WO2013035695A1 - Cible de pulvérisation cathodique formée d'un corps fritté à base d'un alliage cu-te - Google Patents

Cible de pulvérisation cathodique formée d'un corps fritté à base d'un alliage cu-te Download PDF

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WO2013035695A1
WO2013035695A1 PCT/JP2012/072463 JP2012072463W WO2013035695A1 WO 2013035695 A1 WO2013035695 A1 WO 2013035695A1 JP 2012072463 W JP2012072463 W JP 2012072463W WO 2013035695 A1 WO2013035695 A1 WO 2013035695A1
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target
based sintered
alloy
sputtering target
sputtering
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由将 小井土
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Jx日鉱日石金属株式会社
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of switching materials, e.g. deposition of layers
    • H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
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    • H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
    • H10N70/8828—Tellurides, e.g. GeSbTe

Definitions

  • a Cu—Te sintered sputtering target having a high bending strength with few defects such as abnormal discharge, nodule, arcing, etc. by setting the size of segregation in the target to a predetermined value or less.
  • a thin film made of a Cu—Te alloy material has been used as a resistance change recording material, that is, as a medium for recording information using resistance change.
  • a method of forming a thin film made of this Cu—Te alloy material it is usually performed by means generally called physical vapor deposition, such as vacuum vapor deposition or sputtering.
  • the magnetron sputtering method is often used in view of operability and film stability.
  • a film is formed by sputtering, in which positive ions such as Ar ions are physically collided with a target placed on the cathode, and the material constituting the target is released by the collision energy, and the substrate on the anode side facing the target is released. This is done by stacking films having the same composition as the target material.
  • the coating method by sputtering has a feature that a thin film in angstrom units to a thick film of several tens of ⁇ m can be formed at a stable film formation speed by adjusting the processing time, supply power, and the like.
  • abnormal structures such as nodules (abnormal protrusions) and craters (abnormal dents) are generated on the target surface.
  • Micro arcing occurred as a base point, and these themselves were mixed in the thin film as a foreign substance in the form of clusters (aggregates of atoms) called particles.
  • Conventional resistance change recording layers mainly use metal oxides such as NiO, TaO 2 and TiO 2 and perovskite complex oxides such as PrCaMnO 3 and Cr-doped SrZrO 3 .
  • metal oxides such as NiO, TaO 2 and TiO 2
  • perovskite complex oxides such as PrCaMnO 3 and Cr-doped SrZrO 3 .
  • the track record of using a chalcogenide compound such as a Cu-Te alloy as a sputtering target is poor, and the characteristics required when sputtering this material and the problems in manufacturing the target are not fully understood. It was the current situation.
  • a 5N purity Cu wire and Te shot are prepared as raw materials, these are prepared so as to have a predetermined composition, and then synthesized in an ampule.
  • the ingot was pulverized to a predetermined particle size and then subjected to pressure sintering to produce a Cu—Te based sputtering target.
  • the target made by this method causes large segregation of Cu and Te, so the composition of the target becomes non-uniform, and because the ingot is coarsely pulverized, the particle size distribution becomes non-uniform and the target is uniformly eroded. There was a problem of not being. As a result, a large number of particles were generated due to the generation of nodules and arcing, and the target itself cracked during sputtering due to the weakness of the target itself.
  • Patent Documents 1 to 9 show examples in which Cu and Te are used as an ion source layer for a storage element for stably performing operations such as information recording, and these are formed by sputtering.
  • An example is shown.
  • the invention is centered on the selection of the configuration and material of the storage element such as the lower electrode, ion source layer, storage layer, and upper electrode, and is completely indifferent to the problem of the sputtering target. From this, it can be said that the target used in this case contains the problems of the prior art.
  • the present invention improves the synthesis conditions of the raw material powder used for the Cu—Te alloy-based sintered sputtering target and controls the pulverization method, thereby making the composition and structure of the target uniform and simultaneously increasing the bending strength.
