WO2016208552A1 - Platinum alloy target - Google Patents

Platinum alloy target Download PDF

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Publication number
WO2016208552A1
WO2016208552A1 PCT/JP2016/068326 JP2016068326W WO2016208552A1 WO 2016208552 A1 WO2016208552 A1 WO 2016208552A1 JP 2016068326 W JP2016068326 W JP 2016068326W WO 2016208552 A1 WO2016208552 A1 WO 2016208552A1
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Prior art keywords
alloy
silicide
pthf
powder
sputtering target
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PCT/JP2016/068326
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French (fr)
Japanese (ja)
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政広　泰
恭伸 渡邉
豊和 江口
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田中貴金属工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
    • H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation

Definitions

  • the present invention relates to a sputtering target made of a PtHf alloy. Specifically, the present invention relates to a sputtering target made of a PtHf alloy, which is a novel alloy for forming a silicide film applied to a source / drain electrode of a MOSFET, and a manufacturing method thereof.
  • a layer made of a compound of a metal and a semiconductor is formed on a semiconductor substrate, and the metal is generally joined thereto.
  • a metal film is deposited on a source / drain region on a Si substrate, and heat treatment is performed to form a diffusion layer made of the metal Si compound (silicide).
  • silicide titanium silicide (C54 TiSi 2 ) and cobalt silicide (CoSi 2 ) have been generally known.
  • these silicides are disilicides in which two Si atoms are bonded to one metal atom, and are silicides that consume a relatively large amount of Si.
  • semiconductor devices such as MOSFETs
  • it has been studied to make the junction depth in the source / drain region extremely shallow. In order to meet this demand, it is considered to be effective to use silicide with a small amount of Si consumption during silicidation.
  • Nickel silicide is a monosilicide that consumes a small amount of Si during its formation and has the advantage of low specific resistance, and is therefore most expected as a suitable silicide.
  • the metal thin film for forming silicide such as NiSi is usually manufactured by sputtering.
  • Various sputtering targets are also disclosed regarding the formation of NiSi.
  • NiSi which is currently most useful as a silicide, is not without any problems. That is, NiSi has inferior heat resistance, and there is a problem that it is easily transferred to NiSi 2 which is a more stable phase at high temperatures.
  • the phase transition to NiSi 2 has problems that the Si consumption increases and that the resistance of the silicide region is increased and the interface roughness is deteriorated. Therefore, it is necessary to severely manage the heat treatment conditions during silicidation, which affects the production efficiency.
  • the present invention has been made based on the above background, and it is an object of the present invention to clarify the structure of silicide capable of exhibiting characteristics corresponding to NiSi and to provide a sputtering target for forming such silicide.
  • the present inventors examined the development of a silicide based on platinum silicide (PtSi) as a silicide that has excellent heat resistance without phase transition even at high temperatures and can replace conventional NiSi.
  • PtSi is monosilicide similar to NiSi and consumes less Si.
  • PtNi has the advantage that it has excellent heat resistance due to the high heat resistance of Pt, and the phase structure does not change even at high temperatures.
  • the silicide preferably has a work function close to that of Si (n-Si or p-Si) constituting the substrate and a small barrier height. Therefore, it is preferable to have a work function near midgap with respect to Si.
  • the work function of Si is 4.05 eV for n-Si and 5.12 eV for p-Si.
  • the silicide (PtSi) is considered to have a high barrier height against n-Si.
  • hafnium hafnium
  • Si silicon having high heat resistance and having a midgap work function with respect to Si (n, p).
  • Hf hafnium
  • a sputtering target made of a PtHf alloy was developed as a precursor material for forming a silicide made of this Hf-added PtSi.
  • the present invention is a platinum alloy sputtering target made of a PtHf alloy
  • the PtHf alloy is a platinum alloy sputtering target having an Hf content of 10% by mass to 90% by mass.
  • the present invention is a sputtering target composed of a PtHf alloy, and the Hf content in the composition range is 10 mass% or more and 90 mass% or less.
  • Hf has the effect
  • the work function of Hf is 3.9 eV, the work function is lowered by using Hf added to PtSi and can be adjusted to a suitable range.
  • the Hf content of the PtHf alloy constituting the target is 10% by mass or more and 90% by mass or less.
  • the Hf content can be freely set in consideration of the silicide formation process performed after the thin film is formed. For example, in the case where an n-Si region and a p-Si region are formed on a substrate, respectively, in a process in which silicide can be separately formed on the substrate, the Hf content is adjusted to be suitable for each.
  • Targets can be prepared and used individually.
  • silicide is simultaneously formed in both the n-Si region and the p-Si region, one target whose Hf content is adjusted so as to have a work function (preferably around 4.7 eV) serving as a midgap thereof. Can be used.
  • the PtHf alloy sputtering target according to the present invention preferably has a zirconium content of 2.0% by mass or less.
  • Zr is an element that easily forms an oxide, and may cause an oxide to form in the formed thin film. Therefore, Zr is an element to be regulated.
  • Zr is an element that belongs to the same group as Hf (group 4 element), and may be an element that is difficult to remove. Therefore, Zr is an element that should be regulated at the target stage before the thin film is formed.
  • the PtHf alloy sputtering target according to the present invention is preferably such that the total concentration of gas components is 1.0 mass% or less. This is for suppressing gas generation during sputtering and preventing contamination of the thin film.
  • the gas component specifically indicates various elements of oxygen, nitrogen, and carbon. And it is preferable that especially oxygen content shall be 1.0 mass% or less.
  • An example of the production of a sputtering target made of the PtHf alloy of the present invention is a powder metallurgy method.
  • a powder metallurgy method Depending on the composition of the PtHf alloy, solidification cracking or cracking due to the formation of intermetallic compounds may occur during melt casting. If a large-diameter target is to be manufactured, the powder sintering method is preferably applied.
  • a target can be efficiently produced using Pt fine powder, Hf fine powder, or PtHf alloy fine powder without fear of the occurrence of cracks.
  • the fine powder used as a raw material in the powder metallurgy method the fine powder of the PtHf alloy having the composition and purity described above can be applied. Moreover, you may use the metal fine powder which mixed Pt fine powder and Hf fine powder so that it might become the said composition.
  • the average particle size of the powder is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less.
  • the particle size of the fine powder is preferably miniaturized.
  • the particle size difference is smaller in the mixed fine powder. This is because if the particle size difference is large, uniform sintering becomes difficult.
