WO2013035695A1 - Cu-te-alloy-based sintered body sputtering target - Google Patents

Cu-te-alloy-based sintered body sputtering target 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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Japanese (ja)
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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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    • H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
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    • 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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Abstract

A Cu-Te-alloy-based sintered body sputtering target comprising 40 to 90 at% of Te and a remainder made up by unavoidable impurities and Cu, said sputtering target being characterized in that the largest diameter of a segregated part that exists in the target and comprises Cu, Te or an intermetallic compound thereof is 20 μm or less. The purpose of the present invention is to make the composition and the structure of a Cu-Te-alloy-based sintered body sputtering target uniform and, at the same time, increase the bending strength of the target by improving the conditions for the synthesis of a raw material powder to be used for the target and controlling the method for milling the raw material powder to thereby prevent the occurrence of cracking of the target during sputtering effectively and improve the quality of the target, thereby providing a Cu-Te-alloy-based sintered body sputtering target that can form a homogeneous resistive random recording layer.

Description

Ｃｕ－Ｔｅ合金系焼結体スパッタリングターゲットCu-Te alloy-based sintered sputtering target
　ターゲット中の偏析の大きさを所定以下とすることにより、異常放電、ノジュール、アーキング等が発生するという不具合が少なく、抗折力の高いＣｕ－Ｔｅ焼結スパッタリングターゲットを提供する。 Provided is 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.
　近年、抵抗変化記録用材料として、すなわち抵抗変化を利用して情報を記録する媒体としてＣｕ－Ｔｅ合金材料からなる薄膜が用いられるようになってきた。
　このＣｕ－Ｔｅ合金材料からなる薄膜を形成する方法としては、真空蒸着法やスパッタリング法などの、一般に物理蒸着法と言われている手段によって行われるのが普通である。特に、操作性や皮膜の安定性からマグネトロンスパッタリング法を用いて形成することが多い。 In recent years, 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.
As 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. In particular, the magnetron sputtering method is often used in view of operability and film stability.
　スパッタリング法による膜の形成は、陰極に設置したターゲットにＡｒイオンなどの正イオンを物理的に衝突させ、その衝突エネルギーでターゲットを構成する材料を放出させて、対面している陽極側の基板にターゲット材料とほぼ同組成の膜を積層することによって行われる。
　スパッタリング法による被覆法は処理時間や供給電力等を調節することによって、安定した成膜速度でオングストローム単位の薄い膜から数十μｍの厚い膜まで形成できるという特徴を有している。 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 μm can be formed at a stable film formation speed by adjusting the processing time, supply power, and the like.
　従来、抵抗変化記録膜用Ｃｕ－Ｔｅ基合金材料からなる膜をスパッタリング法によって形成しようとすると、ノジュール（異常突起物）やクレーター（異常凹み）などの異常組織がターゲット表面に発生し、これらを基点としてマイクロアーキング（異常放電）が発生し、これら自身がパーティクルと呼ばれるクラスター（原子の集合体）状の異物として薄膜に混入してしまっていた。 Conventionally, when a film made of a Cu—Te based alloy material for a resistance change recording film is formed by sputtering, abnormal structures such as nodules (abnormal protrusions) and craters (abnormal dents) are generated on the target surface. Micro arcing (abnormal discharge) 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.
　また、スパッタリングの際にターゲットのクラック又は割れの発生、形成された薄膜の不均一性、ターゲット用焼結粉の製造工程で吸収される酸素等の多量のガス成分があり、スパッタ膜の膜質に悪影響を与えていた。
　このようなターゲット又はスパッタリングの際の問題は、記録媒体である薄膜の品質や歩留まりを低下させる大きな原因となる。 In addition, there is a large amount of gas components such as the generation of cracks or cracks in the target during sputtering, non-uniformity of the formed thin film, oxygen absorbed in the manufacturing process of the sintered powder for the target, and the film quality of the sputtered film It had an adverse effect.
Such a problem in the target or sputtering is a major cause of lowering the quality and yield of a thin film as a recording medium.
　従来の抵抗変化記録層は、ＮｉＯ、ＴａＯ２、ＴｉＯ２等の金属酸化物、ＰｒＣａＭｎＯ３、ＣｒドープされたＳｒＺｒＯ３等のペロブスカイト系複合酸化物
が主に使用されている。しかしながら、Ｃｕ－Ｔｅ合金のようなカルコゲナイド化合物をスパッタリングターゲットとして使用した実績が乏しく、この材料をスパッタリングする際に求められる特性やターゲットとして製造する上での問題点が十分に把握されていないのが現状であった。 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 . However, 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.
