JP2016023333A - Manufacturing method of lithium nickel oxide sputtering target - Google Patents
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000000843 powder Substances 0.000 claims abstract description 31
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 17
- 238000010304 firing Methods 0.000 claims abstract description 14
- 239000011812 mixed powder Substances 0.000 claims abstract description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910013290 LiNiO 2 Inorganic materials 0.000 claims description 56
- 229910052744 lithium Inorganic materials 0.000 claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 41
- 238000010438 heat treatment Methods 0.000 abstract description 14
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract description 5
- 239000013077 target material Substances 0.000 abstract description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 2
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000007731 hot pressing Methods 0.000 description 6
- 150000002642 lithium compounds Chemical class 0.000 description 6
- 238000002156 mixing Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
Abstract
Description
本発明は、リチウムイオン二次電池の正極材として有用なニッケル酸リチウム（ＬｉＮｉＯ２）膜をスパッタリング成膜するためのニッケル酸リチウムスパッタリングターゲットの製造方法に関する。 The present invention relates to a method for manufacturing a lithium nickelate sputtering target for sputtering a lithium nickelate (LiNiO 2 ) film useful as a positive electrode material for a lithium ion secondary battery.
近年、電子機器などの電源に用いられる高エネルギー密度電池として、リチウム二次電池の需要が高まっている。このリチウムイオン二次電池の正極材には、従来から用いられていたコバルト酸リチウム（ＬｉＣｏＯ２）に代わるニッケル酸リチウム（ＬｉＮｉＯ２）が提案されている。 In recent years, a demand for a lithium secondary battery is increasing as a high energy density battery used for a power source of an electronic device or the like. As a positive electrode material of this lithium ion secondary battery, lithium nickelate (LiNiO 2 ) that replaces the conventionally used lithium cobaltate (LiCoO 2 ) has been proposed.
このニッケル酸リチウムの製造方法として、出発原料である炭酸リチウム（Ｌｉ２ＣＯ３）と酸化ニッケル（ＮｉＯ）とを混合した原料を６１８℃以下の温度で、かつ非酸化雰囲気で焼成し、その後、酸化雰囲気で、かつ６１８℃以上の温度で焼成することにより、ニッケル含有リチウム化合物を得ることが提案されている（例えば、特許文献１を参照）。ここでは、Ｌｉ２ＣＯ３の融点６１８℃以下で、非酸化雰囲気でＮｉＯを不安定化してＬｉとの反応を促進し、その後、酸化雰囲気で昇温することで結晶構造を整えることができる。得られたニッケル含有Ｌｉ化合物をスパッタリングターゲットとして用いて、ＬｉＮｉＯ２膜を成膜している。 As a method for producing this lithium nickelate, a raw material obtained by mixing lithium carbonate (Li 2 CO 3 ) and nickel oxide (NiO) as starting materials is baked in a non-oxidizing atmosphere at a temperature of 618 ° C. or lower, It has been proposed to obtain a nickel-containing lithium compound by baking at a temperature of 618 ° C. or higher in an oxidizing atmosphere (see, for example, Patent Document 1). Here, at a melting point of 618 ° C. or lower of Li 2 CO 3 , NiO is destabilized in a non-oxidizing atmosphere to promote a reaction with Li, and then the temperature is raised in an oxidizing atmosphere, whereby the crystal structure can be adjusted. A LiNiO 2 film is formed using the obtained nickel-containing Li compound as a sputtering target.
一方、ニッケル酸リチウムの他の製造方法としては、ニッケル酸リチウム（ＬｉＮｉＯ２）を成形・焼結してスパッタリングターゲットとすることが提案されている（例えば、特許文献２を参照）。ここでは、予め膜組成を構成する全元素を含む前駆体を作製し、これを酸化することで、ターゲット材の原料を作製した後、この原料を成形、焼結することによりスパッタリングターゲットを作製している。その作製手順としては、先ず、炭酸リチウム（Ｌｉ２ＣＯ３）を溶解・懸濁させた水中に、所定量のＮｉ塩溶液を滴下し、炭酸塩を作製し、ニッケル酸リチウム（ＬｉＮｉＯ２）の原料となる炭酸塩前駆体を得ている。この炭酸塩前駆体を、大気中で、９３０℃、３時間酸化処理して、ＬｉＮｉＯ２のターゲット原料粉を作製している。このターゲット原料粉を成形し、大気中で、前記酸化処理温度よりも高い温度で焼結して、ＬｉＮｉＯ２のスパッタリングターゲットを作製している。 On the other hand, as another manufacturing method of lithium nickelate, it has been proposed to form and sinter lithium nickelate (LiNiO 2 ) to obtain a sputtering target (see, for example, Patent Document 2). Here, a precursor including all elements constituting the film composition is prepared in advance, and this is oxidized to prepare a target material, and then a sputtering target is formed by molding and sintering the raw material. ing. As the preparation procedure, first, a predetermined amount of Ni salt solution is dropped into water in which lithium carbonate (Li 2 CO 3 ) is dissolved and suspended to prepare carbonate, and lithium nickelate (LiNiO 2 ) A carbonate precursor is obtained as a raw material. This carbonate precursor is oxidized in the atmosphere at 930 ° C. for 3 hours to produce LiNiO 2 target raw material powder. The target raw material powder is molded and sintered in the air at a temperature higher than the oxidation treatment temperature to produce a LiNiO 2 sputtering target.
