JP5530270B2 - Cobalt powder and method for producing the same - Google Patents
Cobalt powder and method for producing the same Download PDFInfo
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims description 118
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 229910017052 cobalt Inorganic materials 0.000 claims description 63
- 239000010941 cobalt Substances 0.000 claims description 63
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 35
- 229940044175 cobalt sulfate Drugs 0.000 claims description 33
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 33
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 30
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 229910052700 potassium Inorganic materials 0.000 claims description 19
- 229910052791 calcium Inorganic materials 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 10
- 239000000696 magnetic material Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 2
- ZRLWPMXOMOICQX-UHFFFAOYSA-J cobalt(2+) oxalate Chemical compound C(C(=O)[O-])(=O)[O-].[Co+2].[Co+2].C(C(=O)[O-])(=O)[O-] ZRLWPMXOMOICQX-UHFFFAOYSA-J 0.000 claims 1
- 239000012535 impurity Substances 0.000 description 35
- 239000010409 thin film Substances 0.000 description 23
- 239000010408 film Substances 0.000 description 22
- 239000000843 powder Substances 0.000 description 21
- 238000004544 sputter deposition Methods 0.000 description 21
- 229910052717 sulfur Inorganic materials 0.000 description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- 229910000428 cobalt oxide Inorganic materials 0.000 description 14
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- MWHSMSAKVHVSAS-UHFFFAOYSA-L cobalt(2+);oxalate;dihydrate Chemical compound O.O.[Co+2].[O-]C(=O)C([O-])=O MWHSMSAKVHVSAS-UHFFFAOYSA-L 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- LBFUKZWYPLNNJC-UHFFFAOYSA-N cobalt(ii,iii) oxide Chemical compound [Co]=O.O=[Co]O[Co]=O LBFUKZWYPLNNJC-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005477 sputtering target Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 150000001868 cobalt Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000684 Cobalt-chrome Inorganic materials 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- -1 Na and K Chemical class 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000010952 cobalt-chrome Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MOHVWRCMMMKFST-UHFFFAOYSA-N dioxosilane platinum Chemical compound [Si](=O)=O.[Pt] MOHVWRCMMMKFST-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Description
本発明は、コバルト粉末及びその製造方法であり、アルカリ金属元素、アルカリ土類金属元素、硫黄、酸素、炭素のガス成分（ガス化する成分を含む。）等の不純物が少なく、粒径の細かいコバルト粉末、磁性材を製造するためのスパッタリングターゲットに有用であるコバルト粉末及びその製造方法に関する。 The present invention relates to a cobalt powder and a method for producing the same, and has a small particle size with few impurities such as alkali metal elements, alkaline earth metal elements, sulfur, oxygen, and carbon gas components (including gasifying components). The present invention relates to a cobalt powder useful for a sputtering target for producing a magnetic material and a method for producing the same.
近年、半導体の飛躍的な進歩に端を発して様々な電子機器が生まれ、さらにその性能の向上と新しい機器の開発が日々刻々なされている。
このような中で、電子、デバイス機器がより微小化し、かつ集積度が高まる方向にある。これら多くの製造工程の中で多数の薄膜が形成されるが、コバルトは強磁性体として良く知られた材料である。そして、その特異な金属的性質からコバルト膜、コバルト合金膜、コバルト酸化膜、他の金属元素又は酸化物との混合物膜、コバルトシリサイド膜などとして、多くの電子機器薄膜の形成に利用されている。特に、金属及び酸化物系の磁性材ターゲットに用いられている。
In recent years, various electronic devices have been born from dramatic progress in semiconductors, and further improvements in performance and new devices are being developed every day.
Under such circumstances, electronics and device equipment are becoming smaller and the degree of integration is increasing. Although many thin films are formed in many of these manufacturing processes, cobalt is a well-known material as a ferromagnetic material. And because of its unique metallic properties, it is used for the formation of many electronic equipment thin films such as cobalt films, cobalt alloy films, cobalt oxide films, mixed films with other metal elements or oxides, cobalt silicide films, etc. . In particular, it is used for metal and oxide-based magnetic material targets.
このようなコバルト、コバルト合金及びコバルト酸化物を利用した薄膜は、コバルトターゲットをアルゴン中でスパッタすることにより形成される。
スパッタリング法による薄膜の形成方法は、陰極に設置したターゲットに、Ａｒ＋などの正イオンを物理的に衝突させてターゲットを構成する金属原子をその衝突エネルギーで放出させる手法であり、コバルト若しくはその合金又はコバルトシリサイド等のターゲットを使用し、アルゴンガス雰囲気中でスパッタリングすることによって形成するものである。
Such a thin film using cobalt, a cobalt alloy, and a cobalt oxide is formed by sputtering a cobalt target in argon.
A thin film forming method by sputtering is a technique in which positive ions such as Ar + are physically collided with a target placed on a cathode, and metal atoms constituting the target are released by the collision energy, and cobalt or an alloy thereof Alternatively, it is formed by sputtering in a argon gas atmosphere using a target such as cobalt silicide.
一方、このようなコバルト（合金、化合物を含む）の薄膜を形成する場合に、注意を要することは、半導体デバイスに有害な金属不純物が極めて少ない、すなわちそれ自体が極めて高い純度を必要とすることである。すなわち、スパッタリング後に形成される電極又は配線等が信頼性のある半導体動作性能を保証するためには、次のことが必要である。
（１）Ｎａ、Ｋ等のアルカリ金属元素、Ｃａ等のアルカリ土類金属元素
（２）Ｃ、Ｏ等のガス成分
（３）硫黄
等の不純物をできるだけ含まないようにすることである。
Ｎａ、Ｋ等のアルカリ金属、Ｃａ等のアルカリ土類金属は、ゲート絶縁膜中を容易に移動し、ＭＯＳ−ＬＳＩ界面特性の劣化の原因となり、また、Ｃ、Ｏ等のガス成分は、後述するように、スパッタリングの際のパーティクル発生の原因となるため好ましくない不純物である。
On the other hand, when forming such a thin film of cobalt (including alloys and compounds), it is necessary to pay attention to the fact that metal impurities harmful to semiconductor devices are extremely small, that is, they themselves require extremely high purity. It is. That is, in order to ensure reliable semiconductor operation performance of the electrodes or wirings formed after sputtering, the following is necessary.
(1) Alkali metal elements such as Na and K and alkaline earth metal elements such as Ca (2) Gas components such as C and O (3) Impurities such as sulfur should be contained as little as possible.
Alkaline metals such as Na and K and alkaline earth metals such as Ca easily move in the gate insulating film and cause deterioration of the MOS-LSI interface characteristics, and gas components such as C and O are described later. Thus, it is an undesirable impurity because it causes generation of particles during sputtering.
