JP2013067857A - Cu-Mn ALLOY SPUTTERING TARGET MATERIAL, AND THIN FILM TRANSISTOR WIRING AND THIN FILM TRANSISTOR USING THE SAME - Google Patents

Cu-Mn ALLOY SPUTTERING TARGET MATERIAL, AND THIN FILM TRANSISTOR WIRING AND THIN FILM TRANSISTOR USING THE SAME Download PDF

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JP2013067857A
JP2013067857A JP2012197037A JP2012197037A JP2013067857A JP 2013067857 A JP2013067857 A JP 2013067857A JP 2012197037 A JP2012197037 A JP 2012197037A JP 2012197037 A JP2012197037 A JP 2012197037A JP 2013067857 A JP2013067857 A JP 2013067857A
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film
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Noriyuki Tatsumi
憲之 辰巳
Koshiro Ueda
孝史郎 上田
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Hitachi Cable Ltd
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    • H—ELECTRICITY
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    • 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
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    • H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
    • H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
    • H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System
    • H01L21/2855—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic System by physical means, e.g. sputtering, evaporation
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    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
    • H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
    • H—ELECTRICITY
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    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier
    • H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body
    • H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
    • H01L27/124—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having at least one potential-jump barrier or surface barrier; including integrated passive circuit elements with at least one potential-jump barrier or surface barrier the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or layout of the wiring layers specially adapted to the circuit arrangement, e.g. scanning lines in LCD pixel circuits
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/40—Electrodes ; Multistep manufacturing processes therefor
    • H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
    • H01L29/45—Ohmic electrodes
    • H—ELECTRICITY
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    • H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof  ; Multistep manufacturing processes therefor
    • H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
    • H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
    • H01L29/76—Unipolar devices, e.g. field effect transistors
    • H01L29/772—Field effect transistors
    • H01L29/78—Field effect transistors with field effect produced by an insulated gate
    • H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
    • H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate

Abstract

PROBLEM TO BE SOLVED: To form a Cu-Mn alloy film having high barrier property.SOLUTION: The Cu-Mn alloy sputtering target material 10 is used for forming wiring of a semiconductor element, and comprised of a Cu-Mn alloy containing Mn whose concentration is 8-30 atomic% and inevitable impurities. The average crystal grain size of the Cu-Mn alloy is 10-50 μm.

Description

本発明は、Ｃｕ−Ｍｎ合金スパッタリングターゲット材、それを用いて形成されたＣｕ−Ｍｎ合金膜を有する薄膜トランジスタ配線及び薄膜トランジスタに関する。   The present invention relates to a Cu—Mn alloy sputtering target material, a thin film transistor wiring having a Cu—Mn alloy film formed using the Cu—Mn alloy sputtering target material, and a thin film transistor.

近年、液晶パネルの大画面化や高精細化が進んでいる。パネルメーカーでは、更なる臨場感を求めてスーパーハイビジョン（高画角化）や裸眼３Ｄパネルの実現を目指している。これにしたがい、液晶パネルに用いられる薄膜トランジスタ（ＴＦＴ：Thin Film Transistor）についても、現行のアモルファスシリコン（α−Ｓｉ）半導体を用いたものから、高移動度による高速動作が可能で、閾値電圧のバラツキが少なく、駆動電流均一性に優れた酸化物半導体を用いたＴＦＴの開発が、急ピッチで進められている。酸化物半導体としては、酸化インジウムガリウム亜鉛（ＩｎＧａＺｎＯ：以下、ＩＧＺＯとも記載する）や酸化亜鉛（ＺｎＯ）等の材料の研究が進められており、これらの材質に適した配線電極材料の検討が必要となっている。   In recent years, liquid crystal panels have been increased in screen size and definition. Panel manufacturers are seeking to realize super high vision (high angle of view) and autostereoscopic 3D panels in search of even greater realism. Accordingly, thin film transistors (TFTs) used in liquid crystal panels are also capable of high-speed operation with high mobility from those using current amorphous silicon (α-Si) semiconductors, and variation in threshold voltage. The development of TFTs using oxide semiconductors that are small in number and have excellent drive current uniformity is being promoted at a rapid pace. As oxide semiconductors, materials such as indium gallium zinc oxide (InGaZnO: hereinafter also referred to as IGZO) and zinc oxide (ZnO) are being researched, and it is necessary to examine wiring electrode materials suitable for these materials. It has become.

配線電極材料について、α−Ｓｉ系ＴＦＴの例でその動向をみると、動作速度を高速化するため、従来のアルミニウム（Ａｌ）配線よりも低抵抗の銅（Ｃｕ）配線への切り替えが進んでいる。一方で、Ａｌ配線やＣｕ配線等のメタル配線とα−Ｓｉ半導体との界面には、拡散バリア膜となるモリブデン（Ｍｏ）膜やチタン（Ｔｉ）膜が使用されてきたが、ＭｏやＴｉには材料コストが高いという課題があった。そこで、液晶パネルの製造コスト低減のため、代替となる合金や製造プロセスが検討されている。   Looking at trends in wiring electrode materials in the example of α-Si TFTs, switching to copper (Cu) wiring with lower resistance than conventional aluminum (Al) wiring has progressed in order to increase the operating speed. Yes. On the other hand, a molybdenum (Mo) film or titanium (Ti) film serving as a diffusion barrier film has been used at the interface between metal wiring such as Al wiring or Cu wiring and an α-Si semiconductor. Had the problem of high material costs. Therefore, alternative alloys and manufacturing processes are being studied to reduce the manufacturing cost of liquid crystal panels.

例えば特許文献１，２及び非特許文献１には、銅−マンガン（Ｃｕ−Ｍｎ）合金をα−Ｓｉ系ＴＦＴの全ての電極（ソース−ドレイン及びゲート）に適用することが開示され、その有効性が実証されている。   For example, Patent Documents 1 and 2 and Non-Patent Document 1 disclose that a copper-manganese (Cu-Mn) alloy is applied to all electrodes (source-drain and gate) of an α-Si-based TFT. Sex has been demonstrated.

また、非特許文献２には、テトラエトキシシラン（ＴＥＯＳ）ガスを用いたプラズマＣＶＤ（Chemical Vapor Deposition）により成膜した酸化シリコン（ＳｉＯ2）膜上に、スパッタリングにより成膜したＣｕ−Ｍｎ合金膜について開示されている。係る構成においては、熱処理によりＣｕ−Ｍｎ合金膜中のＭｎがＳｉＯ2膜の界面に移動し、ＳｉＯ2膜から拡散した酸素（Ｏ）と反応してＭｎの酸化膜からなる拡散バリア膜が形成される。非特許文献２では、拡散バリア膜の形成にあたり、熱処理温度、熱処理時間及びＭｎの濃度と、拡散バリア膜の厚さとの関係について検討しており、これによれば、Ｍｎの濃度が高いほど拡散バリア膜の厚さが増加し、３０原子％以上の添加量で拡散バリア膜の成長が飽和する。係る結果については、合金の融点が低下していく間は添加元素の拡散係数が増加するという一般的な傾向に一致するとの考察がなされている。Ｃｕ−Ｍｎ合金の融点は、Ｍｎ濃度が３０原子％付近で最小を示す。したがって、Ｍｎの濃度が３０原子％まではＣｕ−Ｍｎ合金膜中のＭｎの拡散係数は増加し、拡散バリア膜の成長が促進される。一方、Ｍｎの濃度が３０原子％を超えると、添加元素の供給量が充分であってもＭｎの拡散係数は減少傾向となり、拡散バリア膜の成長が飽和する。 Non-Patent Document 2 discloses a Cu—Mn alloy film formed by sputtering on a silicon oxide (SiO 2 ) film formed by plasma CVD (Chemical Vapor Deposition) using tetraethoxysilane (TEOS) gas. Is disclosed. In such a configuration, Mn in the Cu—Mn alloy film moves to the interface of the SiO 2 film by heat treatment and reacts with oxygen (O) diffused from the SiO 2 film to form a diffusion barrier film made of an oxide film of Mn. Is done. Non-Patent Document 2 examines the relationship between the heat treatment temperature, the heat treatment time, the concentration of Mn, and the thickness of the diffusion barrier film in the formation of the diffusion barrier film. The thickness of the barrier film increases, and the growth of the diffusion barrier film is saturated at an addition amount of 30 atomic% or more. It has been considered that such a result agrees with the general tendency that the diffusion coefficient of the additive element increases while the melting point of the alloy decreases. The melting point of the Cu—Mn alloy shows the minimum when the Mn concentration is around 30 atomic%. Therefore, when the Mn concentration is up to 30 atomic%, the diffusion coefficient of Mn in the Cu—Mn alloy film increases and the growth of the diffusion barrier film is promoted. On the other hand, when the concentration of Mn exceeds 30 atomic%, the diffusion coefficient of Mn tends to decrease even if the supply amount of the additive element is sufficient, and the growth of the diffusion barrier film is saturated.

また、非特許文献３には、Ｃｕ−４原子％Ｍｎ合金膜をＩＧＺＯ系ＴＦＴに採用し、良好な結果が得られた旨が開示されている。すなわち、ＩＧＺＯ膜上に、スパッタリングによりＣｕ−４原子％Ｍｎ合金膜を成膜し、一般的なＴＦＴの製造プロセス温度に近い２５０℃で熱処理を行う。これにより、合金膜の界面に酸化マンガン（ＭｎＯｘ）膜を形成し、合金膜中のＣｕがＩＧＺＯ膜中へ拡散することを抑制する。非特許文献３によれば、係る積層膜においては良好なオーミック特性が得られ、接触抵抗が１０-4Ωｃｍと充分低い値が得られたとある。また、電極の加工性についても、ウェットエッチングにより良好な結果が得られている。具体的には、硝酸系のエッチャントを使用しており、Ｃｕ−４原子％Ｍｎ合金膜とＩＧＺＯ膜とのエッチングレートの選択比は１０：１であるとされている。 Non-Patent Document 3 discloses that a Cu-4 atomic% Mn alloy film was adopted for an IGZO-based TFT, and good results were obtained. That is, a Cu-4 atomic% Mn alloy film is formed on the IGZO film by sputtering, and heat treatment is performed at 250 ° C., which is close to a general TFT manufacturing process temperature. Thereby, a manganese oxide (MnOx) film is formed at the interface of the alloy film, and Cu in the alloy film is prevented from diffusing into the IGZO film. According to Non-Patent Document 3, it is said that good ohmic characteristics were obtained in such a laminated film, and a sufficiently low value of contact resistance of 10 −4 Ωcm was obtained. In addition, good results have been obtained by wet etching in terms of electrode processability. Specifically, a nitric acid-based etchant is used, and the etching rate selection ratio between the Cu-4 atomic% Mn alloy film and the IGZO film is 10: 1.