  • Pt fine powder and Hf fine powder As a method for producing Pt fine powder and Hf fine powder, general powder production methods such as chemical methods such as atomizing method, melt spinning method, rotating electrode method, and precipitation method can be applied. It is also possible to obtain a fine powder by mechanically pulverizing an ingot of Pt and Hf with a ball mill or the like.
  • Various atomization methods using gas, water, centrifugal force, and plasma can be applied to the production of fine powder by the atomization method.
  • gas atomization, centrifugal atomization, or the like that does not use water as a medium is preferable.
  • gas atomization the thing by inert gas, such as argon and nitrogen, is preferable.
  • PtHf alloy powder can also be manufactured by alloying (mechanical alloying) with a high energy stirring apparatus such as an attritor using Pt fine powder and Hf fine powder.
  • the PtHf alloy fine powder having a predetermined composition or a mixed powder of Pt fine powder and Hf fine powder becomes a sintered body through a heating process for sintering.
  • the heating temperature for the sintering is preferably 1200 ° C. or higher and 1600 ° C. or lower.
  • it is preferable to perform sintering on pressurization conditions and it is preferable to perform pressurization of 50 MPa or more and 250 MPa or less.
  • a hot pressing method, a hot isostatic pressing method (HIP method), a discharge plasma sintering method (SPS method) or the like is preferable.
  • a sintered body obtained by such powder sintering has a density close to that of a bulk body and becomes a sputtering target made of a PtHf alloy having an appropriate composition (Hf content).
  • the manufacturing method of the sputtering target according to the present invention is not limited to the above powder sintering method, and a melt casting method can also be applied.
  • a melt casting method As a condition for applying the melt casting method, an ingot (bar-shaped or granular) alloyed in advance is used as an alloy raw material, and is melted while forming a melted part as wide as possible adjacent to an arc melting apparatus water-cooled copper mold. Furthermore, it is preferable to apply an alloy ingot as a raw material as fine as possible. According to such a measure, a target having a suitable configuration can be manufactured even with a PtHf alloy that easily cracks at a high melting point.
  • the melt casting method is a process capable of producing a complete bulk body having a density of 100%, which cannot be achieved by powder metallurgy, and a high-quality target can be produced by its suitable operation.
  • the present invention is a sputtering target made of a PtHf alloy in which Hf is alloyed with Pt, and is for forming a PtHf alloy thin film.
  • a silicide having a suitable work function is formed when the alloy thin film is silicided.
  • the Hf-added PtSi silicide (Pt x Hf y Si) formed according to the present invention retains the heat resistance of PtSi, and suppresses an increase in resistance and roughness deterioration during the silicidation heat treatment.
  • a sputtering target was manufactured by a powder metallurgy method using a fine powder of a PtHf alloy as a raw material. Then, PtHf alloy thin film formation and silicidation were performed, and the characteristics of the generated silicide were evaluated.
  • the PtHf alloy powder was made by melting and alloying high-purity Pt and Hf ingots by arc melting to produce a button-shaped ingot, which was mechanically pulverized into a powder.
  • a PtHf alloy having an Hf content of 26.8% by mass was manufactured and pulverized.
  • Two types of alloys, a PtHf alloy powder having a particle size of 50 to 100 ⁇ m (average 70 ⁇ m) and a PtHf alloy powder having a particle size of 50 ⁇ m or less (average 5 ⁇ m), are pulverized by a ball mill equipped with zirconia balls as a pulverization medium. A powder was produced.
  • the produced PtHf alloy was sintered to produce a sputtering target.
  • the PtHf alloy powder was sintered with a HIP apparatus under the conditions of 1000 kgf / cm 2 , 1500 ° C., and 1 hour.
  • the manufactured target had a diameter of 76.2 mm and a thickness of 2.0 mm.
  • the PtHf alloy sputtering target manufactured in this embodiment has few impurities. However, the content of Zr was higher than that of other metal elements. This is considered to be because zirconia was used as a grinding medium in the grinding during the production of the alloy powder. Moreover, the target manufactured in this embodiment has few gas components. During casting of the PtHf alloy, each metal is melted, and it is considered that the gas component was removed at this time.
  • the target manufactured from the alloy powder having a particle size of 50 ⁇ m or less had a density ratio of almost 100% with respect to the bulk material of the alloy.
  • targets manufactured from 50-100 ⁇ m (average 70 ⁇ m) alloy powder had a density ratio of about 86%. Therefore, it was confirmed that a dense target can be obtained by using as fine a fine powder as possible.
  • Second Embodiment In this embodiment, a sputtering target was manufactured by a melt casting method.
  • a plurality of button-shaped PtHf alloy ingots were manufactured by melting and alloying high purity Pt and Hf ingots by arc melting.
  • a PtHf alloy ingot having an Hf content of 37.4% by mass was manufactured. And this was made to adjoin on the water-cooled copper mold of an arc melting apparatus, and it welded by arc melting, and manufactured the disk-shaped ingot.
  • the manufactured disk-shaped PtHf alloy was processed by surface grinding and wire electric discharge machining.
  • the manufactured target had a diameter of 76.2 mm and a thickness of 7.0 mm.
  • FIG. 1 shows a device manufacturing process in this embodiment.
  • FIG. 1A after cleaning the Si substrate (n-Si (100)) (FIG. 1A), wet oxidation is performed to form a SiO 2 layer, and etching is performed to perform patterning (FIG. 1B). ). And a PtHf alloy thin film is formed in the inside (FIG.1 (c)).
  • the substrate surface was cleaned by preliminary sputtering (output 100 W, 5 minutes). Thereafter, a PtHf alloy thin film was sputtered using the target of the first embodiment. The conditions at this time were room temperature and an output of 40 W, and an alloy thin film was formed to 20 nm.
  • Ar is used as the gas ion in sputtering (the pressure in the apparatus is 0.7 Pa).
  • silicidation was performed by heat treatment.
  • the silicidation conditions were set at three processing temperatures of 450 ° C., 500 ° C., and 600 ° C.
  • the treatment atmosphere was nitrogen gas, and the treatment time was 5 minutes.
  • Comparative Example As a comparative example for this embodiment, a Pt thin film was formed instead of PtHf, and this was silicided to manufacture a device.
  • the silicidation procedure and conditions are basically the same as in the first embodiment, and a platinum target (purity of about 100%) was used as the target.