磁性材用コバルトターゲット、特に金属コバルト＋酸化物系ターゲットには、粒径の細かいコバルト粉末が必要である。また、このコバルト粉末にＮａ、Ｋ、Ｃａ、Ｓなどの不純物が含まれると、ターゲットのスパッタ特性やスパッタ膜の特性に悪影響を与えるため、これらの不純物を出来るだけ低い濃度とすることが必要である。 Cobalt targets for magnetic materials, particularly metal cobalt + oxide targets, require fine cobalt powder. In addition, if impurities such as Na, K, Ca, and S are included in this cobalt powder, the sputtering characteristics of the target and the characteristics of the sputtered film are adversely affected. Therefore, it is necessary to make these impurities as low as possible. is there.
一方、コバルト粉末の製造方法には、（１）溶液を中和して水酸化物を得、これを還元する方法、（２）溶液をｐＨ調整しながら炭酸ガスを通じることにより炭酸コバルトを得、これを還元する方法などが知られている。
これらの方法で、溶液のｐＨ調整のためにＮａＯＨ、ＫＯＨ、Ｃａ（ＯＨ）２を用いると、これら元素が不純物として高濃度に混入することが避けられない。そのためアンモニア等が用いられるが、アンモニアを用いる場合はコバルトとアンミン錯体を形成して再溶解するために、収率が悪いという問題があった。
On the other hand, the cobalt powder production method includes (1) a method in which a solution is neutralized to obtain a hydroxide and reduced, and (2) cobalt carbonate is obtained by passing carbon dioxide gas while adjusting the pH of the solution. A method of reducing this is known.
In these methods, when NaOH, KOH, or Ca (OH) 2 is used to adjust the pH of the solution, it is inevitable that these elements are mixed as impurities at a high concentration. Therefore, ammonia or the like is used. However, when ammonia is used, there is a problem in that the yield is poor because it forms an ammine complex with cobalt and redissolves it.
半導体装置等に使用される薄膜は一層薄くかつ短小化される方向にあり、相互間の距離が極めて小さく集積密度が向上しているために、薄膜を構成する物質あるいはその薄膜に含まれる不純物が隣接する薄膜に拡散するという問題が発生する。これにより、自膜及び隣接膜の構成物質のバランスが崩れ、本来所有していなければならない膜の機能が低下するという大きな問題が起こる。
このような薄膜の製造工程において、数百度に加熱される場合があり、また半導体装置を組み込んだ電子機器の使用中にも温度が上昇する。このような温度上昇は前記物質（不純物）の拡散をさらに促進し、拡散による電子機器の機能低下に大きな問題を生ずることとなる。
Thin films used in semiconductor devices and the like are in the direction of being thinner and shorter, and the distance between them is extremely small and the integration density is improved. The problem of diffusing into adjacent thin films arises. As a result, the balance between the constituent materials of the self-membrane and the adjacent membrane is lost, and a serious problem arises that the function of the membrane that must originally be owned is reduced.
In the manufacturing process of such a thin film, it may be heated to several hundred degrees, and the temperature rises even during use of an electronic device incorporating a semiconductor device. Such a temperature increase further promotes the diffusion of the substance (impurities), and causes a serious problem in the function deterioration of the electronic device due to the diffusion.
また、スパッタリング膜の形成に際して、コバルト（合金・化合物）ターゲットに不純物が存在すると、これらに起因してスパッタチャンバ内に浮遊する粗大化した粒子が基板上に付着して薄膜回路を短絡させるといったように、薄膜の突起物の原因となるパーティクルの発生量が増し、またガス成分である酸素、炭素、水素、窒素等が多量に存在すると、スパッタリング中にガスによる突発が原因と考えられる異常放電を起こし、均一な膜が形成されないという問題が発生する。 In addition, when the sputtering film is formed, if there are impurities in the cobalt (alloy / compound) target, coarse particles floating in the sputtering chamber due to these adhere to the substrate and short circuit the thin film circuit. In addition, the amount of particles that cause projections on the thin film increases, and if there are a large amount of gas components such as oxygen, carbon, hydrogen, nitrogen, etc., abnormal discharge, which is thought to be caused by gas bursts, is generated during sputtering. This causes a problem that a uniform film cannot be formed.
このようなことから、不純物となるアルカリ金属元素、アルカリ土類金属元素、硫黄、さらに酸素等のガス成分が低減された高純度のコバルトの製造が望まれる。さらにはＦｅ及びＮｉ等の遷移金属元素、放射性元素も同様に減少させることが望まれていた。
しかしながら、一方では粒径の細かいコバルト粉末が必要であるが、上記のような不純物を低減しようとした場合には、製造条件に制限があり、製造コストの増大を招くという問題を生じた。
For this reason, it is desired to produce high-purity cobalt in which gas components such as alkali metal elements, alkaline earth metal elements, sulfur, and oxygen that are impurities are reduced. Further, it has been desired to reduce the transition metal elements such as Fe and Ni and the radioactive elements as well.
However, on the other hand, cobalt powder having a small particle size is necessary, but when trying to reduce the impurities as described above, the production conditions are limited, resulting in an increase in production cost.
先行技術文献を見ると、下記特許文献１には、硬質金属およびダイヤモンド工具の製造に用いるコバルト粉末及びその製造方法が記載されている。この文献１に記載されている結晶粒径は０．７〜１．１μｍ、不純物濃度がＮａ＜５０ｐｐｍ、Ｃａ＜３０ｐｐｍ、Ｓ＜３０ｐｐｍであり、粒径とＮａ，Ｃａ，Ｓ含有量については、本願発明の目的に合っているが、酸素と炭素の含有量が異常に多く、特許文献１の実施例によれば最低でも、合計で０．８ｗｔ％含む。これは硬質金属及びダイヤモンド工具の製造に用いるコバルト粉末であるが故に許される不純物と考えられるが、本願発明の目的には適合しない。 Looking at the prior art documents, Patent Document 1 listed below describes cobalt powder used in the production of hard metals and diamond tools and the production method thereof. The crystal grain size described in this document 1 is 0.7 to 1.1 μm, the impurity concentration is Na <50 ppm, Ca <30 ppm, S <30 ppm, and the grain size and Na, Ca, S content are as follows: Although meeting the purpose of the present invention, the contents of oxygen and carbon are abnormally high, and according to the example of Patent Document 1, the total content is at least 0.8 wt%. This is considered a permissible impurity because it is a cobalt powder used in the manufacture of hard metals and diamond tools, but is not suitable for the purposes of the present invention.
下記特許文献２には、電解を用いてコバルトの微粉末を製造する方法に関し、コバルトの水溶液系を電解液とし、交流による電解をすることで微粉を製造することが記載され、実施例では１μｍ以下の微粉を得ているが、製造工程が煩雑であるという点と不純物レベルの問題が存在し、これも本願発明の目的には適合しない。 Patent Document 2 described below relates to a method for producing a fine powder of cobalt using electrolysis, and describes that a fine powder is produced by electrolysis by alternating current using an aqueous solution system of cobalt as an electrolytic solution. Although the following fine powder is obtained, there is a problem that the manufacturing process is complicated and there is a problem of impurity level, which is also not suitable for the purpose of the present invention.