しかしながら、前記特許文献１で提案された製造方法では、コバルト酸リチウム（ＬｉＣｏＯ２）と比較して安価な材料から、ニッケル含有リチウム化合物を形成することができるが、この形成されたニッケル含有Ｌｉ化合物には、化学量論組成をから見て、組成ずれが発生しやすく、単相のニッケル酸リチウム（ＬｉＮｉＯ２）を得ることができなかった。 However, in the manufacturing method proposed in Patent Document 1, a nickel-containing lithium compound can be formed from an inexpensive material as compared with lithium cobaltate (LiCoO 2 ). In view of the stoichiometric composition, compositional deviation was likely to occur, and single-phase lithium nickelate (LiNiO 2 ) could not be obtained.
また、前記特許文献２で提案された製造方法によっても、化学量論組成から組成ずれのあるニッケル含有リチウム化合物を焼結してスパッタリングターゲットを作製しているので、ターゲット中においても組成ずれが残っており、このスパッタリングターゲットを用いて形成された膜にも、組成ずれが残ってしまい、目標の成分組成、即ち、ＬｉＮｉＯ２を有する膜が得られない。 Moreover, since the sputtering target is produced by sintering the nickel-containing lithium compound having a composition deviation from the stoichiometric composition also by the manufacturing method proposed in Patent Document 2, the composition deviation remains in the target. Therefore, the composition deviation also remains in the film formed using this sputtering target, and a film having a target component composition, that is, LiNiO 2 cannot be obtained.
そこで、本発明は、炭酸リチウム（Ｌｉ２ＣＯ３）と酸化ニッケル（ＮｉＯ）とをターゲット原料として、化学量論組成を有し、組成ずれのないニッケル酸リチウムスパッタリングターゲットを提供することを目的とする。 Therefore, the present invention has an object to provide a lithium nickelate sputtering target having a stoichiometric composition and having no composition deviation, using lithium carbonate (Li 2 CO 3 ) and nickel oxide (NiO) as target raw materials. To do.
本発明者らは、Ｌｉ２ＣＯ３とＮｉＯとの混合粉末を、酸化雰囲気で、Ｌｉ２ＣＯ３の融点以上の温度で焼成すると、Ｌｉ２ＣＯ３がＮｉＯと反応して、塊状のＬｉＮｉＯ２を得ることができ、これを粉砕して得たＬｉＮｉＯ２粉末は、ＬｉＮｉＯ２相で形成され、Ｌｉ２ＣＯ３が含まれていないという知見を得た。そこで、この得られたＬｉＮｉＯ２粉末を、還元雰囲気で、前記温度より低い温度で焼結することによって、化学量論組成から組成ずれのないニッケル酸リチウム（ＬｉＮｉＯ２）の焼結体を得られることが判明した。さらに、この焼結後に、酸化雰囲気、高い温度で本焼結すると、この焼結体の密度及び相対密度を向上できることも判明した。 The present inventors, the mixed powder of Li 2 CO 3 and NiO, in an oxidizing atmosphere, and baked at a temperature above the melting point of Li 2 CO 3, Li 2 CO 3 reacts with NiO, massive LiNiO 2 The LiNiO 2 powder obtained by pulverizing this was formed of a LiNiO 2 phase, and it was found that Li 2 CO 3 was not contained. Therefore, by sintering the obtained LiNiO 2 powder in a reducing atmosphere at a temperature lower than the above temperature, a sintered body of lithium nickelate (LiNiO 2 ) having no composition deviation from the stoichiometric composition can be obtained. It has been found. Furthermore, it has also been found that the density and relative density of the sintered body can be improved by performing main sintering in an oxidizing atmosphere and at a high temperature after the sintering.
