WO2014021334A1 - Corps d'oxyde fritté et cible de pulvérisation - Google Patents

Corps d'oxyde fritté et cible de pulvérisation Download PDF

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WO2014021334A1
WO2014021334A1 PCT/JP2013/070632 JP2013070632W WO2014021334A1 WO 2014021334 A1 WO2014021334 A1 WO 2014021334A1 JP 2013070632 W JP2013070632 W JP 2013070632W WO 2014021334 A1 WO2014021334 A1 WO 2014021334A1
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Prior art keywords
sintered body
target
powder
pores
oxide
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PCT/JP2013/070632
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English (en)
Japanese (ja)
Inventor
健治 尾身
原　慎一
向後　雅則
謙一 伊藤
哲夫 渋田見
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東ソー株式会社
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Priority claimed from JP2012168553A external-priority patent/JP5998712B2/ja
Priority claimed from JP2012183562A external-priority patent/JP5904056B2/ja
Application filed by 東ソー株式会社 filed Critical 東ソー株式会社
Publication of WO2014021334A1 publication Critical patent/WO2014021334A1/fr

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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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    • C04B2235/95—Products characterised by their size, e.g. microceramics
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
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    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/407—Copper

Definitions

  • the present invention relates to an oxide sintered body mainly composed of indium, gallium, zinc, and oxygen, which is suitable for a semiconductor film sputtering target (IGZO target).
  • IGZO target semiconductor film sputtering target
  • An oxide containing indium oxide-gallium oxide-zinc oxide (also referred to as IGZO) or an oxide semiconductor film containing these as a main component has an advantage of higher mobility than an amorphous silicon film, and high mobility is required.
  • Application is progressing as an organic EL thin film transistor (TFT) device.
  • TFT organic EL thin film transistor
  • the formation of the IGZO thin film is generally performed by a sputtering method using an IGZO sintered body because a large area can be easily obtained and a high performance film can be obtained.
  • a sputtering method using an IGZO sintered body because a large area can be easily obtained and a high performance film can be obtained.
  • Variation in IGZO thin film characteristics is a problem in which the elemental composition ratio of In, Ga, and Zn in an IGZO thin film formed by a sputtering method fluctuates with an increase in target usage rate.
  • Patent Document 1 has already pointed out that the thin film composition is likely to fluctuate when a plurality of crystal phases are present in the sintered body, but it is actually a target composed only of a homologous single-phase structure.
  • the crystal structure of the IGZO sintered body often includes a homologous crystal structure having a highly anisotropic layered structure, and therefore is caused by extremely low strength.
  • Patent Document 2 shows that the bending strength is increased to 58 MPa by using a crystal layer containing a spinel structure.
  • the bending strength 14.3 kg / mm ⁇ 2 > (about 140 MPa) is obtained by setting it as the crystal phase containing a spinel structure and a bixbite.
  • these methods limit the composition of the IGZO film, the composition ratios of In, Ga, and Zn in the IGZO sintered body cannot be determined as appropriate in order to optimize the film characteristics.
  • Patent Document 4 a metal element having a positive tetravalent or higher of 100 ppm to 10,000 ppm is contained in the IGZO target, and the sintered body is obtained. Is reduced to less than 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm to reduce arcing.
  • the characteristics of the IGZO film may be deteriorated, so that it is not an effective method.
  • An object of the present invention is to improve the characteristic variation of an IGZO thin film, which is a problem of a large-sized sputtering target for an oxide semiconductor film, and to improve the generation of cracks during target production and sputtering.
  • An object of the present invention is to provide an oxide sintered body suitable for an IGZO sputtering target having a high quality and a high yield that is optimum for the application.
  • the present inventors have obtained a sintered body having a homologous crystal structure represented by InGaZnO 4 , and the crystal grain size, relative density, and bending strength of the sintered body are constant values. Oxidation that improves cracking during sputtering even when used as a cylindrical sputtering target capable of supplying high power, as well as improving the yield in large-size target manufacturing required for mass production equipment.
  • the present inventors have found that a sintered product can be obtained and have completed the present invention.
  • the present invention has the following gist.
  • the oxide sintered body of the present invention it is possible to improve the yield in the production of a large size target required in a mass production apparatus, and also when used as a cylindrical sputtering target capable of supplying high power, during sputtering.
  • a sputtering target capable of suppressing the occurrence of cracks is possible.
  • FIG. 2 is a microcrack observation photograph of a sintered body test piece shown in Example 1-2. The numbers in the photographs indicate the observed microcracks. It is a microcrack observation photograph of the sintered compact test piece shown in Comparative Example 1-2. The relationship between the bending strength and the pore number ratio (grain boundary / inside grain) of the IGZO sintered bodies obtained in Examples 2-5 to 2-9 and Comparative Examples 2-3 to 2-5 is shown.
  • FIG. FIG. 3 is a graph showing the relationship between the Zr concentration of the IGZO sintered bodies obtained in Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-7 and the relative density of the sintered bodies.
  • FIG. 6 is a graph showing the relationship between the Zr concentration and the transmittance of the IGZO films obtained in Example 3-1 to Example 3-4 and Comparative Example 3-1 to Comparative Example 3-7.
  • FIG. 6 is a schematic cross-sectional view showing the structure of TFT elements fabricated in Example 3-1 to Example 3-4 and Comparative Example 3-1 to Comparative Example 3-7.
  • FIG. 7 is a graph showing the relationship between the Zr concentration and mobility of TFT elements obtained in Example 3-1 to Example 3-4 and Comparative Example 3-1 to Comparative Example 3-7.