下記特許文献３には、コバルトのシュウ酸塩を焙焼後、気相中に分散させた状態で水素還元してＣｏ粉を得る方法が記載されているが、コバルトのシュウ酸塩ありきの焙焼技術に関する発明であって、肝心の製造法については、製造工程と不純物レベルの問題については記載がなく、これも本願発明の目的には適合しない。 Patent Document 3 below describes a method in which cobalt oxalate is roasted and then reduced by hydrogen in a state dispersed in the gas phase to obtain Co powder. It is an invention related to roasting technology, and there is no description about the manufacturing process and the problem of impurity level in the essential manufacturing method, which also does not meet the object of the present invention.
下記特許文献４には、シュウ酸塩の難溶性を利用してＣｏの回収を行う方法が記載されており、二次電池廃材から油を含む液でコバルトを抽出した後、水系の液で逆抽出し、この液に対してシュウ酸を用いることが記載されている。
しかし、後述する本願発明のように硫酸に富む液からＳの少ないコバルトを回収する手法とは目的が異なる。
Patent Document 4 listed below describes a method for recovering Co by utilizing the insolubility of oxalate. After extracting cobalt from a secondary battery waste material with a liquid containing oil, it is reversed with an aqueous liquid. Extraction and use of oxalic acid for this liquid is described.
However, the purpose is different from the method of recovering cobalt with a small amount of S from a liquid rich in sulfuric acid as in the present invention described later.
下記特許文献５には、シュウ酸コバルトの難溶性を利用してコバルトの除去を行う方法が記載されている。コバルトを含有するシクロヘキサンから水相へコバルトを抽出後、シュウ酸を加えてコバルトを除去するというものであるが、前記文献４と同様に、本願発明とは目的が異なる。 Patent Document 5 listed below describes a method for removing cobalt by utilizing the poor solubility of cobalt oxalate. Cobalt is extracted from cyclohexane containing cobalt into an aqueous phase, and then oxalic acid is added to remove cobalt. Similar to the above-mentioned document 4, the object of the present invention is different.
下記特許文献６には、純度の悪いコバルト金属から高純度の硫酸コバルトを製造する方法及びこの水溶液を用いた水酸化物の製造方法が記載されている。
高純度硫酸コバルト溶液の製造に関しては、酸化とｐＨ調整によりＦｅとＳｉを、硫化によりＮｉを除くとしている。水酸化物の製造方法は、得られた高純度の硫酸コバルト溶液にＮａＯＨを加えて水酸化コバルトを沈殿させるものである。Ｎａの含有の問題が存在し、これも本願発明の目的には適合しない。
Patent Document 6 listed below describes a method for producing high-purity cobalt sulfate from poor-purity cobalt metal and a method for producing a hydroxide using this aqueous solution.
Regarding the production of a high purity cobalt sulfate solution, Fe and Si are removed by oxidation and pH adjustment, and Ni is removed by sulfuration. In the method for producing hydroxide, NaOH is added to the obtained high-purity cobalt sulfate solution to precipitate cobalt hydroxide. There is a problem of containing Na, which is also not suitable for the purpose of the present invention.
本発明は、上記の諸問題点の解決、特にアルカリ金属元素、アルカリ土類金属元素、硫黄及び酸素、炭素等のガス成分を極力低減させたコバルト粉末であり、かつ微細な粉末を安定してかつ容易に製造できる方法を開発し、薄膜を構成する物質の相互拡散に起因する汚染物質の抑制及びパーティクルや異常放電現象が生じないスパッタリングターゲット等に有効であるコバルト粉末を低コストで提供することを目的としたものである。
具体的には、Ｎａ、Ｋ、Ｃａなどの不純物の混入を避けつつ、同時に収率が高いコバルト粉末の製造方法であって、さらに微細な粉末を収率よく得ることを目的とする。
The present invention is a cobalt powder in which gas components such as alkali metal elements, alkaline earth metal elements, sulfur, oxygen, and carbon are reduced as much as possible, and a fine powder can be stably stabilized. To develop a method that can be easily manufactured, and to provide low-cost cobalt powder that is effective for the suppression of pollutants caused by mutual diffusion of materials that make up a thin film and for sputtering targets that do not generate particles or abnormal discharge phenomena. It is aimed at.
Specifically, it is a method for producing a cobalt powder having a high yield while avoiding the mixing of impurities such as Na, K, and Ca, and an object is to obtain a finer powder with a high yield.
上記問題点を解決するための技術的な手段は、高純度の硫酸コバルトを原料とし、これとシュウ酸と反応させて、微細なシュウ酸コバルトを製造することであり、これを利用して目的とする不純物を低減させ、微細なコバルト粉末を得ることができるとの知見を得た。なお、以下に記載する本願発明の％、ｐｐｍ等の単位は、全て質量（ｍａｓｓ）の表示である。
この知見に基づき、本発明は、
１）Ｓが１００ｐｐｍ以下、Ｎａ、Ｋ、Ｃａがそれぞれ２０ｐｐｍ以下であり、平均粒径が１μｍ以上、５μｍ以下であって、粒径の９０％以上が０．３μｍから１０μｍの範囲にあることを特徴とするコバルト粉末
２）磁性材ターゲットの製造に用いることを特徴とする上記１）に記載のコバルト粉末、を提供する。
The technical means for solving the above problems is to produce fine cobalt oxalate by using high purity cobalt sulfate as a raw material and reacting it with oxalic acid. As a result, it was found that a fine cobalt powder can be obtained. In addition, units such as% and ppm in the present invention described below are all expressed in mass.
Based on this finding, the present invention
1) S is 100 ppm or less, Na, K, and Ca are each 20 ppm or less, the average particle size is 1 μm or more and 5 μm or less, and 90% or more of the particle size is in the range of 0.3 μm to 10 μm. 2. Cobalt powder characterized in 2) Cobalt powder described in 1) above, which is used for producing a magnetic material target.
また、本発明は、
３）硫酸コバルト水溶液に、液温を３５°Ｃ以上、８０°Ｃ以下に保持した状態でシュウ酸を添加し反応させて、シュウ酸コバルトとして沈殿させ、これを分取及び還元してコバルト粉末とすることを特徴とするコバルト粉末の製造方法
４）硫酸コバルト水溶液に、液温を３５°Ｃ以上、８０°Ｃ以下に保持した状態でシュウ酸を添加し反応させて、シュウ酸を反応させてシュウ酸コバルトとして沈殿させ、これを分取及び還元して上記１）〜２）のいずれか一項に記載のコバルト粉末とすることを特徴とするコバルト粉末の製造方法
５）反応させるときの液温を６０°Ｃ以上、８０°Ｃ以下に保持することを特徴とする上記３）〜４）のいずれか一項に記載のコバルト粉末の製造方法
６）硫酸コバルト水溶液のコバルト濃度が１０ｇ／Ｌ〜１１０ｇ／Ｌであることを特徴とする上記３）〜５）のいずれか一項に記載のコバルト粉末の製造方法、を提供する。
The present invention also provides:
3) Add oxalic acid to a cobalt sulfate aqueous solution while maintaining the liquid temperature at 35 ° C. or higher and 80 ° C. or lower to cause it to precipitate as cobalt oxalate. 4) Cobalt powder manufacturing method characterized in that 4) Oxalic acid is added to a cobalt sulfate aqueous solution while the liquid temperature is maintained at 35 ° C. or higher and 80 ° C. or lower to react, thereby causing oxalic acid to react. Then, it is precipitated as cobalt oxalate, and this is fractionated and reduced to obtain the cobalt powder according to any one of the above 1) to 2). The method for producing a cobalt powder according to any one of 3) to 4) above, wherein the liquid temperature is maintained at 60 ° C. or higher and 80 ° C. or lower. 6) The cobalt concentration of the aqueous cobalt sulfate solution is 10 g / L ~ 1 The method of producing cobalt powder according to any one of the above 3) to 5), which is a 0 g / L, to provide.