　このため、Ｃｕ－Ｔｅ合金ターゲットを用いてスパッタリングする際に発生する、パーティクル、異常放電（アーキング）、ターゲット上のノジュールやクレーターの発生、ターゲットのクラック又は割れの発生、さらにはターゲット中に含まれる多量の酸素等のガス成分を避けることができなかった。 For this reason, particles, abnormal discharge (arcing), generation of nodules and craters on the target, generation of cracks or cracks in the target, and generation of cracks or cracks in the target are generated when sputtering using a Cu—Te alloy target. A large amount of gas components such as oxygen could not be avoided.
　従来のＣｕ－Ｔｅ基スパッタリング用ターゲットの製造方法として、原料として、純度５ＮのＣｕワイヤーとＴｅショットを準備し、これらを所定の組成となるように調合した後、アンプル内で合成し、得られたインゴットを所定の粒度まで粉砕した後、加圧焼結を行ってＣｕ－Ｔｅ基スパッタリング用ターゲットを製造していた。 As a conventional method for producing a target for Cu-Te based sputtering, 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.
　しかしながら、この製法で作られたターゲットは、ＣｕとＴｅの大きな偏析を生じるために、ターゲットの組成が不均一となり、またインゴットを粗粉砕したために、粒度分布も不均一となり、ターゲットが均一にエロージョンされないという問題があった。その結果、ノジュールやアーキングの発生によるパーティクルが大量発生し、ターゲット自体の強度が弱いことで、スパッタ中にターゲットが割れるといった事象も見られた。 However, 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.
　従来技術を見ると、下記特許文献１～９に、情報の記録等の動作を安定して行うための記憶素子用のイオン源層として、ＣｕとＴｅを用いる例と、これらをスパッタリングにより成膜する例が示されている。
　しかし、この場合は、下部電極、イオン源層、記憶層、上部電極などの、記憶素子の構成と材料の選択することが中心の発明であり、スパッタリングターゲットの問題には、全く無関心である。このことから、この場合に使用するターゲットは、従来技術の問題を内包していると言える。 Looking at the prior art, the following 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.
However, in this case, 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.
特開２００５－１９７６３４号公報JP 2005-197634 A 特開２００６－１７３２６７号公報JP 2006-173267 A 特開２００６－３２４４２５号公報JP 2006-324425 A 特開２００６－３５１７８０号公報JP 2006-351780 A 特開２００７－１５７９４１号公報JP 2007-157941 A 特開２００７－１５７９４２号公報JP 2007-157842 A 特開２００７－２０１２７０号公報JP 2007-201270 A 特開２００７－２９４７４５号公報JP 2007-294745 A 特開２００９－０４３７５８号公報JP 2009-043758 A
　本発明は、Ｃｕ－Ｔｅ合金系焼結体スパッタリングターゲットに使用する原料粉末の合成条件の改良と粉砕方法を制御することにより、ターゲットの組成と組織の均一化を図り、同時に抗折力を高めることで、スパッタ中の割れを効果的に防止して、その品質を改善し、均質な抵抗変化記録層を形成できるＣｕ－Ｔｅ合金系焼結体スパッタリングターゲットを提供することを課題とする。 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. Thus, 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.
　上記問題点を解決するための技術的な手段は、安定しかつ均質な抵抗変化記録層を形成するためのＣｕ－Ｔｅ合金系焼結体スパッタリングターゲットは、原料粉末の合成条件の改良と粉砕方法を工夫することによって得ることができ、これによってターゲット組織の分散性と均一性を向上させると共に、ターゲットの機械的強度を向上させ、安定したスパッタが実現するとの知見を得た。 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.
　この知見に基づき、本発明は、下記の発明を提供するものである。
　１）Ｔｅ：４０～９０ａｔ％、残部不可避的不純物とＣｕからなるＣｕ－Ｔｅ合金系焼結体スパッタリングターゲットであって、該ターゲットに存在するＣｕ、Ｔｅ又はこれらの金属間化合物からなる偏析部の最大径が２０μｍ以下であることを特徴とするＣｕ－Ｔｅ合金系焼結体スパッタリングターゲット。
　２）Ｃｕ、Ｔｅ又はこれらの金属間化合物からなる偏析部の最大径が１０μｍ以下であることを特徴とする請求項１記載のＣｕ－Ｔｅ系焼結体スパッタリングターゲット。
　３）Ｃｕ－Ｔｅ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍ以下であり、該ターゲットの抗折力が７０Ｍｐａ以上であることを特徴とする請求項１又は２に記載のＣｕ－Ｔｅ系焼結体スパッタリングターゲット。
　４）Ａｌ及び又はＧｅを、最大で５０ａｔ％含有することを特徴とする上記１）～３）のいずれか一項に記載のＣｕ－Ｔｅ系焼結体スパッタリングターゲット。
　５）Ｚｒを、最大で５０ａｔ％含有することを特徴とする上記１）～４）のいずれか一項に記載のＣｕ－Ｔｅ系焼結体スパッタリングターゲット。 Based on this knowledge, 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 μm 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 μm or less.