  • the electrical characteristics of the semiconductor device manufactured as described above were evaluated.
  • the evaluation test was performed by measuring current density-voltage characteristics (JV characteristics) with a semiconductor parameter analyzer.
  • FIG. 2 shows the JV characteristics of the device (PtHf silicide alloy film) manufactured in this embodiment. From this result, the device manufactured in this embodiment showed a linear increase in current density with respect to both forward and reverse voltage application.
  • the substrate is n-Si and the behavior at a negative potential is particularly important, but it can be said that the present embodiment exhibits good characteristics.
  • the JV characteristics (FIG. 3) in the comparative example did not show an increase in current density when a negative potential was applied.
  • the silicide alloy film (PtHf silicide) according to the present embodiment has a low Schottky barrier height because the work function is appropriately adjusted.
  • the device behavior was suitable at any temperature.
  • the current density was particularly high when treated at 450 ° C.
  • a PtSi-based silicide excellent in heat resistance can be manufactured through the PtHf alloy thin film.
  • This silicide has a work function suitable for Si (n-Si, p-Si) by alloying with Hf.
  • the present invention is suitable for silicide formation in the source / drain regions of Si-based semiconductor elements such as MOSFETs.

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Abstract

The present invention is a platinum alloy sputtering target which is constituted of a Pt-Hf alloy, the Pt-Hf alloy having an Hf content of 10-90 mass%. In the present invention, electrical properties were improved by adding Hf from the standpoint of work function while directing attention to Pt as a metal which forms a high-heat-resistant silicide. The present invention makes it possible to efficiently produce a thin Pt-Hf film. This thin Pt-Hf film can be made to exhibit properties equivalent to those of NiSi by silicidation.

Description

白金合金ターゲットPlatinum alloy target
　本発明は、ＰｔＨｆ合金からなるスパッタリングターゲットに関する。詳しくは、ＭＯＳＦＥＴのソース／ドレイン電極等に適用されるシリサイド膜を形成するための新規な合金である、ＰｔＨｆ合金からなる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 sputtering target made of a PtHf alloy. Specifically, the present invention relates to a sputtering target made of a PtHf alloy, which is a novel alloy for forming a silicide film applied to a source / drain electrode of a MOSFET, and a manufacturing method thereof.
　半導体集積回路において金属／半導体接合を形成するため、半導体基板に金属と半導体との化合物からなる層を形成し、ここに金属を接合することが一般に行われている。例えば、ＭＯＳＦＥＴ等のＳｉ系半導体素子においては、Ｓｉ基板上のソース／ドレイン領域に金属膜を蒸着し、熱処理をすることで前記金属のＳｉ化合物（シリサイド）からなる拡散層を形成する。 In order to form a metal / semiconductor junction in a semiconductor integrated circuit, a layer made of a compound of a metal and a semiconductor is formed on a semiconductor substrate, and the metal is generally joined thereto. For example, in a Si-based semiconductor element such as a MOSFET, a metal film is deposited on a source / drain region on a Si substrate, and heat treatment is performed to form a diffusion layer made of the metal Si compound (silicide).
　このシリサイドとしては、かつてはチタンシリサイド（Ｃ５４　ＴｉＳｉ２）やコバルトシリサイド（ＣｏＳｉ２）が一般に知られていた。しかし、これらのシリサイドは、１の金属原子に対して２つのＳｉ原子が結合するダイシリサイドであり、Ｓｉ消費量が比較的多いシリサイドである。近年、ＭＯＳＦＥＴ等の半導体素子においては、更なる微細化、薄型化に対応するため、ソース／ドレイン領域における接合深さの極浅化が検討されている。この要求に対応するため、シリサイド化の際のＳｉ消費量の少ないシリサイドの適用が有力とされている。 As this silicide, titanium silicide (C54 TiSi 2 ) and cobalt silicide (CoSi 2 ) have been generally known. However, these silicides are disilicides in which two Si atoms are bonded to one metal atom, and are silicides that consume a relatively large amount of Si. In recent years, in semiconductor devices such as MOSFETs, in order to cope with further miniaturization and thinning, it has been studied to make the junction depth in the source / drain region extremely shallow. In order to meet this demand, it is considered to be effective to use silicide with a small amount of Si consumption during silicidation.
　ニッケルシリサイド（ＮｉＳｉ）は、その形成時のＳｉ消費量が少ないモノシリサイドであり、比抵抗が低いという利点があることから、好適なシリサイドとして最も期待されている。ここで、ＮｉＳｉ等のシリサイド形成のための金属薄膜は、スパッタリングによって製造されるのが通常である。ＮｉＳｉの形成に関しても、各種のスパッタリングターゲットが開示されている。 Nickel silicide (NiSi) is a monosilicide that consumes a small amount of Si during its formation and has the advantage of low specific resistance, and is therefore most expected as a suitable silicide. Here, the metal thin film for forming silicide such as NiSi is usually manufactured by sputtering. Various sputtering targets are also disclosed regarding the formation of NiSi.
特許第４４０９５７２号明細書Japanese Patent No. 4409572
　上記の通り、シリサイドとして現在最も有用性が認められているＮｉＳｉであるが、問題が全く無いわけではない。即ち、ＮｉＳｉは耐熱性に劣る面があり、高温域でより安定な相であるＮｉＳｉ２へ転移し易いという問題がある。ＮｉＳｉ２への相転移はＳｉ消費量が増大することに加え、シリサイド領域の高抵抗化や界面ラフネスを悪化させるという問題がある。そのためシリサイド化の際の熱処理条件をシビアに管理する必要があり、製造効率に影響を及ぼす。 As described above, NiSi, which is currently most useful as a silicide, is not without any problems. That is, NiSi has inferior heat resistance, and there is a problem that it is easily transferred to NiSi 2 which is a more stable phase at high temperatures. The phase transition to NiSi 2 has problems that the Si consumption increases and that the resistance of the silicide region is increased and the interface roughness is deteriorated. Therefore, it is necessary to severely manage the heat treatment conditions during silicidation, which affects the production efficiency.
　本発明は、上記背景の元になされたものであり、ＮｉＳｉに相当する特性を発揮し得るシリサイドの構成を明らかにし、かかるシリサイドを形成するための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。 The present invention has been made based on the above background, and it is an object of the present invention to clarify the structure of silicide capable of exhibiting characteristics corresponding to NiSi and to provide a sputtering target for forming such silicide.