  • the oxide sintered body of the present invention is a sintered body that includes at least indium, gallium, zinc, and oxygen and has a homologous crystal structure represented by InGaZnO 4 .
  • the “sintered body having a homologous crystal structure represented by InGaZnO 4 ” referred to in the present invention refers to a sintered body having an X-ray diffraction pattern including a peak that matches the diffraction pattern of InGaZnO 4 .
  • X-ray diffraction pattern is consistent with the diffraction pattern of InGaZnO 4, the peaks that are not attributable to the diffraction pattern of InGaZnO 4 It means not included.
  • the oxide sintered body has a homologous crystal structure represented by InGaZnO 4 , the crystal grain size of the oxide sintered body is 5 ⁇ m or less, the relative density is 95% or more, and the oxide sintered body An oxide sintered body having a bending strength of 100 MPa or more becomes an IGZO sintered body without cracks even when the sintered body is produced and when used as a sputtering target.
  • the crystal grain size of the oxide sintered body of the present invention is 5 ⁇ m or less, preferably 4.5 ⁇ m or less, more preferably 4 ⁇ m or less.
  • the relative density of the oxide sintered body of the present invention is 95% or more, preferably 97% or more, more preferably 98% or more, and further preferably 99% or more. If a sintered body having a relative density of less than 95% is used as a target, abnormal discharge may easily occur during sputtering.
  • the bending strength of the oxide sintered body of the present invention is 100 MPa or more, preferably 150 MPa or more, more preferably 200 MPa or more, but usually 300 MPa or less. If the strength of the oxide sintered body is high, cracks are less likely to occur during grinding, and the yield is high, so the productivity is good. Furthermore, even when used for a cylindrical sputtering target in which high power is applied during sputtering, the problem of cracking is unlikely to occur.
  • the open pore ratio of the oxide sintered body of the present invention is preferably 0.2% or less, more preferably 0.15% or less, and particularly preferably 0.1% or less. Usually, it is 0.001% or more.
  • Open pores refer to voids (holes and cracks) having an open path to the outermost surface of the sintered body, and not only when the voids open directly to the surface of the sintered body, but also other voids. It refers to a void that is open to the surface while passing through.
  • the open pore ratio refers to the ratio of the open pore volume to the total volume of the sintered body volume and the open pore volume.
  • the number of microcracks having a length of 3 ⁇ m or more existing in the range of 60 ⁇ m ⁇ 80 ⁇ m of the sintered body is preferably 20 or less, and preferably 10 or less. Is more preferable. More preferably, it does not have a crack of 15 ⁇ m or more in length.
  • this number of microcracks increases, the composition variation of the thin film tends to become more prominent when used as a target. This is thought to be due to the fact that zinc atoms struck out from the target are scattered by water molecules because the water is adsorbed and contained in the crack layer, and the compositional variation of zinc occurs.
  • the diffraction intensity when the incident angle (2 ⁇ ) in X-ray diffraction is 30.3 ° to 30.9 ° is I 1
  • the diffraction intensity is 31.1 ° to 31.5 °.
  • the intensity ratio I 1 / I 2 is preferably 0.85 or more and 1.25 or less, and more preferably 0.90 or more and 1.10 or less.
  • the increase in the diffraction intensity ratio I 1 / I 2 indicates that the growth of the InGaZnO 4 crystal phase in the C-axis direction is selectively advanced.
  • the number of microcracks is reduced by setting the value of the diffraction intensity ratio to a certain value or less. It becomes easy to obtain a sintered body. On the other hand, when the diffraction intensity ratio is less than 0.85, it is difficult to obtain a desired sintered body density, which leads to a decrease in strength and abnormal discharge during sputtering.
  • the ratio of the number of pores existing in the crystal grain boundary to the number of pores existing in the crystal grain is 0.5. Preferably, it is 1 or more, more preferably 1 or more, and particularly preferably 3 or more, but usually 10 or less. If pores exist in the crystal grains, it becomes a fracture source and the strength of the sintered body is significantly reduced. Therefore, it is better that there are fewer pores in the crystal grains, and the pores present in the grains are reduced. The ratio of pores existing in the grains (the number of pores in the grain boundary / the number of pores in the crystal grains) is increased.
  • the oxide sintered body of the present invention preferably contains zirconium in a weight ratio of 20 ppm or more and less than 100 ppm, more preferably 30 ppm or more, and particularly preferably 40 ppm or more.
  • zirconium content is less than 20 ppm, there is no effect of the relative density and strength of the sintered body.
  • the zirconium content is 100 ppm or more, the transmittance of the produced IGZO film starts to decrease, and the TFT element using the IGZO film The field effect mobility (hereinafter referred to as “mobility”) also gradually decreases. Since the TFT element has a higher mobility, the performance of the flat panel display (FPD) is improved.
  • FPD flat panel display
  • the IGZO sintered body contains an amount of impurities that decrease the mobility.
  • the mobility value is preferably as high as possible, and is preferably 15.0 cm 2 / V ⁇ s or more.
  • the zirconium content in the sintered body can be measured by ICP (inductively coupled plasma) analysis.
  • the composition formula is represented by InGaZnO x
  • the value of the oxygen content x in the composition formula is preferably 3.3 ⁇ x ⁇ 4.0. More preferably, 3 ⁇ x ⁇ 3.6.
  • the oxygen content with a value of x less than 4.0 is obtained by causing defects in part of the oxygen element that is a constituent element of the homologous crystal structure represented by InGaZnO 4 .
  • the strength of the oxide sintered body can be further improved, and arcing and particle generation during sputtering can be further reduced. It becomes possible.
