JP2015086459A - Nickel silicide sputtering target and manufacturing method of the same - Google Patents
Nickel silicide sputtering target and manufacturing method of the same Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 37
- 229910021334 nickel silicide Inorganic materials 0.000 title claims abstract description 26
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004544 sputter deposition Methods 0.000 claims abstract description 25
- 230000007547 defect Effects 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 230000000007 visual effect Effects 0.000 claims abstract 2
- 239000000843 powder Substances 0.000 claims description 35
- 239000002994 raw material Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 abstract description 16
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000009466 transformation Effects 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- 238000005336 cracking Methods 0.000 description 9
- 239000000470 constituent Substances 0.000 description 7
- 230000005496 eutectics Effects 0.000 description 7
- 229910005883 NiSi Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910005881 NiSi 2 Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
Description
本発明は、ニッケルシリサイドの成膜が可能であり、またパーティクルの発生を抑えたニッケルシリサイドスパッタリングターゲット及びその製造方法に関する。 The present invention relates to a nickel silicide sputtering target capable of forming a nickel silicide film and suppressing generation of particles, and a method of manufacturing the same.
半導体デバイスの配線や電極として、ニッケルシリサイド膜が利用されている。一般にニッケルシリサイド膜は、スパッタリングによって成膜されている。ニッケルシリサイドスパッタリングターゲットは、ニッケル原料とシリコン原料を所定の割合で秤量し、これを電子ビーム溶解などにより溶解し、得られる合金インゴットを粉砕し、粉砕粉をホットプレス焼結することで、製造することができる。 Nickel silicide films are used as wirings and electrodes of semiconductor devices. Generally, the nickel silicide film is formed by sputtering. The nickel silicide sputtering target is manufactured by weighing a nickel raw material and a silicon raw material at a predetermined ratio, melting the raw material by electron beam melting, etc., pulverizing the resulting alloy ingot, and hot-press sintering the pulverized powder. be able to.
ニッケルシリサイドターゲットの従来技術として、特許文献１〜３には、Ｎｉ３Ｓｉ２化合物とＮｉＳｉ化合物の共晶からなるＮｉ３Ｓｉ２−ＮｉＳｉ共晶粉末と、ＮｉＳｉ化合物とＮｉＳｉ２化合物の共晶からなるＮｉＳｉ−ＮｉＳｉ２共晶粉末とを、ホットプレス焼結することにより、前記共晶粉末が反応してＮｉＳｉ化合物が形成され、ＮｉＳｉ化合物の反応生成相中に、未反応の共晶相が分散分布した組織をもつターゲットについて、開示がある。そして、このような組織をもつスパッタリングターゲットは、成膜中にパーティクルの発生が少ないことが記載されている。 As prior art nickel silicide target, Patent Documents 1 to 3, the eutectic Ni 3 Si 2 compound and Ni 3 Si 2 -NiSi eutectic powder made of eutectic NiSi compounds, NiSi compound and NiSi 2 compound The NiSi-NiSi 2 eutectic powder is subjected to hot press sintering, whereby the eutectic powder reacts to form a NiSi compound, and the unreacted eutectic phase is dispersed in the reaction product phase of the NiSi compound. There are disclosures about targets with distributed organization. It is described that the sputtering target having such a structure generates less particles during film formation.
しかし、上記の製造方法は、焼結の際に合成反応を行うため、反応熱の影響によって、プレス部材とＮｉＳｉとが反応してしまい、焼結体にひびや割れが発生するという問題がある。特に、現在主流である３００ｍｍウエハー用の大型のスパッタリングターゲットを作製する際には、この問題が特に顕著となる。したがって、内部に欠陥の少ない、大型のターゲットを安定して供給することが課題となっている。 However, since the above manufacturing method performs a synthetic reaction at the time of sintering, there is a problem that the press member and NiSi react due to the influence of reaction heat, and the sintered body is cracked or cracked. . In particular, this problem becomes particularly noticeable when a large sputtering target for a 300 mm wafer, which is currently mainstream, is produced. Therefore, it is an issue to stably supply a large target with few defects inside.