特開２０１０−０５０１１２号公報JP 2010-050112 A 特開２００８−２６１８９５号公報JP 2008-261895 A

大西 順雄、外１名、"大型ＴＦＴ液晶パネルのゲート電極とソース・ドレイン電極を共にＣｕ配線にするＣｕ−Ｍｎ合金プロセス技術を東北大が開発≪訂正あり≫"、［online］、２００８年９月９日、日経ＢＰ社「Tech-On!」、［２０１１年５月１１日検索］、インターネット＜URL：http://techon.nikkeibp.co.jp/article/NEWS/20080909/157714＞Juno Onishi, 1 other person, "Tohoku University develops Cu-Mn alloy process technology that makes both the gate electrode and the source / drain electrode of a large TFT liquid crystal panel Cu wiring" << corrected >>, [online], 2008 September 9, Nikkei BP “Tech-On!” [Search May 11, 2011], Internet <URL: http://techon.nikkeibp.co.jp/article/NEWS/20080909/157714> M.Haneda, J.Iijima, and J.koike,"Growth behavior of self-formed barrier at Cu-Mn/SiO2 interface at 250-450℃,"APPLIED PHYSICS LETTERS 90.252107(2007)M. Haneda, J. Iijima, and J. koike, "Growth behavior of self-formed barrier at Cu-Mn / SiO2 interface at 250-450 ℃," APPLIED PHYSICS LETTERS 90.252107 (2007) Pilsang Yun, Junichi Koike,"Microstructure Analysis and Electrical Properties of Cu-Mn Electrode for Back-Channel Etching a-IGZO TFT,"17th International Display Workshops(IDW'10),pp.1873-1876Pilsang Yun, Junichi Koike, "Microstructure Analysis and Electrical Properties of Cu-Mn Electrode for Back-Channel Etching a-IGZO TFT," 17th International Display Workshops (IDW'10), pp. 1873-1876

本発明者等は、上記の非特許文献３の結果を検証すべく、上記に倣ってＩＧＺＯ系ＴＦＴを製作した。電極構造は、低抵抗の純Ｃｕ膜をＣｕ−Ｍｎ合金のバリア膜で挟んだＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ構造のスパッタリング積層膜とした。また、ソース−ドレイン電極上にはＳｉＯ2膜からなる保護膜を形成した。その結果、充分な拡散バリア性が得られた非特許文献３と異なり、ＩＧＺＯ膜中へのＣｕの拡散が原因と思われる素子特性のバラツキがみられた。また、ＳｉＯ2保護膜を形成する際の純Ｃｕ膜の酸化が原因と思われる配線の抵抗値の上昇がみられ、耐酸化性も不充分であった。係る結果から、より高い拡散バリア性及び酸化バリア性（耐酸化性）を有するＣｕ−Ｍｎ合金膜を得ることが急務の課題である。 In order to verify the result of Non-Patent Document 3, the present inventors manufactured an IGZO-based TFT according to the above. The electrode structure was a Cu-Mn / Cu / Cu-Mn structure sputtering laminated film in which a low-resistance pure Cu film was sandwiched between Cu-Mn alloy barrier films. A protective film made of a SiO 2 film was formed on the source-drain electrodes. As a result, unlike Non-Patent Document 3 in which sufficient diffusion barrier properties were obtained, variation in element characteristics that was considered to be caused by diffusion of Cu into the IGZO film was observed. In addition, the resistance value of the wiring increased due to oxidation of the pure Cu film when forming the SiO 2 protective film, and the oxidation resistance was insufficient. From such a result, it is an urgent task to obtain a Cu—Mn alloy film having higher diffusion barrier properties and oxidation barrier properties (oxidation resistance).

本発明の目的は、高いバリア性を有するＣｕ−Ｍｎ合金膜を形成することができるＣｕ−Ｍｎ合金スパッタリングターゲット材、それを用いた薄膜トランジスタ配線及び薄膜トランジスタを提供することである。   An object of the present invention is to provide a Cu—Mn alloy sputtering target material capable of forming a Cu—Mn alloy film having high barrier properties, a thin film transistor wiring and a thin film transistor using the same.

本発明の第１の態様によれば、半導体素子の配線の形成に用いられるＣｕ−Ｍｎ合金スパッタリングターゲット材であって、濃度が８原子％以上３０原子％以下のＭｎと、不可避的不純物とを含むＣｕ−Ｍｎ合金からなり、前記Ｃｕ−Ｍｎ合金の平均結晶粒径が１０μｍ以上５０μｍ以下であるＣｕ−Ｍｎ合金スパッタリングターゲット材が提供される。   According to the first aspect of the present invention, there is provided a Cu—Mn alloy sputtering target material used for forming a wiring of a semiconductor element, wherein Mn has a concentration of 8 atomic% or more and 30 atomic% or less, and unavoidable impurities. There is provided a Cu—Mn alloy sputtering target material comprising a Cu—Mn alloy, wherein the Cu—Mn alloy has an average crystal grain size of 10 μm or more and 50 μm or less.

本発明の第２の態様によれば、Ｃｕ−Ｍｎ合金膜と、純Ｃｕ膜と、Ｃｕ−Ｍｎ合金膜と、がこの順に形成された積層構造を基板上に有し、前記Ｃｕ−Ｍｎ合金膜の少なくとも一方は、第１の態様に記載のＣｕ−Ｍｎ合金スパッタリングターゲット材を用いて形成され、濃度が８原子％以上３０原子％以下のＭｎと、不可避的不純物とを含むＣｕ−Ｍｎ合金からなる薄膜トランジスタ配線が提供される。   According to the second aspect of the present invention, the Cu—Mn alloy film, the pure Cu film, and the Cu—Mn alloy film are formed on the substrate in this order. At least one of the films is formed using the Cu—Mn alloy sputtering target material described in the first embodiment, and includes a Cu—Mn alloy having a concentration of 8 atomic% to 30 atomic% and unavoidable impurities. A thin film transistor wiring comprising:

本発明の第３の態様によれば、前記Ｍｎの濃度が８原子％以上３０原子％以下である前記Ｃｕ−Ｍｎ合金膜中の前記Ｍｎの濃度の標準偏差が０．０５原子％未満である第２の態様に記載の薄膜トランジスタ配線が提供される。   According to the third aspect of the present invention, the standard deviation of the Mn concentration in the Cu—Mn alloy film in which the Mn concentration is 8 atomic% or more and 30 atomic% or less is less than 0.05 atomic%. A thin film transistor wiring according to the second aspect is provided.

本発明の第４の態様によれば、第２又は第３の態様に記載の薄膜トランジスタ配線が、ＩｎＧａＺｎＯ膜から構成される酸化物半導体を介して前記基板上に形成されている薄膜トランジスタが提供される。   According to a fourth aspect of the present invention, there is provided a thin film transistor in which the thin film transistor wiring according to the second or third aspect is formed on the substrate via an oxide semiconductor composed of an InGaZnO film. .

本発明によれば、高いバリア性を有するＣｕ−Ｍｎ合金膜を形成することができる。   According to the present invention, a Cu—Mn alloy film having high barrier properties can be formed.

本発明の一実施形態に係るＣｕ−Ｍｎ合金スパッタリングターゲット材が装着されたスパッタリング装置の縦断面図である。It is a longitudinal cross-sectional view of the sputtering device with which the Cu-Mn alloy sputtering target material which concerns on one Embodiment of this invention was mounted | worn. 本発明の一実施形態に係る薄膜トランジスタの概略断面図である。It is a schematic sectional drawing of the thin-film transistor which concerns on one Embodiment of this invention. 本発明の実施例１〜１２及び比較例１〜７に係る評価サンプルの説明図であって、（ａ）はＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜がブロック状に複数個形成された評価サンプルの平面図であり、（ｂ）はＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜の１ブロックを示す斜視図である。It is explanatory drawing of the evaluation sample which concerns on Examples 1-12 of this invention, and Comparative Examples 1-7, Comprising: (a) is evaluation by which multiple Cu-Mn / Cu / Cu-Mn laminated film was formed in block shape It is a top view of a sample, (b) is a perspective view which shows 1 block of a Cu-Mn / Cu / Cu-Mn laminated film. 本発明の実施例１〜１２及び比較例１〜７に係る評価サンプルのシート抵抗を示すグラフである。It is a graph which shows the sheet resistance of the evaluation sample which concerns on Examples 1-12 of this invention, and Comparative Examples 1-7. 本発明の実施例１，４，７，１０及び１２〜１５並びに比較例８〜１７に係る評価サンプルの平面図である。It is a top view of the evaluation sample which concerns on Example 1, 4, 7, 10, 12-15 of this invention, and Comparative Examples 8-17.