  • the IGZO film produced using this sintered body is excellent in the flatness of the thin film surface, and has the effect of improving the stability of TFT characteristics.
  • indium oxide sintered body, the ratio of gallium and zinc are not particularly limited as long as it is a composition containing a homologous crystal structure represented by InGaZnO 4, having only the homologous crystal structure represented by InGaZnO 4 Sintered bodies are particularly suitable because of the great effect of the present invention.
  • the raw material powder is not particularly limited.
  • metal salt powders such as indium, gallium, zinc chloride, nitrate, carbonate, etc. can be used.
  • Oxide powder is then preferred.
  • the purity of each raw material powder is preferably 99.9% or more, more preferably 99.99% or more. This is because if the purity is low, the impurities contained may adversely affect the TFT formed by the sputtering target using the oxide sintered body of the present invention.
  • the composition of these raw materials is not particularly limited as long as it is a composition that generates a homologous crystal structure represented by InGaZnO 4.
  • the atomic ratio of the metal element is converted.
  • the physical properties of the raw material powder are not particularly limited, but in order to obtain suitable powder physical properties by the powder processing
  • the specific surface area and the average particle diameter of each raw material powder are preferably as follows. Specific surface area of indium oxide: 10.0 to 13.0 m 2 / g and average particle diameter: 0.9 to 1.3 ⁇ m, specific surface area of gallium oxide: 10.0 to 17.0 m 2 / g and average particle diameter: The specific surface area of zinc oxide is 3.0 to 15.0 m 2 / g and the average particle size is 0.2 to 1.5 ⁇ m.
  • the zinc oxide raw material it is easier to obtain suitable powder physical properties by using a powder having a specific surface area of 10.0 to 13.0 m 2 / g and an average particle diameter of 0.20 to 0.35 ⁇ m. Therefore, it is particularly preferable.
  • the processing method of the powder is not particularly limited, but includes dry type using a ball or bead such as alumina or nylon resin, wet type media stirring mill, medialess container rotary mixing, mechanical stirring type mixing, etc.
  • a mixing method is exemplified. Specific examples include a ball mill, a bead mill, an attritor, a vibration mill, a planetary mill, a jet mill, a V-type mixer, a paddle mixer, and a twin-shaft planetary agitation mixer.
  • the amount of raw material powder is adjusted in consideration of the amount of zirconium mixed from them.
  • the specific surface area of the powder after grinding / mixing is in the range of 12.0-15.0 m 2 / g and the average particle size is in the range of 0.35-0.45 ⁇ m,
  • the raw material powder satisfying that the crystallite diameter of zinc oxide in the mixed powder after the treatment is 60 nm or less is preferable.
  • the specific surface area of the powder after pulverization and mixing is more preferably in the range of 12.5 to 14.5 m 2 / g.
  • the treated powder is preferably 2.1% or less, more preferably 1.3% or less, in a temperature range where the volume expansion coefficient of the molded body produced from the powder is 300 to 750 ° C. % Is particularly preferable, and in the temperature range of 1000 to 1200 ° C., it is preferably 4.2% or less, more preferably 2.5% or less, and 0.13% or less. Particularly preferred.
  • the volume expansion coefficient in the present application is an index mainly showing the uniform mixing property of each raw material powder.
  • the dispersion state of each raw material in the mixed powder is not appropriate, severe volume expansion occurs in the process of forming InGaZnO 4 in the firing step, which causes firing cracks.
  • the risk of firing cracks of a large-sized target is greatly reduced even at a relatively high rate of temperature increase.
  • calcination can be performed at 900 to 1200 ° C. after mixing.
  • the calcined powder is preferably pulverized to have an average particle size of 1.0 ⁇ m or less, more preferably 0.1 to 1.0 ⁇ m.
  • molding aids such as polyvinyl alcohol, acrylic polymer, methylcellulose, waxes, and oleic acid may be added to the raw material powder.
  • the solid content concentration in the slurry is 30% to 70%, more preferably 40% to 55%. If the solid content concentration becomes too high, the processing ability is lowered, and desired powder physical properties cannot be obtained. In particular, zinc oxide tends to cause an increase in viscosity and greatly impairs the mixing property with other raw materials, so it is important to adjust it within an appropriate range.
  • the grinding media zirconia beads having high grinding ability are used, and the bead diameter is in the range of ⁇ 0.2 mm to ⁇ 0.4 mm.
  • the total amount of beads charged into the mill is in the range of 5.0 to 6.5 kg, and the bead filling rate relative to the mill volume is in the range of 75 to 85%.
  • the slurry temperature also needs to be strictly controlled, and the mill inlet slurry temperature must be controlled to 15 ° C. or lower, preferably 12 ° C. or lower, and constantly controlled so that the slurry temperature at the mill outlet is 21 ° C. or lower. . Since the slurry temperature rapidly rises due to the milling process, it is preferable to provide the slurry tank with an appropriate cooling mechanism.
  • the type of the dispersant is not particularly limited, but in particular, it is necessary to suppress the change in the slurry viscosity of the zinc oxide powder within a certain range. For this reason, the slurry pH is adjusted to be in the vicinity of the neutral range of 5-9.
  • the amount of the dispersant added is large, the strength of the powder granule after spray drying becomes too high, which leads to a decrease in strength of the molded product and causes fire cracking of the molded product. For this reason, it is necessary to make addition amount smaller than general addition amount, 0.9 wt% or less is preferable, and 0.7 wt% or less is more preferable.
  • Efficient slurry supply to the mill is 0.6 L / min to 1.5 L / min for 1 to 2 passes, which is a heavy burden on the mill, and 1.5 L / min to 3.1 L / min thereafter.
