JP4454253B2 - Phase change recording film having high electrical resistance and sputtering target for forming the phase change recording film - Google Patents

Phase change recording film having high electrical resistance and sputtering target for forming the phase change recording film Download PDF

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JP4454253B2
JP4454253B2 JP2003147237A JP2003147237A JP4454253B2 JP 4454253 B2 JP4454253 B2 JP 4454253B2 JP 2003147237 A JP2003147237 A JP 2003147237A JP 2003147237 A JP2003147237 A JP 2003147237A JP 4454253 B2 JP4454253 B2 JP 4454253B2
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Prior art keywords
phase change
change recording
recording film
electrical resistance
high electrical
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JP2004349599A (en
Inventor
秀樹 堀井
龍湖 河
正熙 朴
荘平 野中
啓 木之下
暁 森
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Samsung Electronics Co Ltd
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Samsung Electronics Co Ltd
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Description

【0001】
【発明の属する技術分野】
この発明は、電気抵抗が高い相変化記録膜およびその相変化記録膜を形成するための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、半導体不揮発メモリーの一種である相変化メモリー(Phase Change RAMまたはOvonics Unified Memory)に用いられる相変化記録層は、通常のDVD−RAMなどの光記録媒体に用いられているGe−Sb−Te系記録膜が広く用いられている。この相変化記録層には結晶状態の相変化材料を用い、書き換えは、その一部をヒーターで急加熱して溶融し、即急冷して部分的に非晶質化させるか、或いは非晶質部を低温でゆっくり加熱して結晶状態に戻すことで行っている。そして読み出しは結晶状態と一部非晶質化した状態の電気抵抗差によって行なっている。この相変化記録層は、相変化記録となる成分組成の合金からなるターゲットを用いてスパッタリングすることにより形成することも知られている(例えば、特許文献1〜3、非特許文献1〜2参照)。
【0003】
【特許文献1】
特表2001−502848号公報
【特許文献2】
特表2002−512439号公報
【特許文献3】
特表2002−540605号公報
【非特許文献1】
「応用物理」第71巻 第12号(2002)第1513〜1517頁
【非特許文献2】
「日経 マイクロデバイス」2002年3月号第70〜78頁
【0004】
【発明が解決しようとする課題】
しかし、非特許文献1にあるように、現状の相変化メモリー素子は書き込み消去時に回路に流れる電流値が大きく、消費電力が大きくなり、また大電流のため、回路への負担が大きいところから微細化の障害となっていた。
【0005】
【課題を解決するための手段】
そこで、本発明者らは、相変化記録膜の抵抗を高くすることで書き込み消去動作時に流れる電流値を低減させるべく研究を行なった。その結果、
(イ)通常のGe−Sb−Te系相変化記録膜において、原子%で(以下、%は原子%を示す)B:0.2〜12%含有した相変化記録膜は、結晶状態での電気抵抗が高くなり、それによって書き込み消去動作時に流れる電流値を低減させることができる、
(ロ)B:0.2〜12%含有したGe−Sb−Te系相変化記録膜は、B:0.2〜12%含有したGe−Sb−Te系ターゲットを用いてスパッタリングすることにより得られる、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、
(1)Ge:15〜22.44%、Sb:15〜23.16%、B:0.2〜12%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電気抵抗が高い相変化記録膜、
(2)Ge:15〜22.16%、Sb:15〜22.16%、B:0.2〜12%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前記(1)記載の電気抵抗が高い相変化記録膜を形成するための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】
この発明の電気抵抗が高い相変化記録膜の成分組成を前述のごとく限定した理由を説明する。
【0008】
(a) B