本発明は、相変態による歪みを防止し、冷却時にターゲットのひびや割れが発生することを防止することができるニッケルシリサイドスパッタリングターゲット及びその製造方法を提供することを課題とする。また、本発明は、スパッタリングの際にパーティクル発生が少なく、膜のユニフォーミティが良好な、高密度ニッケルシリサイドスパッタリングターゲットを提供することを課題とする。 An object of the present invention is to provide a nickel silicide sputtering target capable of preventing distortion due to phase transformation and preventing the target from cracking or cracking during cooling, and a method of manufacturing the same. It is another object of the present invention to provide a high-density nickel silicide sputtering target that generates less particles during sputtering and has a good film uniformity.
上記の課題を解決するために、本発明者は鋭意研究を行った結果、予め所定の組成からなる合金アトマイズ粉を作製し、これをホットプレス焼結することで、得られる焼結体にひびや割れ発生することを防止することができるとの知見を得た。 In order to solve the above-mentioned problems, the present inventor has conducted extensive research, and as a result, an alloy atomized powder having a predetermined composition is prepared in advance, and this is subjected to hot press sintering, thereby cracking the obtained sintered body. The knowledge that it was possible to prevent the occurrence of cracks.
本発明はこの知見に基づき、下記の発明を提供する。
１）Ｓｉを３０〜５０ａｔ％含有し、残部がＮｉ及び不可避的不純物からなり、ターゲットのスパッタ面における０．２５ｍｍ２視野中にある１００μｍ以上の長さをもつ欠陥の平均個数が１０個以下であることを特徴とするスパッタリングターゲット。
２）相対密度が９０％以上であることを特徴とする上記１）記載のスパッタリングターゲット。
３）Ｎｉ原料とＳｉ原料とを所定の割合で秤量し、混合した後、これを真空雰囲気又は不活性雰囲気中で溶解して合成反応を行い、その後、アトマイズ法によりニッケルシリサイド粉末を作製し、次に、この粉末を７００℃〜８５０℃の温度でホットプレス焼結することを特徴とするスパッタリングターゲットの製造方法。
Based on this finding, the present invention provides the following inventions.
1) The average number of defects having a length of 100 μm or more in the 0.25 mm 2 field of view on the sputtering surface of the target containing Si and 30 to 50 at%, the balance being Ni and unavoidable impurities, is 10 or less A sputtering target characterized by being.
2) The sputtering target according to 1) above, wherein the relative density is 90% or more.
3) Ni raw material and Si raw material are weighed at a predetermined ratio and mixed, and then this is dissolved in a vacuum atmosphere or an inert atmosphere to carry out a synthesis reaction. Thereafter, a nickel silicide powder is produced by an atomizing method, Next, this powder is subjected to hot press sintering at a temperature of 700 ° C. to 850 ° C. A method for producing a sputtering target.
本発明によれば、予め所定の組成からなる合金アトマイズ粉を作製し、これを焼結することで、焼結時の合成反応を防ぎ、またプレス温度を調節することで、相変態による歪みを防止し、冷却時のターゲット割れを防止することができるという優れた効果を有する。本発明のスパッタリングターゲットは、スパッタリングの際、パーティクル発生が少なく、ユニフォーミティの良好な膜を形成することができるという優れた効果を有する。さらに、近年の３００ｍｍウエハー用の大型スパッタリングターゲットにおいて、割れの発生が少なく、高密度なものが得られるという優れた効果を有する。 According to the present invention, an alloy atomized powder having a predetermined composition is prepared in advance, and this is sintered to prevent a synthetic reaction during sintering, and by adjusting the press temperature, distortion due to phase transformation can be prevented. It has an excellent effect of preventing and preventing target cracking during cooling. The sputtering target of the present invention has an excellent effect that a film with less particle generation and good uniformity can be formed during sputtering. Furthermore, in recent large-scale sputtering targets for 300 mm wafers, there is an excellent effect that cracks are few and high-density ones can be obtained.