上述のように、非特許文献３にしたがって、スパッタリングにより形成されるＣｕ−Ｍｎ合金膜を含む配線をＩＧＺＯ系ＴＦＴに適用したところ、ＩＧＺＯ膜に対して充分な拡散バリア性が得られなかった。つまり、ＴＦＴ基板内の領域によってはＣｕ−Ｍｎ合金膜中のＣｕがＩＧＺＯ膜中に拡散してしまい、素子特性にバラツキが生じてしまった。また、配線上にＳｉＯ2膜からなる保護膜を形成する際、Ｃｕ−Ｍｎ合金膜の下層の純Ｃｕ膜に対して充分な酸化バリア性（耐酸化性）が得られず、純Ｃｕ膜が酸化されて配線の抵抗値が上がってしまった。 As described above, according to Non-Patent Document 3, when a wiring including a Cu—Mn alloy film formed by sputtering was applied to an IGZO-based TFT, a sufficient diffusion barrier property was not obtained for the IGZO film. That is, depending on the region in the TFT substrate, Cu in the Cu—Mn alloy film diffuses into the IGZO film, resulting in variations in element characteristics. Further, when forming a protective film made of a SiO 2 film on the wiring, sufficient oxidation barrier properties (oxidation resistance) cannot be obtained with respect to the pure Cu film below the Cu—Mn alloy film, and the pure Cu film It was oxidized and the resistance value of the wiring rose.

本発明者等は、ＴＦＴ基板内で素子特性にバラツキがあったことから、拡散バリア性の不足はＣｕ−Ｍｎ合金膜中の基板内でのＭｎの濃度ムラによるものと推測した。つまり、ＩＧＺＯ膜上のＣｕ−Ｍｎ合金膜に熱処理を施してＭｎＯｘを形成する際、ＴＦＴ基板内のＭｎの濃度の低い部分ではＭｎＯｘが形成されるまでにＣｕがＩＧＺＯ膜中に拡散してしまうと考えた。また、酸化バリア性が不足していることから、Ｃｕ−Ｍｎ合金膜中のＭｎの濃度の適正化が必要であると考えた。   The inventors of the present invention presumed that the lack of diffusion barrier properties was due to uneven Mn concentration in the substrate in the Cu-Mn alloy film because of variations in device characteristics within the TFT substrate. That is, when heat-treating the Cu—Mn alloy film on the IGZO film to form MnOx, Cu diffuses into the IGZO film before the MnOx is formed in the portion of the TFT substrate where the Mn concentration is low. I thought. Moreover, since the oxidation barrier property was insufficient, it was considered necessary to optimize the concentration of Mn in the Cu—Mn alloy film.

係る考察を基に、本発明者等は、Ｃｕ−Ｍｎ合金膜のＩＧＺＯ膜に対する拡散バリア性及び純Ｃｕ膜に対する酸化バリア性を向上させるべく、Ｃｕ−Ｍｎ合金膜の形成に用いるスパッタリングターゲット材の組成及び結晶構造等の諸特性を検討することから開始し、鋭意研究を重ねた。その結果、Ｃｕ−Ｍｎ合金スパッタリングターゲット材中の結晶粒径と、これを用いて成膜されたＣｕ−Ｍｎ合金膜中のＭｎの濃度ムラとの間には、相関関係があることを見いだした。また、充分な酸化バリア性を得るために必要なＭｎの濃度の適正値についても知見を得た。   Based on such considerations, the present inventors have developed a sputtering target material used for forming a Cu-Mn alloy film in order to improve the diffusion barrier property of the Cu-Mn alloy film with respect to the IGZO film and the oxidation barrier property with respect to the pure Cu film. We began by studying various properties such as composition and crystal structure, and conducted extensive research. As a result, it has been found that there is a correlation between the crystal grain size in the Cu—Mn alloy sputtering target material and the Mn concentration unevenness in the Cu—Mn alloy film formed using this. . Moreover, knowledge was also acquired about the appropriate value of the density | concentration of Mn required in order to obtain sufficient oxidation barrier property.

本発明は、発明者等が見いだした上記知見に基づくものである。   The present invention is based on the above findings found by the inventors.

＜本発明の一実施形態＞
（１）Ｃｕ−Ｍｎ合金スパッタリングターゲット材
以下に、本発明の一実施形態に係る銅−マンガン（Ｃｕ−Ｍｎ）合金スパッタリングターゲット材１０（後述の図１を参照）について説明する。Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０は、例えば所定の外径と厚さとを備える円板型に形成され、各種半導体素子の配線の形成等に用いられるよう構成される。 <One Embodiment of the Present Invention>
(1) Cu-Mn Alloy Sputtering Target Material Hereinafter, a copper-manganese (Cu-Mn) alloy sputtering target material 10 (see FIG. 1 described later) according to an embodiment of the present invention will be described. The Cu—Mn alloy sputtering target material 10 is formed in a disk shape having a predetermined outer diameter and thickness, for example, and is configured to be used for forming wirings of various semiconductor elements.

Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０を構成するＣｕ−Ｍｎ合金は、純度が共に３Ｎ（９９．９％）以上の無酸素銅（ＯＦＣ：Oxygen-Free Copper）と純マンガン（Ｍｎ）とが所定比率で配合された合金である。すなわち、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０は、例えば濃度が８原子％以上３０原子％以下のＭｎと、不可避的不純物とを含むＣｕ−Ｍｎ合金からなる。   The Cu—Mn alloy constituting the Cu—Mn alloy sputtering target material 10 has a predetermined ratio of oxygen-free copper (OFC) having a purity of 3N (99.9%) or more and pure manganese (Mn). It is an alloy blended with. That is, the Cu—Mn alloy sputtering target material 10 is made of, for example, a Cu—Mn alloy containing Mn having a concentration of 8 atomic% to 30 atomic% and unavoidable impurities.

上記所定濃度のＭｎを含むＣｕ−Ｍｎ合金スパッタリングターゲット材１０を用いると、係る濃度と略同等の濃度のＭｎを含むＣｕ−Ｍｎ合金膜が成膜される。Ｃｕ−Ｍｎ合金膜中のＭｎの濃度が上記所定値以上、つまり、例えば８％以上となることで、例えば後述するＴＦＴ配線の積層構造において、Ｃｕ−Ｍｎ合金膜の下層となる純Ｃｕ膜等に対して充分な酸化バリア性を得ることができる。また、Ｃｕ−Ｍｎ合金膜中のＭｎの濃度が上記所定値以下、つまり、例えば３０％以下となることで、例えば上記積層構造において、ＩＧＺＯ膜や純Ｃｕ膜等のＣｕ−Ｍｎ合金膜と接する膜中にＭｎが拡散することを抑制できる。   When the Cu—Mn alloy sputtering target material 10 containing the predetermined concentration of Mn is used, a Cu—Mn alloy film containing Mn at a concentration substantially equal to the concentration is formed. When the concentration of Mn in the Cu-Mn alloy film is equal to or higher than the predetermined value, that is, 8% or higher, for example, a pure Cu film that is a lower layer of the Cu-Mn alloy film in a laminated structure of TFT wiring described later, etc. Sufficient oxidation barrier properties can be obtained. In addition, when the concentration of Mn in the Cu—Mn alloy film is equal to or less than the predetermined value, that is, 30% or less, for example, in the laminated structure, the Cu—Mn alloy film such as an IGZO film or a pure Cu film is in contact. Mn can be prevented from diffusing into the film.

また、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０を構成するＣｕ−Ｍｎ合金は、その平均結晶粒径が例えば１０μｍ以上５０μｍ以下に調整されている。   Further, the Cu—Mn alloy constituting the Cu—Mn alloy sputtering target material 10 has an average crystal grain size adjusted to, for example, 10 μm or more and 50 μm or less.

本発明者等が見いだした上述の結晶粒径とＭｎの濃度ムラとの相関関係によれば、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０中の結晶粒径が微細になるほど、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０を用いて成膜したＣｕ−Ｍｎ合金膜中のＭｎの濃度ムラが低減し、ＴＦＴ基板面内のＭｎの濃度の均一性が向上する。よって、上記のように、平均結晶粒径を例えば５０μｍ以下とすることで、より均一なＣｕ−Ｍｎ合金膜を形成することができ、素子特性のバラツキを低減することができる。   According to the correlation between the crystal grain size and the Mn concentration unevenness found by the present inventors, the smaller the crystal grain size in the Cu-Mn alloy sputtering target material 10 is, the Cu-Mn alloy sputtering target material becomes. 10 is reduced in Mn concentration unevenness in the Cu—Mn alloy film formed using No. 10, and the uniformity of the Mn concentration in the TFT substrate surface is improved. Therefore, as described above, by setting the average crystal grain size to, for example, 50 μm or less, a more uniform Cu—Mn alloy film can be formed, and variations in device characteristics can be reduced.

以上のようにＣｕ−Ｍｎ合金スパッタリングターゲット材１０を構成することで、係るＣｕ−Ｍｎ合金スパッタリングターゲット材１０を用いて、高い拡散バリア性及び酸化バリア性を有するＣｕ−Ｍｎ合金膜を形成することができる。   By forming the Cu—Mn alloy sputtering target material 10 as described above, a Cu—Mn alloy film having high diffusion barrier properties and oxidation barrier properties is formed using the Cu—Mn alloy sputtering target material 10. Can do.

Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０を構成するＣｕ−Ｍｎ合金は、上述のＴＦＴで拡散バリア膜として用いられるＭｏやＴｉ等に比べて材料コストが安い。上記構成により、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０をＴＦＴの製造に好適に適用することができ、例えばバリア膜等をＣｕ−Ｍｎ合金膜から構成することができるので、ＴＦＴや液晶パネルの製造コストの大幅な低減を図ることができる。   The Cu—Mn alloy constituting the Cu—Mn alloy sputtering target material 10 has a lower material cost than Mo or Ti used as a diffusion barrier film in the above-described TFT. With the above configuration, the Cu—Mn alloy sputtering target material 10 can be suitably applied to the production of TFTs. For example, the barrier film or the like can be constituted of a Cu—Mn alloy film. Can be greatly reduced.