  • the peripheral speed of the mill is set in the range of 5.5 m / sec to 9.5 m / sec, and more preferably in the range of 6.0 m / sec to 8.0 m / sec.
  • the slurry viscosity may increase due to some factor even under the same conditions. In this case, the amount of the dispersant is appropriately added within the above range, and the slurry viscosity is always set to 3000 mPa ⁇ s. It is important to keep the processing stable.
  • a mixed powder having desired physical property values can be obtained by performing pulverization by circulating for 5 to 20 passes, more preferably 5 to 15 passes. If the number of passes is insufficient, it not only causes firing cracks but also makes it difficult to obtain a high-density sintered body. In order to obtain a high-density sintered body, high-temperature or long-time firing is required, and microcracks are likely to be generated inside as in the case of a conventional IGZO sintered body.
  • the final powder state when wet-mixing is performed is not particularly limited.
  • a wet molding method such as cast molding
  • the slurry can be used as it is.
  • the granulation method is not particularly limited, and spray granulation, fluidized bed granulation, rolling granulation, stirring granulation, and the like can be used.
  • spray granulation which is easy to operate and can be processed in large quantities.
  • the molding method can be appropriately selected a molding method capable of molding the raw material powder (or calcined mixed powder if calcined) into a desired shape, and is not particularly limited. Absent. Examples thereof include a press molding method, a casting molding method, and an injection molding method.
  • the molding pressure is not particularly limited as long as it does not cause cracks in the molded body and can be handled, but it is preferable to increase the molding density as much as possible. Therefore, it is also possible to use a method such as cold isostatic pressing (CIP) molding.
  • CIP pressure is preferably for 1 ton / cm 2 or more to obtain a sufficient consolidation effect, more preferably 2 ton / cm 2 or more, especially preferably 2 ⁇ 3ton / cm 2.
  • the binder when the first molding is performed by a casting method and then CIP is performed, the binder may be removed for the purpose of removing moisture and organic substances such as binder remaining in the molded body after CIP. Good. Further, even when the first molding is performed by the press method, the same debinding treatment can be performed when a binder or the like is added in the raw material mixing step.
  • the firing method can use various firing methods (atmospheric pressure sintering, pressure sintering, etc.) suitable for the sintering behavior of the raw material powder, and is not particularly limited. , HIP (isotropic hot pressing), HP (hot pressing), an electromagnetic firing furnace, and the like can be used, but electromagnetic heating is particularly preferable.
  • HIP isotropic hot pressing
  • HP hot pressing
  • an electromagnetic firing furnace and the like can be used, but electromagnetic heating is particularly preferable.
  • electromagnetic wave heating since the sintered body itself is heated from the inside, the sintering proceeds uniformly from the center of the sintered body in an open pore state, and the pores are discharged out of the sintered body. The product has a small temperature distribution and is difficult to crack during firing.
  • the amount of oxygen contained in the sintered body can be greatly reduced.
  • the shrinkage rate inside and outside the molded body is kept the same, sufficient oxygen deficiency can be formed both inside the sintered body and in the sintered body. The oxygen content can be greatly reduced.
  • the firing temperature of the material to be fired is not particularly limited, but is preferably 1300 ° C. to 1500 ° C. or less, more preferably 1350 ° C. to 1450 ° C., in order to obtain a sintered body with high density and high strength. If the temperature is too high, the crystal grain growth of InGaZnO 4 proceeds rapidly, firing cracks occur due to strength reduction due to abnormal grain growth, and the yield decreases. On the other hand, if the holding temperature is too low, the densification does not proceed, so that a high-density sintered body cannot be obtained, which causes an increase in arcing during sputtering. When the temperature is in the range of 1300 ° C. to 1500 ° C., the obtained sintered body has a sufficient InGaZnO 4 homologous crystal structure.
  • the holding time of the object to be baked is not particularly limited, but the holding time is set longer when the baking temperature is low, and conversely the holding time is set shorter when the baking temperature is high.
  • firing with an electric furnace it is preferably 30 minutes to 5 hours. If it is shorter than 30 minutes, there is a difference in the progress of sintering between the surface and the center of the object to be fired, and a high-density sintered body may not be obtained.
  • the time is longer than 5 hours, crystal grains grow and a high-strength sintered body cannot be obtained.
  • the baking by electromagnetic wave heating it is preferable to set it for 5 minutes or more and 1 hour or less. Since electromagnetic heating is heating by self-heating, the temperature difference in the object to be fired is small, and a high-density sintered body can be obtained even if the holding time is shortened.
  • the temperature increase rate of the object to be fired is not particularly limited. However, in order to obtain a high-strength sintered body by shortening the firing time as much as possible to suppress the growth of crystal grains in the sintered body, the temperature rise rate is relatively high. It is preferable to warm. Specifically, it is 20 to 600 ° C./h, preferably 100 to 600 ° C./h, more preferably 200 to 600 ° C./h, and further preferably 300 to 600 ° C./h. For this reason, it is more effective to perform firing using an electromagnetic wave firing furnace capable of rapid heating firing. When the temperature range of 300 to 750 ° C. and 1000 ° C. to 1200 ° C.
  • the volume expansion coefficient of the powder after bead mill pulverization / mixing is 300 to 750 ° C. From the viewpoint of preventing firing cracks of a large target, it is preferable to use a mixed powder having a temperature range of 1.3% or less and a temperature range of 1000 ° C. to 1200 ° C. of 2.5% or less.
  • the molded body may crack if the moisture and binder components volatilize.