　本発明者等は、高温でも相転移のない耐熱性に優れたシリサイドであって、従来のＮｉＳｉに替わり得るものとして、白金シリサイド（ＰｔＳｉ）をベースとしたシリサイドの開発を検討した。ＰｔＳｉは、ＮｉＳｉと同様のモノシリサイドでありＳｉ消費量が少ない。そして、ＰｔＮｉは、Ｐｔの高耐熱性に起因して耐熱性に優れ高温下でも相構造に変化が生じないという利点がある。 The present inventors examined the development of a silicide based on platinum silicide (PtSi) as a silicide that has excellent heat resistance without phase transition even at high temperatures and can replace conventional NiSi. PtSi is monosilicide similar to NiSi and consumes less Si. PtNi has the advantage that it has excellent heat resistance due to the high heat resistance of Pt, and the phase structure does not change even at high temperatures.
　もっとも、ＰｔＳｉもそのままシリサイド電極として使用することは好適ではない。シリサイドは、寄生抵抗を抑制するために、基板を構成するＳｉ（ｎ－Ｓｉ又はｐ－Ｓｉ）に対して仕事関数が近く障壁高さが小さいものが好ましい。従って、Ｓｉに対してｍｉｄｇａｐ付近の仕事関数を有することが好ましい。ここで、Ｓｉの仕事関数は、ｎ－Ｓｉで４．０５ｅＶでありｐ－Ｓｉで５．１２ｅＶである。一方、Ｐｔの仕事関数は５．６５ｅＶであるのでそのシリサイド（ＰｔＳｉ）はｎ－Ｓｉに対する障壁高さが高いと考えられる。 However, it is not preferable to use PtSi as a silicide electrode as it is. In order to suppress parasitic resistance, the silicide preferably has a work function close to that of Si (n-Si or p-Si) constituting the substrate and a small barrier height. Therefore, it is preferable to have a work function near midgap with respect to Si. Here, the work function of Si is 4.05 eV for n-Si and 5.12 eV for p-Si. On the other hand, since the work function of Pt is 5.65 eV, the silicide (PtSi) is considered to have a high barrier height against n-Si.
　そこで本発明者等は鋭意検討を行い、耐熱性の高いＰｔＳｉをベースとし、Ｓｉ（ｎ，ｐ）に対してｍｉｄｇａｐの仕事関数を有し得るシリサイドを製造する手法として、ハフニウム（Ｈｆ）を添加することに想到した。そして、このＨｆ添加ＰｔＳｉからなるシリサイドを形成するための前駆材料として、ＰｔＨｆ合金からなるスパッタリングターゲットを開発した。 Therefore, the present inventors have intensively studied and added hafnium (Hf) as a technique for producing silicide based on PtSi having high heat resistance and having a midgap work function with respect to Si (n, p). I came up with the idea. Then, a sputtering target made of a PtHf alloy was developed as a precursor material for forming a silicide made of this Hf-added PtSi.
　即ち、本発明は、ＰｔＨｆ合金からなる白金合金スパッタリングターゲットであって、前記ＰｔＨｆ合金は、Ｈｆ含有量が１０質量％以上９０質量％以下である白金合金スパッタリングターゲットである。 That is, the present invention is a platinum alloy sputtering target made of a PtHf alloy, and the PtHf alloy is a platinum alloy sputtering target having an Hf content of 10% by mass to 90% by mass.
　上記の通り、本発明は、ＰｔＨｆ合金で構成されたスパッタリングターゲットであり、その組成範囲としてＨｆの含有量を１０質量％以上９０質量％以下とする。 As described above, the present invention is a sputtering target composed of a PtHf alloy, and the Hf content in the composition range is 10 mass% or more and 90 mass% or less.
　Ｐｔは、形成されるシリサイドの構成元素として重要なものであり、上記の通り耐熱性に優れたシリサイドを形成する。そして、Ｈｆは、形成されるシリサイドの仕事関数をＳｉに対してｍｉｄｇａｐ付近に調整する作用を有する。ここで、Ｈｆの仕事関数は、３．９ｅＶであることから、ＰｔＳｉにＨｆを添加するシリサイドにすることでその仕事関数が低下し、好適な範囲に調整することができる。 Pt is important as a constituent element of the formed silicide, and forms silicide having excellent heat resistance as described above. And Hf has the effect | action which adjusts the work function of the silicide formed in the midgap vicinity with respect to Si. Here, since the work function of Hf is 3.9 eV, the work function is lowered by using Hf added to PtSi and can be adjusted to a suitable range.
　ターゲットを構成するＰｔＨｆ合金のＨｆの含有量は、１０質量％以上９０質量％以下とする。このＨｆの含有量は、薄膜形成後に行うシリサイド形成のプロセスを考慮して自由に設定できる。例えば、基板上にｎ－Ｓｉの領域とｐ－Ｓｉの領域がそれぞれ形成されている場合において、それらに別々にシリサイドを形成できるプロセスでは、それぞれにとって好適となるようにＨｆ含有量が調整されたターゲットを個別に用意して使用することができる。また、ｎ－Ｓｉ領域とｐ－Ｓｉ領域の双方に同時にシリサイドを形成する場合、それらのｍｉｄｇａｐとなる仕事関数（４．７ｅＶ前後が好ましい）となるようにＨｆ含有量が調整された一つのターゲットを使用することができる。 The Hf content of the PtHf alloy constituting the target is 10% by mass or more and 90% by mass or less. The Hf content can be freely set in consideration of the silicide formation process performed after the thin film is formed. For example, in the case where an n-Si region and a p-Si region are formed on a substrate, respectively, in a process in which silicide can be separately formed on the substrate, the Hf content is adjusted to be suitable for each. Targets can be prepared and used individually. In addition, when silicide is simultaneously formed in both the n-Si region and the p-Si region, one target whose Hf content is adjusted so as to have a work function (preferably around 4.7 eV) serving as a midgap thereof. Can be used.