したがって、本発明は、上記知見から得られたものであり、前記課題を解決するために以下の構成を採用した。
（１）本発明のニッケル酸リチウムスパッタリングターゲットの製造方法は、Ｌｉ２ＣＯ３粉末とＮｉＯ粉末との混合粉末を、大気中、７００〜９００℃で焼成し、ＬｉＮｉＯ２焼成体を得る焼成工程と、前記ＬｉＮｉＯ２焼成体を粉砕してＬｉＮｉＯ２粉末を得る粉砕工程と、前記ＬｉＮｉＯ２粉末を焼結してＬｉＮｉＯ２焼結体を得る焼結工程と、を備えることを特徴とする。
（２）前記（１）の製造方法における前記焼結工程は、前記ＬｉＮｉＯ２粉末を、還元雰囲気で、４００〜６００℃で加圧焼結して、中間焼結体を得る加圧焼結工程と、前記中間焼結体を、大気中で、７００〜８５０℃で加熱保持して、ＬｉＮｉＯ２焼結体を得る本焼結工程とを含むことを特徴とする。
Therefore, the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems.
(1) The method for producing a lithium nickelate sputtering target of the present invention includes a firing step of firing a mixed powder of Li 2 CO 3 powder and NiO powder at 700 to 900 ° C. in the air to obtain a LiNiO 2 fired body. A pulverizing step of pulverizing the LiNiO 2 fired body to obtain a LiNiO 2 powder, and a sintering step of sintering the LiNiO 2 powder to obtain a LiNiO 2 sintered body.
(2) The sintering step in the production method of (1) is a pressure sintering step in which the LiNiO 2 powder is pressure sintered at 400 to 600 ° C. in a reducing atmosphere to obtain an intermediate sintered body. And a main sintering step in which the intermediate sintered body is heated and held at 700 to 850 ° C. in the atmosphere to obtain a LiNiO 2 sintered body.
本発明に係るニッケル酸リチウムスパッタリングターゲットの製造方法では、Ｌｉ２ＣＯ３とＮｉＯとの混合粉末を、大気中、７００〜９００℃で焼成し、ＬｉＮｉＯ２を得る焼成工程と、前記焼成工程で得られたＬｉＮｉＯ２を粉砕してＬｉＮｉＯ２粉末を得る粉砕工程と、前記粉砕工程で得られたＬｉＮｉＯ２粉末を焼結して焼結体を得る焼結工程とを備えることとし、焼結工程の前に、所定の温度範囲で焼成工程を実施することで、化学量論組成から組成ずれのないニッケル酸リチウム（ＬｉＮｉＯ２）を得ることができ、これを焼結することで、組成ずれのないニッケル酸リチウムスパッタリングターゲットを得ることができる。 In the method for producing a lithium nickelate sputtering target according to the present invention, a mixed powder of Li 2 CO 3 and NiO is fired at 700 to 900 ° C. in the atmosphere to obtain LiNiO 2, and obtained in the firing step. pulverized to obtain a LiNiO 2 powder LiNiO 2 was ground that is, by sintering the LiNiO 2 powder obtained in the pulverizing step and further comprising a sintering step to obtain a sintered body, the sintering process Previously, by performing the firing step in a predetermined temperature range, lithium nickelate (LiNiO 2 ) having no compositional deviation can be obtained from the stoichiometric composition, and by sintering this, there is no compositional deviation. A lithium nickelate sputtering target can be obtained.
ここで、前記焼成工程における焼成温度が、７００℃未満であると、未反応のＬｉ２ＣＯ３が残り、組成ずれの原因となるので好ましくない。一方、その焼成温度が、９００℃を超えると、Ｌｉが蒸発して組成ずれの原因となるので好ましくない。 Here, if the firing temperature in the firing step is less than 700 ° C., unreacted Li 2 CO 3 remains, which causes a composition shift, which is not preferable. On the other hand, when the firing temperature exceeds 900 ° C., Li evaporates and causes a composition shift.
また、本発明に係るニッケル酸リチウムスパッタリングターゲットの製造方法において、前記焼結工程は、前記ＬｉＮｉＯ２粉末を、還元雰囲気中、４００〜６００℃で加圧焼結して中間焼結体を得る加圧焼結（ホットプレス）工程と、前記中間焼結体を、大気中、７００〜８５０℃で加熱保持する本焼結工程とを有することが好ましい。このような工程手順にすることにより、より確実にスパッタリングターゲットの組成ずれを防止することができる。また、より密度の高いスパッタリングターゲットを得ることができる。 In the method for producing a lithium nickelate sputtering target according to the present invention, the sintering step may be performed by pressure-sintering the LiNiO 2 powder at 400 to 600 ° C. in a reducing atmosphere to obtain an intermediate sintered body. It is preferable to include a pressure sintering (hot pressing) step and a main sintering step of heating and holding the intermediate sintered body at 700 to 850 ° C. in the atmosphere. By setting it as such a process procedure, the composition shift | offset | difference of a sputtering target can be prevented more reliably. Moreover, a sputtering target with higher density can be obtained.