本発明のスパッタリングターゲットは、Ｓｉを３０〜５０ａｔ％含有し、残部がＮｉ及び不可避的不純物から構成される。Ｓｉ含有量が３０ａｔ％未満であると、スパッタリングによって成膜した際に、十分な濡れ性が得られず、剥離し易いという問題がある。また、５０ａｔ％超であると、ダイシリサイド（ＮｉＳｉ２）の量が増えてしまい、抵抗値が上がり、所望の膜特性が得られないという問題がある。 The sputtering target of the present invention contains 30 to 50 at% of Si, and the balance is composed of Ni and inevitable impurities. When the Si content is less than 30 at%, there is a problem in that sufficient wettability cannot be obtained when the film is formed by sputtering, and peeling is easy. On the other hand, if it exceeds 50 at%, the amount of disilicide (NiSi 2 ) increases, resulting in a problem that the resistance value increases and desired film characteristics cannot be obtained.
ニッケルシリサイドにおいて、Ｓｉを３０〜５０ａｔ％含有し、残部Ｎｉ及び不可避的不純物からなる組成領域では、ε相、ε’相、σ相、θ相、γ相と複数の結晶構造を持つ複雑な領域となっている。この組成領域においては、焼結温度によって冷却時に結晶構造が変化し、変態反応が生じることとなる。そして、この結晶構造の変化は、焼結体の内部にひび等の欠陥を生じさせ、スパッタリングターゲットの割れ発生の原因となっていた。
さらに、上記組成領域の材料は元々脆性であるため、非常に欠陥が発生しやすいという問題もあった。
In nickel silicide, in a composition region containing 30 to 50 at% of Si and the balance being Ni and inevitable impurities, a complicated region having a plurality of crystal structures such as ε phase, ε ′ phase, σ phase, θ phase, and γ phase It has become. In this composition region, the crystal structure changes upon cooling depending on the sintering temperature, and a transformation reaction occurs. This change in the crystal structure causes defects such as cracks in the sintered body, causing cracks in the sputtering target.
Furthermore, since the material of the composition region is originally brittle, there is a problem that defects are very likely to occur.
本発明は、このような欠陥の発生しやすい組成領域のスパッタリングターゲットのスパッタ面において、電子顕微鏡で５００μｍ×５００μｍの面積を観察する０．２５ｍｍ２の視野中にある１００μｍ以上の長さをもつ欠陥の平均個数を１０個以下とすることができる。さらには、前記欠陥の平均個数を５個以下とすることができる。なお、欠陥の平均個数は、図１に示すように、電子顕微鏡で５箇所（中心１箇所＋４箇所）を観察して、各箇所における欠陥の個数を計数し、その平均値から求める。
ここで、本発明でいう欠陥とは、ターゲット割れの原因となりうる亀裂やひびを意味し、具体的には１〜３μｍ程度の幅を持つマイクロクラックを意味する。また、亀裂やひびの形状がＴ字のように長さと幅が区別つかない場合、長さが最も長いところを、欠陥の長さとする。これにより、ターゲットの割れを防ぐことができ、スパッタリングによる成膜の際に、パーティクルの発生を抑制することができる。
The present invention provides a defect having a length of 100 μm or more in a field of 0.25 mm 2 in which an area of 500 μm × 500 μm is observed with an electron microscope on the sputtering surface of a sputtering target having such a composition region where defects are likely to occur. The average number of can be 10 or less. Furthermore, the average number of the defects can be 5 or less. As shown in FIG. 1, the average number of defects is obtained from the average value by observing five places (one center + four places) with an electron microscope, counting the number of defects in each place.
Here, the defect referred to in the present invention means a crack or a crack that can cause a target crack, and specifically means a microcrack having a width of about 1 to 3 μm. In addition, when the length and width are indistinguishable as the shape of the crack or crack is T-shaped, the longest length is defined as the defect length. Thereby, cracking of the target can be prevented, and generation of particles can be suppressed during film formation by sputtering.