　ここで、本発明に係るＰｔＨｆ合金スパッタリングターゲットは、ジルコニウム含有量が２．０質量％以下であるものが好ましい。Ｚｒは酸化物を形成しやすい元素であり、形成された薄膜中に酸化物を生じさせるおそれがある。そのため、Ｚｒは規制されるべき元素である。また、Ｚｒは、Ｈｆと同族元素（第４族元素）であり、除去し難い元素であることもあるので、薄膜形成前のターゲットの段階で規制されるべき元素である。 Here, the PtHf alloy sputtering target according to the present invention preferably has a zirconium content of 2.0% by mass or less. Zr is an element that easily forms an oxide, and may cause an oxide to form in the formed thin film. Therefore, Zr is an element to be regulated. Zr is an element that belongs to the same group as Hf (group 4 element), and may be an element that is difficult to remove. Therefore, Zr is an element that should be regulated at the target stage before the thin film is formed.
　また、本発明に係るＰｔＨｆ合金スパッタリングターゲットは、ガス成分の合計濃度が１．０質量％以下であるものが好ましい。スパッタリングの際のガス発生を抑制し、薄膜の汚染を防止するためである。ここで、ガス成分とは、具体的には、酸素、窒素、炭素の各種元素を示す。そして、特に、酸素含有量が１．０質量％以下とすることが好ましい。 In addition, the PtHf alloy sputtering target according to the present invention is preferably such that the total concentration of gas components is 1.0 mass% or less. This is for suppressing gas generation during sputtering and preventing contamination of the thin film. Here, the gas component specifically indicates various elements of oxygen, nitrogen, and carbon. And it is preferable that especially oxygen content shall be 1.0 mass% or less.
　次に、本発明に係るスパッタリングターゲットの製造方法について説明する。本発明のＰｔＨｆ合金からなるスパッタリングターゲット製造の一態様としては、粉末冶金法が挙げられる。ＰｔＨｆ合金はその組成にもよるが、溶解鋳造の際、凝固割れや金属間化合物生成による割れが生じる場合がある。大径のターゲットを製造しようとするならば、粉末焼結法の適用が好ましい。粉末冶金法は、Ｐｔ微粉末、Ｈｆ微粉末、若しくは、ＰｔＨｆ合金の微粉末を利用して、前記した割れ発生の懸念なく効率的にターゲットを製造することができる。 Next, a method for manufacturing a sputtering target according to the present invention will be described. An example of the production of a sputtering target made of the PtHf alloy of the present invention is a powder metallurgy method. Depending on the composition of the PtHf alloy, solidification cracking or cracking due to the formation of intermetallic compounds may occur during melt casting. If a large-diameter target is to be manufactured, the powder sintering method is preferably applied. In the powder metallurgy method, a target can be efficiently produced using Pt fine powder, Hf fine powder, or PtHf alloy fine powder without fear of the occurrence of cracks.
　粉末冶金法において原料となる金属微粉末としては、上記した組成・純度のＰｔＨｆ合金の微粉末が適用できる。また、Ｐｔ微粉末、Ｈｆ微粉末を上記組成となるように混合した金属微粉末を使用しても良い。 As the metal fine powder used as a raw material in the powder metallurgy method, the fine powder of the PtHf alloy having the composition and purity described above can be applied. Moreover, you may use the metal fine powder which mixed Pt fine powder and Hf fine powder so that it might become the said composition.
　ＰｔＨｆ合金微粉末、混合金属微粉末のいずれを使用する場合においても、粉末の平均粒径は１００μｍ以下のものが好ましく、５０μｍ以下のものがより好ましい。粗大な粉末を使用した場合、緻密なターゲットを製造し難い。微粉末の粒径は、微細化されてあることが好ましい。更に、混合微粉末において粒径差が小さい方が好ましい。粒径差が大きいと均一な焼結ができにくくなるためである。 When using either PtHf alloy fine powder or mixed metal fine powder, the average particle size of the powder is preferably 100 μm or less, more preferably 50 μm or less. When coarse powder is used, it is difficult to produce a dense target. The particle size of the fine powder is preferably miniaturized. Furthermore, it is preferable that the particle size difference is smaller in the mixed fine powder. This is because if the particle size difference is large, uniform sintering becomes difficult.
　Ｐｔ微粉末、Ｈｆ微粉末の製造方法としては、アトマイズ法、メルトスピニング法、回転電極法、沈殿法等の化学的方法等の一般的な粉末製造法が適用できる。また、Ｐｔ、Ｈｆのインゴットをボールミル等で機械的に粉砕して微粉末を得ることも可能である。アトマイズ法による微粉末製造は、ガス、水、遠心力、プラズマを適用する各種アトマイズ法が適用できる。好ましくは、媒体に水を使用しないガスアトマイズ、遠心アトマイズ等が好ましい。ガスアトマイズについては、アルゴン、窒素等の不活性ガスによるものが好ましい。 As a method for producing Pt fine powder and Hf fine powder, general powder production methods such as chemical methods such as atomizing method, melt spinning method, rotating electrode method, and precipitation method can be applied. It is also possible to obtain a fine powder by mechanically pulverizing an ingot of Pt and Hf with a ball mill or the like. Various atomization methods using gas, water, centrifugal force, and plasma can be applied to the production of fine powder by the atomization method. Preferably, gas atomization, centrifugal atomization, or the like that does not use water as a medium is preferable. About gas atomization, the thing by inert gas, such as argon and nitrogen, is preferable.
　ＰｔＨｆ合金微粉末の製造方法も上記したＰｔ微粉末、Ｈｆ微粉末の製造方法と同様の粉体製造プロセスが適用できる。また、Ｐｔ微粉末とＨｆ微粉末を使用してアトライタ等の高エネルギー攪拌装置による合金化（メカニカルアロイング）でＰｔＨｆ合金粉末を製造することもできる。 A powder production process similar to the above-described production method of Pt fine powder and Hf fine powder can be applied to the production method of PtHf alloy fine powder. Moreover, PtHf alloy powder can also be manufactured by alloying (mechanical alloying) with a high energy stirring apparatus such as an attritor using Pt fine powder and Hf fine powder.
　所定組成のＰｔＨｆ合金微粉末又はＰｔ微粉末とＨｆ微粉末との混合粉末は、焼結のための加熱工程を経て焼結体となる。この焼結のための加熱温度は、１２００℃以上１６００℃以下とするのが好ましい。また、焼結は加圧条件で行うことが好ましく、５０ＭＰａ以上２５０ＭＰa以下の加圧を行うことが好ましい。具体的な焼結プロセスとしては、ホットプレス法、熱間等方圧プレス法（ＨＩＰ法）、放電プラズマ焼結法（ＳＰＳ法）等によるものが好ましい。 The PtHf alloy fine powder having a predetermined composition or a mixed powder of Pt fine powder and Hf fine powder becomes a sintered body through a heating process for sintering. The heating temperature for the sintering is preferably 1200 ° C. or higher and 1600 ° C. or lower. Moreover, it is preferable to perform sintering on pressurization conditions, and it is preferable to perform pressurization of 50 MPa or more and 250 MPa or less. As a specific sintering process, a hot pressing method, a hot isostatic pressing method (HIP method), a discharge plasma sintering method (SPS method) or the like is preferable.
