JP2000228374A - Method for forming metallic thin film, and manufacture of metallic fine particle scattering solution - Google Patents
Method for forming metallic thin film, and manufacture of metallic fine particle scattering solutionInfo
- Publication number
- JP2000228374A JP2000228374A JP11239355A JP23935599A JP2000228374A JP 2000228374 A JP2000228374 A JP 2000228374A JP 11239355 A JP11239355 A JP 11239355A JP 23935599 A JP23935599 A JP 23935599A JP 2000228374 A JP2000228374 A JP 2000228374A
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- Prior art keywords
- metal
- thin film
- substrate
- organic solvent
- forming
- Prior art date
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- Other Surface Treatments For Metallic Materials (AREA)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＬＳＩ基板などの
半導体基板上へのＣｕ、Ａｇ等の配線に利用する金属の
埋め込みを容易にするための金属薄膜形成方法、および
該金属薄膜の形成後、配線金属で半導体基板上の配線
溝、ビアホール、コンタクトホール等の凹部を埋め込む
金属配線形成方法、ならびに該金属薄膜を形成するため
に用いる金属微粒子分散液の作製方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a metal thin film for facilitating embedding of a metal used for wiring such as Cu and Ag on a semiconductor substrate such as an LSI substrate, and a method for forming the metal thin film after forming the metal thin film. The present invention also relates to a method for forming a metal wiring for embedding recesses such as wiring grooves, via holes, and contact holes on a semiconductor substrate with a wiring metal, and a method for preparing a metal fine particle dispersion used for forming the metal thin film.
【０００２】[0002]
【従来の技術】近年の半導体産業におけるＬＳＩの高集
積化および高速化により、半導体基板の配線の微細化と
多層化が進んでいる。そのために配線ピッチが狭まり、
配線間容量や配線遅延によるＬＳＩの性能低下が起こ
る。これを防ぐために、電気抵抗率の低い配線材料と誘
電率の低い層間絶縁膜を用いる必要に迫られ、配線材料
として、従来のＡｌ合金等の代わりに電気抵抗率の低
い、かつ、エレクトロマイグレーション（ＥＭ）耐性の
高いＣｕ、Ａｇを使用する動きが活発になってきてい
る。Ｃｕ成膜技術としてはスパッタ法、ＣＶＤ法、メッ
キ法等があり、配線溝、ビアホール、コンタクトホール
等にＣｕを堆積させる方法が開発されている。これらの
方法のうちメッキ法によりＣｕを成膜する際には、前処
理として、スパッタ法、ＣＶＤ法によりＣｕシード層と
してＣｕ薄膜をつける必要がある。また、Ａｇ成膜技術
としては、スパッタ法等で配線溝、ビアホール、コンタ
クトホール等にＡｇ薄膜を堆積させる方法が研究されて
いる。2. Description of the Related Art With the recent increase in the degree of integration and speed of LSIs in the semiconductor industry, finer wiring and multi-layering of semiconductor substrates have been promoted. As a result, the wiring pitch narrows,
The performance of the LSI is degraded due to the capacitance between wirings and wiring delay. In order to prevent this, it is necessary to use a wiring material having a low electric resistivity and an interlayer insulating film having a low dielectric constant. As a wiring material, instead of a conventional Al alloy or the like, a low electric resistivity and electromigration ( EM) The use of highly resistant Cu and Ag is becoming active. As a Cu film forming technique, there are a sputtering method, a CVD method, a plating method and the like, and a method of depositing Cu in a wiring groove, a via hole, a contact hole or the like has been developed. Among these methods, when forming a Cu film by a plating method, it is necessary to provide a Cu thin film as a Cu seed layer by a sputtering method or a CVD method as a pretreatment. As the Ag film forming technique, a method of depositing an Ag thin film in a wiring groove, a via hole, a contact hole or the like by a sputtering method or the like has been studied.
【０００３】[0003]
【発明が解決しようとする課題】メッキ法でＣｕを成膜
して配線形成する場合、上記したように、前処理とし
て、スパッタ法、ＣＶＤ法によりＣｕシード層であるＣ
ｕ薄膜を引かなければメッキを行うことができないのだ
が、従来のＣｕ薄膜形成法では、次のような問題があっ
た。スパッタ法を用いて基板（例えば、バリア層を含ん
だＳｉ基板）上にＣｕ薄膜を形成すると、図１に示すよ
うに、基板１上の配線溝やビアホール、コンタクトホー
ル等の底部にＣｕ薄膜２が凸状あるいは平坦に形成され
るため、配線溝やホール等の底部のコーナーがメッキを
行うための最適な形状にならないという問題がある。さ
らに、アスペクト比の高い配線溝やホール等に所期の目
的に適ったＣｕ薄膜を形成することが困難であるという
問題もある。また、ＣＶＤ法を用いて基板上にＣｕ薄膜
を形成する場合には、得られる膜質を制御することが困
難であり、さらに、プロセスコストも非常に高価になる
という問題がある。また、Ａｇ成膜技術は、上記したよ
うにスパッタ法等で研究されているが、プロセス中の熱
処理により生じるＡｇ凝集を防ぐことが困難であるとい
う問題がある。In the case of forming a wiring by forming a Cu film by a plating method, as described above, as a pretreatment, a Cu seed layer, which is a Cu seed layer, is formed by a sputtering method or a CVD method.
Although plating cannot be performed unless the u thin film is pulled, the conventional Cu thin film forming method has the following problems. When a Cu thin film is formed on a substrate (for example, a Si substrate including a barrier layer) by a sputtering method, as shown in FIG. 1, a Cu thin film 2 is formed on the bottom of a wiring groove, a via hole, a contact hole, etc. on the substrate 1. Is formed to be convex or flat, so that there is a problem that corners at the bottom of wiring grooves, holes and the like do not have an optimal shape for plating. Further, there is a problem that it is difficult to form a Cu thin film suitable for an intended purpose in a wiring groove or a hole having a high aspect ratio. In addition, when a Cu thin film is formed on a substrate by using the CVD method, it is difficult to control the quality of the obtained film, and further, there is a problem that the process cost becomes extremely high. In addition, although the Ag film forming technique has been studied by the sputtering method or the like as described above, there is a problem that it is difficult to prevent Ag aggregation caused by heat treatment during the process.