（２）Ｃｕ−Ｍｎ合金スパッタリングターゲット材の製造方法
次に、本発明の一実施形態に係るＣｕ−Ｍｎ合金スパッタリングターゲット材１０の製造方法について説明する。 (2) Manufacturing method of Cu-Mn alloy sputtering target material Next, the manufacturing method of the Cu-Mn alloy sputtering target material 10 which concerns on one Embodiment of this invention is demonstrated.

まず、純度が共に３Ｎ（９９．９％）以上の無酸素銅と純Ｍｎとを所定比率で配合し、例えば１１００℃以上１２００℃以下の温度で溶解し鋳造して、例えば濃度が８原子％以上３０原子％以下のＭｎと、不可避的不純物とを含むＣｕ−Ｍｎ合金のインゴットを形成する。   First, oxygen-free copper having a purity of 3N (99.9%) or more and pure Mn are blended at a predetermined ratio, and melted and cast at a temperature of, for example, 1100 ° C. or more and 1200 ° C. or less. A Cu—Mn alloy ingot containing Mn of 30 atomic% or less and unavoidable impurities is formed.

次に、このインゴットを例えば８００℃以上９００℃以下の温度で熱間鍛造した後、例えば５０％以上７０％以下の加工度となるよう冷間圧延を行う。ここで、加工度とは、圧延によるインゴットの厚さの減少率（（圧延後のインゴットの厚さ／圧延前のインゴットの厚さ）×１００（％））である。   Next, this ingot is hot forged at a temperature of, for example, 800 ° C. or more and 900 ° C. or less, and then cold-rolled so as to have a workability of, for example, 50% or more and 70% or less. Here, the workability is a reduction rate of the thickness of the ingot by rolling ((thickness of the ingot after rolling / thickness of the ingot before rolling) × 100 (%)).

続いて、冷間圧延後のインゴットに対し、７００℃以上９００℃以下の温度で熱処理を施し、インゴットを構成するＣｕ−Ｍｎ合金の再結晶化を図る。   Subsequently, the ingot after cold rolling is heat-treated at a temperature of 700 ° C. or higher and 900 ° C. or lower to recrystallize the Cu—Mn alloy constituting the ingot.

ここで、冷間圧延の加工度と、その後の熱処理の温度とを所定の組み合わせとすることで、Ｃｕ−Ｍｎ合金中の結晶粒径を調整することができる。このとき、熱処理の温度が高いと結晶粒径が粗大化する。具体的には、冷間圧延の加工度と熱処理の温度との組み合わせを上記のそれぞれの範囲内から選択し、例えば１０μｍ以上５０μｍ以下の微細結晶粒からなるＣｕ−Ｍｎ合金を得る。   Here, the crystal grain size in the Cu—Mn alloy can be adjusted by setting the cold rolling workability and the temperature of the subsequent heat treatment to a predetermined combination. At this time, if the heat treatment temperature is high, the crystal grain size becomes coarse. Specifically, a combination of the cold rolling workability and the heat treatment temperature is selected from the above ranges, and a Cu—Mn alloy composed of fine crystal grains of, for example, 10 μm or more and 50 μm or less is obtained.

その後、上記所定の結晶構造となったインゴットに鏡面研磨等の機械加工を施して、例えば所定の外径及び厚さを備える円板型に成形する。   Thereafter, the ingot having the predetermined crystal structure is subjected to machining such as mirror polishing, and is formed into a disk shape having a predetermined outer diameter and thickness, for example.

以上により、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０が製造される。   Thus, the Cu—Mn alloy sputtering target material 10 is manufactured.

（３）Ｃｕ−Ｍｎ合金スパッタリングターゲット材を用いた成膜方法
次に、本発明の一実施形態に係るＣｕ−Ｍｎ合金スパッタリングターゲット材１０を用いたスパッタリングにより、Ｃｕ−Ｍｎ合金膜を成膜する方法について、図１を用いて説明する。 (3) Film forming method using Cu—Mn alloy sputtering target material Next, a Cu—Mn alloy film is formed by sputtering using the Cu—Mn alloy sputtering target material 10 according to an embodiment of the present invention. The method will be described with reference to FIG.

図１は、本発明の一実施形態に係るＣｕ−Ｍｎ合金スパッタリングターゲット材１０が装着されたスパッタリング装置２０の縦断面図である。なお、図１に示すスパッタリング装置２０はあくまでも一例であって、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０は、この他、種々のタイプのスパッタリング装置に装着して用いることができる。   FIG. 1 is a longitudinal sectional view of a sputtering apparatus 20 equipped with a Cu—Mn alloy sputtering target material 10 according to an embodiment of the present invention. Note that the sputtering apparatus 20 illustrated in FIG. 1 is merely an example, and the Cu—Mn alloy sputtering target material 10 can be used by being mounted on various types of sputtering apparatuses.

図１に示すように、スパッタリング装置２０は、真空チャンバ２１を備えている。真空チャンバ２１内の上部には基板保持部２２ｓが設けられ、成膜対象となる基板Ｓが、成膜される面を下方に向けて保持される。真空チャンバ２１内の底部にはターゲット保持部２２ｔが設けられ、例えばＣｕ−Ｍｎ合金スパッタリングターゲット材１０が、基板Ｓの被成膜面と対向するよう、スパッタ面を上方に向けて保持される。なお、スパッタリング装置２０内に複数の基板Ｓを保持して、これら基板Ｓを一括処理、或いは連続処理してもよい。   As shown in FIG. 1, the sputtering apparatus 20 includes a vacuum chamber 21. A substrate holding part 22s is provided in the upper part of the vacuum chamber 21, and the substrate S to be deposited is held with the surface to be deposited facing downward. A target holding portion 22t is provided at the bottom of the vacuum chamber 21, and for example, the Cu—Mn alloy sputtering target material 10 is held with the sputtering surface facing upward so as to face the film formation surface of the substrate S. Note that a plurality of substrates S may be held in the sputtering apparatus 20 and these substrates S may be collectively processed or continuously processed.

また、真空チャンバ２１の一方の壁面にはガス供給管２３ｆが接続され、ガス供給管２３ｆと対向する他方の壁面にはガス排気管２３ｖが接続されている。ガス供給管２３ｆには、アルゴン（Ａｒ）ガス等の不活性ガスを真空チャンバ２１内に供給する図示しないガス供給系が接続されている。ガス排気管２３ｖには、Ａｒガス等の真空チャンバ２１内の雰囲気を排気する図示しないガス排気系が接続されている。   A gas supply pipe 23f is connected to one wall surface of the vacuum chamber 21, and a gas exhaust pipe 23v is connected to the other wall surface facing the gas supply pipe 23f. A gas supply system (not shown) for supplying an inert gas such as argon (Ar) gas into the vacuum chamber 21 is connected to the gas supply pipe 23f. A gas exhaust system (not shown) for exhausting the atmosphere in the vacuum chamber 21 of Ar gas or the like is connected to the gas exhaust pipe 23v.

係るスパッタリング装置２０にて基板Ｓへの成膜を行う際は、Ａｒガス等を真空チャンバ２１内に供給し、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０にアース接続し、基板Ｓに正の高電圧が印加されるよう、真空チャンバ２１に対してＤＣ放電電力を投入する。   When film formation on the substrate S is performed by the sputtering apparatus 20, Ar gas or the like is supplied into the vacuum chamber 21 and connected to the ground with the Cu—Mn alloy sputtering target material 10, so that a positive high voltage is applied to the substrate S. DC discharge power is applied to the vacuum chamber 21 so that it is applied.

これにより、主にＣｕ−Ｍｎ合金スパッタリングターゲット材１０と基板Ｓとの間にプラズマが生成され、プラスのアルゴン（Ａｒ+）イオンＧが、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０のスパッタ面に衝突する。Ａｒ+イオンＧの衝突により、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０から叩き出されたＣｕ及びＭｎのスパッタ粒子Ｐが基板Ｓの被成膜面へと堆積されていき、基板Ｓ上には、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０と略同等のＭｎの濃度を有するＣｕ−Ｍｎ合金膜Ｍが形成される。すなわち、Ｃｕ−Ｍｎ合金膜Ｍは、例えば濃度が８原子％以上３０原子％以下のＭｎと、不可避的不純物とを含む。 Thereby, plasma is mainly generated between the Cu—Mn alloy sputtering target material 10 and the substrate S, and positive argon (Ar + ) ions G collide with the sputtering surface of the Cu—Mn alloy sputtering target material 10. . Due to the collision of Ar + ions G, Cu and Mn sputtered particles P knocked out of the Cu—Mn alloy sputtering target material 10 are deposited on the film formation surface of the substrate S, and on the substrate S, Cu A Cu—Mn alloy film M having a concentration of Mn substantially equal to that of the —Mn alloy sputtering target material 10 is formed. That is, the Cu—Mn alloy film M includes, for example, Mn having a concentration of 8 atomic% or more and 30 atomic% or less and unavoidable impurities.

また、このとき、上述したように、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０中の平均結晶粒径は１０μｍ以上５０μｍ以下と微細であるので、Ｃｕ−Ｍｎ合金膜Ｍ中のＭｎの濃度の標準偏差が例えば０．０５原子％未満と、Ｍｎの濃度ムラが少なく良好な均一性を有するＣｕ−Ｍｎ合金膜Ｍが形成される。本発明者等によれば、ときにプラズマに異常放電を生じさせる粗大な結晶粒とは異なり、微細結晶粒にはプラズマの安定性を阻害する要因が少ない。よって、より安定した均一なプラズマが保たれることで、形成されるＣｕ−Ｍｎ合金膜Ｍ中のＭｎの濃度の均一性が向上するものと推察される。   At this time, as described above, since the average crystal grain size in the Cu—Mn alloy sputtering target material 10 is as fine as 10 μm or more and 50 μm or less, the standard deviation of the Mn concentration in the Cu—Mn alloy film M is small. For example, a Cu—Mn alloy film M having good uniformity with less Mn concentration unevenness is formed at less than 0.05 atomic%. According to the inventors, unlike coarse crystal grains that sometimes cause abnormal discharge in plasma, fine crystal grains have few factors that hinder plasma stability. Therefore, it is presumed that the uniformity of Mn concentration in the formed Cu-Mn alloy film M is improved by maintaining a more stable and uniform plasma.

