JP5339830B2 - Thin film transistor wiring film having excellent adhesion and sputtering target for forming this wiring film - Google Patents
Thin film transistor wiring film having excellent adhesion and sputtering target for forming this wiring film Download PDFInfo
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Description
この発明は、密着性に優れた薄膜トランジスター（以下、ＴＦＴという）のゲート電極、ソース電極およびドレイン電極などの配線膜および配線下地膜、並びにこれら配線膜および配線下地膜を形成するためのスパッタリングターゲットに関するものである。 The present invention relates to a wiring film and a wiring base film such as a gate electrode, a source electrode and a drain electrode of a thin film transistor (hereinafter referred to as TFT) having excellent adhesion, and a sputtering target for forming the wiring film and the wiring base film. It is about.
一般に、液晶ディスプレイ、有機ＥＬディスプレイなどフラットパネルディスプレイは、ガラス基板の上に薄膜トランジスター（以下、ＴＦＴという）が形成された構造となっておりており、このＴＦＴのゲート電極、ソース電極およびドレイン電極などの配線膜として銅合金配線膜が使用されている。この銅合金配線膜は、例えば、金属材料全体に対して概ね８０原子％以上のＣｕと、Ｍｇ、Ｔｉ、ＡｌおよびＣｒの金属酸化物形成用金属を金属材料全体に対して０．５〜２０原子％を含有した銅合金からなることが好ましいとされている（特許文献１参照）。
この銅合金配線膜は、スパッタリングにより成膜した後、熱処理される。この熱処理が行われると、銅合金配線膜に含まれる添加元素が銅合金配線膜の表面および裏面に移動し、酸化物となって銅合金配線膜の表面および裏面に添加元素の酸化物層が形成され、この添加元素の酸化物層の生成はガラス基板およびアモルファスＳｉ膜の基本成分であるＳｉなどが銅合金配線膜に拡散浸透するのを阻止して銅合金配線膜の比抵抗の増加を防止するとともにこの添加元素の酸化物層の生成はガラス基板およびアモルファスＳｉ膜に対する銅合金配線膜の密着性が向上するとされている。
さらに、このガラス基板の上に形成されたＴＦＴは、ＴＦＴを確実に作動させるべくＴＦＴのＳｉ膜のダングリングボンドを終端させる目的で、水素化処理（以下、水素アニールという）が行われる（非特許文献１参照）。
The copper alloy wiring film is heat-treated after being formed by sputtering. When this heat treatment is performed, the additive elements contained in the copper alloy wiring film move to the front and back surfaces of the copper alloy wiring film and become oxides, and oxide layers of the additive elements are formed on the front and back surfaces of the copper alloy wiring film. The formation of the oxide layer of this additive element prevents the diffusion of and diffusion of Si, which is a basic component of the glass substrate and amorphous Si film, into the copper alloy wiring film, thereby increasing the specific resistance of the copper alloy wiring film. In addition to preventing, the formation of the oxide layer of this additive element is said to improve the adhesion of the copper alloy wiring film to the glass substrate and the amorphous Si film.
Further, the TFT formed on the glass substrate is subjected to hydrogenation treatment (hereinafter referred to as hydrogen annealing) for the purpose of terminating dangling bonds in the Si film of the TFT in order to operate the TFT reliably (non-hydrogen annealing). Patent Document 1).
Ｃｒ：０．５〜２０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有する銅合金膜、Ｃｒ：０．５〜２０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有する銅合金膜などを形成し熱処理したゲート電極、ソース電極およびドレイン電極などの銅合金配線膜を使用して作製したＴＦＴを、Ｓｉ膜のダングリングボンドを終端させる目的で水素アニールを行うと、前記熱処理により形成された銅合金配線膜の表面および裏面の酸化物層は還元され、その結果、酸化物層が担ってきた密着性やＳｉの銅合金配線膜への拡散防止特性が低下し、特に密着性の低下が著しくなるなどの問題点が生じてきた。 A copper alloy film having a component composition containing Cr: 0.5 to 20 atom%, the balance being Cu and inevitable impurities, Cr: containing 0.5 to 20 atom%, and the balance being Cu and inevitable impurities A TFT fabricated using a copper alloy wiring film such as a gate electrode, a source electrode, and a drain electrode formed by heat treatment by forming a copper alloy film having a component composition is subjected to hydrogen annealing for the purpose of terminating dangling bonds in the Si film. When this is done, the oxide layers on the front and back surfaces of the copper alloy wiring film formed by the heat treatment are reduced. As a result, the adhesion that the oxide layer has carried and the diffusion preventing property of Si to the copper alloy wiring film are reduced. There has been a problem that the adhesiveness has deteriorated, and particularly the adhesiveness has deteriorated significantly.