  • it is an object to provide a Cu—Te alloy-based sintered sputtering target that can effectively prevent cracking during sputtering, improve its quality, and form a uniform resistance change recording layer.
  • the technical means for solving the above-mentioned problems is that a Cu-Te alloy-based sintered sputtering target for forming a stable and homogeneous resistance change recording layer is improved in the synthesis conditions of raw material powder and pulverization method It has been found that the dispersibility and uniformity of the target structure can be improved, the mechanical strength of the target can be improved, and stable sputtering can be realized.
  • the present invention provides the following inventions. 1) Te: 40-90 at%, Cu—Te alloy-based sintered sputtering target composed of Cu, Te, or an intermetallic compound existing in the target, the Cu—Te alloy-based sintered sputtering target composed of the inevitable impurities and Cu. A Cu—Te alloy-based sintered sputtering target having a maximum diameter of 20 ⁇ m or less. 2) The Cu—Te-based sintered sputtering target according to claim 1, wherein the maximum diameter of the segregated portion made of Cu, Te or an intermetallic compound thereof is 10 ⁇ m or less.
  • the average grain size of the crystal grains present in the Cu—Te alloy-based sintered body target is 10 ⁇ m or less, and the bending strength of the target is 70 Mpa or more.
  • Cu—Te based sintered sputtering target is 4) The Cu—Te based sintered sputtering target according to any one of 1) to 3) above, wherein Al and / or Ge are contained at a maximum of 50 at%. 5) The Cu—Te based sintered sputtering target according to any one of 1) to 4) above, wherein Zr is contained in a maximum of 50 at%.
  • FIG. 3 is a view showing an FE-EPMA observation photograph of the surface after sintering in Example 1.
  • FIG. 4 is a view showing an FE-EPMA observation photograph of the surface after sintering in Example 2.
  • FIG. 4 is a view showing an FE-EPMA observation photograph of a surface after sintering in Comparative Example 1.
  • FIG. 4 is a view showing an FE-EPMA observation photograph of a surface after sintering in Comparative Example 2.
  • the Cu—Te alloy-based sintered sputtering target of the present invention is composed of Te: 40 to 90 at%, and the balance is inevitable impurities and Cu.
  • One of the major features of the present invention is that the maximum diameter of the segregated portion made of Cu, Te or these intermetallic compounds existing in the target is 20 ⁇ m or less, and further the maximum diameter of the segregated portion is 10 ⁇ m. Such segregation is formed by causing a composition shift when the Cu—Te alloy is sintered, without forming a uniform composition alloy.
  • the Cu—Te-based sintered sputtering target of the present invention is characterized in that the average grain size of crystal grains present in the target is 10 ⁇ m or less, and the bending strength of the target is 70 Mpa or more. It is. From the viewpoint of improving the bending strength, it is more desirable to prepare the target with Te: 40 to 60 at%, the remainder of inevitable impurities and Cu raw material.
  • the maximum crystal grain size is preferably 10 ⁇ m or less.
  • the diameter of the segregation part is equivalent to the crystal grain size, smaller than that, or even larger than the crystal grain size. Thus, since the diameter of the segregation part is not constant, the average particle diameter of the target is measured by excluding the segregation part.
  • the Cu—Te based sintered sputtering target of the present invention can contain Al and / or Ge in the above composition at a maximum of 50 at%, with the balance being Cu. Further, in the composition of the Cu—Te based sintered body, Zr can be contained at a maximum of 50 at%, and the balance can be Cu. These elements, as cations, easily move through the material and play a role of stabilizing the CuTe metal chalcogenide layer. In particular, since Al and Ge form an oxide when erasing data, the resistance is greatly increased. Thereby, the resistance ratio adjustment, which is a characteristic of ReRAM, can be performed. On the other hand, Zr becomes a cation and becomes easy to move, has a function of lowering resistance and operating stably.
