JP2004323919A - Sputtering target superior in sputtering crack resistance for forming phase-change memory film - Google Patents
Sputtering target superior in sputtering crack resistance for forming phase-change memory film Download PDFInfo
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- sputtering
- sputtering target
- memory film
- crack resistance
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Abstract
Description
【0001】
【発明の属する技術分野】
この発明は、相変化型メモリー膜を形成するための耐スパッタ割れ性に優れたスパッタリングターゲットに関するものである。
【0002】
【従来の技術】
一般に、相変化型不揮発メモリーにはカルコゲナイト半導体として知られているGe−Sb−Te系合金膜が用いられていることは知られており、このGe−Sb−Te系合金膜は電気パルスを加えて自己加熱させることにより結晶状態と非晶質状態を可逆的に相移転させることができ、この相移転により電気抵抗が変化するために、この電気抵抗の変化を記録方法として利用したのが前記相変化型不揮発メモリーである(例えば、非特許文献1参照)。
前記Ge−Sb−Te系合金膜は、原子%で(以下、%は原子%を示す)Ge:20〜30%、Sb:20〜30%を含有し、残部がTeおよび不可避不純物からなる組成を有するであることが知られており、このGe−Sb−Te系合金膜は一般にスパッタリング法により形成されることが知られている(例えば、特許文献1、2、3などを参照)。
【0003】
【非特許文献1】
「応用物理」第71巻 第12号(2002) 第1513〜1517頁
【特許文献1】
特表2001−502848
【特許文献2】
特表2002−512439
【特許文献3】
特表2002−540605
【0004】
【発明が解決しようとする課題】
しかし、従来のGe−Sb−Te系合金製ターゲットは、成膜速度を高めて一層低コストのGe−Sb−Te系合金膜を作製するために高出力でスパッタリングを行うと、ターゲットに割れが発生し、ターゲットの交換を余儀なくされて作業効率を上げることができなかった。
【0005】
【課題を解決するための手段】
そこで、本発明者らは、高出力でスパッタリングを行なってもターゲットに割れが発生することのない耐スパッタ割れ性に優れた相変化型メモリー膜形成用スパッタリングターゲットを開発すべく研究を行なった。
その結果、通常のGe−Sb−Te系スパッタリングターゲットに酸素:0.3〜1.5%含有させたスパッタリングターゲットは、高出力でスパッタリングを行なっても割れることがなくなる、という研究結果が得られたのである。
【0006】
この発明は、かかる研究結果に基づいて成されたものであって、
Ge:20〜30%、Sb:20〜30%を含有し、さらに酸素:0.3〜1.5%を含有し、残部がTeおよび不可避不純物からなる組成を有する耐スパッタ割れ性に優れた相変化型メモリー膜形成用スパッタリングターゲット、に特徴を有するものである。
【0007】
この発明の耐スパッタ割れ性に優れた相変化型メモリー膜形成用スパッタリングターゲットの成分組成を前述のごとく限定した理由を説明する。
(a) 酸素
スパッタリングターゲットに含まれる酸素の量が0.3%未満では高出力での耐スパッタ割れ性に効果をあげることができないので好ましくなく、一方、1.5%を越えて含有させると異常放電が発生してパーティクルが多く発生するようになるので好ましくない。したがって、この発明のスパッタリングターゲットに含まれる酸素含有量を0.3〜1.5%に定めた。この発明のスパッタリングターゲットに含まれる酸素含有量の一層好ましい範囲は0.5〜1.2%である。
【0008】
(b) Ge、Sb
この発明の酸素を含む耐スパッタ割れ性に優れた相変化型メモリー膜形成用スパッタリングターゲットに含まれるGeおよびSbは、Ge:20〜30%、Sb:20〜30%が好ましい。その理由は、Ge:20%未満、Sb:20%未満であっても、またGe:30%を越え、Sb:30%を越えても結晶化時間が長くなって膜の特性が低下するので好ましくないことによるものである。
【0009】
この発明の耐スパッタ割れ性に優れた相変化型メモリー膜形成用スパッタリングターゲットは、所定の成分組成となるように溶解し鋳造して得られたインゴットを粉砕し、この粉砕粉末を大気中で酸化して原料粉末を作製し、この酸化した原料粉末を真空雰囲気中でホットプレスすることにより製造することができる。このようにして得られた耐スパッタ割れ性に優れた相変化型メモリー膜形成用スパッタリングターゲットは、組織が適度に微細であり、その平均結晶粒径は5〜36μmの範囲内にある。
【0010】
【発明の実施の形態】
原料合金を石英ルツボで溶解し、金型に鋳造して表1に示される成分組成のインゴットを作製し、このインゴットをハンマーミルで粉砕することにより36μmアンダーの粉砕粉末を作製し、得られた粉砕粉末を大気中で表1に示される温度および時間保持することにより酸化処理し、表1に示される成分組成を有する原料粉末A〜Mを作製した。
得られた原料粉末A〜Mを金型に充填し、27.3Paの真空雰囲気中、温度:400℃、2時間保持の条件でホットプレスすることにより表2に示される成分組成を有するホットプレス体を作製し、これらホットプレス体を研削加工することにより直径:300mm、厚さ:5mmの寸法を有し表2に示される成分組成を有する本発明ターゲット1〜9、比較ターゲット1〜2および従来ターゲットを作製した。
【0011】
これら本発明ターゲット1〜9、比較ターゲット1〜2および従来ターゲットをモリブデン製の冷却用バッキングプレートに純度:99.999重量%のインジウムろう材にてハンダ付けし、これを直流マグネトロンスパッタリング装置に装入し、ターゲットと基板(この基板として表面に厚さ:100nmのSiO2を形成したSiウエーハを用いた)の間の距離を70mmになるようにセットした後、到達真空度:5×10−5Pa以下になるまで真空引きを行い、その後、Arガスをスパッタガス全圧:1.0Paになるように供給し、表2に示される電力を供給することにより1時間スパッタリングを行い、ターゲットの割れ発生の有無を観察し、その結果を表2に示した。表2において、○は割れが発生しなかったことを示し、×は割れが発生したことを示す。
【0012】
【表1】
【0013】
【表2】
【0014】
表2示される結果から、本発明ターゲット1〜9は高出力でスパッタしても割れが発生しないところから耐スパッタ割れ性に優れていることが分かる。しかし、この発明の条件から外れた酸素を含有する比較ターゲット1〜2および従来ターゲットは低出力で割れが発生したり異常放電が発生してパーティクルが発生したりするので好ましくないことが分かる。
【0015】
【発明の効果】
上述のように、この発明の相変化型メモリー膜形成用スパッタリングターゲットは耐スパッタ割れ性に優れているので高出力で成膜することができ、相変化型メモリー膜のコストを一層下げて相変化型不揮発メモリーのコスト削減を行うことができ、光メディア産業の発展に大いに貢献し得るものである。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a sputtering target having excellent spatter crack resistance for forming a phase change type memory film.