以上、本実施形態によれば、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０を用い、高い拡散バリア性及び酸化バリア性を有するＣｕ−Ｍｎ合金膜を形成することができる。このようにＣｕ−Ｍｎ合金膜Ｍが形成された基板Ｓは、例えば所望の配線パターンにＣｕ−Ｍｎ合金膜Ｍをパターニングして配線が形成された後、ＴＦＴをはじめとする各種の半導体素子として利用される。   As described above, according to this embodiment, a Cu—Mn alloy film having high diffusion barrier properties and oxidation barrier properties can be formed using the Cu—Mn alloy sputtering target material 10. The substrate S on which the Cu—Mn alloy film M is formed in this manner is used as various semiconductor elements including TFTs after the wiring is formed by patterning the Cu—Mn alloy film M in a desired wiring pattern, for example. Used.

（４）薄膜トランジスタの構造
Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０を用いて形成したＣｕ−Ｍｎ合金膜は、上述のように、例えばＩｎＧａＺｎＯより構成されるＩＧＺＯ膜を備える薄膜トランジスタ（ＴＦＴ：Thin Film Transistor）配線として適用することが可能である。以下に、その一例として、薄膜トランジスタとしてのＩＧＺＯ系ＴＦＴ３０の構造について、図２を用いて説明する。図２は、本実施形態に係るＩＧＺＯ系ＴＦＴ３０の概略断面図である。 (4) Structure of Thin Film Transistor As described above, the Cu—Mn alloy film formed using the Cu—Mn alloy sputtering target material 10 is a thin film transistor (TFT) wiring including an IGZO film made of, for example, InGaZnO. It is possible to apply as As an example, the structure of an IGZO TFT 30 as a thin film transistor will be described below with reference to FIG. FIG. 2 is a schematic cross-sectional view of the IGZO TFT 30 according to this embodiment.

図２に示すように、ＩＧＺＯ系ＴＦＴ３０は、例えばガラス基板３１と、ガラス基板３１上に形成されたゲート電極３２と、ゲート電極３２上のソース電極３５Ｓ及びドレイン電極３５Ｄ（以下、ソース−ドレイン電極３５Ｓ，３５Ｄともいう）と、を備える。これらの電極３２，３５Ｓ，３５Ｄは例えば素子ごとに形成され、ガラス基板３１は例えば素子ごとに矩形形状等に切り出されている。或いは、ガラス基板３１は、複数のＩＧＺＯ系ＴＦＴ３０がアレイ状に配列されて切り出されていてもよい。   As shown in FIG. 2, the IGZO TFT 30 includes, for example, a glass substrate 31, a gate electrode 32 formed on the glass substrate 31, a source electrode 35S and a drain electrode 35D on the gate electrode 32 (hereinafter, source-drain electrodes). 35S, 35D). These electrodes 32, 35S, and 35D are formed for each element, for example, and the glass substrate 31 is cut into a rectangular shape for each element, for example. Alternatively, the glass substrate 31 may be cut out by arranging a plurality of IGZO TFTs 30 in an array.

ゲート電極３２には、例えば図示しないゲート配線が接続され、ゲート電極３２上には、ゲート絶縁膜３３を介して、所定パターンに成形された酸化物半導体としてのチャネル部３４が形成されている。ゲート絶縁膜３３は、例えば窒化シリコン（ＳｉＮ）又は酸化シリコン（ＳｉＯ2）等からなる。また、チャネル部３４は、例えばＩｎＧａＺｎＯ4を原料として、スパッタリング等により形成された酸化インジウムガリウム亜鉛（ＩｎＧａＺｎＯ：ＩＧＺＯ）膜からなる。 For example, a gate wiring (not shown) is connected to the gate electrode 32, and a channel portion 34 as an oxide semiconductor formed in a predetermined pattern is formed on the gate electrode 32 via a gate insulating film 33. The gate insulating film 33 is made of, for example, silicon nitride (SiN) or silicon oxide (SiO 2 ). The channel portion 34 is made of an indium gallium zinc oxide (InGaZnO: IGZO) film formed by sputtering or the like using, for example, InGaZnO 4 as a raw material.

チャネル部３４上には、チャネル部３４が備えるバックチャネル３４ｂを挟んで所定パターンに成形されたソース−ドレイン電極３５Ｓ，３５Ｄが形成されている。ソース−ドレイン電極３５Ｓ，３５Ｄには、図示しないソース−ドレイン配線が接続されている。ソース−ドレイン配線には、外部と電気信号をやり取りする図示しない電極パッドが形成されている。   On the channel part 34, source-drain electrodes 35S and 35D are formed in a predetermined pattern with a back channel 34b included in the channel part 34 interposed therebetween. A source-drain wiring (not shown) is connected to the source-drain electrodes 35S, 35D. An electrode pad (not shown) for exchanging electrical signals with the outside is formed on the source-drain wiring.

主に、ソース−ドレイン電極３５Ｓ，３５Ｄ、ソース−ドレイン配線、及び電極パッド等により、本実施形態に係る薄膜トランジスタ（ＴＦＴ）配線が構成される。   The thin film transistor (TFT) wiring according to this embodiment is mainly configured by the source-drain electrodes 35S and 35D, the source-drain wiring, the electrode pad, and the like.

ソース−ドレイン電極３５Ｓ，３５Ｄを含むＴＦＴ配線は、ガラス基板３１側から順に、Ｃｕ−Ｍｎ合金膜としての下部バリア膜３５ｂと、純Ｃｕ膜としての中間膜３５ｍと、Ｃｕ−Ｍｎ合金膜としての上部バリア膜３５ｔと、がこの順に積層された積層構造を有する。   The TFT wiring including the source-drain electrodes 35S and 35D is composed of a lower barrier film 35b as a Cu—Mn alloy film, an intermediate film 35m as a pure Cu film, and a Cu—Mn alloy film in this order from the glass substrate 31 side. The upper barrier film 35t and the upper barrier film 35t are stacked in this order.

下部バリア膜３５ｂ及び上部バリア膜３５ｔは、いずれか一方あるいは両方が上述のＣｕ−Ｍｎ合金スパッタターゲット材１０を用いて形成され、例えば濃度が８原子％以上３０原子％以下、係る濃度の標準偏差が例えば０．０５原子％未満のＭｎと、不可避的不純物とを含むＣｕ−Ｍｎ合金からなる。また、下部バリア膜３５ｂ及び上部バリア膜３５ｔは、例えば膜厚が５０ｎｍ以上１００ｎｍ以下に形成されている。   One or both of the lower barrier film 35b and the upper barrier film 35t are formed using the above-described Cu—Mn alloy sputter target material 10, and the concentration is, for example, 8 atomic% or more and 30 atomic% or less. Is made of a Cu—Mn alloy containing, for example, less than 0.05 atomic% of Mn and inevitable impurities. The lower barrier film 35b and the upper barrier film 35t are formed to have a film thickness of, for example, 50 nm or more and 100 nm or less.

中間膜３５ｍは、例えば純度が３Ｎ（９９．９％）以上の無酸素銅を原料として、スパッタリング等により形成された純Ｃｕからなる。また、中間膜３５ｍは、例えば膜厚が２００ｎｍ以上３００ｎｍ以下に形成されている。   The intermediate film 35m is made of pure Cu formed by sputtering or the like using, for example, oxygen-free copper having a purity of 3N (99.9%) or more as a raw material. Further, the intermediate film 35m is formed with a film thickness of, for example, 200 nm or more and 300 nm or less.

このように、低抵抗の純Ｃｕからなる中間膜３５ｍを、Ｃｕ−Ｍｎ合金からなるバリア膜３５ｂ，３５ｔで挟んだ構造とすることで、ソース−ドレイン電極３５Ｓ，３５ＤやＴＦＴ配線の抵抗を抑えることができる。また、形成したＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜に熱処理を施すことで、チャネル部３４と下部バリア膜３５ｂとの界面（ＩＧＺＯ膜／Ｃｕ−Ｍｎ合金膜）に酸化マンガン（ＭｎＯｘ）膜が形成され、例えば下部バリア膜３５ｂの拡散バリア性を高めることができる。   Thus, the resistance of the source-drain electrodes 35S and 35D and the TFT wiring is suppressed by adopting a structure in which the intermediate film 35m made of low-resistance pure Cu is sandwiched between the barrier films 35b and 35t made of a Cu—Mn alloy. be able to. Further, a heat treatment is performed on the formed Cu—Mn / Cu / Cu—Mn laminated film, so that a manganese oxide (MnOx) film is formed at the interface (IGZO film / Cu—Mn alloy film) between the channel portion 34 and the lower barrier film 35 b. For example, the diffusion barrier property of the lower barrier film 35b can be enhanced.

また、ガラス基板３１上の略全面には、ソース−ドレイン電極３５Ｓ，３５Ｄ及び露出したバックチャネル３４ｂを覆って保護膜３６が形成されている。   A protective film 36 is formed on the substantially entire surface of the glass substrate 31 so as to cover the source-drain electrodes 35S and 35D and the exposed back channel 34b.

保護膜３６は、例えばプラズマＣＶＤ等により形成されたＳｉＯ2からなり、例えば、一酸化二窒素（Ｎ2Ｏ）ガス等の酸化ガスと、水素（Ｈ2）及び水素バランスとしてモノシラン（ＳｉＨ4）ガスを用いて成膜する。 The protective film 36 is made of, for example, SiO 2 formed by plasma CVD or the like, for example, an oxidizing gas such as dinitrogen monoxide (N 2 O) gas, and monosilane (SiH 4 ) as hydrogen (H 2 ) and hydrogen balance. A film is formed using a gas.