  • the Cu—Te-based sintered sputtering target of the present invention having the above characteristics is manufactured through the following steps. Specifically, high-purity (4N level or higher) Cu and Te raw materials are weighed and prepared so as to be 40 to 90 at% Te and the balance Cu, and this is rocked and dissolved at 900 to 1100 ° C. . This is because Cu and Te are mixed uniformly. When deviating from this condition, there arises a problem that an undissolved portion of Cu remains. Next, after this is gradually cooled to 340 to 450 ° C. by natural heat dissipation, the temperature is kept constant at 340 to 450 ° C. for 10 to 20 hours. This is for precipitating the phase according to the phase diagram. When deviating from this, a problem of composition unevenness due to segregation occurs. Then, it is gradually cooled to room temperature by natural heat dissipation to make an ingot. The above process is important in suppressing segregation of components.
  • Example 1 Raw materials of 4N Cu and 4N Te were weighed and prepared so as to be 50 at% Cu-50 at% Te, and dissolved at 1000 ° C. Next, after this was gradually cooled to 420 ° C. by natural heat dissipation, the temperature was kept constant at 420 ° C. for 20 hours. Thereafter, it was gradually cooled to room temperature by natural heat dissipation.
  • the obtained CuTe ingot was pulverized and then jet milled to obtain a CuTe raw material powder having an average particle size of 2 to 3 ⁇ m. This was hot-pressed to obtain a target shape, and then the surface was ground and bonded to a backing plate, and surface polishing was performed to obtain a sputtering target. The relative density of these targets was 99% or more.
  • FIG. 1 shows an FE-EPMA observation photograph of the sintered target surface obtained in Example 1.
  • segregation was suppressed, and the maximum diameter of the segregation part existing in the sputtering target of Example 1 was reduced to 20 ⁇ m or less. That is, no segregated portion of Cu, Te or Cu—Te intermetallic compound having a maximum diameter of 20 ⁇ m or more was present over the entire erosion surface. Further, the average grain size of the crystal grains present in the Cu—Te alloy based sintered compact target was 10 ⁇ m or less.
  • the bending strength was 128 Mpa (50 at% Cu), and the bending strength of the target of the present invention: 70 Mpa or more was achieved.
  • Example 2 Raw materials of 4N Cu and 4N Te were weighed and prepared so as to be 60 at% Cu-40 at% Te, and dissolved at 1000 ° C. Next, after this was gradually cooled to 420 ° C. by natural heat dissipation, the temperature was kept constant at 420 ° C. for 20 hours. Thereafter, it was gradually cooled to room temperature by natural heat dissipation.
  • the obtained CuTe ingot was pulverized and then jet milled to obtain a CuTe raw material powder having an average particle size of 2 to 3 ⁇ m. This was hot-pressed to obtain a target shape, and then the surface was ground and bonded to a backing plate, and surface polishing was performed to obtain a sputtering target. The relative density of these targets was 99% or more.
  • FIG. 2 shows an FE-EPMA observation photograph of the target surface after sintering obtained in Example 2.
  • segregation was suppressed, and the maximum diameter of the segregation part existing in the sputtering target of Example 2 was reduced to 20 ⁇ m or less. That is, no segregated portion of Cu, Te or Cu—Te intermetallic compound having a maximum diameter of 10 ⁇ m or more was present over the entire erosion surface. Further, the average grain size of the crystal grains present in the Cu—Te alloy based sintered compact target was 10 ⁇ m or less.
  • the bending strength was 78 Mpa (60 at% Cu), and the bending strength of the target of the present invention: 70 Mpa or more was achieved.
  • the maximum diameter of the segregation part exceeded 20 ⁇ m, and the one with large segregation reached the maximum diameter of 50 ⁇ m. And this segregation part was scattered over the whole erosion surface with the target of Cu or Te.
  • the bending strength of the target of Comparative Example 1 was 47 Mpa, and the bending strength of the target of the present invention of the present invention: 70 Mpa or more could not be achieved.
  • the average grain size of the crystal grains present in the Cu—Te alloy-based sintered compact target exceeded 10 ⁇ m and was 28 ⁇ m.
  • the maximum diameter of the segregation part exceeded 20 ⁇ m, and the one with large segregation reached the maximum diameter of 50 ⁇ m. And this segregation part was scattered over the whole erosion surface with the target of Cu or Te.
  • the bending strength of the target of Comparative Example 2 was 31 Mpa, and the bending strength of the target of the present invention: 70 Mpa or more could not be achieved.
  • the average grain size of the crystal grains present in the Cu—Te alloy-based sintered body target exceeded 10 ⁇ m and was 22 ⁇ m.