3) The average grain size of the crystal grains present in the Cu—Te alloy-based sintered body target is 10 μm or less, and the bending strength of the target is 70 Mpa or more. Cu—Te based sintered sputtering target.
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%.
　本発明は、Ｃｕ－Ｔｅ合金系焼結体スパッタリングターゲットに使用する原料粉末の合成条件の改良と粉砕方法を制御することにより、ターゲットの組成と組織の均一化を図ることが可能となり、これによってターゲットの偏析を防止し、異常組織を抑制することができるので、これらを起点とする異常放電を防止することが可能となり、アーキングによるパーティクルの発生を抑制することができ、さらにスパッタ膜の均一性が向上するという優れた効果を有する。
　また、同時にターゲットの抗折力を高めることができるので、スパッタ中の割れを効果的に防止して、その品質を改善し、均質な抵抗変化記録層を形成できるＣｕ－Ｔｅ合金系焼結体スパッタリングターゲットを得ることができる。 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.
実施例１の焼結後の表面のＦＥ－ＥＰＭＡ観察写真を示す図である。3 is a view showing an FE-EPMA observation photograph of the surface after sintering in Example 1. FIG. 実施例２の焼結後の表面のＦＥ－ＥＰＭＡ観察写真を示す図である。4 is a view showing an FE-EPMA observation photograph of the surface after sintering in Example 2. FIG. 比較例１の焼結後の表面のＦＥ－ＥＰＭＡ観察写真を示す図である。4 is a view showing an FE-EPMA observation photograph of a surface after sintering in Comparative Example 1. FIG. 比較例２の焼結後の表面のＦＥ－ＥＰＭＡ観察写真を示す図である。4 is a view showing an FE-EPMA observation photograph of a surface after sintering in Comparative Example 2. FIG.
　本発明のＣｕ－Ｔｅ合金系焼結体スパッタリングターゲットは、Ｔｅ：４０～９０ａｔ％、残部不可避的不純物とＣｕからなる。該ターゲットに存在するＣｕ、Ｔｅ又はこれらの金属間化合物からなる偏析部の最大径が２０μｍ以下、さらには偏析部の最大径が１０μｍであることが、本願発明の大きな特徴の一つである。このような偏析は、Ｃｕ－Ｔｅ合金の焼結の際に、均一な組成の合金とならずに、組成ずれを起こすことにより形成される。
　偏析部が大きくなると、後述する比較例に示すように、異常放電、ノジュール、アーキングが多発して、パーティクルの多いスパッタ膜が形成され、本願発明の目的を達成することができない。また、抗折力が低下するために、スパッタリング中に割れが発生することもある。 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 μm or less, and further the maximum diameter of the segregated portion is 10 μm. Such segregation is formed by causing a composition shift when the Cu—Te alloy is sintered, without forming a uniform composition alloy.
When the segregation portion becomes large, abnormal discharge, nodules, and arcing occur frequently as shown in a comparative example described later, and a sputtered film with many particles is formed, and the object of the present invention cannot be achieved. In addition, since the bending strength is reduced, cracks may occur during sputtering.
　さらに、本願発明のＣｕ－Ｔｅ系焼結体スパッタリングターゲットは、当該ターゲットに存在する結晶粒の平均粒径が１０μｍ以下であり、該ターゲットの抗折力が７０Ｍｐａ以上であることも特徴の一つである。抗折力向上の観点から見れば、ターゲットをＴｅ：４０～６０ａｔ％、残部不可避不純物とＣｕの原料で作製することがより望ましい。
　また、最大結晶粒径は１０μｍ以下であることが好ましい。前記偏析部の径は、結晶粒径同等のもの、それよりも小さなもの、さらには結晶粒径を超える大きさのものも存在する。このように偏析部の径は一定ではないので、ターゲットの平均粒径は、前記偏析部を除外して平均粒径を計測する。 Furthermore, 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 μm 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 μm 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.
　本発明のＣｕ－Ｔｅ系焼結体スパッタリングターゲットは、上記組成においてＡｌ及び又はＧｅを、最大で５０ａｔ％含有させ、残部をＣｕとすることができる。また、Ｃｕ－Ｔｅ系焼結体の前記組成において、Ｚｒを最大で５０ａｔ％含有させ、残部をＣｕとすることができる。
　これらの元素は、陽イオンとして、材料中を容易に移動し、ＣｕＴｅの金属カルコゲナイド層を安定化させる役割を担う。特に、Ａｌ、Ｇｅは、データの消去時に酸化物を形成するため、抵抗が大幅に増加する。これによりＲｅＲＡＭの特徴である抵抗比調整を行うことができる。一方、Ｚｒは陽イオンとなり移動し易くなり、抵抗を下げ、安定的に動作させる機能を持つ。 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.
