & Co. KG | Sputtering target and method for its manufacturing |
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1997
- 1997-11-27 CN CN97108322A patent/CN1120899C/en not_active Expired - Fee Related
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| CN1333103C (en) * | 2003-10-10 | 2007-08-22 | 桂林电子工业学院 | High-density ITO targe material and preparing method thereof |
| US9920420B2 (en) | 2005-02-01 | 2018-03-20 | Tosoh Corporation | Sintered body, sputtering target and molding die, and process for producing sintered body employing the same |
| CN101111627B (en) * | 2005-02-01 | 2012-05-09 | 东曹株式会社 | Sinter, sputtering target and molding die, and production process of sintered compact |
| US8419400B2 (en) | 2005-02-01 | 2013-04-16 | Tosoh Corporation | Sintered body, sputtering target and molding die, and process for producing sintered body employing the same |
| CN102498233A (en) * | 2009-09-18 | 2012-06-13 | 株式会社钢臂功科研 | Metal oxide-metal composite sputtering target |
| CN102173817A (en) * | 2011-01-30 | 2011-09-07 | 河北鹏达新材料科技有限公司 | Method for preparing indium tin oxide (ITO) target |
| CN103787651A (en) * | 2012-10-30 | 2014-05-14 | 宁波江丰电子材料有限公司 | Manufacturing method of indium-tin oxide target material |
| CN103787651B (en) * | 2012-10-30 | 2015-07-08 | 宁波江丰电子材料股份有限公司 | Manufacturing method of indium-tin oxide target material |
| CN105624612A (en) * | 2016-03-29 | 2016-06-01 | 苏州方昇光电装备技术有限公司 | Metal evaporation device applied to evaporation coatings |
| CN107459345A (en) * | 2017-07-31 | 2017-12-12 | 洛阳晶联光电材料有限责任公司 | A kind of sintering method of indium tin oxide rotary target material |
| CN107459345B (en) * | 2017-07-31 | 2020-06-09 | 洛阳晶联光电材料有限责任公司 | Sintering method of indium tin oxide rotary target material |
| CN109721356A (en) * | 2017-10-27 | 2019-05-07 | 辽宁法库陶瓷工程技术研究中心 | The preparation method of thermal barrier coating large scale zirconia ceramics target |
| CN108218419A (en) * | 2018-01-15 | 2018-06-29 | 宁波纳诺特新材料科技有限公司 | A kind of preparation method of indium tin oxide ceramic target |
| CN108218419B (en) * | 2018-01-15 | 2020-12-01 | 宁波纳诺特新材料科技有限公司 | Preparation method of indium tin oxide ceramic target material |
| CN108950494A (en) * | 2018-07-30 | 2018-12-07 | 常州苏晶电子材料有限公司 | The production method of strip molybdenum target material |
| CN111763914A (en) * | 2020-06-12 | 2020-10-13 | 厦门虹鹭钨钼工业有限公司 | Method for controlling content of non-metal elements in tungsten-silicon target material |
| CN114436642A (en) * | 2020-11-06 | 2022-05-06 | 湖南七点钟文化科技有限公司 | Preparation method of indium tin oxide alloy target material |
| CN112592173A (en) * | 2020-12-15 | 2021-04-02 | 株洲火炬安泰新材料有限公司 | Preparation method of ITO (indium tin oxide) sintered target material |
| CN113999000A (en) * | 2021-10-21 | 2022-02-01 | 宁波江丰电子材料股份有限公司 | Method for recycling ITO waste target |
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