  • the temperature rising rate is preferably 20 to 100 ° C./h in the temperature range of 100 to 400 ° C., for example, and 20 to 100 ° C./h in the temperature range of 100 to 600 ° C. Is more preferable.
  • required from X-ray diffraction is 60 nm or less.
  • Indium oxide is a substance that has good electromagnetic wave absorption characteristics from low temperature to high temperature near room temperature and is easily self-heating
  • gallium oxide is a substance that has poor electromagnetic wave absorption characteristics and hardly self-heats
  • zinc oxide absorbs electromagnetic waves at low temperatures. It is a substance exhibiting temperature dependency that the electromagnetic wave absorption characteristics are improved when the characteristics are poor and the temperature exceeds a specific temperature.
  • IGZO is a composite material system in which materials having completely different electromagnetic wave absorption characteristics coexist, and in the case of heating using electromagnetic waves, there is a high possibility of causing cracking or abnormal grain growth due to local heating.
  • the raw material powder having a diameter of 60 nm or less it is possible to obtain a uniform sintered body that is not cracked even in electromagnetic wave heating.
  • the crystallite diameter obtained from the X-ray diffraction of the raw material powder referred to in the present application is the crystallite diameter separately from the X-ray diffraction peak derived from the crystal structure of each raw material Is the maximum value when.
  • microwaves used in the present invention continuous or pulsed microwaves such as 2.45 GHz generated from magnetron or gyrotron, millimeter waves such as 28 GHz, or submillimeter waves can be used.
  • the selection of the frequency of the electromagnetic wave an appropriate one can be selected from the electromagnetic wave absorption characteristics of the object to be fired.
  • a microwave of 2.45 GHz is preferable.
  • the cooling rate is 150 ° C./h or more, preferably 200 ° C./h or more, more preferably 250 ° C./h or more, and further preferably 300 ° C./h or more from the firing temperature to 1100 ° C.
  • the temperature drop rate is not particularly limited, and can be appropriately determined in consideration of the capacity of the sintering furnace, the size and shape of the sintered body, ease of cracking, and the like.
  • the obtained sintered body is formed into a desired shape such as a plate shape, a circular shape, or a cylindrical shape by using a machining machine such as a surface grinder, a cylindrical grinder, a lathe, a cutting machine, or a machining center. To grind. Furthermore, a sputtering target using the sintered body of the present invention as a target material is obtained by bonding (bonding) a backing plate made of oxygen-free copper, titanium, or the like to the backing tube or backing tube using indium solder or the like as necessary. Can do.
  • the size of the sintered body is not particularly limited, but since the sintered body according to the present invention has high strength, a large target can be manufactured.
  • a large-sized sintered body having a length of 310 mm ⁇ width of 310 mm (target surface area 961 cm 2 ) or more can be produced.
  • a large sintered body having an outer diameter of 91 mm ⁇ ⁇ 90 mm (target surface area 257 cm 2 ) or more can be produced.
  • the area of the target surface refers to the area of the surface of the sintered body to be sputtered, and in the case of a multi-part target composed of a plurality of sintered bodies, the side to be sputtered in each sintered body
  • the surface area of the sintered body is the area of the target surface in the multi-division target.
  • the thickness of the target is not particularly limited, but is preferably 4 mm or more and 15 mm or less. If it is thinner than 4 mm, the target utilization is low and not economical. On the other hand, when the thickness is larger than 15 mm, the sintered body becomes heavy, and thus handling equipment or the like is required in the targeting step.
  • Open pore ratio It calculated by the equation (4) from the sintered body volume calculated by the Archimedes method and the open pore volume calculated by the equation (3).
  • Open pore volume (wet weight-dry weight) / density of water (3)
  • Open pore rate (Open pore volume / (sintered body volume + open pore volume)) ⁇ 100 (%) (4)
  • Observation of microcracks Sampling is performed at 10 arbitrary positions after grinding 0.5 mm or more from the outermost surface.
  • an observation surface is created by a cross-sectional ion milling method (apparatus: cross section polisher IB-09020CP manufactured by JEOL Ltd.), and then a conductive coating (osmium coating) is applied to the observation surface. And then observed.
  • Detector Backscattered electron detector measurement method: Counts the number of cracks having a length of 3 ⁇ m or more in an arbitrary region of 60 ⁇ m ⁇ 80 ⁇ m. When it is recognized that the end of the crack is connected to the end of one or more other cracks, they are combined and counted as one. When it is recognized that two or more cracks intersect, each is counted independently.
  • volume expansion coefficient the volume expansion of the molded object which generate
  • the firing conditions are both a temperature rising rate and a temperature falling rate of 100 ° C./h, a holding time at a temperature T of 1 hour, and the atmosphere is fired in an air atmosphere.
  • the firing temperature T By changing the firing temperature T in steps of 20 ° C., plotting the volume expansion coefficient at each firing temperature T and performing smoothing, a volume expansion coefficient profile in a predetermined temperature range is obtained.
  • Average particle diameter (D50) Measuring device Laser diffraction particle size distribution measuring device (SALD-7100, manufactured by Shimadzu Corporation) Measurement method: 0.3 to 0.5 g of the weighed raw material powder is placed in 30 ml of a sodium hexametaphosphate solution (0.2%), and is measured after dispersion for 1 minute at an output of 200 W with an ultrasonic disperser.
  • SALD-7100 Laser diffraction particle size distribution measuring device
  • Oxygen content Samples were cut out from the sintered body after grinding 0.5 mm or more from the outermost surface and measured by an impulse furnace melting-infrared absorption method (LECO TC436 oxygen / nitrogen analyzer). LECO standard samples were used for calibration of the apparatus. The measurement was performed at arbitrary five locations, and the average value was used as official data.