[0002]
[Prior art]
It is generally known that a phase-change nonvolatile memory uses a Ge—Sb—Te alloy film known as a chalcogenite semiconductor, and this Ge—Sb—Te alloy film is applied with an electric pulse. By self-heating, the crystalline state and the amorphous state can be reversibly phase-transferred, and the electric resistance changes due to this phase transition, so the change in electric resistance was used as a recording method. It is a phase-change nonvolatile memory (for example, see Non-Patent Document 1).
The Ge—Sb—Te-based alloy film contains 20% to 30% of Ge and 20% to 30% of Sb in atomic% (hereinafter, “%” indicates atomic%), with the balance being Te and unavoidable impurities. It is known that this Ge—Sb—Te alloy film is generally formed by a sputtering method (for example, see Patent Documents 1, 2, and 3).
[0003]
[Non-patent document 1]
"Applied Physics" Vol. 71, No. 12, (2002), pp. 1513-1517 [Patent Document 1]
Special table 2001-502848
[Patent Document 2]
Table 2002-512439
[Patent Document 3]
Table 2002-540605
[0004]
[Problems to be solved by the invention]
However, the conventional Ge—Sb—Te based alloy target is subject to cracking when sputtering at high output to increase the deposition rate and produce a lower cost Ge—Sb—Te based alloy film. This caused the target to be replaced and the work efficiency could not be improved.
[0005]
[Means for Solving the Problems]
Therefore, the present inventors have conducted research to develop a sputtering target for forming a phase change type memory film which is excellent in spatter cracking resistance without causing cracks in the target even when sputtering at high output.
As a result, a research result is obtained that a sputtering target containing 0.3 to 1.5% oxygen in a normal Ge-Sb-Te-based sputtering target does not crack even when sputtering at high output. It was.
[0006]
The present invention has been made based on such research results,
Ge: 20 to 30%, Sb: 20 to 30%, oxygen: 0.3 to 1.5%, the balance being Te and unavoidable impurities. Excellent in spatter crack resistance. A sputtering target for forming a phase change memory film.
[0007]
The reason why the component composition of the sputtering target for forming a phase change type memory film having excellent spatter crack resistance according to the present invention is limited as described above will be described.
(A) If the amount of oxygen contained in the oxygen sputtering target is less than 0.3%, the effect on spatter crack resistance at high output cannot be improved, and it is not preferable. It is not preferable because abnormal discharge occurs and many particles are generated. Therefore, the oxygen content contained in the sputtering target of the present invention is set to 0.3 to 1.5%. A more preferable range of the oxygen content contained in the sputtering target of the present invention is 0.5 to 1.2%.
[0008]
(B) Ge, Sb
Ge and Sb contained in the sputtering target for forming a phase change type memory film having excellent resistance to spatter cracking containing oxygen of the present invention are preferably Ge: 20 to 30% and Sb: 20 to 30%. The reason is that, even if Ge is less than 20% and Sb is less than 20%, and if it exceeds Ge: 30% and Sb exceeds 30%, the crystallization time becomes long and the characteristics of the film deteriorate. This is because it is not favorable.