　このような粉末焼結で得られる焼結体は、バルク体に近い密度を有し、適切な組成（Ｈｆ含有量）のＰｔＨｆ合金からなるスパッタリングターゲットとなる。 A sintered body obtained by such powder sintering has a density close to that of a bulk body and becomes a sputtering target made of a PtHf alloy having an appropriate composition (Hf content).
　また、本発明に係るスパッタリングターゲットの製造方法は、上記の粉末焼結法に限定されるものではなく、溶解鋳造法も適用できる。溶解鋳造法適用の条件としては、予め、合金したインゴット(棒状、若しくは粒状)を合金原材料として、アーク溶解装置水冷銅鋳型上に隣接し、出来る限り広範囲で溶融部を形成しながら溶解する。更には、この原材料となる合金インゴットは、できる限り細かいものを適用するのが好ましい。このような対応によれば、高融点で割れが生じやすいＰｔＨｆ合金であっても、好適な構成のターゲットを製造することができる。溶解鋳造法は粉末冶金法では達成できない密度１００％の完全なバルク体を製造することができるプロセスであり、その好適な運用により高品質なターゲットを製造することができる。 Further, the manufacturing method of the sputtering target according to the present invention is not limited to the above powder sintering method, and a melt casting method can also be applied. As a condition for applying the melt casting method, an ingot (bar-shaped or granular) alloyed in advance is used as an alloy raw material, and is melted while forming a melted part as wide as possible adjacent to an arc melting apparatus water-cooled copper mold. Furthermore, it is preferable to apply an alloy ingot as a raw material as fine as possible. According to such a measure, a target having a suitable configuration can be manufactured even with a PtHf alloy that easily cracks at a high melting point. The melt casting method is a process capable of producing a complete bulk body having a density of 100%, which cannot be achieved by powder metallurgy, and a high-quality target can be produced by its suitable operation.
　本発明はＰｔにＨｆを合金化したＰｔＨｆ合金からなるスパッタリングターゲットであり、ＰｔＨｆ合金薄膜を形成するためのものである。Ｈｆの合金化により、合金薄膜をシリサイド化したとき好適な仕事関数のシリサイドが形成される。本発明により形成されるＨｆ添加ＰｔＳｉシリサイド（ＰｔｘＨｆｙＳｉ）は、ＰｔＳｉが有する耐熱性を保持しており、シリサイド化の熱処理の際に抵抗上昇やラフネス悪化も抑制されている。 The present invention is a sputtering target made of a PtHf alloy in which Hf is alloyed with Pt, and is for forming a PtHf alloy thin film. By alloying Hf, a silicide having a suitable work function is formed when the alloy thin film is silicided. The Hf-added PtSi silicide (Pt x Hf y Si) formed according to the present invention retains the heat resistance of PtSi, and suppresses an increase in resistance and roughness deterioration during the silicidation heat treatment.
本実施形態に係るＰｔＨｆターゲットを用いたデバイス製造工程を説明する図。The figure explaining the device manufacturing process using the PtHf target concerning this embodiment. 本実施形態で製造したデバイスのＪ－Ｖ特性を示す図。The figure which shows the JV characteristic of the device manufactured by this embodiment. 比較例で製造したデバイスのＪ－Ｖ特性を示す図。The figure which shows the JV characteristic of the device manufactured by the comparative example.
　以下、本発明の実施形態について説明する。 Hereinafter, embodiments of the present invention will be described.
第１実施形態：本実施形態では、ＰｔＨｆ合金の微粉末を原料とし、粉末冶金法によりスパッタリングターゲットを製造した。そして、ＰｔＨｆ合金薄膜形成及びシリサイド化を行い、生成するシリサイドの特性を評価した。 First Embodiment : In this embodiment, a sputtering target was manufactured by a powder metallurgy method using a fine powder of a PtHf alloy as a raw material. Then, PtHf alloy thin film formation and silicidation were performed, and the characteristics of the generated silicide were evaluated.
　ＰｔＨｆ合金粉末は、高純度のＰｔ及びＨｆの地金をアーク溶解で溶融・合金化しボタン状のインゴットを製造し、これを機械粉砕して粉末とした。本実施形態では、Ｈｆ含有量２６．８質量％のＰｔＨｆ合金を製造しこれを微粉末化した。粉砕媒体としてジルコニアボールを備えるボールミルで粉砕を行い、篩で分級し、粒径５０～１００μｍ（平均７０μｍ）のＰｔＨｆ合金粉末と、粒径５０μｍ以下（平均５μｍ）のＰｔＨｆ合金粉末の２種類の合金粉末を製造した。 The PtHf alloy powder was made by melting and alloying high-purity Pt and Hf ingots by arc melting to produce a button-shaped ingot, which was mechanically pulverized into a powder. In this embodiment, a PtHf alloy having an Hf content of 26.8% by mass was manufactured and pulverized. Two types of alloys, a PtHf alloy powder having a particle size of 50 to 100 μm (average 70 μm) and a PtHf alloy powder having a particle size of 50 μm or less (average 5 μm), are pulverized by a ball mill equipped with zirconia balls as a pulverization medium. A powder was produced.
　次に、製造したＰｔＨｆ合金を焼結してスパッタリングターゲットを製造した。ＰｔＨｆ合金粉末をＨＩＰ装置にて、１０００ｋｇｆ／ｃｍ２、１５００℃、１時間の条件で焼結した。製造されたターゲットの寸法は、直径７６．２ｍｍ、厚さ２．０ｍｍであった。 Next, the produced PtHf alloy was sintered to produce a sputtering target. The PtHf alloy powder was sintered with a HIP apparatus under the conditions of 1000 kgf / cm 2 , 1500 ° C., and 1 hour. The manufactured target had a diameter of 76.2 mm and a thickness of 2.0 mm.