  • LECO TC436 oxygen / nitrogen analyzer an impulse furnace melting-infrared absorption method
  • Transmittance The transmittance was measured using a spectrophotometer (U-4100, manufactured by Hitachi, Ltd.).
  • TFT characteristics A voltage generator (REGULATED DC POWER SUPPLY, manufactured by Kikusui Electronics Co., Ltd., PAS160-2), a voltage measuring device (DIGITM ULTIMETER Kikusui Electronics Co., Ltd., DME1600), and an ADC current measuring device (DIGITAL ELECTEOMETER 8240) are used. Measured.
  • the weighed powder was slurried with 10 kg of pure water, and 90 g (0.6 wt%) of a polyacrylate dispersant was added to prepare a slurry having a solid content concentration of 60%.
  • a bead mill with an internal volume of 2.5 L is filled with 80% ⁇ 0.3 mm zirconia beads, and the slurry is circulated through the mill at a mill peripheral speed of 7.5 m / sec and a slurry supply rate of 2.5 L / min. Processed.
  • Example 1-1 The mixed powder of the condition (a) was filled in the mold while being tapped, and was subjected to CIP treatment at a pressure of 2 ton / cm 2 to obtain three plate molds and three cylindrical molds. Next, this compact was set in a resistance heating type electric furnace, placed on an alumina setter, and fired under the conditions shown in Table 2. Approximate dimensions: 420 mm long x 310 mm wide x 6 mm thick Plate-shaped sintered bodies (target surface area: 1302 cm 2 ) and three cylindrical sintered bodies of outer diameter 91 mm ⁇ height 170 mm ⁇ thickness 7 mm (target surface area: 486 cm 2 ) were obtained. . Table 2 shows the presence or absence of firing cracks in the obtained sintered body as firing yield, and the relative density and composition variation rate of the sintered body were measured for one of the obtained plate-type sintered bodies. Table 3 shows values of physical properties.
  • the obtained flat plate-shaped sintered body was processed to 101.6 mm ⁇ ⁇ 6 mmt, and then bonded to an oxygen-free copper backing plate with indium solder to obtain a sputtering target.
  • sputtering was performed under the following conditions to form an IGZO film on the glass substrate.
  • Target rotation 5 rpm
  • Example 1-2 to Example 1-6 Using the mixed powder of any of the conditions (b) to (d), three flat plate molded bodies and three cylindrical molded bodies were obtained in the same manner as in Example 1-1. Next, this compact was set in a resistance heating type electric furnace, placed on an alumina setter, and fired under the conditions described in Table 2. Table 2 shows the presence or absence of firing cracks in the obtained sintered body as firing yield, and the relative density and composition variation rate of the sintered body were measured for one of the obtained plate-type sintered bodies. Table 3 shows values of physical properties. A microcrack observation photograph of the sintered compact test piece shown in Example 1-2 is shown in FIG. The numbers in the photographs indicate the observed microcracks. For Examples 1-4 to 1-6, the arcing characteristics during sputtering were also measured.
  • Example 1-1 to Comparative Example 1-4 Using the mixed powder of the condition (e) or (f), three flat molded bodies and three cylindrical molded bodies were obtained in the same manner as in Example 1-1 (Comparative Example 1-1, Comparative Example). For Example 1-3, only flat plate molded body). Next, this compact was set in a resistance heating type electric furnace, placed on an alumina setter, and fired under the conditions described in Table 2. The presence or absence of firing cracks in the obtained sintered body is shown in Table 2 as the firing yield, and the relative density of the sintered body and the composition variation rate were measured for one of the obtained sintered bodies. Values are shown in Table 3. A microcrack observation photograph of the sintered body test piece shown in Comparative Example 1-2 is shown in FIG. For Comparative Examples 1-2 and 1-4, the arcing characteristics during sputtering were also measured.
  • Three types of (a) to (c) were made by changing the number of wet bead mill treatments using 0.3 mm ⁇ zirconia beads in a state where the weighed powder was slurried with pure water and the slurry concentration was 50 wt%. A slurry of was obtained. At this time, a dispersant was appropriately added so that the slurry viscosity was 1000 ps or less. Next, the pulverized slurry was granulated and dried using a spray dryer to obtain a raw material powder. Table 4 shows the measurement results of the crystallite diameter calculated from the number of grinding treatments and the X-ray diffraction of the obtained powder.
  • a molded body of 30 mm ⁇ 30 mm ⁇ 10 mmt was produced by a die press at a pressure of 300 kg / cm 2 , and then subjected to CIP treatment at a pressure of 2 ton / cm 2 .
  • Firing temperature 1400 ° C Holding time: 1 hour Temperature rising rate: 300 ° C./hour Atmosphere: Air Temperature decreasing rate: 300 ° C./hour (from 1400 ° C. to 1100 ° C.)
  • Table 4 shows the fire cracking situation, relative density, and X-ray diffraction measurement results of the obtained sintered body.
  • Example 2-4 The raw material powder was weighed in the same manner as in Example 2-1, and the weighed powder and a resin ball with a core of 15 mm in diameter were placed in a polyethylene pot and mixed for 20 hours by a dry ball mill to prepare a mixed powder. This powder was pulverized three times in a counter jet air type counter jet mill. Next, in order to improve the moldability of the powder, the pulverized powder was put in a polyethylene pot, and the compaction was performed for 10 hours by dry mixing with a rotating ball mill using the resin balls. Table 4 shows the measurement results of the crystallite diameter calculated from the X-ray diffraction of the obtained powder (d). Next, this powder was molded and fired in the same manner as in Example 2-1. Table 4 shows the fire cracking situation, relative density, and X-ray diffraction measurement results of the obtained sintered body.