上記の通り、本発明は、特にアルカリ金属元素、アルカリ土類金属元素、硫黄及び酸素、炭素等のガス成分を極力低減させたコバルト粉末であり、かつ微細な粉末を安定してかつ容易に製造できる方法であり、薄膜を構成する物質の相互拡散に起因する汚染物質の抑制及びパーティクルや異常放電現象が生じないスパッタリングターゲットの製造に有効である微細な粉末を収率よく得ることができるという著しい効果を有する。 As described above, the present invention is a cobalt powder in which gas components such as alkali metal elements, alkaline earth metal elements, sulfur, oxygen, and carbon are reduced as much as possible, and a fine powder is stably and easily produced. It is a method that can reduce the amount of contaminants caused by interdiffusion of substances constituting the thin film and that it is possible to obtain a fine powder that is effective for producing a sputtering target that does not cause particles or abnormal discharge phenomenon with high yield. Has an effect.
また、本発明のコバルト粉末を用いて製造したターゲットにより成膜したスパッタリング膜は、ゲート絶縁膜中を移動しＭＯＳ−ＬＳＩ界面特性の劣化の原因となるＮａ、Ｋ等のアルカリ金属元素、Ｃａ等のアルカリ土類金属元素、および硫黄が減少し、素子のソフトエラーがなくなり、界面接合部のトラブルが減少し、薄膜を構成する物質あるいはその薄膜に含まれる不純物が隣接する薄膜に拡散するという問題がなくなるので、自膜及び隣接膜の構成物質のバランスを崩すことがなく、本来所有する膜の機能が低下するという問題もなくなる効果を有する。スパッタリング後に形成される電極又は配線等が信頼性のある半導体動作性を十分に保証することができるという優れた効果を有する。 Moreover, the sputtering film formed by the target manufactured using the cobalt powder of the present invention moves through the gate insulating film and causes deterioration of the MOS-LSI interface characteristics, such as alkali metal elements such as Na and K, Ca, etc. The problem is that the alkaline earth metal elements and sulfur are reduced, the soft error of the element is eliminated, the trouble at the interface junction is reduced, and the substances constituting the thin film or impurities contained in the thin film diffuse into the adjacent thin film Therefore, the balance between the constituent materials of the self-film and the adjacent film is not lost, and the problem that the function of the originally owned film is reduced is eliminated. An electrode or wiring formed after sputtering has an excellent effect that reliable semiconductor operability can be sufficiently ensured.
さらに、このスパッタリング膜の形成に際して、コバルト（合金・化合物）ターゲット中の不純物が減少、特にガス成分である酸素、炭素が減少しているので、スパッタチャンバ内に浮遊する粗大化した粒子が基板上に付着して薄膜回路を短絡させるようなことがなくなり、また薄膜の突起物の原因となるパーティクルの発生量も減少する。さらにスパッタリング中に、ガスによる突発が原因と考えられる異常放電を起こすこともなくなり、コバルト成膜の電気抵抗も小さいという著しい特徴を有する。 Furthermore, during the formation of this sputtering film, impurities in the cobalt (alloy / compound) target are reduced, especially oxygen and carbon, which are gas components, are reduced, so that coarse particles floating in the sputtering chamber are formed on the substrate. This prevents the thin film circuit from being short-circuited due to adhesion, and also reduces the amount of particles that cause thin film protrusions. Furthermore, there is no remarkable discharge during the sputtering, which causes abnormal discharge which is considered to be caused by gas, and the electric resistance of the cobalt film formation is small.
本発明で使用するコバルト粉末の原料は、コバルト塩水溶液であり、特に硫酸コバルトを使用する。原料としては高純度の硫酸コバルト水溶液が廃液として発生しているため、これを利用するのが望ましい。コバルトを硫酸に溶解することによっても得ることができ、原料がコバルト塩水溶液（硫酸コバルト）であれば、特に制限はない。 The raw material of the cobalt powder used in the present invention is a cobalt salt aqueous solution, and particularly cobalt sulfate is used. As a raw material, since a high-purity cobalt sulfate aqueous solution is generated as a waste liquid, it is desirable to use this. It can also be obtained by dissolving cobalt in sulfuric acid, and there is no particular limitation as long as the raw material is a cobalt salt aqueous solution (cobalt sulfate).
加温しつつコバルト塩（硫酸コバルト）とシュウ酸とを反応させてシュウ酸コバルトを得ること、これを還元し、粉砕してコバルト粉末とすることにより、不純物濃度が少なく、粒径の小さいコバルト粉末を得ることができる。
具体的には、濃度１ｇ／Ｌ〜飽和濃度の範囲の硫酸コバルト水溶液を用意する。硫酸コバルト水溶液を３５°Ｃ〜８０°Ｃ、好ましくは６０°Ｃ〜８０°Ｃの範囲に加熱して攪拌しつつ、シュウ酸２水和物の粉末を加え、シュウ酸コバルトを沈殿、乾燥させ、シュウ酸コバルト２水和物を得る。
Cobalt oxalate is obtained by reacting cobalt salt (cobalt sulfate) and oxalic acid while heating, and this is reduced and pulverized to obtain cobalt powder. A powder can be obtained.
Specifically, an aqueous cobalt sulfate solution having a concentration of 1 g / L to a saturated concentration is prepared. While heating and stirring the cobalt sulfate aqueous solution in the range of 35 ° C to 80 ° C, preferably 60 ° C to 80 ° C, the powder of oxalic acid dihydrate is added to precipitate and dry the cobalt oxalate. To obtain cobalt oxalate dihydrate.
還元方法としては、シュウ酸コバルト粉末を焙焼して得た酸化物粉末を、たとえば気相中に分散させた状態で加熱して水素還元し、そのまま単分散の微細金属粒子を得ることができる。
この還元方法は既に知られている技術であり、本発明のシュウ酸コバルトの還元方法には制限はないが、シュウ酸コバルトを一旦焙焼して酸化物を経由し、還元雰囲気で加熱処理することで金属に還元し、それをボールミルなどで粉砕することが、量産性等を考慮すると好ましい。
いずれにしても、本発明のシュウ酸コバルト粉末を中間原料とすることにより、粒径が細かく、かつ粒径分布が狭いコバルト粉末を得ることができる。
As a reduction method, oxide powder obtained by roasting cobalt oxalate powder is heated and reduced in hydrogen, for example, in a state dispersed in a gas phase, and monodispersed fine metal particles can be obtained as they are. .