　上記の特徴を持つ本願発明のＣｕ－Ｔｅ系焼結体スパッタリングターゲットは次のような工程を経て製造する。
　具体的には、高純度の（４Ｎレベル以上）ＣｕとＴｅの原料を、４０～９０ａｔ％Ｔｅ、残部Ｃｕとなるように、秤量・調合し、これを９００～１１００°Ｃで揺動溶解する。これは、ＣｕとＴｅを均一に混ぜ合わせるためである。
　この条件を逸脱した場合には、Ｃｕの未固溶部が残存するという不具合が生ずる。次に、これを３４０～４５０°Ｃまでは自然放熱により徐冷した後、３４０～４５０°Ｃで１０～２０時間、温度を一定に保持する。これは状態図通りの相を析出させるためである。これを逸脱する場合には偏析による組成ムラという不具合が生ずる。
　その後、室温まで自然放熱により徐冷しインゴットとする。以上の工程は、成分の偏析を抑制する上で、重要である。 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.
　次に、得られたＣｕＴｅインゴットを乳鉢で粉砕した後、ジェットミル粉砕し、平均粒径が２～３μｍのＣｕＴｅ原料粉とする。
　ボールミルやアトライターの摩砕では、粉同士が凝集し易いので、好ましくはジエットミル、ハンマーミル、スタンプミルなどの瞬間的に打撃を与える粉砕方法を採用するのが良い。また、後者の場合は、高効率での粉砕が可能であるという利点もある。
　次に、粉砕した原料粉をホットプレスして、ターゲット形状とした後、表面を研削加工、バッキングプレート板へのボンディングを経て表面研磨加工を行い、スパッタリングターゲットを得る。Ａｌ、Ｇｅ、Ｚｒを添加する場合には、同様にして原料粉末を作製するか、又はそれぞれの粉末を単に混合し、ホットプレスしてターゲットとする。これらの製造工程によって、ターゲットの相対密度を、９９％以上に高密度化が達成できる。 Next, the obtained CuTe ingot is pulverized in a mortar and then jet milled to obtain a CuTe raw material powder having an average particle diameter of 2 to 3 μm.
In ball milling or attritor grinding, powders are likely to aggregate, and therefore, a grinding method that instantaneously strikes, such as a jet mill, a hammer mill, or a stamp mill, is preferably employed. In the latter case, there is also an advantage that pulverization with high efficiency is possible.
Next, after the pulverized raw material powder is hot pressed to obtain a target shape, the surface is ground and subjected to surface polishing through bonding to a backing plate to obtain a sputtering target. In the case of adding Al, Ge, Zr, raw material powders are produced in the same manner, or the respective powders are simply mixed and hot pressed to obtain a target. By these manufacturing steps, the relative density of the target can be increased to 99% or more.
　ここでは、最も代表的な５０ａｔ％Ｃｕ－５０ａｔ％Ｔｅと４０ａｔ％Ｃｕ－６０ａｔ％Ｔｅのターゲットの例を、下記実施例１、２に説明する。
　なお、以下の実施例はあくまで一例であり、この例に制限されるものではない。すなわち、本発明の技術思想の範囲内で、実施例以外の態様あるいは変形を全て包含するものである。 Here, examples of the most typical targets of 50 at% Cu-50 at% Te and 40 at% Cu-60 at% Te will be described in Examples 1 and 2 below.
The following embodiment is merely an example, and the present invention is not limited to this example. That is, all aspects or modifications other than the embodiments are included within the scope of the technical idea of the present invention.
（実施例１）
　４ＮのＣｕと４ＮのＴｅの原料を、５０ａｔ％Ｃｕ－５０ａｔ％Ｔｅとなるように秤量・調合し、これを１０００°Ｃで溶解した。次に、これを４２０°Ｃまでは自然放熱により徐冷した後、４２０°Ｃで２０時間、温度を一定に保持した。その後、室温まで自然放熱により徐冷した。 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.
　得られたＣｕＴｅインゴットを乳鉢粉砕した後、ジェットミル粉砕し、平均粒径が２～３μｍのＣｕＴｅ原料粉とした。これをホットプレスして、ターゲット形状とした後、表面を研削加工、バッキングプレート板へのボンディングを経て表面研磨加工を行い、スパッタリングターゲットを得た。これらのターゲットの相対密度は９９％以上であった。 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 μm. 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.