  • Comparative Example 2 abnormal discharge, nodules, and arcing occurred frequently, resulting in a sputtered film with many particles. Further, in Comparative Example 2, cracks occurred during use. These were considered to be caused by the fact that the synthesis conditions and the pulverization method of the raw material powder used for the Cu—Te alloy-based sintered sputtering target were not appropriately performed.
  • the obtained CuTeGe ingot was pulverized and then jet milled to obtain a CuTeGe raw material powder having an average particle size of 2 to 3 ⁇ m. This was hot-pressed to obtain a target shape, and then the surface was ground and bonded to a backing plate, and surface polishing was performed to obtain a sputtering target. The relative density of these targets was 99% or more.
  • Example 3 As a result of FE-EPMA observation of the surface of the sintered target obtained in Example 3, as in Example 1, segregation was suppressed, and the maximum diameter of the segregated part existing in the sputtering target of Example 3 was 20 ⁇ m or less. Diminished. That is, the segregation part of Cu, Te, Ge or these intermetallic compounds whose maximum diameter is 20 micrometers or more did not exist over the whole erosion surface. Further, the average grain size of the crystal grains present in the Cu—Te—Ge alloy based sintered compact target was 10 ⁇ m or less.
  • Example 4N Cu, 4N Te and 4N Al raw materials are weighed and prepared to be 42.5at% Cu-42.5at% Te-15at% Al. Therefore, the CuTeAl raw material powder was hot-pressed as it was to obtain a target shape.
  • the surface of the obtained target material was ground and subjected to surface polishing after bonding to a backing plate plate to obtain a sputtering target.
  • the relative density of these targets was 99% or more.
  • Example 4 As a result of FE-EPMA observation of the target surface after sintering obtained in Example 4, as in Example 1, segregation was suppressed, and the maximum diameter of the segregated portion existing in the sputtering target of Example 4 was 20 ⁇ m or less. Diminished. That is, there was no segregated portion of Cu, Te, Ge, Al or an intermetallic compound having a maximum diameter of 20 ⁇ m or more over the entire erosion surface. The average grain size of the crystal grains present in the Cu—Te—Al alloy-based sintered body target was 10 ⁇ m or less.
  • the bending strength was 128 Mpa, and the bending strength of the target of the present invention: 70 Mpa or more was achieved.
  • Example 5 Raw materials of 4N Cu, 4N Te, 4N Al and 4N Zr were weighed and prepared so as to be 14 at% Cu-22 at% Te-50 at% Al-14 at% Zr. When these mixed powders were prepared by dissolution, there was a concern that they would become very active substances, so the mixture of CuTeAlZr raw powder was directly hot pressed to the target shape, and then the surface was ground and backed Surface polishing was performed after bonding to the plate to obtain a sputtering target. The relative density of these targets was 99% or more.
  • Example 5 As a result of FE-EPMA observation of the target surface after sintering obtained in Example 5, segregation was suppressed as in Example 1.
  • the segregation part present in such a sputtering target can be controlled by adjusting the particle size of the powder and the hot press temperature, and Example 5 satisfied the conditions of the present invention. Further, the average grain size of the crystal grains present in the Cu—Te—Al—Zr alloy based sintered compact target was 10 ⁇ m or less.
  • the bending strength was 80 Mpa, and the bending strength of the target of the present invention: 70 Mpa or more was achieved.
  • the cooling temperature pattern after synthesis of raw materials, it is possible to suppress the occurrence of large segregation parts after sintering, and to improve the bending strength by optimizing the particle size of Cu, Te, Al, and Zr raw material powders. It was possible to realize.
  • the present invention makes it possible to make the composition and structure of the target uniform by improving the synthesis conditions of the raw material powder used for the Cu—Te alloy-based sintered sputtering target and controlling the pulverization method. Since segregation of the target can be prevented and abnormal structure can be suppressed, abnormal discharge starting from these can be prevented, generation of particles due to arcing can be suppressed, and the uniformity of the sputtered film Has an excellent effect of improving. At the same time, since the bending strength of the target can be increased, it is possible to effectively prevent cracking during sputtering, improve its quality, and form a uniform resistance change recording layer. A sputtering target can be obtained. Therefore, since the film forming conditions are stable, it is extremely useful as a resistance change recording material, that is, a medium for recording information using resistance change.