そこで、本発明者等は、水素アニールが行われても銅合金配線膜の表面および裏面に形成された酸化物層が還元されにくく、したがって、酸化物層が担ってきた密着性の低下が少ない銅合金配線膜を得るべく研究を行った。
その結果、Ｃｒ：３．９〜２０原子％、ＭｎおよびＡｌのうちの１種または２種の合計：０．１〜２０原子％を、ＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように含有し、さらに、必要に応じてＭｇ：０．１〜５原子％を含有し、残部がＣｕおよび不可避不純物からなる組成を有し、この組成を有する銅合金膜は、従来のＣｒおよびＡｌをそれぞれ単独で含むＣｒ：０．５〜２０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有する銅合金膜およびＡｌ：０．５〜２０原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有する銅合金膜に比べて、熱処理して形成された酸化物層が還元されにくく、したがって、水素アニール後の密着性の低下が小さいことからＴＦＴの配線膜として優れた特性を有する、という研究結果が得られたのである。
Therefore, the inventors of the present invention hardly reduce the oxide layers formed on the front surface and the back surface of the copper alloy wiring film even if hydrogen annealing is performed, and therefore, there is little decrease in adhesion that the oxide layer has assumed. Research was conducted to obtain a copper alloy wiring film.
As a result, Cr: 3.9 to 20 atomic%, total of one or two of Mn and Al: 0.1 to 20 atomic%, and the total of Cr, Mn and Al exceeds 5 to 25 atomic% In addition, if necessary, Mg: 0.1 to 5 atomic% is contained, the remainder has a composition consisting of Cu and inevitable impurities, and the copper alloy film having this composition is In addition, the conventional Cr and Al containing Cr: 0.5 to 20 atomic%, the copper alloy film having a component composition consisting of Cu and inevitable impurities and Al: 0.5 to 20 atomic% The oxide layer formed by heat treatment is less likely to be reduced compared to a copper alloy film having a component composition consisting of Cu and inevitable impurities, and the decrease in adhesion after hydrogen annealing is therefore small. As wiring film of TFT Having properties is the research results were obtained that.
この発明は、上記の研究結果に基づいてなされたものであって、
（１）Ｃｒ：３．９〜２０原子％、ＭｎおよびＡｌのうちの１種または２種の合計：０．１〜２０原子％を、ＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように含有し、残部がＣｕおよび不可避不純物からなる組成を有する銅合金膜からなり、ガラス基板との界面にＭｎおよびＡｌのうちの１種または２種を含有する複酸化物が形成されるＴＦＴ用配線膜、
（２）Ｃｒ：３．９〜２０原子％、ＭｎおよびＡｌのうちの１種または２種の合計：０．１〜２０原子％を、ＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように含有し、さらに、Ｍｇ：０．１〜５原子％を含有し、残部がＣｕおよび不可避不純物からなる組成を有する銅合金膜からなり、ガラス基板との界面にＭｎおよびＡｌのうちの１種または２種を含有する複酸化物が形成されるＴＦＴ用配線膜、に特徴を有するものである。
This invention was made based on the above research results,
(1) Cr: 3.9 to 20 atomic%, total of one or two of Mn and Al: 0.1 to 20 atomic%, and the total of Cr, Mn and Al is more than 5 to 25 atomic% A complex oxide containing one or two of Mn and Al at the interface with the glass substrate, comprising a copper alloy film having a composition comprising Cu and unavoidable impurities in the balance . A wiring film for TFT in which is formed ,
(2) Cr: 3.9 to 20 atomic%, total of one or two of Mn and Al: 0.1 to 20 atomic%, and the total of Cr, Mn and Al is more than 5 to 25 atomic% In addition, Mg: 0.1-5 atomic%, further comprising a copper alloy film having a composition consisting of Cu and inevitable impurities , Mn and at the interface with the glass substrate It is characterized by a TFT wiring film in which a double oxide containing one or two of Al is formed .