【０００４】本発明は、この様な従来のＣｕ、Ａｇ膜の
配線形成技術の問題点を解決するためになされたもので
ある。Ｃｕ薄膜の場合は、膜質の制御が容易であるこ
と、プロセスコストが安価であることに加え、配線溝、
ビアホールやコンタクトホール等の凹部を有する半導体
基板に対し、凹部にＣｕ薄膜を凹状に形成すること（図
２）で、その後のメッキ法によるＣｕ埋め込みを容易に
し、さらには、スパッタ法、ＣＶＤ法によるＣｕ埋め込
みをも容易にする方法を提供することを課題とし、ま
た、Ａｇ薄膜の場合は、Ｃｕ薄膜の場合と同様に膜質の
制御が容易であること、プロセスコストが安価であるこ
とと共に、プロセス中に生じるＡｇの凝集を防ぐことの
できる方法を提供することを課題としている。The present invention has been made to solve such a problem of the conventional wiring forming technology of Cu and Ag films. In the case of a Cu thin film, in addition to easy control of film quality and low process cost, wiring grooves,
By forming a Cu thin film in a concave shape on a semiconductor substrate having a concave portion such as a via hole or a contact hole (FIG. 2), Cu embedding by a subsequent plating method is facilitated, and further, by a sputtering method or a CVD method. It is an object of the present invention to provide a method for facilitating the embedding of Cu. In the case of an Ag thin film, control of film quality is easy as in the case of a Cu thin film, the process cost is low, and the process cost is low. It is an object of the present invention to provide a method capable of preventing aggregation of Ag occurring therein.
【０００５】[0005]
【課題を解決するための手段】本発明の金属薄膜形成方
法は、配線溝、ビアホール、コンタクトホール等の凹部
を有する半導体基板上の凹部に凹状に金属薄膜を形成す
るものであり、それによってスパッタ法、メッキ法、Ｃ
ＶＤ法等により配線材料で該凹部を埋め込むことが容易
になる。According to the present invention, there is provided a method of forming a metal thin film in a concave shape on a semiconductor substrate having a concave portion such as a wiring groove, a via hole or a contact hole. Method, plating method, C
It becomes easy to fill the recess with a wiring material by a VD method or the like.
【０００６】本発明の金属薄膜形成法は、配線溝、ビア
ホール、コンタクトホール等の凹部に配線に利用する金
属を埋め込む前の半導体基板上に、金属原子集合体を有
機溶媒に分散させた金属微粒子分散液を塗布し、塗布膜
の形成された基板を焼成して該基板上の有機物質を蒸
発、燃焼させ、所望により、焼成により生じた酸化物を
還元することによって、該基板上に金属薄膜を形成する
ことからなる。According to the method of forming a metal thin film of the present invention, metal fine particles obtained by dispersing an aggregate of metal atoms in an organic solvent on a semiconductor substrate before embedding metal used for wiring in recesses such as wiring grooves, via holes, and contact holes. The dispersion liquid is applied, and the substrate on which the coating film is formed is baked to evaporate and burn the organic substance on the substrate, and if necessary, the oxide generated by the calcination is reduced, whereby the metal thin film is formed on the substrate. To form
【０００７】前記焼成を、真空雰囲気中、大気雰囲気
中、または真空雰囲気と大気雰囲気との二段階で行うこ
とが好ましく、通常、１００〜４５０℃で、１〜３０分
間行われる。焼成温度が１００℃未満だと有機物質が十
分に蒸発、燃焼されず、また、４５０℃を超えると半導
体素子に熱的ダメージを与えるという問題がある。前記
還元は、真空雰囲気中またはほぼ４％以下の水素を含ん
だ不活性ガス雰囲気中で行うことが好ましく、通常、２
００〜４５０℃で１〜６０分間行われる。水素濃度に関
しては、水素の爆発下限がほぼ４％であることから、安
全のために水素濃度を４％程度以下に希釈したガスを用
いることが好ましい。また、還元温度が２００℃未満だ
と還元が十分に行われないため、薄膜中に部分的に酸化
銅が残留してしまい、４５０℃を超えると半導体素子に
熱的ダメージを与えるという問題がある。このような焼
成・還元のプロセスを行うことで、所期の金属薄膜が形
成できる。The sintering is preferably performed in a vacuum atmosphere, an air atmosphere, or in two stages of a vacuum atmosphere and an air atmosphere, and is usually performed at 100 to 450 ° C. for 1 to 30 minutes. If the firing temperature is lower than 100 ° C., the organic substance is not sufficiently evaporated and burned. If the firing temperature is higher than 450 ° C., the semiconductor element is thermally damaged. The reduction is preferably performed in a vacuum atmosphere or an inert gas atmosphere containing about 4% or less of hydrogen.
It is performed at 00 to 450 ° C. for 1 to 60 minutes. Regarding the hydrogen concentration, since the lower limit of the explosion of hydrogen is almost 4%, it is preferable to use a gas diluted to a hydrogen concentration of about 4% or less for safety. If the reduction temperature is lower than 200 ° C., the reduction is not performed sufficiently, so that copper oxide partially remains in the thin film, and if it exceeds 450 ° C., the semiconductor element is thermally damaged. . By performing such a firing / reducing process, an intended metal thin film can be formed.
【０００８】本発明の金属配線形成法は、上記のように
して凹部を有する基板上に予め金属薄膜を形成させた
後、該金属微粒子分散液の塗布工程および焼成工程を繰
り返して該凹部を複数層の金属薄膜で埋め込むか、また
はスパッタ法、メッキ法、ＣＶＤ法等により、配線に利
用する金属、例えばＣｕ、Ａｇで該基板上の凹部を埋め
込むことからなる。これにより、該凹部を完全に埋め込
むことができる。In the metal wiring forming method of the present invention, a metal thin film is formed in advance on a substrate having a concave portion as described above, and then the coating and baking steps of the metal fine particle dispersion are repeated to form the plurality of concave portions. The method includes embedding a concave portion on the substrate with a metal used for wiring, for example, Cu or Ag, by embedding with a metal thin film of the layer, or by sputtering, plating, CVD, or the like. Thereby, the concave portion can be completely buried.
【０００９】本発明で用いる、金属原子集合体が有機溶
媒に分散してなる金属微粒子分散液としては、以下記載
するような方法で作製する金属微粒子分散液の他に、Ｃ
ｕ微粒子が有機溶媒に分散した市販のＣｕ微粒子分散液
（真空冶金株式会社製、パーフェクトカッパー（商品
名））等がある。この市販のＣｕ微粒子分散液は、Ｃｕ
がコロイド粒子状態で存在しているものであり、本発明
でいう金属原子集合体分散液の範疇に含まれるものとす
る。The metal fine particle dispersion obtained by dispersing a metal atom aggregate in an organic solvent used in the present invention includes a metal fine particle dispersion prepared by the method described below,
There are commercially available Cu fine particle dispersions in which u fine particles are dispersed in an organic solvent (Perfect Copper (trade name) manufactured by Vacuum Metallurgy Co., Ltd.) and the like. This commercially available Cu fine particle dispersion is Cu Cu
Is present in the form of colloidal particles, and is included in the category of the metal atom aggregate dispersion according to the present invention.