ここで、予めＮ2Ｏガスのみのプラズマ照射による前処理を施し、チャネル部３４のＩＧＺＯ膜中の酸素を飽和させた後、Ｎ2ＯとＳｉＨ4／Ｈ2ガスによるＳｉＯ2膜を生成することにより、チャネル部３４のＩＧＺＯ膜中の酸素欠損量を良好な半導体特性を得るための適度なものとすることができる。 Here, pre-treatment by plasma irradiation with only N 2 O gas is performed in advance to saturate oxygen in the IGZO film of the channel portion 34, and then an SiO 2 film is formed by N 2 O and SiH 4 / H 2 gas. As a result, the amount of oxygen vacancies in the IGZO film of the channel portion 34 can be made appropriate for obtaining good semiconductor characteristics.

しかしながら、上記手法による保護膜３６の形成時には、ソース−ドレイン電極３５Ｓ，３５Ｄ等の配線も酸化雰囲気に曝されることとなる。このため、上述のように、非特許文献３の記載に基づき製作したＩＧＺＯ系ＴＦＴにおいては、純Ｃｕからなる中間膜の酸化が原因とみられる配線の抵抗値の上昇が生じてしまった。   However, when the protective film 36 is formed by the above method, wirings such as the source-drain electrodes 35S and 35D are also exposed to the oxidizing atmosphere. For this reason, as described above, in the IGZO TFT manufactured based on the description of Non-Patent Document 3, the resistance value of the wiring, which is considered to be caused by the oxidation of the intermediate film made of pure Cu, has been increased.

そこで、本実施形態では、上部バリア膜３５ｔや下部バリア膜３５ｂのＭｎの濃度を例えば８原子％以上としている。これにより、例えば上部バリア膜３５ｔの酸化バリア性（耐酸化性）が向上し、Ｎ2Ｏガスのプラズマ等の酸化雰囲気中で、下層である中間膜３５ｍを構成する純Ｃｕの酸化を抑制することができる。 Therefore, in the present embodiment, the Mn concentration in the upper barrier film 35t and the lower barrier film 35b is set to 8 atomic% or more, for example. Thereby, for example, the oxidation barrier property (oxidation resistance) of the upper barrier film 35t is improved, and the oxidation of pure Cu constituting the lower intermediate film 35m is suppressed in an oxidizing atmosphere such as plasma of N 2 O gas. be able to.

また、本実施形態では、上部バリア膜３５ｔや下部バリア膜３５ｂのＭｎの濃度を例えば３０原子％以下としている。これにより、チャネル部３４を構成するＩＧＺＯ膜や、純Ｃｕ膜としての中間膜３５ｍ等、バリア膜３５ｔ，３５ｂと接する膜へのＭｎの拡散を抑制することができる。   In the present embodiment, the Mn concentration in the upper barrier film 35t and the lower barrier film 35b is set to 30 atomic% or less, for example. Thereby, it is possible to suppress the diffusion of Mn into the film in contact with the barrier films 35t and 35b, such as the IGZO film constituting the channel portion 34 and the intermediate film 35m as a pure Cu film.

また、本実施形態では、上部バリア膜３５ｔや下部バリア膜３５ｂの形成に用いるＣｕ−Ｍｎ合金スパッタリングターゲット材１０は、例えば平均結晶粒径が１０μｍ以上５０μｍ以下のＣｕ−Ｍｎ合金からなる。これにより、例えば下部バリア膜３５ｂ中のＭｎの濃度の均一性が向上し、ガラス基板３１上の略全面において下部バリア膜３５ｂの拡散バリア性が向上する。すなわち、熱処理によりＭｎＯｘ膜を形成する際、下部バリア膜３５ｂの下層のチャネル部３４へのＣｕの拡散をガラス基板３１上の略全面において抑制することができる。よって、ＩＧＺＯ系ＴＦＴ３０の素子特性のバラツキを低減することができ、ＩＧＺＯ系ＴＦＴ３０や液晶パネルの製造歩留まりを向上させることができる。   In this embodiment, the Cu—Mn alloy sputtering target material 10 used for forming the upper barrier film 35t and the lower barrier film 35b is made of, for example, a Cu—Mn alloy having an average crystal grain size of 10 μm to 50 μm. Thereby, for example, the uniformity of the concentration of Mn in the lower barrier film 35b is improved, and the diffusion barrier property of the lower barrier film 35b is improved over substantially the entire surface of the glass substrate 31. That is, when the MnOx film is formed by the heat treatment, the diffusion of Cu to the channel part 34 below the lower barrier film 35b can be suppressed over substantially the entire surface of the glass substrate 31. Therefore, variation in element characteristics of the IGZO TFT 30 can be reduced, and the manufacturing yield of the IGZO TFT 30 and the liquid crystal panel can be improved.

なお、Ｃｕ−Ｍｎ合金スパッタリングターゲット材１０を用いて形成可能なＴＦＴの構成は、上記に記載のものに限られない。例えば、上記とは異なる膜構成を有するＩＧＺＯ系ＴＦＴや、ＺｎＯ系ＴＦＴ、或いはα−Ｓｉ系ＴＦＴ等にもＣｕ−Ｍｎ合金スパッタリングターゲット材１０を用いることができる。また、ＴＦＴのみならず、Ｓｉ太陽電池素子等のＳｉ半導体を用いた各種の半導体素子にＣｕ−Ｍｎ合金スパッタリングターゲット材１０を適用可能である。   In addition, the structure of TFT which can be formed using the Cu-Mn alloy sputtering target material 10 is not restricted to the above-mentioned thing. For example, the Cu—Mn alloy sputtering target material 10 can be used for an IGZO-based TFT, a ZnO-based TFT, an α-Si-based TFT, or the like having a film configuration different from the above. Moreover, the Cu-Mn alloy sputtering target material 10 is applicable not only to TFT but also to various semiconductor elements using Si semiconductor such as Si solar cell element.

以上、本発明の実施形態について具体的に説明したが、本発明は上述の実施形態に限定されるものではなく、その要旨を逸脱しない範囲で種々変更可能である。   As mentioned above, although embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, It can change variously in the range which does not deviate from the summary.

本発明の実施例に係るＣｕ−Ｍｎ合金膜における酸化バリア性及び拡散バリア性の評価結果について、以下に説明する。   The evaluation results of the oxidation barrier property and the diffusion barrier property in the Cu—Mn alloy film according to the example of the present invention will be described below.

（１）酸化バリア性の評価
以下の表１を参照しながら、酸化バリア性の評価に係る実施例１〜１２について比較例１〜７と共に説明する。 (1) Evaluation of oxidation barrier properties Examples 1 to 12 relating to the evaluation of oxidation barrier properties are described together with Comparative Examples 1 to 7 with reference to Table 1 below.

Figure 2013067857
Figure 2013067857

（評価サンプルの製作）
まず、図３に示す実施例１〜１２及び比較例１〜７に係る評価サンプルを以下の手順で製作した。図３は、実施例１〜１２及び比較例１〜７に係る評価サンプルの説明図であって、（ａ）はＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜がブロック状に複数個形成された評価サンプルの平面図であり、（ｂ）はＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜の１ブロックを示す斜視図である。 (Production of evaluation samples)
First, evaluation samples according to Examples 1 to 12 and Comparative Examples 1 to 7 shown in FIG. 3 were produced according to the following procedure. FIG. 3 is an explanatory diagram of evaluation samples according to Examples 1 to 12 and Comparative Examples 1 to 7, in which (a) shows a plurality of Cu—Mn / Cu / Cu—Mn laminated films formed in a block shape. It is a top view of an evaluation sample, (b) is a perspective view which shows 1 block of a Cu-Mn / Cu / Cu-Mn laminated film.

５０ｍｍ角のガラス基板５１上に、ＩｎＧａＺｎＯ4スパッタリングターゲット材を用い、スパッタリングにより３０ｎｍの厚さにＩＧＺＯ膜５４を形成した。 An IGZO film 54 having a thickness of 30 nm was formed on a 50 mm square glass substrate 51 by sputtering using an InGaZnO 4 sputtering target material.

次に、３ｍｍ角の開口部を２ｍｍ間隔で１００マス（縦１０マス×横１０マス）有するメタルマスク（図示せず）を、ＩＧＺＯ膜５４の形成されたガラス基板５１上に保持した状態で、Ｃｕ−Ｍｎ合金膜５５ｂ、純Ｃｕ膜５５ｍ、Ｃｕ−Ｍｎ合金膜５５ｔをこの順に積層し、Ｃｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜を３ｍｍ角のブロック状に１００個、ＩＧＺＯ膜５４上に形成した。   Next, in a state where a metal mask (not shown) having openings of 3 mm square and 100 squares (10 vertical and 10 horizontal) at intervals of 2 mm is held on the glass substrate 51 on which the IGZO film 54 is formed, A Cu-Mn alloy film 55b, a pure Cu film 55m, and a Cu-Mn alloy film 55t are laminated in this order, and 100 Cu-Mn / Cu / Cu-Mn laminated films in a 3 mm square block shape are formed on the IGZO film 54. Formed.