前記（１）および（２）記載の銅合金膜は、添加元素であるＣｒ、Ｍｎ、Ａｌの含有量が多くなるほど密着性は向上するが抵抗値が高くなり、フラットパネルディスプレイ用配線膜として使用すると消費電力が増加する。そのために、前記（１）および（２）記載の銅合金膜をＴＦＴ用配線の下地膜として形成し、この下地膜の上に純銅膜を形成したのち熱処理して積層ＴＦＴ用配線膜として使用することができ、この発明は、この下地膜をも含むものである。したがって、この発明は、
（３）Ｃｒ：３．９〜２０原子％、ＭｎおよびＡｌのうちの１種または２種の合計：０．１〜２０原子％を、ＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように含有し、残部がＣｕおよび不可避不純物からなる組成を有する銅合金膜からなり、ガラス基板との界面にＭｎおよびＡｌのうちの１種または２種を含有する複酸化物が形成されるＴＦＴ用配線下地膜、
（４）Ｃｒ：３．９〜２０原子％、ＭｎおよびＡｌのうちの１種または２種の合計：０．１〜２０原子％を、ＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように含有し、さらに、Ｍｇ：０．１〜５原子％を含有し、残部がＣｕおよび不可避不純物からなる組成を有する銅合金膜からなり、ガラス基板との界面にＭｎおよびＡｌのうちの１種または２種を含有する複酸化物が形成されるＴＦＴ用配線下地膜、に特徴を有するものである。
The copper alloy film described in the above (1) and (2) is used as a wiring film for a flat panel display, as the content of the additive elements Cr, Mn, and Al increases, the adhesion is improved but the resistance value is increased. Then, power consumption increases. For this purpose, the copper alloy film described in the above (1) and (2) is formed as a base film for TFT wiring, a pure copper film is formed on this base film, and then heat-treated to be used as a laminated TFT wiring film. The present invention also includes this base film. Therefore, the present invention
(3) Cr: 3.9 to 20 atomic%, total of one or two of Mn and Al: 0.1 to 20 atomic%, and the total of Cr, Mn and Al is more than 5 to 25 atomic% A complex oxide containing one or two of Mn and Al at the interface with the glass substrate, comprising a copper alloy film having a composition comprising Cu and unavoidable impurities in the balance . A wiring substrate film for TFT in which is formed ,
(4) Cr: 3.9 to 20 atomic%, total of one or two of Mn and Al: 0.1 to 20 atomic%, and the total of Cr, Mn and Al is more than 5 to 25 atomic% In addition, Mg: 0.1-5 atomic%, further comprising a copper alloy film having a composition consisting of Cu and inevitable impurities , Mn and at the interface with the glass substrate This is characterized by a TFT wiring base film on which a double oxide containing one or two of Al is formed .
前記（１）〜（２）記載の配線膜および前記（３）〜（４）記載の配線下地膜を形成するには、Ｃｒを４．８〜２０原子％、ＭｎおよびＡｌのうちの１種または２種を合計で０．１〜２０原子％を、ＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように含有し、さらに必要に応じてＭｇ：０．１〜５原子％を含有し、残部がＣｕおよび不可避不純物からなる成分組成を有する銅合金ターゲットを用いてスパッタリングすることにより得られる。この発明はこの銅合金ターゲットを含むものであり、この発明は、
（５）Ｃｒ：４．８〜２０原子％、ＭｎおよびＡｌのうちの１種または２種の合計：０．１〜２０原子％を、ＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように含有し、残部がＣｕおよび不可避不純物からなる組成を有する配線膜形成用スパッタリングターゲット、
（６）Ｃｒ：４．８〜２０原子％、ＭｎおよびＡｌのうちの１種または２種の合計：０．１〜２０原子％を、ＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように含有し、さらに、Ｍｇ：０．１〜５原子％を含有し、残部がＣｕおよび不可避不純物からなる組成を有する配線膜形成用スパッタリングターゲット、に特徴を有するものである。
In order to form the wiring film described in (1) to (2) and the wiring base film described in (3) to (4), Cr is 4.8 to 20 atomic%, one of Mn and Al. Or it contains 0.1-20 atomic% in total of 2 types so that the sum total of Cr, Mn, and Al exists in the range of more than 5-25 atomic%, and also Mg: 0.1-0.1 as needed It is obtained by sputtering using a copper alloy target that contains 5 atomic% and the balance is composed of Cu and inevitable impurities. This invention includes this copper alloy target, and this invention
(5) Cr: 4.8 to 20 atomic%, total of one or two of Mn and Al: 0.1 to 20 atomic%, and the total of Cr, Mn and Al exceeds 5 to 25 atomic% A sputtering target for forming a wiring film having a composition containing Cu and unavoidable impurities,
(6) Cr: 4.8 to 20 atomic%, total of one or two of Mn and Al: 0.1 to 20 atomic%, and the total of Cr, Mn and Al is more than 5 to 25 atomic% The sputtering target for forming a wiring film has a composition containing Mg: 0.1 to 5 atomic%, and the balance of Cu and inevitable impurities. .