　製造したターゲットについて、不純物元素の分析及び密度測定を行った。元素分析はＩＣＰ分析と、ガス成分をＯＮ分析、ＣＳ分析を行った。表１に、分析結果を示す。 For the manufactured target, impurity element analysis and density measurement were performed. For elemental analysis, ICP analysis, gas component ON analysis, and CS analysis were performed. Table 1 shows the analysis results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　本実施形態で製造したＰｔＨｆ合金スパッタリングターゲットは、不純物が少ないことが分かる。もっとも、Ｚｒの含有量が他の金属元素よりも多かった。これは合金粉末製造の際の粉砕で粉砕媒体としてジルコニアを使用したためと考えられる。また、本実施形態で製造したターゲットは、ガス成分は少ない。ＰｔＨｆ合金の鋳造の際、各金属を溶融することになるが、この際にガス成分が除去されたものと考えられる。 It can be seen that the PtHf alloy sputtering target manufactured in this embodiment has few impurities. However, the content of Zr was higher than that of other metal elements. This is considered to be because zirconia was used as a grinding medium in the grinding during the production of the alloy powder. Moreover, the target manufactured in this embodiment has few gas components. During casting of the PtHf alloy, each metal is melted, and it is considered that the gas component was removed at this time.
　また、密度に関して、５０μｍ以下（平均５μｍ）の粒径の合金粉末から製造したターゲットは、合金のバルク材に対してほぼ１００％の密度比であった。これに対して、５０～１００μｍ（平均７０μｍ）の合金粉末から製造したターゲットは、約８６％の密度比であった。よって、できるだけ微細な微粉末を使用することで緻密なターゲットを得ることができることが確認された。 Moreover, regarding the density, the target manufactured from the alloy powder having a particle size of 50 μm or less (average of 5 μm) had a density ratio of almost 100% with respect to the bulk material of the alloy. In contrast, targets manufactured from 50-100 μm (average 70 μm) alloy powder had a density ratio of about 86%. Therefore, it was confirmed that a dense target can be obtained by using as fine a fine powder as possible.
第２実施形態：本実施形態は、溶解鋳造法でスパッタリングターゲットを製造した。 Second Embodiment : In this embodiment, a sputtering target was manufactured by a melt casting method.
高純度のＰｔ及びＨｆの地金をアーク溶解で溶融・合金化しボタン状のＰｔＨｆ合金インゴットを複数製造した。本実施形態では、Ｈｆ含有量３７．４質量％のＰｔＨｆ合金インゴットを製造した。そして、これをアーク溶解装置の水冷銅鋳型上に隣接させ、アーク溶解で溶接し、円盤状のインゴットを製造した。次に、製造した円盤状のＰｔＨｆ合金を平面研削とワイヤー放電加工により加工した。製造されたターゲットの寸法は、直径７６．２ｍｍ、厚さ７．０ｍｍであった。 A plurality of button-shaped PtHf alloy ingots were manufactured by melting and alloying high purity Pt and Hf ingots by arc melting. In this embodiment, a PtHf alloy ingot having an Hf content of 37.4% by mass was manufactured. And this was made to adjoin on the water-cooled copper mold of an arc melting apparatus, and it welded by arc melting, and manufactured the disk-shaped ingot. Next, the manufactured disk-shaped PtHf alloy was processed by surface grinding and wire electric discharge machining. The manufactured target had a diameter of 76.2 mm and a thickness of 7.0 mm.
　製造したターゲットについて、不純物元素の分析及び密度測定を行った。元素分析はＩＣＰ分析と、ガス成分をＯＮ分析、ＣＳ分析を行った。表２に、分析結果を示す。この第２実施形態で製造したＰｔＨｆ合金スパッタリングターゲットも不純物が少ないことが確認できる。 For the manufactured target, impurity element analysis and density measurement were performed. For elemental analysis, ICP analysis, gas component ON analysis, and CS analysis were performed. Table 2 shows the analysis results. It can be confirmed that the PtHf alloy sputtering target manufactured in the second embodiment also has few impurities.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
第３実施形態：ここでは、第１実施形態で製造したＰｔＨｆ合金スパッタリングターゲット（平均粒径５μｍ以下の合金粉末から製造したもの）を用いて、ＰｔＨｆ合金薄膜の製造及びシリサイド形成を行った。 Third Embodiment : Here, a PtHf alloy thin film and silicide formation were performed using the PtHf alloy sputtering target manufactured in the first embodiment (produced from an alloy powder having an average particle size of 5 μm or less).
　本実施形態では、Ｓｉ基板にＰｔＨｆシリサイド薄膜を形成してショットキーダイオードを製造し、このデバイスの電気特性を評価した。図１に本実施形態におけるデバイス製造工程を示す。本実施形態では、Ｓｉ基板（ｎ－Ｓｉ（１００））を洗浄した後（図１（ａ））、ウェット酸化してＳｉＯ２層を形成しエッチング処理してパターニングを行う（図１（ｂ））。そして、その内部にＰｔＨｆ合金薄膜を形成する（図１（ｃ））。 In this embodiment, a PtHf silicide thin film was formed on a Si substrate to manufacture a Schottky diode, and the electrical characteristics of this device were evaluated. FIG. 1 shows a device manufacturing process in this embodiment. In the present embodiment, after cleaning the Si substrate (n-Si (100)) (FIG. 1A), wet oxidation is performed to form a SiO 2 layer, and etching is performed to perform patterning (FIG. 1B). ). And a PtHf alloy thin film is formed in the inside (FIG.1 (c)).
　ＰｔＨｆ合金薄膜の形成に際して、まず、基板表面を予備スパッタ（出力１００Ｗ、５分間）してクリーニングした。その後、第１実施形態のターゲットを用いてＰｔＨｆ合金薄膜をスパッタリングした。このときの条件は、室温、出力４０Ｗとし、合金薄膜を２０ｎｍ成膜した。尚、本実施形態ではスパッタリングにおけるガスイオンとして、Ａｒを用いた（装置内の圧力０．７Ｐａとした）。 When forming the PtHf alloy thin film, first, the substrate surface was cleaned by preliminary sputtering (output 100 W, 5 minutes). Thereafter, a PtHf alloy thin film was sputtered using the target of the first embodiment. The conditions at this time were room temperature and an output of 40 W, and an alloy thin film was formed to 20 nm. In this embodiment, Ar is used as the gas ion in sputtering (the pressure in the apparatus is 0.7 Pa).