　図１に実施例１によって得た焼結後のターゲット表面のＦＥ－ＥＰＭＡ観察写真を示す。この図１に示すように、偏析が抑制され、実施例１のスパッタリングターゲットに存在する偏析部の最大径は２０μｍ以下に減少した。すなわち最大径が２０μｍ以上のＣｕ、Ｔｅ又はＣｕ－Ｔｅ金属間化合物の偏析部は、エロージョン面全体に渡って存在しなかった。また、Ｃｕ－Ｔｅ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍ以下であった。 FIG. 1 shows an FE-EPMA observation photograph of the sintered target surface obtained in Example 1. As shown in FIG. 1, segregation was suppressed, and the maximum diameter of the segregation part existing in the sputtering target of Example 1 was reduced to 20 μm or less. That is, no segregated portion of Cu, Te or Cu—Te intermetallic compound having a maximum diameter of 20 μm 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 μm or less.
　さらに、抗折力については、１２８ Ｍｐａ（５０ａｔ％Ｃｕ）であり、本願発明のターゲットの抗折力：７０Ｍｐａ以上を達成していた。原料合成後の冷却温度パターンを工夫することで焼結後に大きな偏析部が発生することを抑制すると共に、ＣｕＴｅ原料粉の粒径を最適化することで抗折力アップを実現することが可能であった。 Furthermore, 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. By devising the cooling temperature pattern after synthesis of raw materials, it is possible to suppress the occurrence of large segregation parts after sintering, and it is possible to increase the bending strength by optimizing the particle size of the CuTe raw material powder. there were.
　また、実際にスパッタリングを行って比較した所、実施例によるものは、異常放電、ノジュール、アーキングが少なく良好なスパッタ膜が得られた。 In addition, when sputtering was actually performed and compared, according to the example, a good sputtered film with less abnormal discharge, nodules, and arcing was obtained.
（実施例２）
　４ＮのＣｕと４ＮのＴｅの原料を、６０ａｔ％Ｃｕ－４０ａｔ％Ｔｅとなるように秤量・調合し、これを１０００°Ｃで溶解した。次に、これを４２０°Ｃまでは自然放熱により徐冷した後、４２０°Ｃで２０時間、温度を一定に保持した。その後、室温まで自然放熱により徐冷した。 (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.
　得られたＣｕＴｅインゴットを乳鉢粉砕した後、ジェットミル粉砕し、平均粒径が２～３μｍのＣｕＴｅ原料粉とした。これをホットプレスして、ターゲット形状とした後、表面を研削加工、バッキングプレート板へのボンディングを経て表面研磨加工を行い、スパッタリングターゲットを得た。これらのターゲットの相対密度は９９％以上であった。 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 μm. 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.
　図２に実施例２によって得た焼結後のターゲット表面のＦＥ－ＥＰＭＡ観察写真を示す。この図２に示すように、偏析が抑制され、実施例２のスパッタリングターゲットに存在する偏析部の最大径は２０μｍ以下に減少した。すなわち最大径が１０μｍ以上の、Ｃｕ、Ｔｅ又はＣｕ－Ｔｅ金属間化合物の偏析部は、エロージョン面全体に渡って存在しなかった。また、Ｃｕ－Ｔｅ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍ以下であった。 FIG. 2 shows an FE-EPMA observation photograph of the target surface after sintering obtained in Example 2. As shown in FIG. 2, segregation was suppressed, and the maximum diameter of the segregation part existing in the sputtering target of Example 2 was reduced to 20 μm or less. That is, no segregated portion of Cu, Te or Cu—Te intermetallic compound having a maximum diameter of 10 μm 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 μm or less.
　さらに、抗折力については、７８ Ｍｐａ（６０ａｔ％Ｃｕ）であり、本願発明のターゲットの抗折力：７０Ｍｐａ以上を達成していた。原料合成後の冷却温度パターンを工夫することで焼結後に大きな偏析部が発生することを抑制すると共に、ＣｕＴｅ原料粉の粒径を最適化することで抗折力アップを実現することが可能であった。 Furthermore, 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. By devising the cooling temperature pattern after synthesis of raw materials, it is possible to suppress the occurrence of large segregation parts after sintering, and it is possible to increase the bending strength by optimizing the particle size of the CuTe raw material powder. there were.
　また、実際にスパッタリングを行って比較した所、実施例によるものは、異常放電、ノジュール、アーキングが少なく良好なスパッタ膜が得られた。 In addition, when sputtering was actually performed and compared, according to the example, a good sputtered film with less abnormal discharge, nodules, and arcing was obtained.