This reduction method is a known technique, and the method for reducing cobalt oxalate according to the present invention is not limited. However, the cobalt oxalate is once roasted and then heated in a reducing atmosphere via an oxide. In view of mass productivity, it is preferable to reduce it to a metal and pulverize it with a ball mill or the like.
In any case, by using the cobalt oxalate powder of the present invention as an intermediate raw material, a cobalt powder having a fine particle size and a narrow particle size distribution can be obtained.
シュウ酸コバルトの還元は、例えば以下の手順で行う。大気中で３５０°Ｃ〜１０００°Ｃで焙焼し、酸化コバルトとし、粉砕して酸化コバルト粉末とする。このとき、高温になると酸化コバルト粒子が成長して粗大化し、目的の粒径を満たすことが難しくなるため、できれば３５０°Ｃ〜５００°Ｃ程度が好ましい。この酸化コバルト粉末を水素雰囲気で５００〜８００°Ｃで２時間〜２４時間還元する。あるいは、シュウ酸コバルトをそのまま水素雰囲気で、５００〜８００°Ｃで２時間〜２４時間還元してもよい。 The reduction of cobalt oxalate is performed, for example, by the following procedure. It is roasted at 350 ° C. to 1000 ° C. in the atmosphere to form cobalt oxide, and pulverized to obtain cobalt oxide powder. At this time, when the temperature becomes high, the cobalt oxide particles grow and become coarse, and it becomes difficult to satisfy the target particle size. The cobalt oxide powder is reduced at 500 to 800 ° C. for 2 to 24 hours in a hydrogen atmosphere. Alternatively, cobalt oxalate may be reduced as it is in a hydrogen atmosphere at 500 to 800 ° C. for 2 to 24 hours.
ここで、硫酸コバルト水溶液の濃度が低い場合は収率が低くなり、濃度が高い場合は温度変化などによって飽和溶解度を超えて硫酸コバルト自体の沈殿が発生しやすくなる。したがって、好ましくはコバルト濃度が１０ｇ／Ｌ〜１１０ｇ／Ｌ、より好ましくは５０〜１１０g／Ｌの範囲で行うのが望ましい。
なお、焙焼温度、水素還元温度が高いほど、処理時間が長いほど、Ｓなどの不純物が抜けやすく、かつ結晶性が高くなって粉砕しやすい。逆に粒径分布は広くなる傾向がある。
Here, when the concentration of the aqueous cobalt sulfate solution is low, the yield is low, and when the concentration is high, precipitation of cobalt sulfate itself easily occurs exceeding the saturation solubility due to temperature change or the like. Accordingly, the cobalt concentration is preferably 10 g / L to 110 g / L, more preferably 50 to 110 g / L.
The higher the roasting temperature and the hydrogen reduction temperature, the longer the treatment time, the easier it is for impurities such as S to escape and the higher the crystallinity and the easier the pulverization. Conversely, the particle size distribution tends to be broad.
上記の条件でシュウ酸コバルトを生成させることにより、シュウ酸コバルトの粒径を細かくできるため、シュウ酸コバルト粉を還元することにより、結果として得られるコバルト粉末の粒径が細かく、かつ粒径分布が狭い粉末を得ることができる。 By generating cobalt oxalate under the above conditions, the particle size of cobalt oxalate can be made finer. By reducing the cobalt oxalate powder, the resulting cobalt powder has a fine particle size and a particle size distribution. A narrow powder can be obtained.
上記の工程を採用することにより、微細なコバルト粉末を得ることができ、これをまとめると、次のようになる。
（１）シュウ酸塩としてコバルトを沈殿させることで、粒径の細かい塩が得られる。これを（いったん酸化物を経由する場合を含め）水素還元し、粉砕することで粒径の細かいコバルト粉とすることができる。シュウ酸コバルト塩が細かいため、酸化後の粉砕及び還元後の粉砕がより簡単なものとなる。
（２）シュウ酸塩としてコバルトを沈殿させることで、中和剤を用いたｐＨ調整をしなくてもコバルトを回収することが可能である。また、シュウ酸塩は不純物の巻き込みも少ないため、溶液成分からの不純物残留も少ない。さらに、加熱しながらの反応により、不純物の巻き込みをより低減できる。
（３）シュウ酸塩としてコバルトを沈殿させることで、シュウ酸コバルトは難溶性のため、水酸化物と比べてコバルト回収率が良い。
By adopting the above steps, a fine cobalt powder can be obtained, which is summarized as follows.
(1) By precipitating cobalt as an oxalate, a salt with a fine particle size can be obtained. This can be reduced to hydrogen (including once via an oxide) and pulverized to obtain fine cobalt powder. Since the cobalt oxalate is fine, pulverization after oxidation and pulverization after reduction become easier.
(2) By precipitating cobalt as an oxalate, it is possible to recover cobalt without adjusting the pH using a neutralizing agent. In addition, since oxalate has a small amount of impurities, there are few impurities remaining from solution components. Furthermore, the entrainment of impurities can be further reduced by the reaction while heating.
(3) By precipitating cobalt as an oxalate, cobalt oxalate is poorly soluble and therefore has a higher cobalt recovery rate than hydroxide.
以上の操作により製造した高純度コバルト粉を、焼結してスパッタリング用ターゲットとする。このようにして製造したコバルトターゲット中には、不純物含有量が少なく、半導体製造用又は磁性材のターゲットとして、好ましい材料が得られる。すなわち、Ｎａ、Ｋ等のアルカリ金属元素及びＣａ等のアルカリ土類金属元素がそれぞれ２０ｐｐｍ以下、硫黄（Ｓ）が１００ｐｐｍ、好ましくは４０ｐｐｍ以下、酸素（Ｏ）が５０００ｐｐｍ以下、炭素（Ｃ）が１００ｐｐｍ以下であるコバルト粉末を得ることができる。
また、平均粒径が１μｍ以上、５μｍ以下であって、粒径の９０％以上が０．３μｍから１０μｍの範囲にあるコバルト粉末を得ることが可能となる。
The high-purity cobalt powder produced by the above operation is sintered to obtain a sputtering target. The cobalt target thus produced has a low impurity content, and a preferable material can be obtained for semiconductor production or as a magnetic material target. That is, alkali metal elements such as Na and K and alkaline earth metal elements such as Ca are each 20 ppm or less, sulfur (S) is 100 ppm, preferably 40 ppm or less, oxygen (O) is 5000 ppm or less, and carbon (C) is 100 ppm. The following cobalt powder can be obtained.
In addition, it is possible to obtain a cobalt powder having an average particle diameter of 1 μm or more and 5 μm or less and 90% or more of the particle diameter in the range of 0.3 μm to 10 μm.
このコバルト粉から製造したターゲットを用いてスパッタリング成膜したコバルト膜は、ゲート絶縁膜中を移動しＭＯＳ−ＬＳＩ界面特性の劣化の原因となるＮａ、Ｋ等のアルカリ金属、Ｃａ等のアルカリ土類金属が減少し、界面接合部のトラブルが減少する。
さらに、薄膜を構成する物質あるいはその薄膜に含まれる不純物が隣接する薄膜に拡散するという問題がなくなり、自膜及び隣接膜の構成物質のバランスを崩すことがなく、本来所有する膜の機能が低下するという問題もなくなる。
したがって、スパッタリング後に形成される磁性材、電極又は配線等が信頼性のある半導体動作性を十分に保証することができる。
A cobalt film formed by sputtering using a target manufactured from this cobalt powder moves in the gate insulating film and causes deterioration of MOS-LSI interface characteristics, and alkali metals such as Na and K, and alkaline earth metals such as Ca. The metal is reduced and the trouble at the interface junction is reduced.
Furthermore, there is no problem of diffusion of substances constituting the thin film or impurities contained in the thin film into the adjacent thin film, and the function of the originally owned film is reduced without losing the balance between the constituent materials of the self film and the adjacent film. The problem of doing is also eliminated.
Therefore, the magnetic material, electrode or wiring formed after sputtering can sufficiently ensure reliable semiconductor operability.
さらに、このスパッタリング膜の形成に際して、コバルト（合金・化合物）ターゲット中の不純物、特にガス成分である酸素、炭素等が減少しているので、スパッタチャンバ内に浮遊する粗大化した粒子が基板上に付着して薄膜回路を短絡させるようなことがなくなり、また薄膜の突起物の原因となるパーティクルの発生量が減少し、さらにスパッタリング中に、ガスによる突発が原因と考えられる異常放電を起こすこともなくなる。 Further, when forming the sputtering film, impurities in the cobalt (alloy / compound) target, particularly oxygen and carbon as gas components are reduced, so that coarse particles floating in the sputtering chamber are formed on the substrate. There is no longer a short circuit on the thin film circuit due to adhesion, and the amount of particles that cause thin film protrusions is reduced. In addition, abnormal discharge that may be caused by gas bursts may occur during sputtering. Disappear.
次に、本発明の実施例について説明する。なお、本実施例はあくまで１例であり、この例に制限されるものではない。すなわち、本発明の技術思想に含まれる本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。 Next, examples of the present invention will be described. In addition, a present Example is an example to the last, and is not restrict | limited to this example. That is, all the aspects or modifications other than the present Example included in the technical idea of the present invention are included.
（実施例１）
コバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を３５°Ｃに加熱して攪拌しつつ、シュウ酸２水和物粉末を加え、シュウ酸コバルト沈殿を得た。これを乾燥させて得られたシュウ酸コバルト２水和物の、Ｃｏの含有量と不純物濃度の分析結果は表１の通りである。また、このときのコバルトの回収率は９１．０％であった。
この実施例１では、表１に示すように、Ｃｏ３２％、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であり、硫黄（Ｓ）の含有量は、３０ｐｐｍであり、本願発明の目的を達成するための十分な低減効果が得られた。
なお、本実施例１ではコバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を用いたが、硫酸コバルト水溶液のコバルト濃度が１０ｇ／Ｌ〜１１０ｇ／Ｌの範囲にある場合にも、同等の結果が得られた。
Example 1
While heating and stirring an aqueous cobalt sulfate solution having a cobalt concentration of 100 g / L to 35 ° C., oxalic acid dihydrate powder was added to obtain a cobalt oxalate precipitate. Table 1 shows the analysis results of Co content and impurity concentration of cobalt oxalate dihydrate obtained by drying this. Moreover, the recovery rate of cobalt at this time was 91.0%.
In Example 1, as shown in Table 1, Co 32%, Na, K, and Ca are all less than 10 ppm, and the content of sulfur (S) is 30 ppm. In order to achieve the object of the present invention, A sufficient reduction effect was obtained.
In Example 1, a cobalt sulfate aqueous solution having a cobalt concentration of 100 g / L was used, but the same result was obtained when the cobalt concentration of the cobalt sulfate aqueous solution was in the range of 10 g / L to 110 g / L. .
得られたシュウ酸コバルト２水和物を大気中５００°Ｃで焙焼し、酸化コバルトを得た。この酸化コバルトをボールミルで２時間粉砕し、酸化コバルト粉末とし、これを６５０°Ｃ、水素雰囲気でコバルト金属まで還元し、さらにボールミルで２時間粉砕してコバルト粉末とした。得られたコバルト粉末の不純物濃度分析結果は表２の通りである。
また、コバルト粉末の平均粒径が１μｍ以上、５μｍ以下であって、粒径の９０％以上が０．３μｍから１０μｍの範囲にあった。
表２に示すように、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であり、硫黄（Ｓ）の含有量は、９０ｐｐｍであり、本願発明の目的を達成するための十分な低減効果が得られた。
The obtained cobalt oxalate dihydrate was roasted at 500 ° C. in the atmosphere to obtain cobalt oxide. The cobalt oxide was pulverized with a ball mill for 2 hours to obtain cobalt oxide powder, which was reduced to cobalt metal at 650 ° C. in a hydrogen atmosphere, and further pulverized with a ball mill for 2 hours to obtain cobalt powder. Table 2 shows the impurity concentration analysis results of the obtained cobalt powder.
Further, the average particle diameter of the cobalt powder was 1 μm or more and 5 μm or less, and 90% or more of the particle diameter was in the range of 0.3 μm to 10 μm.
As shown in Table 2, Na, K, and Ca are all less than 10 ppm, the content of sulfur (S) is 90 ppm, and a sufficient reduction effect for achieving the object of the present invention was obtained. .
（実施例２）
コバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を６０°Ｃに加熱して攪拌しつつ、シュウ酸２水和物粉末を加え、シュウ酸コバルト沈殿を得た。これを乾燥させて得られたシュウ酸コバルト２水和物のＣｏの含有量と不純物濃度分析結果は表１の通りである。また、このときのコバルト回収率は９０．３％であった。
この実施例２では、表１に示すように、Ｃｏ３１．９％、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であり、硫黄（Ｓ）の含有量も、１０ｐｐｍ未満であった。いずれも、本願発明の目的を達成するための十分な低減効果が得られた。
なお、本実施例２ではコバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を用いたが、硫酸コバルト水溶液のコバルト濃度が１０ｇ／Ｌ〜１１０ｇ／Ｌの範囲にある場合にも、同等の結果が得られた。
(Example 2)
While heating and stirring an aqueous cobalt sulfate solution having a cobalt concentration of 100 g / L at 60 ° C., oxalic acid dihydrate powder was added to obtain a cobalt oxalate precipitate. Table 1 shows the Co content and impurity concentration analysis results of cobalt oxalate dihydrate obtained by drying this. Moreover, the cobalt recovery rate at this time was 90.3%.
In Example 2, as shown in Table 1, Co 31.9%, Na, K, and Ca were all less than 10 ppm, and the content of sulfur (S) was also less than 10 ppm. In any case, a sufficient reduction effect for achieving the object of the present invention was obtained.
In Example 2, a cobalt sulfate aqueous solution having a cobalt concentration of 100 g / L was used, but the same result was obtained when the cobalt concentration of the cobalt sulfate aqueous solution was in the range of 10 g / L to 110 g / L. .
得られたシュウ酸コバルト２水和物を大気中５００°Ｃで焙焼し、酸化コバルトを得た。この酸化コバルトをボールミルで２時間粉砕し、酸化コバルト粉末とし、これを６５０°Ｃ、水素雰囲気でコバルト金属まで還元し、さらにボールミルで２時間粉砕してコバルト粉末とした。得られたコバルト粉末の不純物濃度分析結果は表２の通りである。また、コバルト粉末の平均粒径が１μｍ以上、５μｍ以下であって、粒径の９０％以上が０．３μｍから１０μｍの範囲にあった。
表２に示すように、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であり、硫黄（Ｓ）の含有量は、６０ｐｐｍであり、本願発明の目的を達成するための十分な低減効果が得られた。
The obtained cobalt oxalate dihydrate was roasted at 500 ° C. in the atmosphere to obtain cobalt oxide. The cobalt oxide was pulverized with a ball mill for 2 hours to obtain cobalt oxide powder, which was reduced to cobalt metal at 650 ° C. in a hydrogen atmosphere, and further pulverized with a ball mill for 2 hours to obtain cobalt powder. Table 2 shows the impurity concentration analysis results of the obtained cobalt powder. Further, the average particle diameter of the cobalt powder was 1 μm or more and 5 μm or less, and 90% or more of the particle diameter was in the range of 0.3 μm to 10 μm.
As shown in Table 2, Na, K, and Ca are all less than 10 ppm, the content of sulfur (S) is 60 ppm, and a sufficient reduction effect for achieving the object of the present invention was obtained. .
（実施例３）
コバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を８０°Ｃに加熱して攪拌しつつ、シュウ酸２水和物粉末を加え、シュウ酸コバルト沈殿を得た。これを乾燥させて得られたシュウ酸コバルト２水和物の不純物濃度分析結果は、表１のとおりである。また、このときのコバルト回収率は８９．８％であった。
この実施例３では、表１に示すように、Ｃｏ３２．０％、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であり、硫黄（Ｓ）の含有量も、１０ｐｐｍ未満であった。いずれも、本願発明の目的を達成するための十分な低減効果が得られた。
なお、本実施例３ではコバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を用いたが、硫酸コバルト水溶液のコバルト濃度が１０ｇ／Ｌ〜１１０ｇ／Ｌの範囲にある場合にも、同等の結果が得られた。
(Example 3)
While heating and stirring an aqueous cobalt sulfate solution having a cobalt concentration of 100 g / L at 80 ° C., oxalic acid dihydrate powder was added to obtain a cobalt oxalate precipitate. The results of impurity concentration analysis of cobalt oxalate dihydrate obtained by drying this are shown in Table 1. Moreover, the cobalt recovery rate at this time was 89.8%.
In Example 3, as shown in Table 1, Co 32.0%, Na, K, and Ca were all less than 10 ppm, and the content of sulfur (S) was also less than 10 ppm. In any case, a sufficient reduction effect for achieving the object of the present invention was obtained.
In Example 3, a cobalt sulfate aqueous solution having a cobalt concentration of 100 g / L was used, but the same result was obtained when the cobalt concentration of the cobalt sulfate aqueous solution was in the range of 10 g / L to 110 g / L. .
得られたシュウ酸コバルト２水和物を大気中５００°Ｃで焙焼し、酸化コバルトを得た。この酸化コバルトをボールミルで２時間粉砕し、酸化コバルト粉末とし、これを６５０°Ｃ、水素雰囲気でコバルト金属まで還元し、さらにボールミルで２時間粉砕してコバルト粉末とした。得られたコバルト粉末の不純物濃度分析結果は表２の通りである。
また、コバルト粉末の平均粒径が１μｍ以上、５μｍ以下であって、粒径の９０％以上が０．３μｍから１０μｍの範囲にあった。
表２に示すように、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であり、硫黄（Ｓ）の含有量は、３２ｐｐｍであり、本願発明の目的を達成するための十分な低減効果が得られた。
The obtained cobalt oxalate dihydrate was roasted at 500 ° C. in the atmosphere to obtain cobalt oxide. The cobalt oxide was pulverized with a ball mill for 2 hours to obtain cobalt oxide powder, which was reduced to cobalt metal at 650 ° C. in a hydrogen atmosphere, and further pulverized with a ball mill for 2 hours to obtain cobalt powder. Table 2 shows the impurity concentration analysis results of the obtained cobalt powder.
Further, the average particle diameter of the cobalt powder was 1 μm or more and 5 μm or less, and 90% or more of the particle diameter was in the range of 0.3 μm to 10 μm.
As shown in Table 2, Na, K, and Ca are all less than 10 ppm, and the content of sulfur (S) is 32 ppm, and a sufficient reduction effect for achieving the object of the present invention was obtained. .
（比較例１）
コバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を室温で攪拌しつつ、シュウ酸２水和物粉末を加え、シュウ酸コバルト沈殿を得た。これを乾燥させて得られたシュウ酸コバルト2水和物の不純物濃度分析結果は表１のとおりである。このときのコバルト回収率は９１．６％であった。
表１に示すように、Ｃｏ３２．４％、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であったが、硫黄（Ｓ）の含有量は、３１０ｐｐｍと増加した。いずれも、本願発明の目的を達成することはできなかった。
なお、本比較例１ではコバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を用いたが、硫酸コバルト水溶液のコバルト濃度が１０ｇ／Ｌ〜１１０ｇ／Ｌの範囲にある場合にも、同等の結果となった。
(Comparative Example 1)
While stirring an aqueous cobalt sulfate solution having a cobalt concentration of 100 g / L at room temperature, oxalic acid dihydrate powder was added to obtain a cobalt oxalate precipitate. The results of impurity concentration analysis of cobalt oxalate dihydrate obtained by drying this are shown in Table 1. The cobalt recovery rate at this time was 91.6%.
As shown in Table 1, Co 32.4%, Na, K, and Ca were all less than 10 ppm, but the content of sulfur (S) increased to 310 ppm. In either case, the object of the present invention could not be achieved.
In Comparative Example 1, a cobalt sulfate aqueous solution having a cobalt concentration of 100 g / L was used, but the same result was obtained when the cobalt concentration of the cobalt sulfate aqueous solution was in the range of 10 g / L to 110 g / L.
得られたシュウ酸コバルト２水和物を大気中５００°Ｃで焙焼し、酸化コバルトを得た。この酸化コバルトをボールミルで２時間粉砕し、酸化コバルト粉末とし、これを６５０°Ｃ、水素雰囲気でコバルト金属まで還元し、さらにボールミルで２時間粉砕してコバルト粉末とした。得られたコバルト粉末の不純物濃度分析結果は表２の通りである。
表２に示すように、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であったが、硫黄（Ｓ）の含有量は、１０００ｐｐｍであり、本願発明の目的を達成するための十分な低減効果が得られなかった。
また、Ｓはコバルトが粉砕できそうな温度（７００°Ｃ）で水素還元しても除去しきれなかった。
The obtained cobalt oxalate dihydrate was roasted at 500 ° C. in the atmosphere to obtain cobalt oxide. The cobalt oxide was pulverized with a ball mill for 2 hours to obtain cobalt oxide powder, which was reduced to cobalt metal at 650 ° C. in a hydrogen atmosphere, and further pulverized with a ball mill for 2 hours to obtain cobalt powder. Table 2 shows the impurity concentration analysis results of the obtained cobalt powder.
As shown in Table 2, Na, K, and Ca were all less than 10 ppm, but the content of sulfur (S) was 1000 ppm, and a sufficient reduction effect for achieving the object of the present invention was obtained. I couldn't.
Further, S could not be completely removed by hydrogen reduction at a temperature (700 ° C.) at which cobalt could be crushed.
（比較例２）
コバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液をアンモニア水でｐＨ＝８に中和して水酸化コバルトを得た。水酸化コバルトの不純物濃度分析結果は表１の通りである。このときのコバルト回収率は６０．５％であった。
表１に示すように、Ｃｏ５９．８％、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であったが、硫黄（Ｓ）の含有量は、５５０００ｐｐｍと著しく増加した。いずれも、本願発明の目的を達成することはできなかった。
なお、本比較例２ではコバルト濃度１００ｇ／Ｌの硫酸コバルト水溶液を用いたが、硫酸コバルト水溶液のコバルト濃度が１０ｇ／Ｌ〜１１０ｇ／Ｌの範囲にある場合にも、同等の結果となった。
(Comparative Example 2)
A cobalt sulfate aqueous solution having a cobalt concentration of 100 g / L was neutralized with ammonia water to pH = 8 to obtain cobalt hydroxide. The results of impurity concentration analysis of cobalt hydroxide are shown in Table 1. The cobalt recovery rate at this time was 60.5%.
As shown in Table 1, Co 59.8%, Na, K, and Ca were all less than 10 ppm, but the content of sulfur (S) was remarkably increased to 55000 ppm. In either case, the object of the present invention could not be achieved.
In Comparative Example 2, a cobalt sulfate aqueous solution having a cobalt concentration of 100 g / L was used, but the same result was obtained when the cobalt concentration of the cobalt sulfate aqueous solution was in the range of 10 g / L to 110 g / L.
得られた水酸化コバルトを大気中５００°Ｃで焙焼し、酸化コバルトを得た。この酸化コバルトをボールミルで２時間粉砕し、酸化コバルト粉末とし、これを６５０°Ｃ、水素雰囲気でコバルト金属まで還元し、さらにボールミルで２時間粉砕してコバルト粉末とした。得られたコバルト粉末の不純物濃度分析結果は表２の通りである。
表２に示すように、Ｎａ、Ｋ、Ｃａはいずれも１０ｐｐｍ未満であったが、硫黄（Ｓ）の含有量は、３３０００ｐｐｍと著しく増大し、本願発明の目的を達成するための十分な低減効果が得られなかった。
また、Ｓはコバルトが粉砕できそうな温度（７００°Ｃ）で水素還元しても除去しきれなかった。
The obtained cobalt hydroxide was roasted at 500 ° C. in the atmosphere to obtain cobalt oxide. The cobalt oxide was pulverized with a ball mill for 2 hours to obtain cobalt oxide powder, which was reduced to cobalt metal at 650 ° C. in a hydrogen atmosphere, and further pulverized with a ball mill for 2 hours to obtain cobalt powder. Table 2 shows the impurity concentration analysis results of the obtained cobalt powder.
As shown in Table 2, Na, K, and Ca were all less than 10 ppm, but the content of sulfur (S) was remarkably increased to 33000 ppm, which was a sufficient reduction effect to achieve the object of the present invention. Was not obtained.
Further, S could not be completely removed by hydrogen reduction at a temperature (700 ° C.) at which cobalt could be crushed.
次に、実施例１、実施例２、比較例１のコバルト粉と高純度の白金粉、クロム粉、二酸化珪素粉を用いて、さらに１１００°Ｃ、１．５ｈｒでホットプレスし、コバルト−クロム−白金−二酸化珪素系磁性材ターゲットとした。
混合比は、５２．２６ｗｔ.％Ｃｏ‐８．２１ｗｔ．％Ｃｒ‐３３．１８ｗｔ．％Ｐｔ‐６．３５ｗｔ．％ＳｉＯ２である。これらのターゲットを使用してスパッタリングによる成膜のパーティクルの発生個数を比較した。
このとき、パーティクルの発生個数が、比較例１では１００ケ／ウエハーで、著しく多いのに対し、実施例１及び実施例２ではそれぞれ８ケ／ウエハー、１０ケ／ウエハーであり、いずれも低く本発明の方が優れていた。
このように本発明の純度が向上したことにより、電気抵抗が減少し、またスパッタリング時のパーティクルの発生個数も著しく減少しているのが分かる。
Next, using the cobalt powder of Example 1, Example 2, and Comparative Example 1 and high-purity platinum powder, chromium powder, and silicon dioxide powder, hot pressing was further performed at 1100 ° C. for 1.5 hours to obtain cobalt-chromium. A platinum-silicon dioxide magnetic material target was used.
The mixing ratio was 52.26 wt.% Co-8.21 wt. % Cr-33.18 wt. % Pt-6.35 wt. % SiO 2 . Using these targets, the number of particles generated by sputtering was compared.
At this time, the number of particles generated was 100 / wafer in Comparative Example 1, which was remarkably large, whereas in Examples 1 and 2, 8 / wafer and 10 / wafer, respectively. The invention was superior.
Thus, it can be seen that the improvement in the purity of the present invention results in a decrease in electrical resistance and a significant decrease in the number of particles generated during sputtering.
上記の通り、本発明は、特にアルカリ金属元素、アルカリ土類金属元素、硫黄及び酸素、炭素等のガス成分を極力低減させたコバルト粉末であり、かつ微細な粉末を安定してかつ容易に製造できる方法であり、薄膜を構成する物質の相互拡散に起因する汚染物質の抑制及びパーティクルや異常放電現象が生じないスパッタリングターゲットの製造に有効である微細な粉末を収率よく得ることできるという著しい効果を有するので、特に磁性材ターゲット用コバルト粉末として有用である。 As described above, the present invention is a cobalt powder in which gas components such as alkali metal elements, alkaline earth metal elements, sulfur, oxygen, and carbon are reduced as much as possible, and a fine powder is stably and easily produced. It is a method that can reduce the amount of contaminants caused by interdiffusion of substances that make up the thin film, and that it is possible to obtain fine powders that are effective for producing sputtering targets that are free from particles and abnormal discharge phenomena. Therefore, it is particularly useful as a cobalt powder for a magnetic material target.
Claims (6)
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| JP6800413B2 (en) * | 2015-12-28 | 2020-12-16 | 国立大学法人山形大学 | Oxalate degradation methods and complex compounds for oxalate degradation |
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| DE19822663A1 (en) * | 1998-05-20 | 1999-12-02 | Starck H C Gmbh Co Kg | Sintered metal and alloy powders for powder metallurgical applications and processes for their production and their use |
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