適度な結晶化温度の上昇は非晶質状態の安定性を高め、メモリーとして用いた場合に保持特性の向上が期待できるが、必要以上に高くなると結晶化が困難となり、また、融点があまりにも上昇すると、溶融させることが困難となって結晶化、非晶質化(書き込み、消去)のために大きな電力が必要になるなど好ましくないことが起こる。かかる理由から相変化記録膜に含まれるB成分の量は0.2%未満では膜の抵抗値を上げる効果が少ないので好ましくなく、一方、12%を越えて含有させると結晶化温度と融点の上昇が大きくなるので好ましくない。したがって、この発明の相変化記録膜に含まれるBの含有量を0.2〜12%に定めた。この発明の相変化記録膜に含まれるB含有量の一層好ましい範囲は1.0〜10.0%である。
【0009】
(b) Ge、Sb
この発明の電気抵抗が高い相変化記録膜に含まれるGeおよびSbは、Ge:15〜22.44%、Sb:15〜23.16%が好ましい。その理由は、Ge:15%未満、Sb:15%未満であっても、またGe:22.44%を越え、Sb:23.16%を越えても抵抗値が低くなったり結晶化時間が長くなって好ましくないことによるものである。
【0010】
この発明の電気抵抗が高い相変化記録膜は、結晶化後に四探針法により測定した比抵抗値が5×10-2Ω・cm以上(一層好ましくは8×10-2Ω・cm以上)であることが必要であり、その理由は比抵抗値が5×10-2Ω・cm未満では回路に大きな電流が流れ、そのために消費電力が大きくなり、また微細化時の障害になるので好ましくないことによるものである。また、非晶質状態のGe−Sb−Te合金の比抵抗は通常1×103Ω・cm程度であり、安定した読み出しのためには結晶時と非晶質時で少なくとも1桁半程度の抵抗差があることが好ましい。このため、結晶時の相変化記録膜の抵抗値は5×101Ω・cm以下が必要であり、したがって、この発明の相変化記録膜の結晶化後に四探針法により測定した比抵抗値を5×10-2Ω・cm〜5×101Ω・cmに定めた。
【0011】
この発明の相変化記録膜を形成するためのスパッタリングターゲットは、この発明の相変化記録膜の成分組成と同じ成分組成を有する合金をArガス雰囲気中で溶解した後、鉄製モールドに出湯して合金インゴットを作製し、これらを不活性ガス雰囲気中で粉砕して合金粉末を作製し、この合金粉末を真空ホットプレスすることにより作製する。前記真空ホットプレスは、圧力:146〜155MPa、温度:370〜430℃、1〜2時間保持の条件で行なわれ、その後、モールドの温度が270〜300℃まで下がった時点で冷却速度:1〜3℃/min.で常温まで冷却することにより行われることが一層好ましい。
【0012】
【発明の実施の形態】
Ge、Sb、TeおよびBをArガス雰囲気中で溶解し鋳造して合金インゴットを作製し、この合金インゴットをAr雰囲気中で粉砕することにより、いずれも粒径:250μm以下の合金粉末を作製した。
【0013】
これら合金粉末を温度:400℃、圧力:146MPaで真空ホットプレスすることによりホットプレス体を作製し、これらホットプレス体を超硬バイトを使用し、旋盤回転数:200rpmの条件で研削加工することにより直径:125mm、厚さ:5mmの寸法を有する円盤状の表1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1を作製した。
【0014】
【表1】

Figure 0004454253
【0015】
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1をそれぞれ銅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(表面に厚さ:100nmのSiO2を形成したSiウエーハ)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、全圧:1.0PaになるまでArガスを供給し、
・基板温度:室温、
・投入電力:50W(0.4W/cm2)、
の条件でスパッタリングを行い、基板の表面に厚さ:300nmを有する本発明相変化記録膜:1〜9、比較相変化記録膜1〜2および従来相変化記録膜1を形成した。
このようにして得られた本発明相変化記録膜:1〜9、比較相変化記録膜1〜2および従来相変化記録膜1の成分組成をICP(誘導結合プラズマ法)により分析し、その結果を表2に示した。
さらに、得られた本発明相変化記録膜:1〜9、比較相変化記録膜1〜2および従来相変化記録膜1を真空中、300℃に5分間保持して結晶化した後、四探針法で比抵抗を測定し、さらに上記と同じ条件で直径:120mmのポリカーボネート基板上に3μmの厚さで成膜し、付いた膜を全量剥離して粉末化したものについてDTA(示差熱分析法)により毎分200mlのArフロー中、昇温速度10℃/分の条件で結晶化温度および融点を測定し、その結果を表2に示した。なお、本測定に用いた試料は15mgで統一した。ここでは150〜300℃付近に現れる発熱ピークを結晶化温度とし、550〜700℃付近に現れる吸熱ピークを融点とした。
【0016】
【表2】
Figure 0004454253
【0017】
表1〜2示される結果から、本発明ターゲット1〜9を用いてスパッタリングすることにより得られた結晶化させた本発明相変化記録膜:1〜9は、従来ターゲット1を用いてスパッタリングすることにより得られた結晶化させた従来相変化記録膜1に比べて比抵抗が高いことが分かる。しかし、この発明の条件から外れた成分組成を有する比較ターゲット1〜2を用いてスパッタリングすることにより得られた結晶化させた比較相変化記録膜1〜2は比抵抗が小さくなったり、結晶化温度および融点が上がりすぎたりして好ましくないことが分かる。
【0018】
【発明の効果】
上述のように、この発明によると、適度に高い抵抗値が得られ、書き込み消去動作時の電流値を低減し、低消費電力化、デバイスの微細化に寄与し、相変化型不揮発メモリー膜の特性の向上およびコスト削減を行うことができるとともに、新しい半導体メモリー産業の発展に大いに貢献し得るものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a phase change recording film having a high electric resistance and a sputtering target for forming the phase change recording film.