（比較例１）
　４ＮのＣｕと４ＮのＴｅの原料を、５０ａｔ％Ｃｕ－５０ａｔ％Ｔｅとなるように秤量・調合し１０００°Ｃで溶解した。その後、そのまま室温まで自然放熱により徐冷した。得られたＣｕＴｅインゴットを乳鉢粉砕し、平均粒径が２０～３０μｍＣｕＴｅ原料粉とした。 (Comparative 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. Thereafter, it was gradually cooled to room temperature by natural heat dissipation. The obtained CuTe ingot was pulverized to obtain a CuTe raw material powder having an average particle size of 20 to 30 μm.
　次に、これをホットプレスしてターゲット形状とした後、表面を研削加工、バッキングプレート板へのボンディングを経て表面研磨加工を行い、スパッタリングターゲットを得た。これらのターゲットの相対密度は９９％以上であった。 Next, this was hot pressed to obtain a target shape, and then the surface 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.
　しかしながら、比較例１のスパッタリングターゲットは、図３に示すように、偏析部の最大径が２０μｍを超え、偏析の大きいものは、最大径が５０μｍに達した。そして、この偏析部はＣｕ又はＴｅのターゲットとのエロージョン面全体に渡って散在していた。また、比較例１のターゲットの、抗折力は４７Ｍｐａであり、本願発明の本願発明のターゲットの抗折力：７０Ｍｐａ以上を達成することができなかった。また、Ｃｕ－Ｔｅ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍを超え、２８μｍであった。 However, in the sputtering target of Comparative Example 1, as shown in FIG. 3, the maximum diameter of the segregation part exceeded 20 μm, and the one with large segregation reached the maximum diameter of 50 μm. And this segregation part was scattered over the whole erosion surface with the target of Cu or Te. Moreover, 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. In addition, the average grain size of the crystal grains present in the Cu—Te alloy-based sintered compact target exceeded 10 μm and was 28 μm.
　そして、比較例１によるものは、異常放電、ノジュール、アーキングが多発して、パーティクルの多いスパッタ膜となった。これらは、Ｃｕ－Ｔｅ合金系焼結体スパッタリングターゲットに使用する原料粉末の合成条件と粉砕方法が適切に行われなかったことに原因があり、ターゲットの組成と組織の均一化を図ることができなかった。 And, according to Comparative Example 1, abnormal discharge, nodules, and arcing frequently occurred, resulting in a sputtered film with many particles. These are due to the fact that the synthesis conditions and pulverization method of the raw material powder used for the Cu—Te alloy-based sintered sputtering target have not been properly performed, and the target composition and structure can be made uniform. There wasn't.
（比較例２）
　４ＮのＣｕと４ＮのＴｅの原料を、６０ａｔ％Ｃｕ－４０ａｔ％Ｔｅとなるように秤量・調合し１０００°Ｃで溶解した。その後、そのまま室温まで自然放熱により徐冷した。得られたＣｕＴｅインゴットを乳鉢粉砕し、平均粒径が２０～３０μｍＣｕＴｅ原料粉とした。 (Comparative 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. Thereafter, it was gradually cooled to room temperature by natural heat dissipation. The obtained CuTe ingot was pulverized to obtain a CuTe raw material powder having an average particle size of 20 to 30 μm.
　次に、これをホットプレスしてターゲット形状とした後、表面を研削加工、バッキングプレート板へのボンディングを経て表面研磨加工を行い、スパッタリングターゲットを得た。これらのターゲットの相対密度は９９％以上であった。 Next, this was hot pressed to obtain a target shape, and then the surface 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.
　しかしながら、比較例１のスパッタリングターゲットは、図４に示すように、偏析部の最大径が２０μｍを超え、偏析の大きいものは、最大径が５０μｍに達した。そして、この偏析部はＣｕ又はＴｅのターゲットとのエロージョン面全体に渡って散在していた。また、比較例２のターゲットの、抗折力は３１Ｍｐａとなり、本願発明のターゲットの抗折力：７０Ｍｐａ以上を達成することができなかった。また、Ｃｕ－Ｔｅ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍを超え、２２μｍであった。 However, in the sputtering target of Comparative Example 1, as shown in FIG. 4, the maximum diameter of the segregation part exceeded 20 μm, and the one with large segregation reached the maximum diameter of 50 μm. And this segregation part was scattered over the whole erosion surface with the target of Cu or Te. Moreover, 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. In addition, the average grain size of the crystal grains present in the Cu—Te alloy-based sintered body target exceeded 10 μm and was 22 μm.
　そして、比較例２によるものは、異常放電、ノジュール、アーキングが多発して、パーティクルの多いスパッタ膜となった。さらに、この比較例２では、使用中にクラックが発生した。これらは、Ｃｕ－Ｔｅ合金系焼結体スパッタリングターゲットに使用する原料粉末の合成条件と粉砕方法が適切に行われなかったことに原因があると考えられた。 And, according to 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.