【００１０】本発明の金属微粒子分散液の作製法は、次
の通りである。窒素等の不活性雰囲気下、高沸点の有機
溶媒と非イオン界面活性剤のような界面活性剤との混合
液中に有機金属化合物を滴下し、これを大気中で加熱
（例えば、６０℃〜１５０℃）、撹拌することにより、
該有機金属化合物中の金属原子を析出せしめる。析出し
た金属原子は混合液中のミセルに取り込まれ、その中で
金属原子は金属クラスター乃至微粒子の範囲のサイズか
らなる金属原子集合体に成長し、分散液中で金属クラス
ター乃至微粒子からなる金属原子集合体の状態で存在す
る。このような金属クラスターは原子数個からなるもの
であり、金属微粒子は原子数千個からなるものである。
これらの金属原子集合体は非イオン界面活性剤の存在に
より安定化しているので、金属原子集合体が該有機溶媒
中に安定に分散された状態の分散液が作製される。The method for preparing the metal fine particle dispersion of the present invention is as follows. Under an inert atmosphere such as nitrogen, an organometallic compound is dropped into a mixture of a high-boiling organic solvent and a surfactant such as a nonionic surfactant, and the mixture is heated in the air (for example, 60 ° C. 150 ° C.) by stirring.
Metal atoms in the organometallic compound are precipitated. The precipitated metal atoms are taken into micelles in the mixed solution, in which the metal atoms grow into metal atom aggregates having a size in the range of metal clusters or fine particles. It exists in an aggregate state. Such a metal cluster is composed of several atoms, and the metal fine particles are composed of thousands of atoms.
Since these metal atom aggregates are stabilized by the presence of the nonionic surfactant, a dispersion in which the metal atom aggregates are stably dispersed in the organic solvent is produced.
【００１１】使用される有機溶媒は、キシレン、トルエ
ン、ドデシルベンゼン、ミネラルスピリット、トリデカ
ン、およびα−テルピネオールから選ばれる高沸点有機
溶媒が好ましい。また、使用される界面活性剤は、ポリ
オキシエチレンラウリルエーテルのようなポリオキシエ
チレンアルキルエーテル、ポリエチレングリコールモノ
アルキレート、およびポリオキシエチレンアルキルアミ
ンから選ばれる非イオン界面活性剤が好ましい。使用さ
れる有機金属化合物は、ヘキサフルオロアセチルアセト
ン銅トリメチルビニルシラン[(ｈｆａｃ)Ｃｕ(ｔｍｖ
ｓ)]、ヘキサフルオロアセチルアセトン銅ジメチル−
１，５シクロオクタジエン[(ｈｆａｃ)Ｃｕ(ＤＭＣＯ
Ｄ)]、ヘキサフルオロアセチルアセトン銅トリエトキシ
ビニルシラン[(ｈｆａｃ)Ｃｕ(ｔｅｏｖｓ)]、ビスジピ
バロイルメタン銅[(ｄｐｍ)2Ｃｕ]、ビスヘキサフルオ
ロアセチルアセトン銅[(ｈｆａｃ)2Ｃｕ]、ヘキサフル
オロアセチルアセトン銀トリメチルホスフィン[(ｈｆａ
ｃ)Ａｇ(ｔｍｐ)]、およびナフテン酸銅から選ばれる化
合物が好ましい。かくして得られた金属原子集合体含有
分散液は、有機金属化合物を５〜３０ｗｔ％含むものが
好ましく、また、界面活性剤を５〜４５ｗｔ％含むもの
が好ましい。有機金属化合物の濃度が５ｗｔ％未満だと
有効な厚さの金属薄膜を形成するには実用的ではなく、
また、該濃度は３０ｗｔ％を超えると安定な分散液を作
製することが困難であり、仮に作製できても高粘度とな
り、スピンコートにより埋め込みを行うことが困難であ
る。界面活性剤の濃度が５ｗｔ％未満だと安定な分散液
を作製することが困難であり、また、該濃度が４５ｗｔ
％を超えると分散液の粘度が高くなり、スピンコートに
より埋め込みを行うことが困難である。The organic solvent used is preferably a high boiling organic solvent selected from xylene, toluene, dodecylbenzene, mineral spirit, tridecane, and α-terpineol. The surfactant used is preferably a nonionic surfactant selected from polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyethylene glycol monoalkylate, and polyoxyethylene alkylamine. The organometallic compound used is hexafluoroacetylacetone copper trimethylvinylsilane [(hfac) Cu (tmv
s)], hexafluoroacetylacetone copper dimethyl-
1,5 cyclooctadiene [(hfac) Cu (DMCO
D)], hexafluoroacetylacetone copper triethoxyvinylsilane [(hfac) Cu (teovs)], bisdipivaloylmethane copper [(dpm) 2 Cu], bishexafluoroacetylacetone copper [(hfac) 2 Cu], hexa Fluoroacetylacetone silver trimethylphosphine [(hfa
c) Ag (tmp)] and a compound selected from copper naphthenate. The thus-obtained dispersion containing metal atom aggregates preferably contains 5 to 30 wt% of an organic metal compound, and preferably contains 5 to 45 wt% of a surfactant. If the concentration of the organometallic compound is less than 5 wt%, it is not practical to form a metal thin film having an effective thickness,
On the other hand, if the concentration exceeds 30 wt%, it is difficult to produce a stable dispersion, and even if it can be produced, it has a high viscosity, and it is difficult to embed by spin coating. If the concentration of the surfactant is less than 5 wt%, it is difficult to produce a stable dispersion, and the concentration of the surfactant is 45 wt%.
%, The viscosity of the dispersion becomes high, and it is difficult to perform embedding by spin coating.
【００１２】本発明で用いることのできる市販のＣｕ微
粒子分散液は、例えば上記したような製品であり、半導
体基板上に金属薄膜を形成する際の乾燥・焼成工程で蒸
発するような有機溶媒、好ましくは１００℃以上で蒸発
する有機溶媒と、平均粒径０．１μｍ以下のＣｕ金属微
粒子、またはＣｕ金属含有微粒子とを混合してなり、該
微粒子の表面が該有機溶媒で覆われて個々に独立して分
散している粘度が１００ｃＰ以下の分散液である。ま
た、Ｃｕ微粒子の濃度は、５〜７０ｗｔ％、好ましくは
１５〜５０ｗｔ％である。Ｃｕ金属含有微粒子は、Ｃｕ
金属元素以外にＣｕへの溶解度が低く、かつ半導体基板
の基材（絶縁層構成材料）と反応しやすい金属又はこれ
らの金属を含む化合物を少なくとも一種含有していても
よく、これにより基材との接着性が向上されうる。この
金属元素の具体的な例としては、例えば、Ｍｇ、Ａｌ、
Ｂ、Ｔａ、Ｎｂ及びＶから選ばれれる金属又はこれら金
属を含む化合物が挙げられる。本発明により作製される
上記金属微粒子分散液も、このようなＣｕ以外の金属ま
たはこれら金属含有化合物を含んでいてもよい。The commercially available Cu fine particle dispersion which can be used in the present invention is, for example, the above-mentioned product, and an organic solvent which evaporates in a drying / firing step when forming a metal thin film on a semiconductor substrate. Preferably, an organic solvent that evaporates at 100 ° C. or higher is mixed with Cu metal fine particles having an average particle diameter of 0.1 μm or less, or Cu metal-containing fine particles, and the surfaces of the fine particles are individually covered with the organic solvent. It is a dispersion liquid having a viscosity of 100 cP or less which is independently dispersed. The concentration of the Cu fine particles is 5 to 70 wt%, preferably 15 to 50 wt%. Cu metal-containing fine particles are Cu
In addition to the metal element, it may contain at least one kind of metal having low solubility in Cu and easily reacting with the substrate (insulating layer constituent material) of the semiconductor substrate or a compound containing these metals. Can be improved in adhesiveness. Specific examples of the metal element include, for example, Mg, Al,
A metal selected from B, Ta, Nb, and V, or a compound containing these metals. The metal fine particle dispersion prepared according to the present invention may also contain such a metal other than Cu or a metal-containing compound.
【００１３】本発明によれば、金属微粒子、金属含有微
粒子は、該微粒子分散液の形態で、半導体基板上のアス
ペクト比の大きい配線溝、ビアホール、コンタクトホー
ル等の凹部に対しても何らの問題もなく入り込み、そし
て、所定の雰囲気中、所定の温度・時間で加熱されるこ
とにより、該分散液の分散媒等が蒸発され、燃焼され、
微粒子同士が融着して凹部内に凹状の金属薄膜を形成で
きる。この凹状の金属薄膜は、基板の凹部に対してコン
フォーマルな状態からアスペクト比を減少させる状態ま
で任意に制御できる。According to the present invention, metal fine particles and metal-containing fine particles, in the form of a fine particle dispersion, have no problem with respect to a concave portion such as a wiring groove, a via hole, or a contact hole having a large aspect ratio on a semiconductor substrate. Without entering, and by heating in a predetermined atmosphere at a predetermined temperature and time, the dispersion medium and the like of the dispersion are evaporated and burned,
The fine particles are fused together to form a concave metal thin film in the concave portion. This concave metal thin film can be arbitrarily controlled from a conformal state to a concave state of the substrate to a state in which the aspect ratio is reduced.
【００１４】本発明では、上記したように、半導体基板
の凹部に予め金属薄膜を凹状に形成することで、半導体
基板に対して、スパッタ法、メッキ法等による配線金属
材料の埋め込みを容易にすることができる。スパッタ法
の場合は、作製された金属薄膜が凹状であり、しかもア
スペクト比を減少させるように堆積させることが可能な
ので、スパッタ法でさらに配線金属を堆積させ続け、配
線溝、ビアホール、コンタクトホール等の凹部を完全に
埋め込むことができる。また、メッキ法の場合は、凹部
に対しコンフォーマルに形成された凹状薄膜から等方的
にメッキされていくため、ボイドが発生し難くなる。ま
た、本発明によれば、凹状の金属薄膜を形成した後、同
じ金属微粒子分散液を用い、同様に該分散液の塗布工程
および焼成工程を複数回繰り返して、半導体基板の凹部
を複数層の金属薄膜で完全に埋め込むこともできる。本
発明において金属薄膜を作製するために用いる金属微粒
子分散液の金属と配線金属材料の金属とは同じものであ
ることが好ましいが、異なっていてもよい。According to the present invention, as described above, a metal thin film is formed in a concave portion of a semiconductor substrate in advance, thereby facilitating embedding of a wiring metal material into the semiconductor substrate by a sputtering method, a plating method, or the like. be able to. In the case of the sputtering method, since the produced metal thin film is concave and can be deposited so as to reduce the aspect ratio, wiring metal is continuously deposited by the sputtering method, and wiring grooves, via holes, contact holes, etc. Can be completely embedded. Further, in the case of the plating method, since the concave portions are isotropically plated from the concave thin film formed conformally, voids are hardly generated. Further, according to the present invention, after forming the concave metal thin film, the same metal fine particle dispersion is used, and the application step and the firing step of the dispersion liquid are similarly repeated a plurality of times, so that the concave portions of the semiconductor substrate are formed in a plurality of layers. It can be completely embedded with a metal thin film. In the present invention, the metal of the fine metal particle dispersion used for preparing the metal thin film and the metal of the wiring metal material are preferably the same, but may be different.
【００１５】[0015]
【実施例】次に、実施例により本発明を詳細に説明する
が、本発明はこれらの例によってなんら限定されるもの
ではない。Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
【００１６】実施例１ 本実施例では、金属微粒子分散液として市販のＣｕ微粒
子分散液（真空冶金株式会社製、パーフェクトカッパー
（商品名））を用いて、Ｓｉ基板上に設けられた配線
溝、ビアホール、コンタクトホールを処理した。このＳ
ｉ基板には０．３〜５μｍの配線溝と０．１５〜２μｍ
のビアホール、コンタクトホールがあり、該配線溝およ
びホールを含む基板表面にはスパッタにより、ＴｉＮの
バリヤ層が厚さ７０ｎｍで形成されていた。Example 1 In this example, a commercially available Cu fine particle dispersion (Perfect Copper (trade name) manufactured by Vacuum Metallurgy Co., Ltd.) was used as a metal fine particle dispersion, and a wiring groove provided on a Si substrate was prepared. Via holes and contact holes were processed. This S
The i-substrate has a wiring groove of 0.3 to 5 μm and 0.15 to 2 μm.
A via layer and a contact hole were provided, and a barrier layer of TiN was formed with a thickness of 70 nm on the substrate surface including the wiring groove and the hole by sputtering.
【００１７】上記の基板をスピンコーターにセットして
１０００ｒｐｍで回転させ、その上方から上記のＣｕ微
粒子分散液を滴下し、２０００ｒｐｍでスピンコートし
た。基板表面に液膜のある状態の基板を１０Ｐａの真空
雰囲気中、３５０℃で１分間加熱して有機溶媒および残
留有機成分を蒸発、燃焼させた。次に、１×１０-6Ｐａ
の真空雰囲気中、４００℃で３０分間加熱して、焼成プ
ロセスでの燃焼により一部のＣｕがＣｕＯになってしま
ったものをＣｕに還元した。このようにしてＣｕ微粒子
同士が融着して、配線溝、ビアホール、コンタクトホー
ル等の凹部内に凹状のＣｕシード層としてのＣｕ薄膜を
形成できた。凹状のＣｕシード層を付けることにより、
その後の工程で、スパッタ法を用いて配線金属としての
Ｃｕを配線溝、ビアホール、コンタクトホール等に埋め
込みやすくなった。また、メッキ法の場合は、アスペク
ト比８までの配線溝、ビアホール、コンタクトホール等
にＣｕを容易に埋め込むことができた。The above substrate was set on a spin coater and rotated at 1000 rpm, and the above-mentioned Cu fine particle dispersion was dropped from above and spin-coated at 2,000 rpm. The substrate having a liquid film on the substrate surface was heated at 350 ° C. for 1 minute in a vacuum atmosphere of 10 Pa to evaporate and burn the organic solvent and residual organic components. Next, 1 × 10 −6 Pa
Was heated in a vacuum atmosphere at 400 ° C. for 30 minutes to reduce Cu to CuO in which part of Cu turned into CuO by burning in the firing process. In this way, the Cu fine particles were fused together, and a Cu thin film as a concave Cu seed layer could be formed in a concave portion such as a wiring groove, a via hole, or a contact hole. By attaching a concave Cu seed layer,
In a subsequent step, Cu as a wiring metal was easily buried in a wiring groove, a via hole, a contact hole, or the like by using a sputtering method. In the case of plating, Cu could be easily embedded in wiring grooves, via holes, contact holes and the like having an aspect ratio of up to 8.
【００１８】実施例２ 実施例１の基板をスピンコーターにセットして１０００
ｒｐｍで回転させ、その上方から実施例１のＣｕ微粒子
分散液を滴下し、２０００ｒｐｍでスピンコートした。
基板表面に液膜のある状態の基板を１０Ｐａの真空雰囲
気中、３５０℃で１分間加熱し、続いて大気中、３００
℃で３分間加熱して有機溶媒および残留有機成分を蒸
発、燃焼させた。次に、４％程の水素を含んだ不活性ガ
ス雰囲気中、２５０℃で３０分間加熱して、焼成プロセ
スでの燃焼により一部のＣｕがＣｕＯになってしまった
ものをＣｕに還元した。このようにしてＣｕ微粒子同士
が融着して、配線溝、ビアホール、コンタクトホール等
の凹部内に凹状のＣｕシード層としてのＣｕ薄膜を形成
できた。この凹状のＣｕシード層を付けることにより、
その後の工程で、スパッタ法を用いてＣｕを配線溝、ビ
アホール、コンタクトホール等の凹部内に埋め込みやす
くなった。また、メッキ法の場合は、アスペクト比８ま
での配線溝、ビアホール、コンタクトホール等の凹部内
にＣｕを容易に埋め込むことができた。Example 2 The substrate of Example 1 was set on a spin coater and 1000
After rotating at rpm, the Cu microparticle dispersion of Example 1 was dropped from above, and spin-coated at 2000 rpm.
The substrate having a liquid film on the substrate surface is heated at 350 ° C. for 1 minute in a vacuum atmosphere of 10 Pa,
C. for 3 minutes to evaporate and burn the organic solvent and residual organic components. Next, heating was performed at 250 ° C. for 30 minutes in an inert gas atmosphere containing about 4% of hydrogen to reduce Cu to CuO in which part of Cu turned into CuO by burning in the firing process. In this way, the Cu fine particles were fused together, and a Cu thin film as a concave Cu seed layer could be formed in a concave portion such as a wiring groove, a via hole, or a contact hole. By attaching this concave Cu seed layer,
In a subsequent step, Cu was easily buried in a recess such as a wiring groove, a via hole, or a contact hole by using a sputtering method. In the case of the plating method, Cu could be easily buried in recesses such as wiring grooves, via holes, and contact holes having an aspect ratio of up to 8.
【００１９】実施例３ 有機金属化合物としてヘキサフルオロアセチルアセトン
銅トリメチルビニルシラン、分散溶媒としてα−テルピ
ネオール、界面活性剤としてポリオキシエチレンラウリ
ルエーテルを用いて、以下のようにして金属原子集合体
含有分散液を調製した。窒素雰囲気下、分散溶媒（６０
ｗｔ％）と界面活性剤（２０ｗｔ％）の混合液中に有機
金属化合物（２０ｗｔ％）を滴下し、大気中８０℃で１
日撹拌することにより、Ｃｕクラスター乃至Ｃｕ微粒子
の範囲のサイズからなった金属原子集合体含有分散液を
調製した。Example 3 Using hexafluoroacetylacetone copper trimethylvinylsilane as an organometallic compound, α-terpineol as a dispersion solvent, and polyoxyethylene lauryl ether as a surfactant, a dispersion containing metal atom aggregates was prepared as follows. Prepared. Under a nitrogen atmosphere, a dispersion solvent (60
wt.) and a surfactant (20 wt.%) are dropped into a mixture of the organic metal compound (20 wt.
By stirring for a day, a metal atom aggregate-containing dispersion having a size ranging from Cu clusters to Cu fine particles was prepared.
【００２０】上記の金属原子集合体含有分散液を用い、
Ｓｉ基板上に設けられた配線溝、ホールを処理した。こ
のＳｉ基板には０．３〜５μｍの配線溝と０．１５〜２
μｍのビアホール、コンタクトホールが設けられ、これ
らの配線溝およびホールを含む基板表面にはスパッタに
より、ＴｉＮのバリヤ層が厚さ７０ｎｍで形成されてい
た。上記の基板をスピンコーターにセットして１０００
ｒｐｍで回転させ、その上方から上記金属原子集合体含
有分散液を滴下し、２０００ｒｐｍでスピンコートし
た。基板表面に液膜のある状態の基板を１０Ｐａの真空
雰囲気中、３５０℃で１分間、続いて大気中、３００℃
で３分間加熱して、有機溶媒および残留有機成分を蒸
発、燃焼させた。次いで、４％程の水素を含んだ不活性
ガス雰囲気中、２５０℃で３０分間加熱して、焼成プロ
セスでの燃焼により一部のＣｕがＣｕＯになってしまっ
たものをＣｕに還元した。こうして各Ｃｕ原子集合体同
士が融着して、配線溝、ビアホール、コンタクトホール
等の凹部内に凹状のＣｕ薄膜を形成できた。この凹状の
Ｃｕ薄膜をつけることにより、その後の工程で、スパッ
タ法を用いて、配線材料のＣｕを配線溝、ビアホール、
コンタクトホール等の凹部内に埋め込みやすくなった。
また、メッキ法の場合は、アスペクト比８までの配線
溝、ビアホール、コンタクトホール等を容易に埋め込む
ことができた。Using the above-mentioned metal atom aggregate-containing dispersion,
The wiring grooves and holes provided on the Si substrate were processed. The Si substrate has a wiring groove of 0.3 to 5 μm and a groove of 0.15 to 2 μm.
A via hole and a contact hole of μm were provided, and a barrier layer of TiN was formed with a thickness of 70 nm on the surface of the substrate including these wiring grooves and holes by sputtering. The above substrate was set on a spin coater and 1000
The dispersion liquid containing the metal atom aggregate was dropped from above, and spin-coated at 2,000 rpm. A substrate having a liquid film on the substrate surface is placed in a vacuum atmosphere of 10 Pa at 350 ° C. for 1 minute, and then in air at 300 ° C.
For 3 minutes to evaporate and burn the organic solvent and residual organic components. Next, the mixture was heated at 250 ° C. for 30 minutes in an inert gas atmosphere containing about 4% of hydrogen, and Cu which was partially converted into CuO by combustion in the firing process was reduced to Cu. In this manner, the Cu atom aggregates were fused to each other, and a concave Cu thin film could be formed in a concave portion such as a wiring groove, a via hole, or a contact hole. By providing this concave Cu thin film, in a subsequent step, Cu of the wiring material is transferred to the wiring groove, via hole,
It is easy to embed in a concave part such as a contact hole.
Further, in the case of the plating method, wiring grooves, via holes, contact holes and the like having an aspect ratio of up to 8 could be easily buried.
【００２１】実施例４ 本実施例では、金属原子集合体含有分散液を、有機金属
化合物としてヘキサフルオロアセチルアセトン銅ジメチ
ル−１，５シクロオクタジエン、分散溶媒としてミネラ
ルスピリット、界面活性剤としてポリオキシエチレンラ
ウリルエーテルを用いて作製した場合の例を示す。作製
法は実施例３に記載した方法に従い、有機金属化合物：
界面活性剤：分散溶媒＝１５：１５：７０（ｗｔ％）と
して行った。Example 4 In this example, a dispersion containing a metal atom aggregate was prepared by using hexafluoroacetylacetone copper dimethyl-1,5-cyclooctadiene as an organometallic compound, mineral spirit as a dispersion solvent, and polyoxyethylene as a surfactant. An example in the case of using lauryl ether is shown. The preparation was performed according to the method described in Example 3, and the organometallic compound:
Surfactant: dispersion solvent = 15: 15: 70 (wt%).
【００２２】実施例３と同じ基板をスピンコーターにセ
ットして１０００ｒｐｍで回転させ、その上方から上記
の金属原子集合体含有分散液を滴下し、２０００ｒｐｍ
でスピンコートした。基板表面に液膜のある状態の基板
を１０Ｐａの真空雰囲気中、３５０℃で１分間加熱して
有機溶媒および残留有機成分を蒸発、燃焼させた。次
に、１×１０-6Ｐａの真空雰囲気中、４００℃で３０分
間加熱して、燃焼により一部のＣｕがＣｕＯになってし
まったものを還元してＣｕにした。こうして各Ｃｕ原子
集合体同士が融着し、配線溝、ビアホール、コンタクト
ホール等の凹部内に凹状のＣｕ薄膜を形成できた。この
Ｃｕ薄膜形成法を同様の手順で繰り返し、Ｃｕ薄膜を５
層重ねることで、アスペクト比６までの配線溝、ビアホ
ール、コンタクトホール等の凹部を完全に埋め込むこと
ができた。The same substrate as in Example 3 was set on a spin coater, rotated at 1000 rpm, and the above-mentioned metal atom aggregate-containing dispersion was dropped from above, and the rotation speed was increased to 2,000 rpm.
Was spin-coated. The substrate having a liquid film on the substrate surface was heated at 350 ° C. for 1 minute in a vacuum atmosphere of 10 Pa to evaporate and burn the organic solvent and residual organic components. Next, it was heated at 400 ° C. for 30 minutes in a vacuum atmosphere of 1 × 10 −6 Pa to reduce Cu to CuO in which part of Cu was converted to CuO by burning. In this way, each Cu atom aggregate was fused together, and a concave Cu thin film could be formed in a concave portion such as a wiring groove, a via hole, or a contact hole. This Cu thin film forming method is repeated in the same procedure,
By stacking layers, recesses such as wiring grooves, via holes, and contact holes having an aspect ratio of up to 6 could be completely filled.
【００２３】実施例５ 本実施例では、金属原子集合体含有分散液を、有機金属
化合物としてヘキサフルオロアセチルアセトン銀トリメ
チルホスフィン[(ｈｆａｃ)Ａｇ(ｔｍｐ)]、分散溶媒と
してα−テルピネオール、界面活性剤としてポリエチレ
ングリコールモノラウリレートを用いて作製した場合の
例を示す。作製法は実施例３に記載した方法に従い、有
機金属化合物：界面活性剤：分散溶媒＝１５：２５：６
０として行った。Example 5 In this example, a dispersion containing a metal atom aggregate was prepared by using silver hexafluoroacetylacetone trimethylphosphine [(hfac) Ag (tmp)] as an organometallic compound, α-terpineol as a dispersion solvent, and a surfactant. As an example, the case of using polyethylene glycol monolaurate is shown. The preparation was performed according to the method described in Example 3, and the organometallic compound: surfactant: dispersion solvent = 15: 25: 6
Performed as 0.
【００２４】実施例３と同じ基板をスピンコーターにセ
ットして１０００ｒｐｍで回転させ、その上方から上記
の金属原子集合体含有分散液を滴下し、２０００ｒｐｍ
でスピンコートした。基板表面に液膜のある状態の基板
を１０Ｐａの真空雰囲気中、３５０℃で１分間加熱して
有機溶媒および残留有機成分を蒸発または燃焼させた。
こうして各Ａｇ原子集合体同士が融着し、配線溝、ビア
ホール、コンタクトホール等の凹部内に凹状のＡｇ薄膜
を形成できた。この凹状のＡｇ薄膜をつけることによ
り、その後の工程で、スパッタ法を用いて、配線材料の
Ａｇを配線溝、ビアホール、コンタクトホール等の凹部
内に埋め込みやすくなった。また、上記Ａｇ薄膜形成法
を同様の手順で５回繰り返し、Ａｇ薄膜を５層重ねるこ
とで、アスペクト比６までの配線溝、ビアホール、コン
タクトホール等の凹部を完全に埋め込むことができた。The same substrate as in Example 3 was set on a spin coater, rotated at 1000 rpm, and the above-mentioned metal atom aggregate-containing dispersion was dropped from above, and the rotation speed was increased to 2,000 rpm.
Was spin-coated. The substrate having a liquid film on the substrate surface was heated at 350 ° C. for 1 minute in a vacuum atmosphere of 10 Pa to evaporate or burn the organic solvent and residual organic components.
Thus, each Ag atom aggregate was fused together, and a concave Ag thin film could be formed in a concave portion such as a wiring groove, a via hole, or a contact hole. By providing the concave Ag thin film, it becomes easier to embed Ag of the wiring material in the recesses such as the wiring grooves, via holes, and contact holes by using the sputtering method in the subsequent step. In addition, the above-described Ag thin film forming method was repeated five times in the same procedure, and five Ag thin films were overlapped to completely fill recesses such as wiring grooves, via holes, and contact holes with an aspect ratio of up to 6.
【００２５】[0025]
【発明の効果】本発明の金属薄膜形成法では、基板の凹
部に対して、分散液の粘度、濃度のパラメータや塗布条
件を変化させることにより、凹部内にコンフォーマルな
状態、またはアスペクト比を減少させる状態に塗布が可
能である。従って、本発明の金属薄膜形成法を用い半導
体基板上の配線溝、ビアホール、コンタクトホール等の
凹部内に凹状金属薄膜が形成された後、スパッタ法、メ
ッキ法などにより、この凹部を配線金属で容易に埋め込
むことができる。また、この金属薄膜を複数層重ねるこ
とにより、アスペクト比の高い凹部であっても完全に埋
め込むことができる。According to the method for forming a metal thin film of the present invention, a conformal state or an aspect ratio is formed in a concave portion of a substrate by changing a parameter of a viscosity and a concentration of a dispersion and a coating condition with respect to the concave portion of the substrate. It is possible to apply in a state where it is reduced. Therefore, after a concave metal thin film is formed in a concave portion such as a wiring groove, a via hole, or a contact hole on a semiconductor substrate by using the metal thin film forming method of the present invention, the concave portion is formed with a wiring metal by a sputtering method, a plating method, or the like. Can be easily embedded. In addition, by stacking a plurality of metal thin films, even a concave portion having a high aspect ratio can be completely buried.
【００２６】また、本発明の金属微粒子分散液作製法に
よれば、半導体基板の該凹部内に凹状の金属薄膜を形成
できる分散液が得られる。Further, according to the method for preparing a metal fine particle dispersion of the present invention, a dispersion capable of forming a concave metal thin film in the concave portion of the semiconductor substrate is obtained.
【図１】従来例により、スパッタ法を用いて基板上に形
成した金属薄膜の模式的断面図FIG. 1 is a schematic cross-sectional view of a metal thin film formed on a substrate by sputtering according to a conventional example.
【図２】本発明の方法により、基板上に形成した金属薄
膜の模式的断面図FIG. 2 is a schematic cross-sectional view of a metal thin film formed on a substrate by the method of the present invention.
１ バリア層を含んだＳｉ基板 ２ 金属薄膜 1 Si substrate including barrier layer 2 Metal thin film
───────────────────────────────────────────────────── フロントページの続き (72)発明者 村上 裕彦 茨城県つくば市東光台５−９−７ 日本真 空技術株式会社筑波超材料研究所内 (72)発明者 山川 洋幸 茨城県つくば市東光台５−９−７ 日本真 空技術株式会社筑波超材料研究所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hirohiko Murakami 5-9-7 Tokodai, Tsukuba, Ibaraki Japan Inside Tsukuba Super Materials Research Laboratory, Japan Vapor Technology Co., Ltd. (72) Inventor Hiroyuki Yamakawa 5 Tokodai, Tsukuba, Ibaraki -9-7 Nippon Vacuum Technology Co., Ltd. Tsukuba Super Materials Laboratory
Claims (10)
の凹部に配線に利用する金属を埋め込む前の半導体基板
上に、金属原子集合体が有機溶媒に分散された金属微粒
子分散液を塗布し、塗布膜の形成された基板を焼成して
該基板上の有機物質を蒸発、燃焼させ、該基板上に金属
薄膜を形成することを特徴とする金属薄膜形成方法。1. A metal fine particle dispersion in which a metal atom aggregate is dispersed in an organic solvent is applied to a semiconductor substrate before a metal used for wiring is embedded in a recess of a wiring groove, a via hole, or a contact hole, and a coating film is formed. B) forming a metal thin film on the substrate by baking the substrate on which the organic substance is evaporated and burning to form a metal thin film on the substrate.
を還元することを特徴とする請求項１記載の金属薄膜形
成方法。2. The method for forming a metal thin film according to claim 1, wherein after the firing, an oxide generated by the firing is reduced.
中、または該真空雰囲気中と大気雰囲気中との二段階
で、１００〜４５０℃で行うことを特徴とする請求項１
または２記載の金属薄膜形成方法。3. The method according to claim 1, wherein the calcination is performed at 100 to 450 ° C. in a vacuum atmosphere, in an air atmosphere, or in two stages of the vacuum atmosphere and the air atmosphere.
Or the method of forming a metal thin film according to 2.
活性ガス雰囲気中または真空雰囲気中、２００〜４５０
℃で行うことを特徴とする請求項２または３記載の金属
薄膜形成方法。4. The reduction is carried out in an inert gas atmosphere containing 4% or less of hydrogen or in a vacuum atmosphere.
The method according to claim 2 or 3, wherein the method is carried out at a temperature of ° C.
活性剤と高沸点有機溶媒との混合液に有機金属化合物を
添加し、次いで加熱して該有機金属化合物中の金属を析
出させ、該金属の原子のクラスター乃至微粒子の範囲の
サイズからなる金属原子集合体を調製し、該金属原子集
合体を非イオン界面活性剤の存在により安定化させて作
製された分散液であることを特徴とする請求項１〜４の
いずれかに記載の金属薄膜形成方法。5. The metal fine particle dispersion is prepared by adding an organometallic compound to a mixed solution of a nonionic surfactant and a high-boiling organic solvent, and then heating to precipitate a metal in the organometallic compound. It is a dispersion prepared by preparing a metal atom aggregate having a size in the range of clusters or fine particles of metal atoms and stabilizing the metal atom aggregate by the presence of a nonionic surfactant. The method for forming a metal thin film according to claim 1.
ドデシルベンゼン、ミネラルスピリット、トリデカン、
およびα−テルピネオールから選ばれる高沸点有機溶媒
であり、また、前記分散液が、界面活性剤として、ポリ
オキシエチレンアルキルエーテル、ポリエチレングリコ
ールモノアルキレート、およびポリオキシエチレンアル
キルアミンから選ばれる非イオン界面活性剤を含んでい
ることを特徴とする請求項１〜５のいずれかに記載の金
属薄膜形成方法。6. The organic solvent is xylene, toluene,
Dodecylbenzene, mineral spirit, tridecane,
And a high-boiling organic solvent selected from α-terpineol, and the dispersion is a nonionic interface selected from polyoxyethylene alkyl ether, polyethylene glycol monoalkylate, and polyoxyethylene alkylamine as a surfactant. The method according to any one of claims 1 to 5, further comprising an activator.
の凹部を有する半導体基板上に、金属原子集合体が有機
溶媒に分散された金属微粒子分散液を塗布し、塗布膜の
形成された基板を焼成して該基板上の有機物質を蒸発、
燃焼させ、該基板上に金属薄膜を形成させた後、該金属
微粒子分散液の塗布工程および焼成工程を繰り返して該
凹部を複数層の金属薄膜で埋め込むか、または、スパッ
タ法、メッキ法およびＣＶＤ法により配線に利用する金
属で該凹部を埋め込むことを特徴とする金属配線形成方
法。7. A fine metal particle dispersion in which a metal atom aggregate is dispersed in an organic solvent is applied on a semiconductor substrate having a recess of a wiring groove, a via hole, and a contact hole, and the substrate on which the coating film is formed is baked. To evaporate the organic material on the substrate,
After burning to form a metal thin film on the substrate, the coating process and the firing process of the metal fine particle dispersion are repeated to fill the recesses with a plurality of layers of metal thin films, or a sputtering method, a plating method and a CVD method. Forming the recesses with a metal used for wiring by a method.
の混合液に有機金属化合物を添加し、次いで加熱して該
有機金属化合物中の金属を析出させ、該金属の原子のク
ラスター乃至微粒子の範囲のサイズからなる金属原子集
合体を調製し、該金属原子集合体を非イオン界面活性剤
の存在により安定化させて、該集合体が該有機溶媒中に
安定に分散された分散液を作製することを特徴とする金
属微粒子分散液の作製方法。8. An organometallic compound is added to a mixture of a nonionic surfactant and a high-boiling organic solvent, followed by heating to precipitate the metal in the organometallic compound. A metal atom aggregate having a size in the range of is prepared, the metal atom aggregate is stabilized by the presence of a nonionic surfactant, and a dispersion in which the aggregate is stably dispersed in the organic solvent is obtained. A method for producing a metal fine particle dispersion, characterized by being produced.
ドデシルベンゼン、ミネラルスピリット、トリデカン、
およびα−テルピネオールから選ばれる高沸点有機溶媒
であり、前記非イオン界面活性剤が、ポリオキシエチレ
ンアルキルエーテル、ポリエチレングリコールモノアル
キレート、およびポリオキシエチレンアルキルアミンか
ら選ばれる界面活性剤であることを特徴とする請求項８
記載の金属微粒子分散液の作製方法。9. The method according to claim 9, wherein the organic solvent is xylene, toluene,
Dodecylbenzene, mineral spirit, tridecane,
And a high-boiling organic solvent selected from α-terpineol, wherein the nonionic surfactant is a surfactant selected from polyoxyethylene alkyl ether, polyethylene glycol monoalkylate, and polyoxyethylene alkylamine. Claim 8
A method for producing the metal fine particle dispersion according to the above.
ロアセチルアセトン銅トリメチルビニルシラン[(ｈｆａ
ｃ)Ｃｕ(ｔｍｖｓ)]、ヘキサフルオロアセチルアセトン
銅ジメチル−１，５シクロオクタジエン[(ｈｆａｃ)Ｃ
ｕ(ＤＭＣＯＤ)]、ヘキサフルオロアセチルアセトン銅
トリエトキシビニルシラン[(ｈｆａｃ)Ｃｕ(ｔｅｏｖ
ｓ)]、ビスジピバロイルメタン銅[(ｄｐｍ)2Ｃｕ]、ビ
スヘキサフルオロアセチルアセトン銅[(ｈｆａｃ)2Ｃ
ｕ]、ヘキサフルオロアセチルアセトン銀トリメチルホ
スフィン[(ｈｆａｃ)Ａｇ(ｔｍｐ)]、およびナフテン酸
銅から選ばれる化合物であることを特徴とする請求項８
または９に記載の金属微粒子分散液の作製方法。10. The organic metal compound is hexafluoroacetylacetone copper trimethylvinylsilane [(hfa
c) Cu (tmvs)], copper hexafluoroacetylacetone dimethyl-1,5-cyclooctadiene [(hfac) C
u (DMCOD)], hexafluoroacetylacetone copper triethoxyvinylsilane [(hfac) Cu (teov
s)], bisdipivaloylmethane copper [(dpm) 2 Cu], bishexafluoroacetylacetone copper [(hfac) 2 C
u], silver hexafluoroacetylacetone trimethylphosphine [(hfac) Ag (tmp)], and copper naphthenate.
Or the method for producing a metal fine particle dispersion according to item 9.
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| JP23935599A JP3953237B2 (en) | 1998-12-02 | 1999-08-26 | Method for forming metal thin film and method for producing metal fine particle dispersion |
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|---|---|---|---|
| JP34324198 | 1998-12-02 | ||
| JP10-343241 | 1998-12-02 | ||
| JP23935599A JP3953237B2 (en) | 1998-12-02 | 1999-08-26 | Method for forming metal thin film and method for producing metal fine particle dispersion |
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| Publication Number | Publication Date |
|---|---|
| JP2000228374A true JP2000228374A (en) | 2000-08-15 |
| JP3953237B2 JP3953237B2 (en) | 2007-08-08 |
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|---|---|---|---|---|
| JP2002093904A (en) * | 2000-08-31 | 2002-03-29 | Hynix Semiconductor Inc | Method for forming dual damascene wiring |
| JP2002141351A (en) * | 2000-10-31 | 2002-05-17 | Japan Science & Technology Corp | Circuit board and method of forming metal wiring |
| WO2003069662A1 (en) * | 2002-02-18 | 2003-08-21 | Hitachi, Ltd. | Method for manufacturing semiconductor device, and semiconductor device |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002093904A (en) * | 2000-08-31 | 2002-03-29 | Hynix Semiconductor Inc | Method for forming dual damascene wiring |
| JP4532768B2 (en) * | 2000-08-31 | 2010-08-25 | 株式会社ハイニックスセミコンダクター | Method for forming dual damascene wiring |
| JP2002141351A (en) * | 2000-10-31 | 2002-05-17 | Japan Science & Technology Corp | Circuit board and method of forming metal wiring |
| WO2003069662A1 (en) * | 2002-02-18 | 2003-08-21 | Hitachi, Ltd. | Method for manufacturing semiconductor device, and semiconductor device |
| JP2003257890A (en) * | 2002-03-07 | 2003-09-12 | Seiko Epson Corp | Method for filling substance, method for forming film, device and its fabricating method |
| US7238615B2 (en) | 2003-01-15 | 2007-07-03 | Seiko Epson Corporation | Formation method for metal element, production method for semiconductor device, production method for electronic device, semiconductor device, electronic device, and electronic equipment |
| JP2006518103A (en) * | 2003-02-17 | 2006-08-03 | アルシメール・エス・アー | Surface coating method, fabrication of microelectronic interconnects using the method, and integrated circuit |
| JP2007134481A (en) * | 2005-11-10 | 2007-05-31 | Sony Corp | Method for manufacturing semiconductor device |
| KR101323701B1 (en) * | 2011-08-16 | 2013-10-30 | 한국과학기술원 | Method for fabrcrating metal layer |
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