この発明の前記（５）および（６）記載の銅合金ターゲットは、まず純度：９９．９９％以上の無酸素銅を、不活性ガス雰囲気中、高純度グラファイトるつぼ内で高周波溶解し、得られた溶湯にＣｒを４．８〜２０原子％を添加し、さらにＭｎおよびＡｌのうちの１種または２種を合計で０．１〜２０原子％を添加してＣｒとＭｎとＡｌの合計が５超〜２５原子％の範囲内にあるように溶解し、得られた溶湯を不活性ガス雰囲気中で鋳造し凝固させたのち、さらに必要に応じて熱間圧延し、最後に歪取り焼鈍を施すことにより作製することができる。
また、このターゲットは、まず、ＣｕとＣｒの母合金粉末、ＣｕとＭｎの母合金粉末、ＣｕとＡｌの母合金粉末をガスアトマイズにより作製し、これら母合金粉末をホットプレスすることにより作製してもよい。
このようにして得られたターゲットをバッキングプレートに接合し、通常の条件でスパッタリングすることによりこの発明の銅合金配線膜および配線下地膜を形成する。
The copper alloy target according to the above (5) and (6) of the present invention is obtained by first high-frequency melting oxygen-free copper having a purity of 99.99% or more in a high-purity graphite crucible in an inert gas atmosphere. In addition, 4.8 to 20 atom% of Cr is added to the molten metal, and one or two of Mn and Al are added in a total amount of 0.1 to 20 atom% to obtain a total of Cr, Mn and Al. After being melted so that it is in the range of more than 5 to 25 atomic%, the resulting molten metal is cast and solidified in an inert gas atmosphere, and then hot-rolled as necessary, and finally subjected to strain relief annealing. It can produce by applying.
In addition, this target is prepared by first producing a mother alloy powder of Cu and Cr, a mother alloy powder of Cu and Mn, and a mother alloy powder of Cu and Al by gas atomization, and hot-pressing these mother alloy powders. Also good.
The copper target wiring film and wiring base film of the present invention are formed by joining the target thus obtained to a backing plate and sputtering under normal conditions.
この発明の配線膜および配線下地膜の成分組成の範囲を前述のごとく限定した理由を説明する。
Ｃｒ：
Ｃｒは、ＴＦＴにおける配線膜を構成する銅合金膜のヒロックおよびボイドなどの熱欠陥の発生を抑制して耐マイグレーション性を向上させ、さらに熱処理に際してＣｕとの複酸化物を銅合金膜の表面および裏面に形成してガラス基板の主成分であるＳｉなどが銅合金配線膜に拡散浸透するのを阻止し、さらに銅合金配線膜の比抵抗の増加を防止するとともにガラス基板に対する銅合金配線膜の密着性を向上させる作用を有するが、その含有量が３．９原子％未満では所望の効果が得られないので好ましくなく、一方、２０原子％を越えて含有しても特性の向上が認められず、さらに比抵抗値は増加するので好ましくない。したがって、銅合金膜に含まれるＣｒを３．９〜２０原子％に定めた。
Ｍｎ、Ａｌ：
これら成分は、Ｃｒと共存して含有させることにより、拡散防止能、密着性、化学的安定性を向上させる。その理由は、以下のごとく考えられる。
熱処理に際してＣｒはＳｉとの複酸化物を形成しないが、Ｍｎ、ＡｌはＣｕのみならずＳｉとの複酸化物を銅合金配線膜／ガラス基板の界面に形成して、ガラス基板の主成分であるＳｉなどが銅合金配線膜に拡散浸透することをより一層阻止し、ガラス基板に対する銅合金配線膜の密着性を一層向上させる作用を有する。さらに、化学的安定性の高いＳｉとの複酸化物を形成することから、銅合金配線膜の化学的安定性を一層向上させる。
しかし、Ｍｎ、Ａｌのうちの１種または２種を合計で０．１原子％未満含有しても所望の機能（拡散防止能、密着性、化学的安定性）を向上させる効果が得られないので好ましくなく、一方、２０原子％を越えて含有しても特性の向上が認められず、さらに、銅合金配線膜の比抵抗値が上昇するので好ましくない。したがって、この発明の銅合金配線膜に含まれるＭｎ、Ａｌのうちの１種または２種を合計を０．１〜２０原子％に定めた。
ＣｒとＭｎとＡｌの合計：
銅合金配線膜または配線下地膜に含まれるＣｒとＭｎとＡｌの合計を５超〜２５原子％の範囲内に限定したのは、ＣｒとＭｎとＡｌの合計が５原子％以下では上述した所望の機能を向上させる効果が得られないので好ましくなく、一方、ＣｒとＭｎとＡｌの合計が２５原子％を超えるようになると、特性の向上が認められず、さらに比抵抗値が上昇するので好ましくないことによるものである。
The reason why the range of the component composition of the wiring film and wiring base film of the present invention is limited as described above will be described.