ここで、加圧焼結（ホットプレス）工程における加熱温度が、４００℃未満であると、密度を向上する効果が低くなるので好ましくない。一方、その加熱温度が、６００℃を超えると、ＬｉＮｉＯ２が還元されて組成ずれの原因となるので好ましくない。なお、還元雰囲気のホットプレス工程においては、一部のＬｉＮｉＯ２が還元され、組成ずれが発生しても、次の、大気中での本焼成工程により、ＬｉＮｉＯ２に戻るので、組成ずれの問題は生じない。ただし、この場合であっても、加圧焼結工程における加熱温度が、６００℃を超えて過度に還元されると、スパッタリングターゲットに組成ずれとして残る場合がある。 Here, if the heating temperature in the pressure sintering (hot pressing) step is less than 400 ° C., the effect of improving the density is lowered, which is not preferable. On the other hand, when the heating temperature exceeds 600 ° C., LiNiO 2 is reduced, which causes a composition shift. In the hot press process in a reducing atmosphere, even if a part of the LiNiO 2 is reduced and a composition shift occurs, it returns to LiNiO 2 by the next main firing step in the air, so there is a problem of the composition shift. Does not occur. However, even in this case, if the heating temperature in the pressure sintering process exceeds 600 ° C. and is excessively reduced, it may remain as a composition shift in the sputtering target.
また、前記本焼結工程における加熱温度が、７００℃未満であると、ターゲット密度を向上する効果が低くなるので好ましくない。一方、その加熱温度が、８５０℃を超えると、Ｌｉが蒸発して組成ずれの原因となるので好ましくない。 Further, if the heating temperature in the main sintering step is less than 700 ° C., the effect of improving the target density is lowered, which is not preferable. On the other hand, when the heating temperature exceeds 850 ° C., Li evaporates and causes a composition shift, which is not preferable.
以上の様に、本発明に係るニッケル酸リチウムスパッタリングターゲットの製造方法によれば、Ｌｉ２ＣＯ３粉末とＮｉＯ粉末との混合粉末を、大気中、７００〜９００℃で焼成し、ＬｉＮｉＯ２焼成体を得る焼成工程と、前記ＬｉＮｉＯ２焼成体を粉砕して得たＬｉＮｉＯ２粉末を焼結してＬｉＮｉＯ２焼結体を得る焼結工程と、を備えているので、化学量論組成からずれた組成を有するニッケル含有リチウム化合物の生成を低減した単相のニッケル酸リチウム（ＬｉＮｉＯ２）を得ることができる。 As described above, according to the manufacturing method of the lithium nickel oxide sputtering target according to the present invention, a mixed powder of Li 2 CO 3 powder, NiO powder, in the air and then calcined at 700 to 900 ° C., LiNiO 2 sintered body and the obtained sintering step, a sintering step of obtaining a LiNiO 2 sintered body by sintering the LiNiO 2 powder obtained by pulverizing the LiNiO 2 fired body is provided with the, deviated from the stoichiometric composition A single-phase lithium nickelate (LiNiO 2 ) with reduced generation of a nickel-containing lithium compound having a composition can be obtained.
さらに、前記焼結工程が、前記ＬｉＮｉＯ２粉末を、還元雰囲気中、４００〜６００℃で加圧焼結して中間焼結体を得る加圧焼結（ホットプレス）工程と、前記中間焼結体を、大気中、７００〜８５０℃で加熱保持する本焼結工程とを有することにより、より確実にスパッタリングターゲットの組成ずれを防止することができ、より密度の高いスパッタリングターゲットを得ることができる。 Further, the sintering step includes a pressure sintering (hot pressing) step in which the LiNiO 2 powder is subjected to pressure sintering at 400 to 600 ° C. in a reducing atmosphere to obtain an intermediate sintered body, and the intermediate sintering. By having a main sintering step in which the body is heated and held at 700 to 850 ° C. in the atmosphere, the composition deviation of the sputtering target can be prevented more reliably, and a sputtering target with higher density can be obtained. .