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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
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  • Metallurgy (AREA)
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  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Manufacturing Optical Record Carriers (AREA)
  • Optical Record Carriers And Manufacture Thereof (AREA)

Abstract

L'invention concerne une cible de pulvérisation cathodique formée d'un corps fritté à base d'un alliage Cu-Te, comprenant 40 à 90 % atomiques de Te, le reste étant constitué par les impuretés inévitables et Cu, ladite cible de pulvérisation cathodique étant caractérisée par le fait que le diamètre le plus grand d'une partie ayant subi une ségrégation qui existe dans la cible et comprend Cu, Te ou un composé intermétallique de ceux-ci est de 20 µm ou moins. La présente invention a pour but de rendre uniforme la composition et la structure d'une cible de pulvérisation cathodique formée d'un corps fritté à base d'un alliage Cu-Te, et en même temps, d'augmenter la résistance à la flexion de la cible par amélioration des conditions pour la synthèse d'une poudre de départ à utiliser pour la cible et contrôle du procédé de broyage de la poudre de départ pour empêcher de cette façon l'apparition d'une fissuration de la cible pendant la pulvérisation cathodique de façon efficace et améliorer la qualité de la cible, permettant ainsi de fournir une cible de pulvérisation cathodique formée d'un corps fritté à base d'un alliage Cu-Te qui peut former une couche d'enregistrement aléatoire résistive homogène.
PCT/JP2012/072463 2011-09-08 2012-09-04 Cible de pulvérisation cathodique formée d'un corps fritté à base d'un alliage cu-te WO2013035695A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015146311A1 (fr) * 2014-03-28 2015-10-01 Jx日鉱日石金属株式会社 CIBLE DE PULVÉRISATION CONTENANT UN ALLIAGE Al-Te-Cu-Zr ET SON PROCÉDÉ DE PRODUCTION
TWI667354B (zh) * 2014-10-09 2019-08-01 日商Ｊｘ日鑛日石金屬股份有限公司 由Ａｌ－Ｔｅ－Ｃｕ－Ｚｒ系合金組成之濺鍍靶及其製造方法

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JPS6213569A (ja) * 1985-07-10 1987-01-22 Mitsubishi Metal Corp ＴｅまたはＴｅ合金製スパツタリング用焼結タ−ゲツト
JPH03162570A (ja) * 1989-11-20 1991-07-12 Toshiba Corp スパッタリングターゲットおよびその製造方法
JP2001223183A (ja) * 1996-11-14 2001-08-17 Hitachi Metals Ltd Ａｌ系電極膜および液晶ディスプレイ
JP2006173267A (ja) * 2004-12-14 2006-06-29 Sony Corp 記憶素子及び記憶装置
JP2009043758A (ja) * 2007-08-06 2009-02-26 Sony Corp 記憶素子および記憶装置
WO2010026924A1 (fr) * 2008-09-02 2010-03-11 ソニー株式会社 Élément de stockage et dispositif de stockage
JP2011026679A (ja) * 2009-07-28 2011-02-10 Sony Corp ターゲット及びその製造方法、メモリ及びその製造方法

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Publication number Priority date Publication date Assignee Title
US4857373A (en) * 1987-03-31 1989-08-15 E. I. Du Pont De Nemours And Company Optical recording element
JP2004162109A (ja) * 2002-11-12 2004-06-10 Nikko Materials Co Ltd スパッタリングターゲット及び同製造用粉末

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6213569A (ja) * 1985-07-10 1987-01-22 Mitsubishi Metal Corp ＴｅまたはＴｅ合金製スパツタリング用焼結タ−ゲツト
JPH03162570A (ja) * 1989-11-20 1991-07-12 Toshiba Corp スパッタリングターゲットおよびその製造方法
JP2001223183A (ja) * 1996-11-14 2001-08-17 Hitachi Metals Ltd Ａｌ系電極膜および液晶ディスプレイ
JP2006173267A (ja) * 2004-12-14 2006-06-29 Sony Corp 記憶素子及び記憶装置
JP2009043758A (ja) * 2007-08-06 2009-02-26 Sony Corp 記憶素子および記憶装置
WO2010026924A1 (fr) * 2008-09-02 2010-03-11 ソニー株式会社 Élément de stockage et dispositif de stockage
JP2011026679A (ja) * 2009-07-28 2011-02-10 Sony Corp ターゲット及びその製造方法、メモリ及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015146311A1 (fr) * 2014-03-28 2015-10-01 Jx日鉱日石金属株式会社 CIBLE DE PULVÉRISATION CONTENANT UN ALLIAGE Al-Te-Cu-Zr ET SON PROCÉDÉ DE PRODUCTION
JPWO2015146311A1 (ja) * 2014-03-28 2017-04-13 Ｊｘ金属株式会社 Ａｌ−Ｔｅ−Ｃｕ−Ｚｒ合金からなるスパッタリングターゲット及びその製造方法
TWI667354B (zh) * 2014-10-09 2019-08-01 日商Ｊｘ日鑛日石金屬股份有限公司 由Ａｌ－Ｔｅ－Ｃｕ－Ｚｒ系合金組成之濺鍍靶及其製造方法

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