Cr:
Cr suppresses the occurrence of thermal defects such as hillocks and voids in the copper alloy film constituting the wiring film in the TFT, thereby improving the migration resistance. Further, a double oxide with Cu is added to the surface of the copper alloy film during the heat treatment. It is formed on the back surface to prevent diffusion of Si and the like, which are the main components of the glass substrate, into the copper alloy wiring film, and further to prevent an increase in the specific resistance of the copper alloy wiring film and Although it has the effect of improving the adhesion, it is not preferable if the content is less than 3.9 atomic% because the desired effect cannot be obtained. On the other hand, even if the content exceeds 20 atomic%, the improvement of the characteristics is recognized. Furthermore, since the specific resistance value further increases, it is not preferable. Therefore, Cr contained in the copper alloy film is set to 3.9 to 20 atomic%.
Mn, Al:
By containing these components together with Cr, the diffusion preventing ability, adhesion, and chemical stability are improved. The reason is considered as follows.
In heat treatment, Cr does not form a double oxide with Si, but Mn and Al form not only Cu but also a double oxide with Si at the interface of the copper alloy wiring film / glass substrate. It has a function of further preventing diffusion of some Si and the like into the copper alloy wiring film and further improving the adhesion of the copper alloy wiring film to the glass substrate. Furthermore, since a double oxide with Si having high chemical stability is formed, the chemical stability of the copper alloy wiring film is further improved.
However, the effect of improving a desired function (diffusion prevention ability, adhesion, chemical stability) cannot be obtained even if one or two of Mn and Al are contained in a total of less than 0.1 atomic%. On the other hand, if the content exceeds 20 atomic%, the improvement in characteristics is not observed, and the specific resistance value of the copper alloy wiring film is increased. Therefore, the total of one or two of Mn and Al contained in the copper alloy wiring film of the present invention is set to 0.1 to 20 atomic%.
Total of Cr, Mn and Al:
The total of Cr, Mn, and Al contained in the copper alloy wiring film or wiring base film is limited to the range of more than 5 to 25 atomic%. It is not preferable because the effect of improving the function cannot be obtained. On the other hand, if the total of Cr, Mn and Al exceeds 25 atomic%, the improvement in characteristics is not observed, and the specific resistance value is further increased. It is due to not.
Ｍｇ：
Ｍｇは結晶粒を微細化し、フラットパネルディスプレイにおけるＴＦＴの配線膜を構成する銅合金膜のヒロックおよびボイドなどの熱欠陥の発生を抑制して耐マイグレーション性を向上させ、さらに熱処理に際して銅合金膜の表面および裏面にＭｇを含有した酸化物層を形成してガラス基板の主成分であるＳｉなどが銅合金配線膜に拡散浸透するのを阻止し、銅合金配線膜の比抵抗の増加を防止するとともにガラス基板に対する銅合金配線膜の密着性を向上させる作用を有するので必要に応じて含有させるが、その含有量が０．１原子％未満では所望の効果が得られないので好ましくなく、一方、５原子％を越えて含有しても特性の向上が認められず、さらに比抵抗値は増加して配線膜としては十分な機能を示さなくなるので好ましくない。したがって、銅合金膜に含まれるＭｇを０．１〜５原子％に定めた。
Mg:
Mg refines the crystal grains and suppresses the occurrence of thermal defects such as hillocks and voids in the copper alloy film constituting the TFT wiring film in flat panel displays, thereby improving migration resistance. An oxide layer containing Mg is formed on the front and back surfaces to prevent Si, the main component of the glass substrate, from diffusing and penetrating into the copper alloy wiring film, thereby preventing an increase in specific resistance of the copper alloy wiring film. In addition, since it has an effect of improving the adhesion of the copper alloy wiring film to the glass substrate, it is contained as necessary, but if the content is less than 0.1 atomic%, the desired effect cannot be obtained, which is not preferable, Even if the content exceeds 5 atomic%, the improvement of characteristics is not recognized, and the specific resistance value is further increased, so that a sufficient function as a wiring film is not exhibited. Therefore, Mg contained in the copper alloy film is set to 0.1 to 5 atomic%.