  • Example 2-1 A sintered body was obtained in the same manner as in Example 2-1, except that the pulverization process was performed once with a wet bead mill.
  • Table 4 shows the measurement results of the crystallite diameter calculated from the X-ray diffraction of the obtained powder (e), and the fire cracking status, relative density, and X-ray diffraction measurement results of the obtained sintered body.
  • Example 2-2 The raw material powder was weighed in the same manner as in Example 2-1, and the weighed powder and zirconia balls having a diameter of 15 mm were put in a polyethylene pot and mixed by a dry ball mill for 24 hours to prepare a mixed powder.
  • Table 4 shows the measurement results of the crystallite diameter calculated from the X-ray diffraction of the obtained powder (f). Next, this powder was molded and fired in the same manner as in Example 2-1. Table 4 shows the fire cracking situation, relative density, and X-ray diffraction measurement results of the obtained sintered body.
  • Example 2-5 to Example 2-9 Using the powder of Example 2-3, the size of the compact was set to 120 mm ⁇ 210 mm ⁇ 10 mmt, and (g) to (g)- Five types of sintered bodies (k) were obtained.
  • Table 5 shows the measurement results of the firing conditions and the relative density, crystal grain size, pore number ratio (grain boundary / inside grain), bending strength, and X-ray diffraction of the obtained sintered body.
  • Example 2-3 Comparative Example 2-5
  • a molded body was obtained in the same manner as in Example 2-1, except that the size of the molded body was 120 mm ⁇ 210 mm ⁇ 10 mmt using the powder of Example 2-3.
  • this molded body was placed on an alumina setter in an electric furnace and fired under the following conditions except for the firing conditions shown in Table 5, and three types of firings (l) to (n) were performed.
  • a ligature was obtained.
  • Atmosphere Air Temperature drop rate: 200 ° C / h (from 1400 ° C to 1100 ° C)
  • Table 5 shows the measurement results of the relative density, crystal grain size, pore number ratio (grain boundary / inside grain), bending strength, and X-ray diffraction of the obtained sintered body.
  • the relationship between the bending strength and the pore number ratio (grain boundary / inside grain) of the IGZO sintered bodies obtained in Examples 2-5 to 2-9 and Comparative Examples 2-3 to 2-5 is shown. 3 shows.
  • Example 2-10 to Example 2-13 Sintered bodies were produced in the same manner as in Example 2-7, except that flat and cylindrical shaped bodies having various sizes were produced.
  • the flat plate-shaped sintered body was processed by a surface grinder, and the cylindrical sintered body was processed by a cylindrical grinder. No cracks were observed in the sintered body after processing.
  • Table 6 shows the size of the obtained sintered body and the presence or absence of occurrence of cracks.
  • cylindrical sintered bodies were bonded to titanium backing tubes, respectively, and used as targets, then attached to a rotary cathode type sputtering apparatus, and sputtered to a remaining thickness of 1 mm under the following conditions. .
  • Example 3-1 to Example 3-4 Comparative Example 3-1 to Comparative Example 3-3
  • Seven types of mixed powders (a) to (g) were obtained by changing the addition amount of zirconium oxide. These powders were slurried with pure water, and in a state where the slurry concentration was 50 wt%, dispersion treatment was performed with a wet bead mill using 0.3 mm ⁇ zirconia beads. At this time, a dispersant was appropriately added so that the slurry viscosity was 1000 ps or less.
  • these dispersion-treated slurries are granulated and dried with a spray dryer, and using these powders, a molded body of 150 mm ⁇ ⁇ 10 mmt is produced by a die press at a pressure of 300 kg / cm 2 , CIP treatment was performed at a pressure of 2 ton / cm 2 .
  • this compact was fired in an electric furnace.
  • the heating rate was 100 ° C./hour from room temperature to 1400 ° C.
  • the firing temperature was 1400 ° C. and the holding time was 1 hour.
  • the temperature decreasing rate was 200 ° C./hour from 1400 ° C. to 1100 ° C.
  • it was naturally cooled and taken out after the furnace temperature reached 50 ° C. or lower.
  • After processing the obtained sintered body to 101.6 mm ⁇ ⁇ 6 mmt it was bonded to an oxygen-free copper backing plate with indium solder to obtain a sputtering target. Sputtering was performed using this target under the following conditions, an IGZO film was formed on a glass substrate, and the transmittance was measured.
  • Electrode Al Gas: Argon (100%) Pressure: 0.45Pa Power supply: DC Input power: 200 W (2.5 W / cm 2 ) Substrate temperature: Room temperature Film thickness: 50 nm (both source and drain)
  • Table 7 shows the measurement results of the identified species by the zirconia concentration, the relative density, the bending strength, and the X-ray diffraction (XRD) of the obtained sintered body, and the measurement results of the mobility of the obtained TFT element.
  • Example 3-4 to Comparative Example 3-7 Four types of mixed powders (h) to (k) were produced in the same manner as in Example 3-1, except that the addition amount of zirconium oxide was changed. These powders were subjected to a dispersion treatment in a counter jet air type counter jet mill. Next, in order to improve the moldability of the powder, these dispersed powders are put in a polyethylene pot, and compacted by dry mixing for 10 hours with a rotating ball mill using a resin ball with a core of 15 mm in diameter. Went. Next, these powders were molded and fired in the same manner as in Example 3-1. The transmittance and mobility of the obtained sintered body were measured under the same conditions as in Example 3-1.