[0002]
[Prior art]
In general, a phase change recording layer used in a phase change memory (Phase Change RAM or Ovonics Unified Memory) which is a kind of semiconductor nonvolatile memory is a Ge-Sb-Te used in an optical recording medium such as a normal DVD-RAM. System recording films are widely used. This phase change recording layer uses a phase change material in a crystalline state, and rewriting is performed by rapidly heating a part of the phase change recording layer with a heater and then immediately cooling down to make it partially amorphous or amorphous. This is done by slowly heating the part at a low temperature to return to the crystalline state. Reading is performed by the difference in electrical resistance between the crystalline state and the partially amorphous state. This phase change recording layer is also known to be formed by sputtering using a target made of an alloy having a component composition for phase change recording (see, for example, Patent Documents 1 to 3 and Non-Patent Documents 1 and 2). ).
[0003]
[Patent Document 1]
JP-T-2001-502848 [Patent Document 2]
Japanese translation of PCT publication No. 2002-512439 [Patent Document 3]
Japanese translation of PCT publication No. 2002-540605 [Non-patent document 1]
“Applied Physics” Vol. 71, No. 12 (2002), pages 1513 to 1517 [Non-patent Document 2]
Nikkei Microdevice, March 2002, pages 70-78
[Problems to be solved by the invention]
However, as described in Non-Patent Document 1, the current phase change memory element has a large current value flowing through the circuit at the time of writing and erasing, power consumption is large, and because of the large current, the load on the circuit is very small. It has become an obstacle to conversion.
[0005]
[Means for Solving the Problems]
Therefore, the present inventors have studied to reduce the value of the current flowing during the write / erase operation by increasing the resistance of the phase change recording film. as a result,
(A) In a normal Ge—Sb—Te phase change recording film, the phase change recording film containing 0.2 to 12% in atomic% (hereinafter,% indicates atomic%) is in a crystalline state. The electric resistance becomes high, and thereby the current value flowing during the write / erase operation can be reduced.
(B) A Ge—Sb—Te phase change recording film containing B: 0.2 to 12% is obtained by sputtering using a Ge—Sb—Te system target containing B: 0.2 to 12%. The result of the research was obtained.