（実施例３）
　４ＮのＣｕと４ＮのＴｅと４ＮのＧｅの原料を、４２．５ａｔ％Ｃｕ－４２．５ａｔ％Ｔｅ－１５ａｔ％Ｇｅとなるように秤量・調合し、これを１０００°Ｃで溶解した。次に、これを４２０°Ｃまでは自然放熱により徐冷した後、４２０°Ｃで２０時間、温度を一定に保持した。その後、室温まで自然放熱により徐冷した。 (Example 3)
Raw materials of 4N Cu, 4N Te and 4N Ge were weighed and prepared so as to be 42.5 at% Cu-42.5 at% Te-15 at% Ge, 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.
　得られたＣｕＴｅＧｅインゴットを乳鉢粉砕した後、ジェットミル粉砕し、平均粒径が２～３μｍのＣｕＴｅＧｅ原料粉とした。これをホットプレスして、ターゲット形状とした後、表面を研削加工、バッキングプレート板へのボンディングを経て表面研磨加工を行い、スパッタリングターゲットを得た。これらのターゲットの相対密度は９９％以上であった。 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 μm. 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.
　実施例３によって得た焼結後のターゲット表面のＦＥ－ＥＰＭＡ観察した結果、実施例１と同様に、偏析が抑制され、実施例３のスパッタリングターゲットに存在する偏析部の最大径は２０μｍ以下に減少した。すなわち最大径が２０μｍ以上のＣｕ、Ｔｅ、Ｇｅ又はこれらの金属間化合物の偏析部は、エロージョン面全体に渡って存在しなかった。また、Ｃｕ－Ｔｅ－Ｇｅ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍ以下であった。 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 μm 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 μm or less.
　さらに、抗折力については、９０Ｍｐａであり、本願発明のターゲットの抗折力：７０Ｍｐａ以上を達成していた。原料合成後の冷却温度パターンを工夫することで焼結後に大きな偏析部が発生することを抑制すると共に、Ｃｕ、Ｔｅ、Ｇｅ原料粉の粒径を最適化することで抗折力アップを実現することが可能であった。 Furthermore, the bending strength was 90 Mpa, and the bending strength of the target of the present invention: 70 Mpa or more was achieved. By devising 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, Ge raw material powder. It was possible.
（実施例４）
　４ＮのＣｕと４ＮのＴｅと４ＮのＡｌの原料を、４２．５ａｔ％Ｃｕ－４２．５ａｔ％Ｔｅ－１５ａｔ％Ａｌとなるように秤量・調合し、これらの混合粉末を溶解で作製すると、非常に活性な物質となることが懸念されたので、ＣｕＴｅＡｌ原料粉の混合物を、そのままホットプレスして、ターゲット形状とした。 (Example 4)
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.
　得られたターゲット材料の表面を研削加工、バッキングプレート板へのボンディングを経て表面研磨加工を行い、スパッタリングターゲットを得た。これらのターゲットの相対密度は９９％以上であった。 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.
　実施例４によって得た焼結後のターゲット表面のＦＥ－ＥＰＭＡ観察した結果、実施例１と同様に、偏析が抑制され、実施例４のスパッタリングターゲットに存在する偏析部の最大径は２０μｍ以下に減少した。すなわち最大径が２０μｍ以上のＣｕ、Ｔｅ、Ｇｅ、Ａｌ又はこれらの金属間化合物の偏析部は、エロージョン面全体に渡って存在しなかった。また、Ｃｕ－Ｔｅ－Ａｌ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍ以下であった。 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 μm 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 μm 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 μm or less.
　さらに、抗折力については、１２８Ｍｐａであり、本願発明のターゲットの抗折力：７０Ｍｐａ以上を達成していた。原料合成後の冷却温度パターンを工夫することで焼結後に大きな偏析部が発生することを抑制すると共に、Ｃｕ、Ｔｅ、Ａｌ原料粉の粒径を最適化することで抗折力アップを実現することが可能であった。 Furthermore, the bending strength was 128 Mpa, and the bending strength of the target of the present invention: 70 Mpa or more was achieved. By devising 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 raw material powder It was possible.
（実施例５）
　４ＮのＣｕと４ＮのＴｅと４ＮのＡｌと４ＮのＺｒの原料を、１４ａｔ％Ｃｕ－２２ａｔ％Ｔｅ－５０ａｔ％Ａｌ－１４ａｔ％Ｚｒとなるように秤量・調合した。これらの混合粉末を溶解で作製すると、非常に活性な物質となることが懸念されたので、ＣｕＴｅＡｌＺｒ原料粉の混合物を、そのままホットプレスして、ターゲット形状とした後、表面を研削加工、バッキングプレート板へのボンディングを経て表面研磨加工を行い、スパッタリングターゲットを得た。これらのターゲットの相対密度は９９％以上であった。 (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.