上下のＣｕ−Ｍｎ合金膜５５ｔ，５５ｂはいずれも、純度が共に３Ｎの無酸素銅及び純Ｍｎを原料として、上述の実施形態と略同様の手順で製作された外径が１００ｍｍ、厚さが５ｍｍの円板型のＣｕ−Ｍｎ合金スパッタリングターゲット材を用い、上述の実施形態と同様の手法のスパッタリングにより５０ｎｍの厚さに形成した。ただし、表１に示すように、実施例１〜１２及び比較例１〜７に係る評価サンプルごとに、Ｍｎの濃度及びＣｕ−Ｍｎ合金中の平均結晶粒径が異なるＣｕ−Ｍｎ合金スパッタリングターゲット材を用意し、これを用いて各評価サンプルの成膜を行った。   Both the upper and lower Cu—Mn alloy films 55t and 55b are made of oxygen-free copper having a purity of 3N and pure Mn as raw materials, and the outer diameter is 100 mm and the thickness is substantially the same as that of the above-described embodiment. A 5 mm disc-shaped Cu—Mn alloy sputtering target material was used and formed to a thickness of 50 nm by sputtering in the same manner as in the above embodiment. However, as shown in Table 1, for each of the evaluation samples according to Examples 1 to 12 and Comparative Examples 1 to 7, a Cu—Mn alloy sputtering target material in which the concentration of Mn and the average crystal grain size in the Cu—Mn alloy are different. Was prepared, and each evaluation sample was formed into a film using this.

Ｃｕ−Ｍｎ合金中の上記平均結晶粒径は、上述のように、インゴットの冷間圧延時の加工度と、その後の熱処理時の温度とを適宜、所定の組み合わせとすることで調整した。具体例を挙げると、Ｍｎの濃度が１３．９原子％に調整された実施例４においては、加工度を５５％とし熱処理の温度を７５０℃として、４０μｍの平均結晶粒径を得た。   As described above, the average crystal grain size in the Cu-Mn alloy was adjusted by appropriately combining the degree of processing during cold rolling of the ingot and the temperature during subsequent heat treatment. As a specific example, in Example 4 in which the Mn concentration was adjusted to 13.9 atomic%, the degree of processing was 55%, the temperature of heat treatment was 750 ° C., and an average crystal grain size of 40 μm was obtained.

純Ｃｕ膜５５ｍは、純度が３Ｎの無酸素銅スパッタリングターゲット材を用い、スパッタリングにより３００ｎｍの厚さに形成した。ＩＧＺＯ膜５４を含む各膜のスパッタリング時の成膜条件を表２に示す。   The pure Cu film 55m was formed to a thickness of 300 nm by sputtering using an oxygen-free copper sputtering target material having a purity of 3N. Table 2 shows the film formation conditions during sputtering of each film including the IGZO film 54.

Figure 2013067857
Figure 2013067857

次に、ＣＶＤ装置を用い、図３に示す評価サンプルそれぞれをＮ2Ｏガスのプラズマに曝した。このとき、３０ｎｍの厚さのＩＧＺＯ膜中に酸素を十分飽和させるため、Ｎ2Ｏガスのプラズマによる曝露時間を１分間とした。その他のプラズマ条件を表３に示す。 Next, each of the evaluation samples shown in FIG. 3 was exposed to N 2 O gas plasma using a CVD apparatus. At this time, in order to sufficiently saturate oxygen in the IGZO film having a thickness of 30 nm, the exposure time by plasma of N 2 O gas was set to 1 minute. Other plasma conditions are shown in Table 3.

Figure 2013067857
Figure 2013067857

（シート抵抗の測定）
続いて、上記のように製作した実施例１〜１２及び比較例１〜７に係る評価サンプルそれぞれについて、各評価サンプルが備えるＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜のシート抵抗を測定した。測定方法には、３ｍｍ角の各積層膜の４隅付近に電極の針を当てて行うファン・デル・パウ（van der Pauw）法を用いた。測定結果を上記の表１に示す。また、表１に示す測定結果をグラフ化したものを図４に示す。図４は、Ｃｕ−Ｍｎ合金スパッタリングターゲット材中に含まれるＭｎの濃度と、これにより形成されるＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜のシート抵抗との関係を示すグラフである。図４の横軸はＣｕ−Ｍｎ合金スパッタリングターゲット材中に含まれるＭｎの濃度（原子％）であり、縦軸は対応するＣｕ−Ｍｎ／Ｃｕ／Ｃｕ−Ｍｎ積層膜のシート抵抗（ｍΩ／□）である。 (Sheet resistance measurement)
Subsequently, for each of the evaluation samples according to Examples 1 to 12 and Comparative Examples 1 to 7 manufactured as described above, the sheet resistance of the Cu—Mn / Cu / Cu—Mn multilayer film included in each evaluation sample was measured. As a measuring method, a van der Pauw method in which electrode needles were applied near the four corners of each 3 mm square laminated film was used. The measurement results are shown in Table 1 above. Further, FIG. 4 shows a graph of the measurement results shown in Table 1. FIG. 4 is a graph showing the relationship between the concentration of Mn contained in the Cu—Mn alloy sputtering target material and the sheet resistance of the Cu—Mn / Cu / Cu—Mn laminated film formed thereby. The horizontal axis of FIG. 4 is the concentration (atomic%) of Mn contained in the Cu—Mn alloy sputtering target material, and the vertical axis is the sheet resistance (mΩ / □) of the corresponding Cu—Mn / Cu / Cu—Mn laminated film. ).

表１及び図４に示すように、Ｃｕ−Ｍｎ合金スパッタリングターゲット材中のＭｎの濃度が、実施例１〜１２のように８原子％以上３０原子％以下の範囲内では、形成される積層膜のシート抵抗は略７０ｍΩ／□の一定値を示した。しかし、比較例１及び２のように、Ｍｎの濃度が８原子％未満では、シート抵抗が急激に上昇した。また、比較例３〜７のように、Ｍｎの濃度が３０原子％を超えた場合もシート抵抗の上昇がみられた。   As shown in Table 1 and FIG. 4, when the concentration of Mn in the Cu—Mn alloy sputtering target material is in the range of 8 atomic% or more and 30 atomic% or less as in Examples 1 to 12, a laminated film is formed. The sheet resistance was a constant value of approximately 70 mΩ / □. However, as in Comparative Examples 1 and 2, when the Mn concentration was less than 8 atomic%, the sheet resistance increased rapidly. Further, as in Comparative Examples 3 to 7, an increase in sheet resistance was also observed when the Mn concentration exceeded 30 atomic%.

Ｍｎの濃度が８原子％未満におけるこのようなシート抵抗の上昇は、形成されるＣｕ−Ｍｎ合金膜５５ｔの酸化バリア性が低く、純Ｃｕ膜５５ｍが酸化して高抵抗化してしまったことによると考えられる。また、Ｍｎの濃度が３０原子％を超えた場合のシート抵抗の上昇は、Ｃｕ−Ｍｎ合金膜５５ｔ，５５ｂ中のＭｎが純Ｃｕ膜５５ｍ中へ拡散して、純Ｃｕ膜５５ｍが高抵抗化してしまったことによると考えられる。係るＭｎの拡散は、下層のＩＧＺＯ膜５４に対しても起こっていると考えられる。   Such an increase in sheet resistance when the Mn concentration is less than 8 atomic% is due to the fact that the formed Cu—Mn alloy film 55t has a low oxidation barrier property, and the pure Cu film 55m is oxidized to increase its resistance. it is conceivable that. Further, when the Mn concentration exceeds 30 atomic%, the increase in sheet resistance is caused by the diffusion of Mn in the Cu—Mn alloy films 55t and 55b into the pure Cu film 55m, and the pure Cu film 55m having a high resistance. This is probably due to the fact that It is considered that such Mn diffusion occurs also in the underlying IGZO film 54.

以上の結果から、Ｃｕ−Ｍｎ合金スパッタリングターゲット材を構成するＣｕ−Ｍｎ合金が、８原子％以上３０原子％以下のＭｎの濃度を有していれば、良好な酸化バリア性を備えるＣｕ−Ｍｎ合金膜を形成できることが分かった。   From the above results, if the Cu-Mn alloy constituting the Cu-Mn alloy sputtering target material has a concentration of Mn of 8 atomic% or more and 30 atomic% or less, Cu-Mn having a good oxidation barrier property. It was found that an alloy film can be formed.

（２）拡散バリア性の評価
次に、以下の表４を参照しながら、拡散バリア性の評価に係る実施例１，４，７，１０及び１２〜１５について比較例８〜１７と共に説明する。 (2) Evaluation of Diffusion Barrier Properties Next, Examples 1, 4, 7, 10 and 12 to 15 related to the evaluation of diffusion barrier properties will be described together with Comparative Examples 8 to 17 with reference to Table 4 below.

Figure 2013067857
Figure 2013067857

（評価サンプルの製作）
まず、図５に示す実施例１，４，７，１０及び１２〜１５並びに比較例８〜１７に係る評価サンプルを以下の手順で製作した。図５は、実施例１，４，７，１０及び１２〜１５並びに比較例８〜１７に係る評価サンプルの平面図である。 (Production of evaluation samples)
First, evaluation samples according to Examples 1, 4, 7, 10, and 12 to 15 and Comparative Examples 8 to 17 shown in FIG. FIG. 5 is a plan view of evaluation samples according to Examples 1, 4, 7, 10, and 12-15 and Comparative Examples 8-17.

３ｍｍ角の開口部を２ｍｍ間隔で１００マス（縦１０マス×横１０マス）有するメタルマスク（図示せず）を、５０ｍｍ角のガラス基板６１上に保持した状態で、Ｃｕ−Ｍｎ合金膜６５をガラス基板６１上に直接成膜し、Ｃｕ−Ｍｎ合金の単膜を３ｍｍ角のブロック状に１００個、形成した。   In a state where a metal mask (not shown) having 3 mm square openings at 2 mm intervals with 100 squares (vertical 10 squares × horizontal 10 squares) is held on a 50 mm square glass substrate 61, the Cu—Mn alloy film 65 is formed. The film was directly formed on the glass substrate 61, and 100 single films of Cu-Mn alloy were formed in a 3 mm square block shape.