[0009]
The sputtering target for forming a phase change type memory film having excellent resistance to spatter cracking of the present invention is obtained by pulverizing an ingot obtained by melting and casting so as to have a predetermined component composition, and oxidizing the pulverized powder in the atmosphere. To produce a raw material powder, and hot-pressing the oxidized raw material powder in a vacuum atmosphere. The thus obtained sputtering target for forming a phase change type memory film having excellent spatter cracking resistance has a moderately fine structure and an average crystal grain size in the range of 5 to 36 μm.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
The raw material alloy was melted in a quartz crucible and cast into a mold to produce an ingot having the component composition shown in Table 1, and the ingot was pulverized with a hammer mill to produce a pulverized powder having a size of 36 μm under. The pulverized powder was oxidized by maintaining the temperature and the time shown in Table 1 in the atmosphere to prepare raw material powders A to M having the component compositions shown in Table 1.
The obtained raw material powders A to M are filled in a mold, and hot-pressed in a vacuum atmosphere of 27.3 Pa at a temperature of 400 ° C. for 2 hours to obtain a hot press having a component composition shown in Table 2. By subjecting the hot-pressed bodies to grinding processing, the targets 1 to 9 of the present invention, the dimensions of which are 300 mm and the thickness: 5 mm, and having the component compositions shown in Table 2, and the comparative targets 1-2 and Conventionally, a target was manufactured.
[0011]
These targets 1 to 9 of the present invention, comparative targets 1 and 2, and a conventional target were soldered to a molybdenum cooling backing plate with indium brazing material having a purity of 99.999% by weight, and this was mounted on a DC magnetron sputtering apparatus. After setting the distance between the target and the substrate (a Si wafer having a thickness of 100 nm of SiO 2 formed on its surface as a substrate) was set to 70 mm, the ultimate vacuum degree was 5 × 10 −. Vacuuming is performed until the pressure becomes 5 Pa or less, and then, Ar gas is supplied so as to have a total pressure of the sputtering gas: 1.0 Pa, and sputtering is performed for 1 hour by supplying the power shown in Table 2 to perform sputtering of the target. The occurrence of cracks was observed, and the results are shown in Table 2. In Table 2, ○ indicates that cracks did not occur, and X indicates that cracks occurred.
[0012]
[Table 1]
[0013]
[Table 2]
[0014]
From the results shown in Table 2, it can be seen that the targets 1 to 9 of the present invention do not crack even when sputtered at a high output, and thus are excellent in spatter crack resistance. However, it can be seen that the comparative targets 1 and 2 containing oxygen out of the conditions of the present invention and the conventional target are not preferable because cracks are generated at low output and particles are generated due to abnormal discharge.
[0015]
【The invention's effect】
As described above, the sputtering target for forming a phase-change memory film of the present invention has excellent resistance to spatter cracking, so that it can be formed at a high output. It can reduce the cost of non-volatile memory and can greatly contribute to the development of the optical media industry.
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JP2003120933A JP4172015B2 (en) | 2003-04-25 | 2003-04-25 | Sputtering target for phase change memory film formation with excellent spatter crack resistance |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2010137485A1 (en) | 2009-05-27 | 2010-12-02 | Jx日鉱日石金属株式会社 | Sintered body target and method for producing sintered body |
KR20160078478A (en) | 2014-03-25 | 2016-07-04 | 제이엑스금속주식회사 | Sputtering target of sintered sb-te-based alloy |
CN112739847A (en) * | 2018-11-20 | 2021-04-30 | 三菱综合材料株式会社 | Sputtering target |
-
2003
- 2003-04-25 JP JP2003120933A patent/JP4172015B2/en not_active Expired - Lifetime
Cited By (10)
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WO2010137485A1 (en) | 2009-05-27 | 2010-12-02 | Jx日鉱日石金属株式会社 | Sintered body target and method for producing sintered body |
US20120097530A1 (en) * | 2009-05-27 | 2012-04-26 | Jx Nippon Mining & Metals Corporation | Target of Sintered Compact, and Method of Producing the Sintered Compact |
TWI426142B (en) * | 2009-05-27 | 2014-02-11 | Jx Nippon Mining & Metals Corp | Sintered body and sintered body |
JP2014029025A (en) * | 2009-05-27 | 2014-02-13 | Jx Nippon Mining & Metals Corp | Sintered compact target and method for producing sintered compact |
US9299543B2 (en) * | 2009-05-27 | 2016-03-29 | Jx Nippon Mining & Metals Corporation | Target of sintered compact, and method of producing the sintered compact |
KR20160145839A (en) | 2009-05-27 | 2016-12-20 | 제이엑스금속주식회사 | Sintered body target and method for producing sintered body |
KR20190112857A (en) | 2009-05-27 | 2019-10-07 | 제이엑스금속주식회사 | Sintered body target and method for producing sintered body |
KR20160078478A (en) | 2014-03-25 | 2016-07-04 | 제이엑스금속주식회사 | Sputtering target of sintered sb-te-based alloy |
US10854435B2 (en) | 2014-03-25 | 2020-12-01 | Jx Nippon Mining & Metals Corporation | Sputtering target of sintered Sb—Te-based alloy |
CN112739847A (en) * | 2018-11-20 | 2021-04-30 | 三菱综合材料株式会社 | Sputtering target |
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