　実施例５によって得た焼結後のターゲット表面のＦＥ－ＥＰＭＡ観察した結果、実施例１と同様に、偏析が抑制された。このようなスパッタリングターゲットに存在する偏析部については、粉末の粒径やホットプレス温度を調整することにより制御可能であり、本実施例５は本願発明の条件を満たしていた。また、Ｃｕ－Ｔｅ－Ａｌ－Ｚｒ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍ以下であった。 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 μm or less.
　さらに、抗折力については、８０Ｍｐａであり、本願発明のターゲットの抗折力：７０Ｍｐａ以上を達成していた。原料合成後の冷却温度パターンを工夫することで焼結後に大きな偏析部が発生することを抑制すると共に、Ｃｕ、Ｔｅ、Ａｌ、Ｚｒ原料粉の粒径を最適化することで抗折力アップを実現することが可能であった。 Furthermore, the bending strength was 80 Mpa, and the bending strength of the target of the present invention: 70 Mpa or more was achieved. By devising 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.
　また、実際にスパッタリングを行って比較した所、実施例によるものは、異常放電、ノジュール、アーキングが少なく良好なスパッタ膜が得られた。 In addition, when sputtering was actually performed and compared, according to the example, a good sputtered film with less abnormal discharge, nodules, and arcing was obtained.
　本発明は、Ｃｕ－Ｔｅ合金系焼結体スパッタリングターゲットに使用する原料粉末の合成条件の改良と粉砕方法を制御することにより、ターゲットの組成と組織の均一化を図ることが可能となり、これによってターゲットの偏析を防止し、異常組織を抑制することができるので、これらを起点とする異常放電を防止することが可能となり、アーキングによるパーティクルの発生を抑制することができ、さらにスパッタ膜の均一性が向上するという優れた効果を有する。また、同時にターゲットの抗折力を高めることができるので、スパッタ中の割れを効果的に防止して、その品質を改善し、均質な抵抗変化記録層を形成できるＣｕ－Ｔｅ合金系焼結体スパッタリングターゲットを得ることができる。したがって、成膜条件が安定しているので、抵抗変化記録用材料、すなわち抵抗変化を利用して情報を記録する媒体として極めて有用である。 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.

Claims (5)

  1. 　Ｔｅ：４０～９０ａｔ％、残部不可避的不純物とＣｕからなるＣｕ－Ｔｅ合金系焼結体スパッタリングターゲットであって、該ターゲットに存在するＣｕ、Ｔｅ又はこれらの金属間化合物からなる偏析部の最大径が２０μｍ以下であることを特徴とするＣｕ－Ｔｅ合金系焼結体スパッタリングターゲット。 Te: 40 to 90 at%, the remaining diameter of the Cu-Te alloy-based sintered sputtering target composed of inevitable impurities and Cu, and the maximum diameter of the segregated portion composed of Cu, Te or an intermetallic compound existing in the target A Cu—Te alloy-based sintered sputtering target characterized by having a thickness of 20 μm or less.
  2. 　Ｃｕ、Ｔｅ又はこれらの金属間化合物からなる偏析部の最大径が１０μｍ以下であることを特徴とする請求項１記載のＣｕ－Ｔｅ系焼結体スパッタリングターゲット。 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 μm or less.
  3. 　Ｃｕ－Ｔｅ合金系焼結体ターゲットに存在する結晶粒の平均粒径が１０μｍ以下であり、該ターゲットの抗折力が７０Ｍｐａ以上であることを特徴とする請求項１又は２に記載のＣｕ－Ｔｅ系焼結体スパッタリングターゲット。 3. The Cu— according to claim 1, wherein the average grain size of the crystal grains present in the Cu—Te alloy-based sintered body target is 10 μm or less, and the bending strength of the target is 70 Mpa or more. Te-based sintered sputtering target.
  4. 　Ａｌ及び又はＧｅを、最大で５０ａｔ％含有することを特徴とする請求項１～３のいずれか一項に記載のＣｕ－Ｔｅ系焼結体スパッタリングターゲット。 The Cu-Te sintered sputtering target according to any one of claims 1 to 3, wherein Al and / or Ge are contained in a maximum of 50 at%.
  5. 　Ｚｒを、最大で５０ａｔ％含有することを特徴とする請求項１～４のいずれか一項に記載のＣｕ－Ｔｅ系焼結体スパッタリングターゲット。 The Cu-Te based sintered sputtering target according to any one of claims 1 to 4, wherein Zr is contained at a maximum of 50 at%.
PCT/JP2012/072463 2011-09-08 2012-09-04 Cu-te-alloy-based sintered body sputtering target WO2013035695A1 (en)

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