Ｃｕ−Ｍｎ合金膜６５は、上記酸化バリア性の評価時と同様の原料及び手順で製作された外径が１００ｍｍ、厚さが５ｍｍの円板型のＣｕ−Ｍｎ合金スパッタリングターゲット材を用い、上記表２のＣｕ−Ｍｎ合金膜と同一条件のスパッタリングにより、膜厚のみ上記と異なる５００ｎｍの厚さに形成した。ただし、表４に示すように、実施例１，４，７，１０及び１２〜１５並びに比較例８〜１７に係る評価サンプルごとに、Ｍｎの濃度及びＣｕ−Ｍｎ合金中の平均結晶粒径が異なるＣｕ−Ｍｎ合金スパッタリングターゲット材を用意し、これを用いて各評価サンプルの成膜を行った。   The Cu—Mn alloy film 65 is a disc-shaped Cu—Mn alloy sputtering target material having an outer diameter of 100 mm and a thickness of 5 mm manufactured by the same raw materials and procedures as in the evaluation of the oxidation barrier property. By sputtering under the same conditions as the Cu—Mn alloy film in Table 2, only the film thickness was formed to a thickness of 500 nm different from the above. However, as shown in Table 4, for each of the evaluation samples according to Examples 1, 4, 7, 10, and 12 to 15 and Comparative Examples 8 to 17, the concentration of Mn and the average crystal grain size in the Cu—Mn alloy are Different Cu—Mn alloy sputtering target materials were prepared, and each evaluation sample was formed using this.

このうち、実施例１，４，７，１０及び１２については、上述の酸化バリア性の評価において、これらと番号の重複する実施例と同様の条件で製作されたＣｕ−Ｍｎ合金スパッタリングターゲット材を用いて成膜した。すなわち、上記と同様、Ｍｎの濃度が１３．９原子％の実施例４においては、加工度を５５％とし熱処理の温度を７５０℃として、４０μｍの平均結晶粒径を得た。   Among these, in Examples 1, 4, 7, 10 and 12, in the evaluation of the oxidation barrier property described above, the Cu—Mn alloy sputtering target material manufactured under the same conditions as those of the example having the same number as these were used. Used to form a film. That is, in the same manner as described above, in Example 4 where the Mn concentration was 13.9 atomic%, the average crystal grain size of 40 μm was obtained at a processing degree of 55% and a heat treatment temperature of 750 ° C.

また、比較例８〜１７については、それぞれが実施例１，４，７，１０及び１２〜１５のいずれかと同等のＭｎの濃度を備え、平均結晶粒径については所定値から外れる値となるＣｕ−Ｍｎ合金スパッタリングターゲット材を用いて成膜した。具体例を挙げると、実施例４と同等の１３．９原子％のＭｎの濃度を備える比較例１１においては、加工度を５５％とし熱処理の温度を８７０℃として、７０μｍの平均結晶粒径を得た。   Moreover, about Comparative Examples 8-17, each is provided with the density | concentration of Mn equivalent to any of Example 1, 4, 7, 10, and 12-15, and it becomes the value which remove | deviates from a predetermined value about an average crystal grain diameter. A film was formed using a -Mn alloy sputtering target material. As a specific example, in Comparative Example 11 having a Mn concentration of 13.9 atomic% equivalent to that in Example 4, the degree of processing was 55%, the heat treatment temperature was 870 ° C., and the average grain size was 70 μm. Obtained.

（Ｍｎの濃度の測定）
続いて、上記のように製作した実施例１，４，７，１０及び１２〜１５並びに比較例８〜１７に係る評価サンプルそれぞれについて、各評価サンプルが備えるＣｕ−Ｍｎ合金膜６５のＭｎの濃度を１００ブロック全てについて測定し、Ｍｎの濃度の平均値及び標準偏差を求めた。測定方法には、エネルギー分散型Ｘ線分光法（Energy-Dispersive X-ray spectroscopy）を用いた。測定結果を上記の表４に示す。 (Measurement of Mn concentration)
Subsequently, for each of the evaluation samples according to Examples 1, 4, 7, 10, and 12 to 15 and Comparative Examples 8 to 17 manufactured as described above, the Mn concentration of the Cu—Mn alloy film 65 included in each evaluation sample Were measured for all 100 blocks, and the average value and standard deviation of the Mn concentration were determined. As a measuring method, energy-dispersive X-ray spectroscopy was used. The measurement results are shown in Table 4 above.

表４に示すように、平均結晶粒径が５０μｍ以下のＣｕ−Ｍｎ合金スパッタリングターゲット材を用いてＣｕ−Ｍｎ合金膜６５を形成した評価サンプルでは、Ｃｕ−Ｍｎ合金膜６５中のＭｎの濃度の標準偏差は概ね０．０５原子％より小さいという結果であった。また、平均結晶粒径が微細であるほど膜中のＭｎの濃度の標準偏差は小さかった。   As shown in Table 4, in the evaluation sample in which the Cu—Mn alloy film 65 is formed using a Cu—Mn alloy sputtering target material having an average crystal grain size of 50 μm or less, the Mn concentration in the Cu—Mn alloy film 65 is The standard deviation was generally less than 0.05 atomic%. The standard deviation of the Mn concentration in the film was smaller as the average crystal grain size was finer.

標準偏差σに対し、統計学上、測定値の９９．７％が含まれるとされる平均値±３σの範囲でみると、本実施例においては、平均結晶粒径が５０μｍ以下で３σは±０．１５原子％未満となっており、充分に小さなバラツキといえる。   In terms of the standard deviation σ, in the range of an average value ± 3σ, which is statistically included 99.7% of the measured value, in this example, the average crystal grain size is 50 μm or less and 3σ is ± It is less than 0.15 atomic%, which is a sufficiently small variation.

以上の結果から、Ｃｕ−Ｍｎ合金スパッタリングターゲット材を構成するＣｕ−Ｍｎ合金が、１０μｍ以上５０μｍ以下の平均結晶粒径を有していれば、Ｍｎの濃度の均一性が良好なＣｕ−Ｍｎ合金膜を形成でき、Ｃｕ−Ｍｎ合金膜の略全域において良好な拡散バリア性が得られることが分かった。   From the above results, if the Cu—Mn alloy constituting the Cu—Mn alloy sputtering target material has an average crystal grain size of 10 μm or more and 50 μm or less, the Cu—Mn alloy having good uniformity of Mn concentration. It was found that a film can be formed and good diffusion barrier properties can be obtained over substantially the entire area of the Cu—Mn alloy film.

１０ Ｃｕ−Ｍｎ合金スパッタリングターゲット材
２０ スパッタリング装置
３０ ＩＧＺＯ系ＴＦＴ（薄膜トランジスタ）
３１ ガラス基板
３２ ゲート電極
３３ ゲート絶縁膜
３４ チャネル部（酸化物半導体）
３５ｂ 下部バリア膜（Ｃｕ−Ｍｎ合金膜）
３５Ｄ ドレイン電極
３５ｍ 中間膜（純Ｃｕ膜）
３５Ｓ ソース電極
３５ｔ 上部バリア膜（Ｃｕ−Ｍｎ合金膜）
３６ 保護膜 10 Cu-Mn alloy sputtering target material 20 Sputtering device 30 IGZO TFT (thin film transistor)
31 Glass substrate 32 Gate electrode 33 Gate insulating film 34 Channel part (oxide semiconductor)
35b Lower barrier film (Cu-Mn alloy film)
35D Drain electrode 35m Intermediate film (pure Cu film)
35S source electrode 35t Upper barrier film (Cu-Mn alloy film)
36 Protective film

Claims (4)

半導体素子の配線の形成に用いられるＣｕ−Ｍｎ合金スパッタリングターゲット材であって、
濃度が８原子％以上３０原子％以下のＭｎと、不可避的不純物とを含むＣｕ−Ｍｎ合金からなり、
前記Ｃｕ−Ｍｎ合金の平均結晶粒径が１０μｍ以上５０μｍ以下である
ことを特徴とするＣｕ−Ｍｎ合金スパッタリングターゲット材。 A Cu-Mn alloy sputtering target material used for forming a wiring of a semiconductor element,
A Cu—Mn alloy containing Mn having a concentration of 8 atomic% to 30 atomic% and unavoidable impurities,
A Cu—Mn alloy sputtering target material, wherein the Cu—Mn alloy has an average crystal grain size of 10 μm or more and 50 μm or less. Ｃｕ−Ｍｎ合金膜と、純Ｃｕ膜と、Ｃｕ−Ｍｎ合金膜と、がこの順に形成された積層構造を基板上に有し、
前記Ｃｕ−Ｍｎ合金膜の少なくとも一方は、
請求項１に記載のＣｕ−Ｍｎ合金スパッタリングターゲット材を用いて形成され、
濃度が８原子％以上３０原子％以下のＭｎと、不可避的不純物とを含むＣｕ−Ｍｎ合金からなる
ことを特徴とする薄膜トランジスタ配線。 The substrate has a laminated structure in which a Cu-Mn alloy film, a pure Cu film, and a Cu-Mn alloy film are formed in this order,
At least one of the Cu-Mn alloy films is
It is formed using the Cu-Mn alloy sputtering target material according to claim 1,
A thin film transistor wiring comprising a Cu-Mn alloy containing Mn at a concentration of 8 atomic% to 30 atomic% and unavoidable impurities. 前記Ｍｎの濃度が８原子％以上３０原子％以下である前記Ｃｕ−Ｍｎ合金膜中の前記Ｍｎの濃度の標準偏差が０．０５原子％未満である
ことを特徴とする請求項２に記載の薄膜トランジスタ配線。 3. The standard deviation of the Mn concentration in the Cu—Mn alloy film having a Mn concentration of 8 atomic% to 30 atomic% is less than 0.05 atomic%. Thin film transistor wiring. 請求項２又は３に記載の薄膜トランジスタ配線が、ＩｎＧａＺｎＯ膜から構成される酸化物半導体を介して前記基板上に形成されている
ことを特徴とする薄膜トランジスタ。 4. The thin film transistor according to claim 2, wherein the thin film transistor wiring is formed on the substrate through an oxide semiconductor composed of an InGaZnO film.
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