[0006]
The present invention has been made based on such research results,
(1) Ge: 15 to 22.44% , Sb: 15 to 23.16% , B: 0.2 to 12% , with the balance being composed of Te and inevitable impurities, phase change with high electrical resistance Recording film,
(2) The content of Ge: 15 to 22.16% , Sb: 15 to 22.16% , B: 0.2 to 12% , with the balance being composed of Te and inevitable impurities It is characterized by a sputtering target for forming a phase change recording film having a high electric resistance.
[0007]
The reason why the component composition of the phase change recording film having high electrical resistance according to the present invention is limited as described above will be described.
[0008]
(A) B
A moderate increase in the crystallization temperature increases the stability of the amorphous state and can be expected to improve the retention characteristics when used as a memory, but if it becomes higher than necessary, crystallization becomes difficult and the melting point is too high. When the temperature rises, it is difficult to melt, and unfavorable things occur, such as requiring large electric power for crystallization and amorphization (writing and erasing). For this reason, if the amount of the B component contained in the phase change recording film is less than 0.2%, the effect of increasing the resistance of the film is small, which is not preferable. On the other hand, if the content exceeds 12%, the crystallization temperature and the melting point are reduced. This is not preferable because the increase is large. Therefore, the content of B contained in the phase change recording film of the present invention is set to 0.2 to 12%. A more preferable range of the B content contained in the phase change recording film of the present invention is 1.0 to 10.0%.
[0009]
(B) Ge, Sb
Ge and Sb electrical resistance is included in the high phase change recording film of the present invention, Ge: 15~ 22.44%, Sb : 15~ 23.16% is preferred. The reason is that even if Ge: less than 15%, Sb: less than 15%, Ge: more than 22.44% , and Sb: more than 23.16% , the resistance value is lowered or the crystallization time is decreased. This is because it is unfavorable because it is long.
[0010]
The phase change recording film having high electrical resistance according to the present invention has a specific resistance value of 5 × 10 −2 Ω · cm or more (more preferably 8 × 10 −2 Ω · cm or more) measured by the four-probe method after crystallization. The reason is that if the specific resistance value is less than 5 × 10 −2 Ω · cm, a large current flows through the circuit, which increases power consumption and is an obstacle to miniaturization. This is due to the absence. In addition, the specific resistance of the Ge—Sb—Te alloy in an amorphous state is usually about 1 × 10 3 Ω · cm. It is preferable that there is a resistance difference. For this reason, the resistance value of the phase change recording film at the time of crystallization needs to be 5 × 10 1 Ω · cm or less. Therefore, the specific resistance value measured by the four-probe method after crystallization of the phase change recording film of the present invention. Was set to 5 × 10 −2 Ω · cm to 5 × 10 1 Ω · cm.
[0011]
The sputtering target for forming the phase change recording film of the present invention is prepared by dissolving an alloy having the same component composition as that of the phase change recording film of the present invention in an Ar gas atmosphere and then pouring it into an iron mold. An ingot is produced, and these are pulverized in an inert gas atmosphere to produce an alloy powder, and the alloy powder is produced by vacuum hot pressing. The vacuum hot press is performed under the conditions of pressure: 146 to 155 MPa, temperature: 370 to 430 ° C., holding for 1 to 2 hours, and then cooling rate: 1 to 1 when the temperature of the mold is lowered to 270 to 300 ° C. 3 ° C./min. More preferably, it is carried out by cooling to room temperature.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
An alloy ingot was prepared by melting and casting Ge, Sb, Te, and B in an Ar gas atmosphere, and by pulverizing the alloy ingot in an Ar atmosphere, an alloy powder having a particle size of 250 μm or less was prepared. .
[0013]
These alloy powders are hot-pressed by vacuum hot pressing at a temperature of 400 ° C. and a pressure of 146 MPa, and these hot-pressed bodies are ground using a cemented carbide tool at a lathe speed of 200 rpm. The present invention targets 1-9, comparative targets 1-2, and conventional target 1 having the component composition shown in Table 1 in the shape of a disk having a diameter of 125 mm and a thickness of 5 mm were prepared.