以上の様に、本発明に係る方法により製造されたニッケル酸リチウムスパッタリングターゲットにおいては、組成ずれを防止した単相のニッケル酸リチウム（ＬｉＮｉＯ２）で構成されているので、このスパッタリングターゲットを用いて、スパッタリング成膜すれば、組成ずれのないニッケル酸リチウム（ＬｉＮｉＯ２）膜が得られる。 As described above, since the lithium nickelate sputtering target manufactured by the method according to the present invention is composed of single-phase lithium nickelate (LiNiO 2 ) that prevents composition deviation, this sputtering target is used. When sputtering film formation is performed, a lithium nickelate (LiNiO 2 ) film having no composition deviation can be obtained.
次に、本発明に係るニッケル酸リチウムスパッタリングターゲットの製造方法について、以下に、実施例により具体的に説明する。 Next, the manufacturing method of the lithium nickelate sputtering target according to the present invention will be specifically described below with reference to examples.
〔実施例〕
先ず、本発明に係るニッケル酸リチウムスパッタリングターゲットを製造するために、原料粉末として、平均粒径Ｄ５０が１５０μｍ、純度４ＮのＬｉ２ＣＯ３粉末（株式会社高純度科学研究所製）と、平均粒径Ｄ５０が１．８μｍ、純度３ＮのＮｉＯ粉末（フルウチ化学株式会社製）とを用意した。そして、以下に示す混合工程、焼成工程、粉砕工程、焼結工程：ホットプレス工程、焼結工程：本焼結工程、機械加工工程の手順に従い、製造を実施した。
〔Example〕
First, in order to manufacture the lithium nickelate sputtering target according to the present invention, Li 2 CO 3 powder (manufactured by High Purity Science Laboratory Co., Ltd.) having an average particle diameter D50 of 150 μm and a purity of 4N as a raw material powder and an average particle A NiO powder (manufactured by Furuuchi Chemical Co., Ltd.) having a diameter D50 of 1.8 μm and a purity of 3N was prepared. And it manufactured according to the procedure of the mixing process shown below, a baking process, a grinding | pulverization process, a sintering process: a hot press process, a sintering process: this sintering process, and a machining process.
（混合工程）
Ｌｉ２ＣＯ３粉末とＮｉＯ粉末とを、モル比が１：２となるように秤量した。秤量した各原料粉末を、ボールミルにより混合し、実施例１〜１１の混合粉末を得た。この混合では、ＺｒＯ２ボールを用い、溶媒にはヘキサンを用いた。得られた各混合粉末を乾燥し、目開き０．５ｍｍの篩にかけた。
(Mixing process)
Li 2 CO 3 powder and NiO powder were weighed so that the molar ratio was 1: 2. The weighed raw material powders were mixed by a ball mill to obtain mixed powders of Examples 1-11. In this mixing, ZrO 2 balls were used and hexane was used as a solvent. Each obtained mixed powder was dried and passed through a sieve having an opening of 0.5 mm.
（焼成工程）
実施例１〜１１の混合粉末をそれぞれ容器に入れ、大気中で、表１に示された加熱温度で、４８時間、加熱保持し、塊状のＬｉＮｉＯ２焼成体を得た。
(Baking process)
Each of the mixed powders of Examples 1 to 11 was placed in a container and heated and held in the air at the heating temperature shown in Table 1 for 48 hours to obtain a massive LiNiO 2 fired body.
（粉砕工程）
得られた塊状のＬｉＮｉＯ２焼成体をそれぞれベッセルによって解砕し、目開き９０μｍの篩にかけて、実施例１〜１１のＬｉＮｉＯ２粉末を得た。
(Crushing process)
The obtained bulk LiNiO 2 fired bodies were each crushed with a vessel and passed through a sieve having an opening of 90 μm to obtain LiNiO 2 powders of Examples 1 to 11.
（焼結工程：ホットプレス工程）
得られた実施例１〜１１のＬｉＮｉＯ２粉末を、それぞれモールドに充填し、真空槽内を１０−２Ｔｏｒｒ（１．３Ｐａ）の到達真空圧力まで排気した後、表１に示す加熱温度で２時間、圧力１４．７ＭＰａでホットプレスすることにより、実施例１〜１１の中間焼結体を得た。
(Sintering process: Hot pressing process)
The obtained LiNiO 2 powders of Examples 1 to 11 were each filled in a mold, the inside of the vacuum chamber was evacuated to an ultimate vacuum pressure of 10 −2 Torr (1.3 Pa), and then heated at 2 at the heating temperature shown in Table 1. The intermediate sintered bodies of Examples 1 to 11 were obtained by hot pressing at a pressure of 14.7 MPa for a time.