  • Table 7 shows the measurement results of the identified species by the zirconia concentration, the relative density, the bending strength, and the X-ray diffraction (XRD) of the obtained sintered body, and the measurement results of the mobility of the obtained TFT element.
  • FIG. 4 shows the relationship between the Zr concentration of the IGZO sintered bodies obtained in Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-7 and the relative density of the sintered bodies.
  • FIG. 5 shows the relationship between the Zr concentration and the transmittance of the IGZO films obtained in Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-7. Further, FIG. 7 shows the relationship between the Zr concentration and mobility of the TFT elements obtained in Examples 3-1 to 3-4 and Comparative Examples 3-1 to 3-7.
  • Example 3-5 to Example 3-7 Using the powder of Example 3-2, flat and cylindrical compacts having various sizes were prepared, and sintered in the same manner as in Example 3-1, to prepare a sintered body. Next, in order to target these sintered bodies, the flat plate-shaped sintered body was processed by a surface grinder, and the cylindrical sintered body was processed by a cylindrical grinder. No cracks were observed in the sintered body after processing. Table 8 shows the size of the obtained sintered body and the presence or absence of occurrence of cracks.
  • Comparative Examples 3-8, 3-9 Using the powder of Comparative Example 3-7, flat and cylindrical compacts having various sizes were prepared, and sintered in the same manner as in Example 1 to prepare sintered bodies. Next, in order to target these sintered bodies, the flat plate-shaped sintered body was processed by a surface grinder, and the cylindrical sintered body was processed by a cylindrical grinder. Table 7 shows the size of the obtained sintered body and the presence or absence of cracking due to processing. Of the produced sintered bodies, a cylindrical sintered body was bonded to a titanium backing tube to make a target, and then attached to a rotating cathode type sputtering apparatus, and sputtered under the same conditions as in Example 2-10. went. Then, the target surface was observed and it confirmed that the crack generate
  • the oxide sintered body of the present invention can be used particularly for a large sputtering target for an oxide semiconductor film.
  • n-Si substrate (gate) 2 SiO 2 (300 nm) 3: Al (source 50 nm) 4: Al (drain 50 nm) 5: IGZO film (50 nm) 6: Interval (200 ⁇ m)

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Abstract

L'invention concerne un corps d'oxyde fritté pour une cible de pulvérisation IGZO de haute qualité et de haut rendement qui est la plus appropriée pour l'utilisation dans des films semi-conducteurs d'oxyde, ledit corps d'oxyde fritté permettant l'amélioration des fluctuations des propriétés dans un film mince IGZO et permettant aussi l'amélioration de l'occurrence de craquage durant la production d'une cible et durant la pulvérisation. L'invention concerne un corps d'oxyde fritté qui contient au moins In, Ga et Zn, a une structure cristalline homologue représentée par la formule : InGaZnO4, et a un diamètre de grain de cristal de 5 μm ou moins, une densité relative de 95% ou plus et une résistance à la fracture par courbure de 100 MPa ou plus.
PCT/JP2013/070632 2012-07-30 2013-07-30 Corps d'oxyde fritté et cible de pulvérisation WO2014021334A1 (fr)

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JP6144858B1 (ja) * 2016-04-13 2017-06-07 株式会社コベルコ科研 酸化物焼結体およびスパッタリングターゲット、並びにそれらの製造方法
WO2018179556A1 (fr) * 2017-03-31 2018-10-04 Ｊｘ金属株式会社 Cible de pulvérisation et son procédé de production
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JP2021002633A (ja) * 2019-06-25 2021-01-07 日新電機株式会社 酸化物半導体の加工法方法及び薄膜トランジスタの製造方法

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JP2021093539A (ja) * 2016-01-18 2021-06-17 株式会社半導体エネルギー研究所 金属酸化物膜及び表示装置
US10865470B2 (en) 2016-01-18 2020-12-15 Semiconductor Energy Laboratory Co., Ltd. Metal oxide film, semiconductor device, and display device
WO2017125796A1 (fr) * 2016-01-18 2017-07-27 株式会社半導体エネルギー研究所 Film d'oxyde métallique, dispositif à semi-conducteur et dispositif d'affichage
US11352690B2 (en) 2016-01-18 2022-06-07 Semiconductor Energy Laboratory Co., Ltd. Metal oxide film, semiconductor device, and display device
US10546960B2 (en) 2016-02-05 2020-01-28 Semiconductor Energy Laboratory Co., Ltd. Metal oxide film, semiconductor device, and manufacturing method of semiconductor device
US10892367B2 (en) 2016-02-05 2021-01-12 Semiconductor Energy Laboratory Co., Ltd. Metal oxide film, semiconductor device, and manufacturing method of semiconductor device
WO2019244509A1 (fr) * 2018-06-19 2019-12-26 三井金属鉱業株式会社 Corps fritté d'oxyde et cible de pulvérisation
CN112262114A (zh) * 2018-06-19 2021-01-22 三井金属矿业株式会社 氧化物烧结体和溅射靶
JPWO2019244509A1 (ja) * 2018-06-19 2021-06-24 三井金属鉱業株式会社 酸化物焼結体およびスパッタリングターゲット
CN112262114B (zh) * 2018-06-19 2022-06-28 三井金属矿业株式会社 氧化物烧结体和溅射靶
JP7282766B2 (ja) 2018-06-19 2023-05-29 三井金属鉱業株式会社 酸化物焼結体およびスパッタリングターゲット
US20220220605A1 (en) * 2021-01-13 2022-07-14 Jx Nippon Mining & Metals Corporation Igzo sputtering target
US11827972B2 (en) * 2021-01-13 2023-11-28 Jx Metals Corporation IGZO sputtering target

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