この発明のＴＦＴ用配線膜およびＴＦＴ用配線下地膜は、熱処理して形成された酸化物層が還元されにくく、したがって、水素アニール後の密着性の低下が小さいことからＴＦＴの配線膜として優れた特性を有し、また、ヒロックおよびボイドの発生がなく、さらにガラス基板表面に対する密着性が一層向上することから高精細化し大型化したフラットパネルディスプレイにおけるＴＦＴ用配線膜を形成することができる。 The TFT wiring film and the TFT wiring base film of the present invention are excellent as a TFT wiring film because the oxide layer formed by heat treatment is difficult to reduce and, therefore, the decrease in adhesion after hydrogen annealing is small. The TFT wiring film can be formed in a flat panel display having high characteristics and a large size because it has characteristics, does not generate hillocks and voids, and further improves the adhesion to the glass substrate surface.
純度：９９．９９質量％の無酸素銅を用意し、この無酸素銅をＡｒガス雰囲気中、高純度グラファイトるつぼ内で高周波溶解し、得られた溶湯にＣｒ、Ｍｎ、Ａｌを添加し、さらに必要に応じてＭｇを添加し、溶解して表１〜２に示される成分組成を有する溶湯となるように成分調整し、得られた溶湯を冷却されたカーボン鋳型に鋳造してインゴットを作製し、さらにこのインゴットを熱間圧延したのち最終的に歪取り焼鈍し、得られた圧延体の表面を旋盤加工して外径：２００ｍｍ×厚さ：１０ｍｍの寸法に加工し、また脆性があり熱間圧延できなかったインゴットは熱間圧延することなく直接インゴットから切り出して外径：２００ｍｍ×厚さ：１０ｍｍの寸法に加工し、表１〜２に示される成分組成を有する円板状の本発明銅合金スパッタリングターゲット（以下、本発明ターゲットという）１〜１７および比較銅合金スパッタリングターゲット（以下、比較ターゲットという）１〜４および従来スパッタリングターゲット（以下、従来ターゲットという）１〜２を作製した。
さらに、無酸素銅製バッキングプレートを用意し、この無酸素銅製バッキングプレートに前記本発明ターゲット１〜１７、比較ターゲット１〜４および従来ターゲット１〜２を重ね合わせ、温度：２００℃でインジウムはんだ付けすることにより本発明ターゲット１〜１７、比較ターゲット１〜４および従来ターゲット１〜２を無酸素銅製バッキングプレートに接合してバッキングプレート付きターゲットを作製した。
Purity: 99.99 mass% oxygen-free copper is prepared, this oxygen-free copper is melted at high frequency in a high-purity graphite crucible in an Ar gas atmosphere, Cr, Mn, Al is added to the resulting molten metal, and If necessary, add Mg, adjust the components so that they melt and become molten metal having the composition shown in Tables 1-2, and cast the molten metal into a cooled carbon mold to produce an ingot. Further, this ingot is hot-rolled and finally subjected to strain relief annealing, and the surface of the obtained rolled body is turned into a diameter of 200 mm × thickness: 10 mm, and it is brittle and has heat. The ingot that could not be hot-rolled was cut out directly from the ingot without being hot-rolled and processed to a size of outer diameter: 200 mm × thickness: 10 mm, and the disk-shaped present invention having the component composition shown in Tables 1 and 2 Copper alloy spat Talling targets (hereinafter referred to as the present invention targets) 1 to 17 and comparative copper alloy sputtering targets (hereinafter referred to as comparative targets) 1 to 4 and conventional sputtering targets (hereinafter referred to as conventional targets) 1 to 2 were produced.
Further, an oxygen-free copper backing plate is prepared, and the present inventive targets 1-17 , comparative targets 1-4, and conventional targets 1-2 are superposed on the oxygen-free copper backing plate, and indium soldered at a temperature of 200 ° C. By this, this invention target 1-17 , the comparison targets 1-4, and the conventional targets 1-2 were joined to the oxygen-free copper backing plate, and the target with a backing plate was produced.