　ＰｔＨｆ合金薄膜の形成後は、熱処理によりシリサイド化を行った。シリサイド化の条件は、処理温度として４５０℃、５００℃、６００℃の３つの条件を設定した。処理雰囲気は窒素ガス中とし、処理時間を５分間とした。 After the PtHf alloy thin film was formed, silicidation was performed by heat treatment. The silicidation conditions were set at three processing temperatures of 450 ° C., 500 ° C., and 600 ° C. The treatment atmosphere was nitrogen gas, and the treatment time was 5 minutes.
　ＰｔＨｆのシリサイド化後、エッチングにより未反応金属を除去し、Ａｌ電極を形成してデバイスとした（図１（ｄ））。エッチングはバッファードフッ酸（ＢＨＦ）と希釈王水（ＨＣｌ：ＨＮＯ３：Ｈ２Ｏ＝３：２：１、温度４０℃）により行った。 After silicidation of PtHf, unreacted metal was removed by etching, and an Al electrode was formed to obtain a device (FIG. 1 (d)). Etching was performed with buffered hydrofluoric acid (BHF) and diluted aqua regia (HCl: HNO 3 : H 2 O = 3: 2: 1, temperature 40 ° C.).
比較例：この実施形態に対する比較例として、ＰｔＨｆに替えてＰｔ薄膜を形成し、これをシリサイド化してデバイスを製造した。シリサイド化の手順、条件は、基本的に第１実施形態と同様であり、ターゲットとして白金ターゲット（純度約１００％）を使用した。 Comparative Example : As a comparative example for this embodiment, a Pt thin film was formed instead of PtHf, and this was silicided to manufacture a device. The silicidation procedure and conditions are basically the same as in the first embodiment, and a platinum target (purity of about 100%) was used as the target.
　以上のようにして製造した半導体デバイスについて電気特性を評価した。評価試験では、半導体パラメータ解析装置により電流密度－電圧特性（Ｊ－Ｖ特性）を測定することで行った。 The electrical characteristics of the semiconductor device manufactured as described above were evaluated. The evaluation test was performed by measuring current density-voltage characteristics (JV characteristics) with a semiconductor parameter analyzer.
　図２は、本実施形態で製造したデバイス（ＰｔＨｆシリサイド合金膜）のＪ－Ｖ特性を示す。この結果から、本実施形態で製造したデバイスは、順方向・逆方向のいずれの電圧印加に対してもリニアな電流密度の上昇が見られた。本実施形態では、基板がｎ－Ｓｉでありマイナス電位における挙動が特に重要であるが、本実施形態は良好な特性を示すといえる。一方、比較例におけるＪ－Ｖ特性（図３）は、マイナス電位印加における電流密度の増加が見られなかった。 FIG. 2 shows the JV characteristics of the device (PtHf silicide alloy film) manufactured in this embodiment. From this result, the device manufactured in this embodiment showed a linear increase in current density with respect to both forward and reverse voltage application. In the present embodiment, the substrate is n-Si and the behavior at a negative potential is particularly important, but it can be said that the present embodiment exhibits good characteristics. On the other hand, the JV characteristics (FIG. 3) in the comparative example did not show an increase in current density when a negative potential was applied.
　そして、測定されたＪ－Ｖ特性から、このシリサイド合金膜（シリサイド化処理温度４５０℃）のショットキー障壁高さを算出すると、本実施形態で０．４５ｅＶであるのに対し、比較例のＰｔシリサイドは、０．８５ｅＶであった。本実施形態に係るシリサイド合金膜（ＰｔＨｆシリサイド）は、仕事関数が適度に調整されていることにより、ショットキー障壁高さが低くなっている。 Then, when the Schottky barrier height of this silicide alloy film (silicidation temperature 450 ° C.) is calculated from the measured JV characteristics, it is 0.45 eV in the present embodiment, whereas Pt of the comparative example Silicide was 0.85 eV. The silicide alloy film (PtHf silicide) according to the present embodiment has a low Schottky barrier height because the work function is appropriately adjusted.
　尚、シリサイド化の温度に関しては、いずれの温度でもデバイスの挙動としては好適なものであった。但し、電流密度は４５０℃で処理したものが特に高かった。 Incidentally, regarding the silicidation temperature, the device behavior was suitable at any temperature. However, the current density was particularly high when treated at 450 ° C.
　本発明に係るＰｔＨｆ合金からなるスパッタリングターゲットによれば、ＰｔＨｆ合金薄膜を経て、耐熱性に優れたＰｔＳｉ系のシリサイドを製造できる。このシリサイドはＨｆの合金化によりＳｉ（ｎ－Ｓｉ、ｐ－Ｓｉ）に対して好適な仕事関数を有する。本発明は、ＭＯＳＦＥＴ等のＳｉ系半導体素子のソース／ドレイン領域におけるシリサイド形成に好適である。 According to the sputtering target made of the PtHf alloy according to the present invention, a PtSi-based silicide excellent in heat resistance can be manufactured through the PtHf alloy thin film. This silicide has a work function suitable for Si (n-Si, p-Si) by alloying with Hf. The present invention is suitable for silicide formation in the source / drain regions of Si-based semiconductor elements such as MOSFETs.

Claims (4)

  1. 　ＰｔＨｆ合金からなる白金合金スパッタリングターゲットであって、前記ＰｔＨｆ合金は、Ｈｆ含有量が１０質量％以上９０質量％以下である白金合金スパッタリングターゲット。 A platinum alloy sputtering target made of a PtHf alloy, wherein the PtHf alloy has a Hf content of 10 mass% to 90 mass%.
  2. 　ジルコニウム含有量が２．０質量％以下である請求項１記載の白金合金スパッタリングターゲット。 The platinum alloy sputtering target according to claim 1, wherein the zirconium content is 2.0 mass% or less.
  3. 　ガス成分の合計濃度が１．０質量％以下である請求項１又は請求項２記載の白金合金スパッタリングターゲット。 The platinum alloy sputtering target according to claim 1 or 2, wherein the total concentration of the gas components is 1.0 mass% or less.
  4. 　酸素含有量が１．０質量％以下である請求項１～請求項３のいずれかに記載の白金合金スパッタリングターゲット。 The platinum alloy sputtering target according to any one of claims 1 to 3, wherein the oxygen content is 1.0 mass% or less.
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