[0014]
[Table 1]
Figure 0004454253
[0015]
These inventive targets 1-9, comparative targets 1-2, and conventional target 1 are each soldered to a copper cooling backing plate with an indium brazing material with a purity of 99.999% by weight, and this is applied to a DC magnetron sputtering apparatus. After charging and setting the distance between the target and the substrate (Si wafer having a thickness of 100 nm of SiO 2 on the surface) to be 70 mm, the ultimate vacuum is 5 × 10 −5 Pa or less. Evacuated until Ar pressure is supplied until the total pressure is 1.0 Pa,
-Substrate temperature: room temperature,
-Input power: 50 W (0.4 W / cm 2 ),
Sputtering was performed under the following conditions to form phase change recording films of the present invention having a thickness of 300 nm: 1 to 9, comparative phase change recording films 1 and 2 and a conventional phase change recording film 1 on the surface of the substrate.
The component compositions of the thus obtained phase change recording films of the present invention: 1 to 9, comparative phase change recording films 1 and 2 and conventional phase change recording film 1 were analyzed by ICP (inductively coupled plasma method), and the results Are shown in Table 2.
Further, the obtained phase change recording films of the present invention: 1 to 9, comparative phase change recording films 1 and 2 and conventional phase change recording film 1 were crystallized by holding them at 300 ° C. for 5 minutes in a vacuum, The specific resistance was measured by the needle method, and the film was formed on a polycarbonate substrate having a diameter of 120 mm with a thickness of 3 μm under the same conditions as described above. The crystallization temperature and the melting point were measured under the conditions of a heating rate of 10 ° C./min in an Ar flow of 200 ml per minute by the above method, and the results are shown in Table 2. The sample used for this measurement was unified at 15 mg. Here, the exothermic peak appearing near 150 to 300 ° C. was defined as the crystallization temperature, and the endothermic peak appearing near 550 to 700 ° C. was defined as the melting point.
[0016]
[Table 2]
Figure 0004454253
[0017]
From the results shown in Tables 1 and 2, crystallized present invention phase change recording films obtained by sputtering using the present invention targets 1 to 9: 1 to 9 are sputtered using the conventional target 1. It can be seen that the specific resistance is higher than that of the crystallized conventional phase change recording film 1 obtained by the above. However, the comparative phase change recording films 1 and 2 crystallized by sputtering using the comparative targets 1 and 2 having component compositions that deviate from the conditions of the present invention have a low specific resistance or are crystallized. It turns out that temperature and melting | fusing point rise too much and are not preferable.
[0018]
【The invention's effect】
As described above, according to the present invention, a reasonably high resistance value can be obtained, the current value during the write / erase operation can be reduced, the power consumption can be reduced, and the device can be miniaturized. It can improve the characteristics and reduce the cost, and can greatly contribute to the development of the new semiconductor memory industry.

Claims (3)

原子%で(以下、%は原子%を示す)Ge:15〜22.44%、Sb:15〜23.16%、B:0.2〜12%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ことを特徴とする電気抵抗が高い相変化記録膜。In atomic% (hereinafter,% indicates atomic%) Ge: 15 to 22.44% , Sb: 15 to 23.16% , B: 0.2 to 12% , with the balance from Te and inevitable impurities A phase change recording film having a high electrical resistance, characterized by comprising: 結晶化後に四探針法により測定した比抵抗値が5×10-2〜5×101Ω・cmであることを特徴とする請求項1記載の電気抵抗が高い相変化記録膜。2. The phase change recording film having a high electrical resistance according to claim 1, wherein a specific resistance value measured by a four-probe method after crystallization is 5 × 10 −2 to 5 × 10 1 Ω · cm. Ge:15〜22.16%、Sb:15〜22.16%、B:0.2〜12%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ことを特徴とする請求項1または2記載の電気抵抗が高い相変化記録膜を形成するためのスパッタリングターゲット。A composition comprising Ge: 15 to 22.16% , Sb: 15 to 22.16% , B: 0.2 to 12% , and the balance comprising Te and inevitable impurities. A sputtering target for forming a phase change recording film having a high electrical resistance according to 2.
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