また、本発明のスパッタリングターゲットは、相対密度９０％以上を達成することができ、さらには、９５％以上を達成することができる。このような密度の向上はスパッタ膜のユニフォーミティを高め、また、スパッタリング時のパーティクルの発生を抑制することができるので、膜の品質向上に寄与することができる。
ここで、相対密度とは、スパッタリングターゲットの実測密度を真密度（理論密度ともいう）で割り返して求めた値である。真密度とはターゲットの構成成分が互いに拡散あるいは反応せずに混在していると仮定したときの密度で、次式で計算される。
式：真密度＝Σ（構成成分の分子量×構成成分のモル比）/Σ（構成成分の分子量×構成成分のモル比／構成成分の文献値密度）
ここで、Σは、ターゲットの構成成分の全てについて、和をとることを意味する。なお、スパッタリングターゲットの実測密度はアルキメデス法で測定される。
Moreover, the sputtering target of the present invention can achieve a relative density of 90% or more, and further can achieve 95% or more. Such an increase in density can increase the uniformity of the sputtered film and can suppress the generation of particles during sputtering, thereby contributing to an improvement in film quality.
Here, the relative density is a value obtained by dividing the measured density of the sputtering target by the true density (also called the theoretical density). The true density is a density when it is assumed that the constituent components of the target are mixed without diffusing or reacting with each other, and is calculated by the following equation.
Formula: True density = Σ (Molecular weight of constituent component × Molar ratio of constituent component) / Σ (Molecular weight of constituent component × Molar ratio of constituent component / Document value density of constituent component)
Here, Σ means taking the sum of all the constituent components of the target. The actual density of the sputtering target is measured by the Archimedes method.
本発明のスパッタリングターゲットは、以下のようにして作製することができる。
まず、Ｎｉ原料とＳｉ原料とを所定の割合で秤量し、混合した後、これを真空雰囲気又は不活性雰囲気中で溶解して合成反応を行い、その後、アトマイズ法によりニッケルシリサイド粉末を作製する。次に、この粉末を７００℃〜８５０℃の温度でホットプレス焼結して焼結体を作製し、得られた焼結体をターゲット形状に機械加工することで、スパッタリングターゲットを作製することができる。
The sputtering target of the present invention can be produced as follows.
First, a Ni raw material and a Si raw material are weighed and mixed at a predetermined ratio, and then mixed in a vacuum atmosphere or an inert atmosphere to perform a synthesis reaction. Thereafter, a nickel silicide powder is produced by an atomizing method. Next, this powder can be hot-press sintered at a temperature of 700 ° C. to 850 ° C. to produce a sintered body, and the resulting sintered body can be machined into a target shape to produce a sputtering target. it can.
本発明において、特に重要なことは、予め焼結前の段階でニッケルシリサイドを合成しておくことである。これにより、焼結時の合成反応を防ぎ、またプレス温度の調節により焼結後の冷却時にニッケルシリサイドの相変態が生じることなく、相変態に起因する歪みを抑制することができるので、冷却時のターゲット割れを防止することを可能とすることができる。
なお、特許文献１〜３は、Ｎｉ板材とＳｉ塊材とを電子ビーム溶解した後、インゴットを粉砕して二種の共晶粉末を作製し、これを混合した後、９６０℃でホットプレスして、ターゲットを製造するものである。これらの技術は、本発明のようにアトマイズ粉を使用するものではなく、焼結温度も高い温度領域になっている。
In the present invention, it is particularly important to synthesize nickel silicide in advance before sintering. This prevents the synthetic reaction during sintering and suppresses distortion due to phase transformation without causing nickel silicide phase transformation during cooling after sintering by adjusting the press temperature. It is possible to prevent cracking of the target.
In Patent Documents 1 to 3, after Ni plate material and Si lump material are melted with an electron beam, ingots are pulverized to produce two types of eutectic powders, mixed, and hot-pressed at 960 ° C. The target is manufactured. These techniques do not use atomized powder as in the present invention, and the sintering temperature is also in a high temperature range.