本発明ターゲット１〜１７、比較ターゲット１〜４および従来ターゲット１〜２を無酸素銅製バッキングプレートにはんだ付けして得られたバッキングプレート付きターゲットを、ターゲットとアモルファスＳｉをコーティングしたガラス基板（直径：２００ｍｍ、厚さ：０．７ｍｍの寸法を有するコーニング社製１７３７のガラス基板）との距離：７０mmとなるようにセットし、
電源：直流方式、
スパッタパワー：６００Ｗ、
到達真空度：４×１０−５Ｐａ、
雰囲気ガス組成：Ａｒ：９０容量％、酸素：１０容量％の混合ガス、
ガス圧：０．２Ｐａ、
ガラス基板加熱温度：１５０℃、
の条件でアモルファスＳｉをコーティングしたガラス基板の表面に、半径：１００ｍｍ、厚さ：３００ｎｍを有し、表３〜５に示される成分組成を有するいずれも円形の本発明配線用銅合金膜１〜３０および比較配線用銅合金膜１〜４および従来配線用銅合金膜１〜２を形成した。得られた本発明配線用銅合金膜１〜１７、比較配線用銅合金膜１〜４および従来配線用銅合金膜１〜２をそれぞれ加熱炉に装入し、１気圧のＡｒ雰囲気中、昇温速度：５℃／ｍｉｎ、最高温度：３５０℃、３０分間保持の熱処理を施した。これら熱処理した円形の本発明配線用銅合金膜１〜１７、比較配線用銅合金膜１〜４および従来配線用銅合金膜１〜２のそれぞれの中心部の比抵抗を四探針法により測定し、それらの結果を表３〜５に示した。
A glass substrate (diameter: coated with a target and amorphous Si), a target with a backing plate obtained by soldering the present invention targets 1-17 , comparative targets 1-4, and conventional targets 1-2 to an oxygen-free copper backing plate. 200 mm, thickness: set to a distance of 70 mm from Corning Corporation 1737 glass substrate having dimensions of 0.7 mm,
Power supply: DC method,
Sputter power: 600W
Ultimate vacuum: 4 × 10 −5 Pa,
Atmospheric gas composition: Ar: 90% by volume, oxygen: 10% by volume of mixed gas,
Gas pressure: 0.2 Pa,
Glass substrate heating temperature: 150 ° C.
On the surface of the glass substrate coated with amorphous Si under the above conditions, each of the copper alloy films for wiring 1 of the present invention having a radius: 100 mm, a thickness: 300 nm, and having the component composition shown in Tables 3 to 5 is circular. 30 and copper alloy films 1 to 4 for comparative wiring and copper alloy films 1 to 2 for conventional wiring were formed. The obtained copper alloy films 1 to 17 for the present invention, copper alloy films 1 to 4 for comparative wiring, and copper alloy films 1 to 2 for conventional wiring were placed in a heating furnace, respectively, and heated in an Ar atmosphere at 1 atm. A heat treatment was performed at a temperature rate of 5 ° C./min, a maximum temperature of 350 ° C., and held for 30 minutes. The specific resistance at the center of each of the heat treated circular copper alloy films 1 to 17 for the present invention, the copper alloy films 1 to 4 for comparative wiring, and the copper alloy films 1 to 2 for conventional wiring is measured by the four-probe method. The results are shown in Tables 3-5.
さらに、これら熱処理を施した本発明配線用銅合金膜１〜１７、比較配線用銅合金膜１〜４および従来配線用銅合金膜１〜２の表面を５０００倍のＳＥＭで５個所の膜表面を観察し、ヒロックおよびボイドの発生の有無を観察し、その結果を表３〜５に示した。 Further, the surfaces of the copper alloy films 1 to 17 for the present invention, the copper alloy films 1 to 4 for comparative wiring, and the copper alloy films 1 to 2 for conventional wiring subjected to these heat treatments are surfaced at five locations by SEM of 5000 times. Were observed for the presence or absence of hillocks and voids, and the results are shown in Tables 3-5.