（焼結工程：本焼結工程）
上記実施例１〜１１の中間焼結体を、大気中、表１に示した加熱温度で、４８時間、加熱保持し、実施例１〜１１の焼結体を得た。
(Sintering process: Main sintering process)
The intermediate sintered bodies of Examples 1 to 11 were heated and held for 48 hours at the heating temperatures shown in Table 1 in the air, and the sintered bodies of Examples 1 to 11 were obtained.
（機械加工工程）
得られた実施例１〜１１の焼結体を機械加工して、直径２００ｍｍ、厚さ５ｍｍの実施例１〜１１のスパッタリングターゲットを作製した。ここで、実施例ごとに、同じスパッタリングターゲットを５個ずつ作製した。
(Machining process)
The obtained sintered bodies of Examples 1 to 11 were machined to produce sputtering targets of Examples 1 to 11 having a diameter of 200 mm and a thickness of 5 mm. Here, five same sputtering targets were produced for every Example.
〔比較例〕
実施例との比較のため、比較例１、２のニッケル酸リチウムスパッタリングターゲットを作製した。各比較例のスパッタリングターゲットは、上記実施例の場合と同様の手順で作製されたが、比較例１、２では、上記の焼成工程における温度が、本発明の温度範囲外となっており、比較例１は、低い場合であり、また、比較例２は、高い場合である。
[Comparative Example]
For comparison with the examples, lithium nickelate sputtering targets of Comparative Examples 1 and 2 were produced. The sputtering target of each comparative example was produced in the same procedure as in the above example, but in comparative examples 1 and 2, the temperature in the above baking step is outside the temperature range of the present invention. Example 1 is a low case, and Comparative Example 2 is a high case.
次いで、作製された実施例１〜１１及び比較例１、２のスパッタリングターゲットについて、以下に示すように、組成ずれの評価を行い、さらに、ターゲット密度及び相対密度を測定した。 Subsequently, about the produced sputtering target of Examples 1-11 and Comparative Examples 1 and 2, as shown below, composition deviation was evaluated and the target density and relative density were further measured.
＜組成ずれの評価＞
下記の条件で、実施例１〜１１及び比較例１、２のスパッタリングターゲットのそれぞれの５サンプルについて、ＸＲＤ測定を実施した。
・試料の準備：得られた焼結体をメノウ乳鉢にて粉砕したものを測定試料とした。
・装置：理学電機社製（ＲＩＮＴ−Ｕｌｔｉｍａ／ＰＣ）
・管球：Ｃｕ
・管電圧：４０ｋＶ
・管電流：４０ｍＡ
・走査範囲（２θ）：１０°〜９０°
・スリットサイズ：発散（ＤＳ）２／３度、散乱（ＳＳ）２／３度、受光（ＲＳ）０．３ｍｍ
・測定ステップ幅：２θで０．０４度
・スキャンスピード：毎分４度
・試料台回転スピード：３０ｒｐｍ
上記測定により得られたＸＲＤパターンにおいて、ＬｉＮｉＯ２相のみが検出された場合を組成ずれ無しとし、ＬｉＮｉＯ２相以外の相、即ち、組成ずれが発生したニッケル含有リチウム化合物相も検出された場合、組成ずれ有とした。５サンプル中、組成ずれのあったサンプルの数を、表２の「組成ずれ発生数」欄に示した。なお、５サンプルいずれにおいても組成ずれ無しの場合は、「０」である。
<Evaluation of composition deviation>
Under the following conditions, XRD measurement was performed on each of the five samples of the sputtering targets of Examples 1 to 11 and Comparative Examples 1 and 2.
-Preparation of sample: The obtained sintered body was pulverized in an agate mortar and used as a measurement sample.
・ Device: Rigaku Electric Co., Ltd. (RINT-Ultima / PC)
・ Tube: Cu
・ Tube voltage: 40kV
・ Tube current: 40 mA
Scanning range (2θ): 10 ° to 90 °
・ Slit size: divergence (DS) 2/3 degrees, scattering (SS) 2/3 degrees, light reception (RS) 0.3 mm
・ Measurement step width: 0.04 degrees at 2θ ・ Scanning speed: 4 degrees per minute ・ Sample stage rotation speed: 30 rpm
In the XRD pattern obtained by the above measurement, when only the LiNiO 2 phase is detected, there is no composition deviation, and when a phase other than the LiNiO 2 phase, that is, a nickel-containing lithium compound phase in which a composition deviation occurs is also detected, It was assumed that there was a composition deviation. The number of samples having a composition deviation among the five samples is shown in the “Number of occurrence of composition deviation” column of Table 2. In addition, when there is no composition deviation in any of the five samples, it is “0”.
なお、本発明に係る方法で製造されたニッケル酸リチウムスパッタリングターゲットの一具体例として、上記実施例１の場合についてのＸ線回折による計測結果のＸＲＤパターンを図１に示した。また、本発明に係る方法で製造されたニッケル酸リチウムスパッタリングターゲットの他の具体例として、上記実施例６の場合についてのＸ線回折による計測結果のＸＲＤパターンを図２に示した。図１及び図２のＸＲＤパターンによれば、単相のＬｉＮｉＯ２相が確認された。さらに、本発明に係る方法で製造されたニッケル酸リチウムスパッタリングターゲットの別の具体例として、実施例１１の場合についてのＸ線回折による計測結果のＸＲＤパターンを図３に示した。図３のＸＲＤパターンによれば、ＬｉＮｉＯ２相と、化学量論組成からずれたニッケル含有リチウム化合物相とが確認された。 In addition, as a specific example of the lithium nickelate sputtering target manufactured by the method according to the present invention, an XRD pattern of a measurement result by X-ray diffraction in the case of Example 1 is shown in FIG. Further, as another specific example of the lithium nickelate sputtering target manufactured by the method according to the present invention, an XRD pattern of a measurement result by X-ray diffraction in the case of Example 6 is shown in FIG. According to the XRD patterns of FIGS. 1 and 2, a single-phase LiNiO 2 phase was confirmed. Furthermore, as another specific example of the lithium nickelate sputtering target manufactured by the method according to the present invention, the XRD pattern of the measurement result by X-ray diffraction in the case of Example 11 is shown in FIG. According to the XRD pattern of FIG. 3, a LiNiO 2 phase and a nickel-containing lithium compound phase deviated from the stoichiometric composition were confirmed.
＜密度の評価＞
得られた実施例１〜１１及び比較例１、２の焼結体を、所定寸法に機械加工した後、重量を測定し嵩密度を求めた。これらの嵩密度を理論密度（４．８１ｇ／ｃｍ３）で割ることで、各々の相対密度を算出した。密度及び相対密度について、それらの結果を、表２の「密度（ｇ／ｃｍ３）」欄及び「相対密度（％）」欄に示した。なお、比較例１、２の場合には、全サンプルにおいて、組成ずれが発生したため、密度及び相対密度を測定しなかった。表２においては、「−」と表記した。
<Evaluation of density>
The obtained sintered bodies of Examples 1 to 11 and Comparative Examples 1 and 2 were machined to predetermined dimensions, and then the weight was measured to determine the bulk density. Each bulk density was calculated by dividing these bulk densities by the theoretical density (4.81 g / cm 3 ). The results of density and relative density are shown in the “Density (g / cm 3 )” column and “Relative density (%)” column of Table 2. In Comparative Examples 1 and 2, since composition shift occurred in all samples, the density and relative density were not measured. In Table 2, it was described as “−”.
上記の表２によれば、実施例１〜６、８〜１０の場合には、いずれも、スパッタリングターゲットの５サンプル中で組成ずれ発生を確認できなかった。さらに、実施例７の場合は、ホットプレス工程の加熱温度が高いため、実施例１１の場合は、本焼成工程の加熱温度が高いため、一部のサンプルで組成ずれが発生したが、いずれの場合も、ターゲット密度及び相対密度を向上することができた。 According to said Table 2, in the case of Examples 1-6 and 8-10, composition deviation generation | occurrence | production was not able to be confirmed in all 5 samples of a sputtering target. Furthermore, in the case of Example 7, since the heating temperature of the hot pressing process is high, in the case of Example 11, the heating temperature of the main baking process is high. Even in this case, the target density and the relative density could be improved.
一方、比較例１の場合には、焼成工程における加熱温度が低く、比較例２の場合には、その加熱温度が高いため、いずれの場合も、全てのサンプルで組成ずれが発生した。 On the other hand, in the case of Comparative Example 1, the heating temperature in the firing step was low, and in the case of Comparative Example 2, the heating temperature was high. Therefore, in all cases, composition deviation occurred in all samples.
以上のことから、本実施例に係るニッケル酸リチウムスパッタリングターゲットの製造方法によれば、Ｌｉ２ＣＯ３とＮｉＯとの混合粉末を、酸化雰囲気で、Ｌｉ２ＣＯ３の融点以上の温度で焼成すると、塊状のＬｉＮｉＯ２を得ることができ、これを粉砕して得たＬｉＮｉＯ２粉末を、還元雰囲気で、前記温度より低い温度で焼結することによって、化学量論組成から組成ずれのないニッケル酸リチウム（ＬｉＮｉＯ２）の焼結体が得られることを確認できた。さらに、この焼結後に、酸化雰囲気、高い温度で本焼結すると、この焼結体の密度及び相対密度を向上できることも確認できた。
From the above, according to the method for producing a lithium nickelate sputtering target according to the present embodiment, when the mixed powder of Li 2 CO 3 and NiO is baked at a temperature equal to or higher than the melting point of Li 2 CO 3 in an oxidizing atmosphere. , can be obtained LiNiO 2 massive, LiNiO 2 powder obtained by pulverizing this, in a reducing atmosphere, by sintering at lower than the temperature temperature, without nickelate compositions deviation from the stoichiometric composition It was confirmed that a sintered body of lithium (LiNiO 2 ) was obtained. Furthermore, it was also confirmed that the density and relative density of the sintered body can be improved by performing main sintering in an oxidizing atmosphere and at a high temperature after the sintering.
Claims (2)
前記ＬｉＮｉＯ２焼成体を粉砕してＬｉＮｉＯ２粉末を得る粉砕工程と、
前記ＬｉＮｉＯ２粉末を焼結してＬｉＮｉＯ２焼結体を得る焼結工程と、
を備えることを特徴とするリチウム含有ニッケル酸化物スパッタリングターゲットの製造方法。 A firing step of firing a mixed powder of Li 2 CO 3 powder and NiO powder in air at 700 to 900 ° C. to obtain a LiNiO 2 fired body;
Pulverizing the LiNiO 2 fired body to obtain LiNiO 2 powder;
Sintering the LiNiO 2 powder to obtain a LiNiO 2 sintered body;
A method for producing a lithium-containing nickel oxide sputtering target, comprising:
前記ＬｉＮｉＯ２粉末を、還元雰囲気で、４００〜６００℃で加圧焼結して、中間焼結体を得る加圧焼結工程と、
前記中間焼結体を、大気中で、７００〜８５０℃で加熱保持して、ＬｉＮｉＯ２焼結体を得る本焼結工程と
を含むことを特徴とする請求項１に記載のリチウム含有ニッケル酸化物スパッタリングターゲットの製造方法。
The sintering step includes
A pressure sintering step in which the LiNiO 2 powder is subjected to pressure sintering at 400 to 600 ° C. in a reducing atmosphere to obtain an intermediate sintered body;
The intermediate-sintered body is heated and held at 700 to 850 ° C. in the atmosphere to obtain a LiNiO 2 sintered body, and the lithium-containing nickel oxidation according to claim 1, A method for manufacturing a sputtering target.
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| CN112321280A (en) * | 2020-11-13 | 2021-02-05 | 北京航大微纳科技有限公司 | Gel injection molding preparation method of nickel oxide-based ceramic target material |
| JP2021113349A (en) * | 2020-01-20 | 2021-08-05 | 株式会社デンソー | Manufacturing method of target |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6340756A (en) * | 1986-08-07 | 1988-02-22 | 旭硝子株式会社 | Indium oxide sintered body for tin-containing physical vapor deposition |
| JPH06510090A (en) * | 1991-09-03 | 1994-11-10 | ソシエテ・ナシオナル・エルフ・アキテーヌ | Target element for cathode sputtering |
| JP2009046340A (en) * | 2007-08-17 | 2009-03-05 | Ulvac Material Kk | Method for producing lithium phosphate sintered compact, and sputtering target |
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2014
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6340756A (en) * | 1986-08-07 | 1988-02-22 | 旭硝子株式会社 | Indium oxide sintered body for tin-containing physical vapor deposition |
| JPH06510090A (en) * | 1991-09-03 | 1994-11-10 | ソシエテ・ナシオナル・エルフ・アキテーヌ | Target element for cathode sputtering |
| JP2009046340A (en) * | 2007-08-17 | 2009-03-05 | Ulvac Material Kk | Method for producing lithium phosphate sintered compact, and sputtering target |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021113349A (en) * | 2020-01-20 | 2021-08-05 | 株式会社デンソー | Manufacturing method of target |
| JP7298490B2 (en) | 2020-01-20 | 2023-06-27 | 株式会社デンソー | Target manufacturing method |
| CN112321280A (en) * | 2020-11-13 | 2021-02-05 | 北京航大微纳科技有限公司 | Gel injection molding preparation method of nickel oxide-based ceramic target material |
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