以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on Examples and Comparative Examples. In addition, a present Example is an example to the last, and is not restrict | limited at all by this example. In other words, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
（実施例１）
Ｓｉ原料とＮｉ原料とを所定の組成となるように秤量し、混合した後、これを真空雰囲気中で溶解して合成反応を行った。次に、アトマイズ法を用いてニッケルシリサイド粉末（アトマイズ粉）を作製した。次に、このアトマイズ粉を真空雰囲気中、温度８００℃、プレス荷重３００ｋｇ／ｃｍ２、保持時間２時間でホットプレス焼結した。その後、この焼結体をスパッタリングターゲット形状に仕上げた。その結果を表１に示す。表１に示す通り、ターゲット組成は、Ｓｉ量：３５．５６ａｔ％、Ｎｉ：残部であり、相対密度は９５．９％と高密度のターゲットが得られた。また、ターゲットのスパッタ面を電子顕微鏡で５００μｍ×５００μｍの面積を、図１の５箇所（中心１箇所＋４箇所）について観察した結果、０．２５ｍｍ２視野中において、１００μｍ以上の長さをもつひびの平均個数は２．０個と少なかった。次に、上記仕上げ加工したターゲットを使用して、スパッタリングを行った。スパッタ条件は、ＤＣスパッタ、スパッタパワー５００Ｗ、Ａｒガス圧０．５Ｐａとし、Ｓｉウエハー（８インチ径）に膜厚２００Åに成膜した。その後、膜中の０．２μｍ以上のパーティクルをパーティクルカウンタで測定した結果、２５個と少なかった。
Example 1
The Si raw material and the Ni raw material were weighed so as to have a predetermined composition, mixed, and then dissolved in a vacuum atmosphere to carry out a synthesis reaction. Next, nickel silicide powder (atomized powder) was produced using an atomizing method. Next, this atomized powder was hot press sintered in a vacuum atmosphere at a temperature of 800 ° C., a press load of 300 kg / cm 2 , and a holding time of 2 hours. Thereafter, this sintered body was finished into a sputtering target shape. The results are shown in Table 1. As shown in Table 1, the target composition was Si amount: 35.56 at%, Ni: balance, and a relative density of 95.9% was obtained as a high-density target. Also, an area of 500 [mu] m × 500 [mu] m the sputtering surface of the target with an electron microscope, five positions in FIG. 1 (one location +4 place center) result of observation for, in 0.25 mm 2 field in more than 100μm in length Motsuhibi The average number was as small as 2.0. Next, sputtering was performed using the above-finished target. The sputtering conditions were DC sputtering, sputtering power of 500 W, Ar gas pressure of 0.5 Pa, and a Si wafer (8 inch diameter) was formed to a thickness of 200 mm. Thereafter, particles having a size of 0.2 μm or more in the film were measured with a particle counter, and as a result, the number was 25 and few.
（実施例２）
Ｓｉ原料とＮｉ原料とを所定の組成となるように秤量し、混合した後、これを真空雰囲気中で溶解して合成反応を行った。次に、アトマイズ法を用いてニッケルシリサイド粉末（アトマイズ粉）を作製した。次に、このアトマイズ粉を真空雰囲気中、温度８２０℃、プレス荷重２９０ｋｇ／ｃｍ２、保持時間３時間でホットプレス焼結した。その後、この焼結体をスパッタリングターゲット形状に仕上げた。表１に示す通り、ターゲット組成は、Ｓｉ量：４７．２２ａｔ％、Ｎｉ：残部であり、相対密度は９７．８％と高密度のターゲットが得られた。また、ターゲットのスパッタ面を電子顕微鏡で５００μｍ×５００μｍの面積を、図１の５箇所（中心１箇所＋４箇所）について観察した結果、０．２５ｍｍ２視野中において、１００μｍ以上の長さをもつひびの平均個数は４．０個と少なかった。次に、上記仕上げ加工したターゲットを使用して、実施例１と同様の条件でスパッタリングを行った。その後、膜中の０．２μｍ以上のパーティクル数をパーティクルカウンタで測定した結果、２２個と少なかった。
(Example 2)
The Si raw material and the Ni raw material were weighed so as to have a predetermined composition, mixed, and then dissolved in a vacuum atmosphere to carry out a synthesis reaction. Next, nickel silicide powder (atomized powder) was produced using an atomizing method. Next, this atomized powder was hot press sintered in a vacuum atmosphere at a temperature of 820 ° C., a press load of 290 kg / cm 2 , and a holding time of 3 hours. Thereafter, this sintered body was finished into a sputtering target shape. As shown in Table 1, the target composition was Si amount: 47.22 at%, Ni: balance, and a relative density of 97.8% was obtained as a high-density target. Also, an area of 500 [mu] m × 500 [mu] m the sputtering surface of the target with an electron microscope, five positions in FIG. 1 (one location +4 place center) result of observation for, in 0.25 mm 2 field in more than 100μm in length Motsuhibi The average number of was as small as 4.0. Next, sputtering was performed under the same conditions as in Example 1 using the finished target. Thereafter, the number of particles of 0.2 μm or more in the film was measured with a particle counter, and as a result, it was as small as 22.
（実施例３）
Ｓｉ原料とＮｉ原料とを所定の組成となるように秤量し、混合した後、これを真空雰囲気中で溶解して合成反応を行った。次に、アトマイズ法を用いてニッケルシリサイド粉末（アトマイズ粉）を作製した。次に、このアトマイズ粉を真空雰囲気中、温度７７０℃、プレス荷重３１０ｋｇ／ｃｍ２、保持時間２時間でホットプレス焼結した。その後、この焼結体をスパッタリングターゲット形状に仕上げた。表１に示す通り、ターゲット組成は、Ｓｉ量：３９．６５ａｔ％、Ｎｉ：残部であり、相対密度は９６．５％と高密度のターゲットが得られた。また、ターゲットのスパッタ面を電子顕微鏡で５００μｍ×５００μｍの面積を、図１の５箇所（中心１箇所＋４箇所）について観察した結果、０．２５ｍｍ２視野中において、１００μｍ以上の長さをもつひびの平均個数は１．０個と少なかった。次に、上記仕上げ加工したターゲットを使用して、実施例１と同様の条件でスパッタリングを行った。その後、膜中の０．２μｍ以上のパーティクル数をパーティクルカウンタで測定した結果、２４個と少なかった。
(Example 3)
The Si raw material and the Ni raw material were weighed so as to have a predetermined composition, mixed, and then dissolved in a vacuum atmosphere to carry out a synthesis reaction. Next, nickel silicide powder (atomized powder) was produced using an atomizing method. Next, this atomized powder was hot press sintered in a vacuum atmosphere at a temperature of 770 ° C., a press load of 310 kg / cm 2 , and a holding time of 2 hours. Thereafter, this sintered body was finished into a sputtering target shape. As shown in Table 1, the target composition was Si amount: 39.65 at%, Ni: balance, and a relative density of 96.5% was obtained as a high-density target. Also, an area of 500 [mu] m × 500 [mu] m the sputtering surface of the target with an electron microscope, five positions in FIG. 1 (one location +4 place center) result of observation for, in 0.25 mm 2 field in more than 100μm in length Motsuhibi The average number was as small as 1.0. Next, sputtering was performed under the same conditions as in Example 1 using the finished target. Thereafter, the number of particles of 0.2 μm or more in the film was measured with a particle counter, and as a result, the number was as small as 24.
（比較例１）
Ｓｉ原料とＮｉ原料とを所定の組成となるように秤量し、混合した後、これを真空雰囲気中で溶解して合成反応を行った。次に、アトマイズ法を用いてニッケルシリサイド粉末（アトマイズ粉）を作製した。次に、このアトマイズ粉を真空雰囲気中、温度６５０℃、プレス荷重２８０ｋｇ／ｃｍ２、保持時間２時間でホットプレス焼結した。その後、この焼結体をスパッタリングターゲット形状に仕上げた。表１に示す通り、ターゲット組成は、Ｓｉ量：３１．２４ａｔ％、Ｎｉ：残部であり、相対密度は８６．２％と密度の低下が見られた。次に、上記仕上げ加工したターゲットを使用して、実施例１と同様の条件でスパッタリングを行った。その後、膜中の０．２μｍ以上のパーティクル数をパーティクルカウンタで測定した結果、４５個と増加していた。
(Comparative Example 1)
The Si raw material and the Ni raw material were weighed so as to have a predetermined composition, mixed, and then dissolved in a vacuum atmosphere to carry out a synthesis reaction. Next, nickel silicide powder (atomized powder) was produced using an atomizing method. Next, this atomized powder was hot press sintered in a vacuum atmosphere at a temperature of 650 ° C., a press load of 280 kg / cm 2 , and a holding time of 2 hours. Thereafter, this sintered body was finished into a sputtering target shape. As shown in Table 1, the target composition was Si amount: 31.24 at%, Ni: the balance, and the relative density was 86.2%, showing a decrease in density. Next, sputtering was performed under the same conditions as in Example 1 using the finished target. Thereafter, the number of particles of 0.2 μm or more in the film was measured with a particle counter, and as a result, increased to 45.
（比較例２）
Ｓｉ原料とＮｉ原料とを所定の組成となるように秤量し、混合した後、これを真空雰囲気中で溶解して合成反応を行った。次に、アトマイズ法を用いてニッケルシリサイド粉末（アトマイズ粉）を作製した。次に、このアトマイズ粉を真空雰囲気中、温度６７０℃、プレス荷重２９０ｋｇ／ｃｍ２、保持時間３時間でホットプレス焼結した。その後、この焼結体をスパッタリングターゲット形状に仕上げた。表１に示す通り、ターゲット組成は、Ｓｉ量：３７．９５ａｔ％、Ｎｉ：残部であり、相対密度は８７．５％と密度の低下が見られた。次に、上記仕上げ加工したターゲットを使用して、実施例１と同様の条件でスパッタリングを行った。その後、膜中の０．２μｍ以上のパーティクル数をパーティクルカウンタで測定した結果、５２個と増加していた。
(Comparative Example 2)
The Si raw material and the Ni raw material were weighed so as to have a predetermined composition, mixed, and then dissolved in a vacuum atmosphere to carry out a synthesis reaction. Next, nickel silicide powder (atomized powder) was produced using an atomizing method. Next, this atomized powder was hot press sintered in a vacuum atmosphere at a temperature of 670 ° C., a press load of 290 kg / cm 2 , and a holding time of 3 hours. Thereafter, this sintered body was finished into a sputtering target shape. As shown in Table 1, the target composition was Si amount: 37.95 at%, Ni: the balance, and the relative density was 87.5%, showing a decrease in density. Next, sputtering was performed under the same conditions as in Example 1 using the finished target. Thereafter, the number of particles of 0.2 μm or more in the film was measured with a particle counter, and as a result, increased to 52 particles.
（比較例３）
Ｓｉ原料とＮｉ原料とを所定の組成となるように秤量し、混合した後、これを真空雰囲気中で溶解して合成反応を行った。次に、アトマイズ法を用いてニッケルシリサイド粉末（アトマイズ粉）を作製した。次に、このアトマイズ粉を真空雰囲気中、温度９５０℃、プレス荷重３１０ｋｇ／ｃｍ２、保持時間１時間でホットプレス焼結した。その後、この焼結体をスパッタリングターゲット形状に仕上げた。表１に示す通り、ターゲット組成は、Ｓｉ量：４５．２３ａｔ％、Ｎｉ：残部であり、このターゲットには割れが発生していた。なお、割れが発生していたため、スパッタリングは行わなかった。
(Comparative Example 3)
The Si raw material and the Ni raw material were weighed so as to have a predetermined composition, mixed, and then dissolved in a vacuum atmosphere to carry out a synthesis reaction. Next, nickel silicide powder (atomized powder) was produced using an atomizing method. Next, this atomized powder was hot press sintered in a vacuum atmosphere at a temperature of 950 ° C., a press load of 310 kg / cm 2 , and a holding time of 1 hour. Thereafter, this sintered body was finished into a sputtering target shape. As shown in Table 1, the target composition was Si amount: 45.23 at%, Ni: the balance, and cracking occurred in this target. In addition, since the crack had generate | occur | produced, sputtering was not performed.
（比較例４）
Ｓｉ原料とＮｉ原料とを所定の組成となるように秤量し、混合した後、これを真空雰囲気中で溶解して合成反応を行った。次に、アトマイズ法を用いてニッケルシリサイド粉末（アトマイズ粉）を作製した。次に、このアトマイズ粉を真空雰囲気中、温度９２０℃、プレス荷重２７０ｋｇ／ｃｍ２、保持時間２時間でホットプレス焼結した。その後、この焼結体をスパッタリングターゲット形状に仕上げた。表１に示す通り、ターゲット組成は、Ｓｉ量：４８．５４ａｔ％、Ｎｉ：残部であり、ターゲットのスパッタ面を電子顕微鏡で５００μｍ×５００μｍの面積を、図１の５箇所（中心１箇所＋４箇所）について観察した結果、０．２５ｍｍ２視野中において、１００μｍ以上の長さをもつひびの平均個数は２１．０個と多かった。次に、上記仕上げ加工したターゲットを使用して、実施例１と同様の条件でスパッタリングを行った。その後、膜中の０．２μｍ以上のパーティクル数をパーティクルカウンタで測定した結果、３５個と増加していた。
(Comparative Example 4)
The Si raw material and the Ni raw material were weighed so as to have a predetermined composition, mixed, and then dissolved in a vacuum atmosphere to carry out a synthesis reaction. Next, nickel silicide powder (atomized powder) was produced using an atomizing method. Next, this atomized powder was hot press sintered in a vacuum atmosphere at a temperature of 920 ° C., a press load of 270 kg / cm 2 , and a holding time of 2 hours. Thereafter, this sintered body was finished into a sputtering target shape. As shown in Table 1, the target composition is Si amount: 48.54 at%, Ni: remainder, and the sputtering surface of the target is measured with an electron microscope in an area of 500 μm × 500 μm, and the five locations in FIG. As a result, the average number of cracks having a length of 100 μm or more in 2 fields of 0.25 mm was as large as 21.0. Next, sputtering was performed under the same conditions as in Example 1 using the finished target. Thereafter, the number of particles of 0.2 μm or more in the film was measured with a particle counter, and as a result, increased to 35 particles.
以上に示すように、ホットプレス焼結時に合成反応を行わないので、焼結時の反応熱の発生を防ぎ、またプレス温度の調節により焼結後の冷却時にニッケルシリサイドの相変態による歪みを防止することができ、冷却時のターゲットのひびや割れを防止することができるという優れた効果を有する。また、本発明のスパッタリングターゲットは、スパッタリングの際、パーティクル発生が少なく、ユニフォーミティの良好な膜を形成することができるという優れた効果を有する。したがって、本発明のスパッタリングターゲットは、半導体デバイスの電極や配線等におけるニッケルシリサイド膜の形成に有用である。 As shown above, since no synthesis reaction occurs during hot press sintering, generation of reaction heat during sintering is prevented, and distortion due to phase transformation of nickel silicide is prevented during cooling after sintering by adjusting the press temperature. And has an excellent effect of preventing cracking and cracking of the target during cooling. In addition, the sputtering target of the present invention has an excellent effect that a film with little particle generation and good uniformity can be formed during sputtering. Therefore, the sputtering target of the present invention is useful for forming a nickel silicide film in an electrode or wiring of a semiconductor device.
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| US9812329B2 (en) | 2015-12-10 | 2017-11-07 | Samsung Electronics Co., Ltd. | Method of fabricating a semiconductor device |
| JP2019206750A (en) * | 2018-04-06 | 2019-12-05 | アプライド マテリアルズ インコーポレイテッドＡｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃｏｒｐｏｒａｔｅｄ | Method for forming metal silicon compound layer, and metal silicon compound layer formed therefrom |
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| US10916433B2 (en) | 2018-04-06 | 2021-02-09 | Applied Materials, Inc. | Methods of forming metal silicide layers and metal silicide layers formed therefrom |
| JP2019206750A (en) * | 2018-04-06 | 2019-12-05 | アプライド マテリアルズ インコーポレイテッドＡｐｐｌｉｅｄ Ｍａｔｅｒｉａｌｓ，Ｉｎｃｏｒｐｏｒａｔｅｄ | Method for forming metal silicon compound layer, and metal silicon compound layer formed therefrom |
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