さらに、前記熱処理を施した本発明配線用銅合金膜１〜１７、比較配線用銅合金膜１〜４および従来配線用銅合金膜１〜２を、
雰囲気：Ｈ２／Ｎ２＝５０／５０（Ｖｏｌ％）の混合ガス（１気圧）、
温度：３００℃、
保持時間：３０分、
の条件で水素アニールを行い、水素アニール前の本発明配線用銅合金膜１〜１７、比較配線用銅合金膜１〜４および従来配線用銅合金膜１〜２並びに水素アニール後の本発明配線用銅合金膜１〜１７、比較配線用銅合金膜１〜４および従来配線用銅合金膜１〜２に、それぞれＪＩＳ-Ｋ５４００に準じ、１ｍｍ間隔で碁盤目状に切れ目を入れた後、３Ｍ社製スコッチテープで引き剥がし、アモルファスＳｉをコーティングしたガラス基板中央部の１０ｍｍ角内でガラス基板に付着していた配線用銅合金膜の面積％を測定する碁盤目付着試験を実施し、その結果を表３〜５に示し、アモルファスＳｉをコーティングしたガラス基板に対する本発明配線用銅合金膜１〜１７、比較配線用銅合金膜１〜４および従来配線用銅合金膜１〜２の密着性を評価した。
Furthermore, the copper alloy films 1-17 for wiring of the present invention subjected to the heat treatment, the copper alloy films 1-4 for comparative wiring, and the copper alloy films 1-2 for conventional wiring,
Atmosphere: H 2 / N 2 = 50/50 (Vol%) mixed gas (1 atm),
Temperature: 300 ° C
Retention time: 30 minutes,
The copper alloy films 1 to 17 for wiring of the present invention before hydrogen annealing, the copper alloy films 1 to 4 for comparative wiring, the copper alloy films 1 to 2 for conventional wiring, and the wiring of the present invention after hydrogen annealing After the copper alloy films 1 to 17 for comparative wiring, the copper alloy films 1 to 4 for comparative wiring, and the copper alloy films 1 to 2 for conventional wiring are cut in a grid pattern at intervals of 1 mm according to JIS-K5400, 3M A cross-cut adhesion test was conducted to measure the area percentage of the copper alloy film for wiring adhered to the glass substrate within 10 mm square in the center of the glass substrate coated with amorphous Si by peeling off with a Scotch tape manufactured by the company. Tables 3 to 5 show the adhesion of the copper alloy films 1 to 17 of the present invention to the glass substrate coated with amorphous Si, the copper alloy films 1 to 4 for comparative wiring, and the copper alloy films 1 to 2 for conventional wiring. evaluated.
表１〜５に示される結果から、
（ｉ）本発明配線用銅合金膜１〜１７は、Ｃｒを単独で含む従来ターゲット１およびＡｌを単独で含む従来ターゲット２を用いてスパッタリングすることにより成膜した従来配線用銅合金膜１および２と比較して、中心部の比抵抗に大差はないが、従来配線用銅合金膜１および２はアモルファスＳｉをコーティングしたガラス基板に対する密着性が水素アニール前後で大きく低下するのに対し、本発明配線用銅合金膜１〜１７は水素アニール前後で密着性が変わらずに優れていること、
（ii）さらに、Ｃｒ、ＭｎおよびＡｌの合計がこの発明の条件から外れて少なく含む比較ターゲット１〜２を用いてスパッタリングすることにより成膜した比較配線用銅合金膜１〜２は水素アニール前後で密着性が低下し、さらにヒロックおよびボイドが発生するのでマイグレーションが発生しやすく、さらにＣｒ、ＭｎおよびＡｌの合計がこの発明の条件から外れて多く含む比較ターゲット３〜４を用いてスパッタリングすることにより成膜した比較配線用銅合金膜３〜４は水素アニール前後で密着性が劣ることはないが、比抵抗が大きくなり過ぎるなど、配線用銅合金膜として少なくとも一つの好ましくない特性が現れること、などが分かる。
From the results shown in Tables 1-5,
(I) The copper alloy films 1 to 17 for wiring of the present invention are formed by sputtering using the conventional target 1 containing Cr alone and the conventional target 2 containing Al alone. Compared to 2, the copper core films 1 and 2 for conventional wiring have a large difference in the adhesion to the glass substrate coated with amorphous Si before and after the hydrogen annealing. Inventive copper alloy films 1 to 17 are excellent in adhesiveness before and after hydrogen annealing,
(Ii) Further, the copper alloy films 1 and 2 for comparative wiring formed by sputtering using the comparative targets 1 and 2 including the total amount of Cr, Mn, and Al deviating from the conditions of the present invention are before and after the hydrogen annealing. Adhesion is reduced, and hillocks and voids are generated, so that migration is likely to occur, and sputtering is performed using comparative targets 3 to 4 that contain a large amount of Cr, Mn, and Al outside the conditions of the present invention. The copper alloy films 3 to 4 for the comparative wiring formed by the above method do not have poor adhesion before and after the hydrogen annealing, but at least one undesired characteristic appears as a copper alloy film for the wiring such that the specific resistance becomes too high. I understand.
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |