JP4362173B2 - Cu ultrafine particle independent dispersion - Google Patents
Cu ultrafine particle independent dispersion Download PDFInfo
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- JP4362173B2 JP4362173B2 JP22646499A JP22646499A JP4362173B2 JP 4362173 B2 JP4362173 B2 JP 4362173B2 JP 22646499 A JP22646499 A JP 22646499A JP 22646499 A JP22646499 A JP 22646499A JP 4362173 B2 JP4362173 B2 JP 4362173B2
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- ultrafine particles
- ultrafine
- independent dispersion
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- 239000011882 ultra-fine particle Substances 0.000 title claims description 40
- 239000006185 dispersion Substances 0.000 title claims description 32
- 239000000758 substrate Substances 0.000 claims description 27
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims description 3
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 3
- 229940088601 alpha-terpineol Drugs 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 150000002897 organic nitrogen compounds Chemical class 0.000 claims description 2
- 150000003377 silicon compounds Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 150000003464 sulfur compounds Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 19
- 239000010409 thin film Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- AXPZDYVDTMMLNB-UHFFFAOYSA-N Benzyl ethyl ether Chemical compound CCOCC1=CC=CC=C1 AXPZDYVDTMMLNB-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- ULBTUVJTXULMLP-UHFFFAOYSA-N butyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCCC ULBTUVJTXULMLP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/10—Details of semiconductor or other solid state devices to be connected
- H01L2924/11—Device type
- H01L2924/12—Passive devices, e.g. 2 terminal devices
- H01L2924/1204—Optical Diode
- H01L2924/12044—OLED
Landscapes
- Parts Printed On Printed Circuit Boards (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Conductive Materials (AREA)
Description
【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の微細な配線を形成し、ビアホール、コンタクトホールを埋設するのに使用するＣｕ超微粒子独立分散液に関する。
【０００２】
【従来の技術】
従来、ＬＳＩ基板等の多層配線を形成する際に、導電性の均一な微細パターンを形成する金属ペーストとして、炭素数５以上のアルコール類、又は有機エステル類を含有する有機溶媒中に粒径１０００Å（０．１μｍ）以下の金属超微粒子がその表面を該有機溶媒で覆われて個々に均一に分散しているものが知られている（例えば、第２５６１５３７号特許公報）。
【０００３】
【発明が解決しようとする課題】
しかしながら、かかる従来技術の金属ペーストにおいては、次のような問題があった。すなわち、ＬＳＩ基板の配線幅が０．２５μｍ、０．１８μｍと微細化が進む中で、塗布された金属ペーストが配線溝内を十分に埋設する前に乾燥が始まったり、また粘度が高いために、微細な溝内部を完全に埋設することが困難となっていた。
【０００４】
本発明は、かかる従来技術の問題点を解決するためになされたものであり、ＬＳＩ基板の微細な配線溝、ビアホール、コンタクトホール等を完全に埋設することができ、導電性の均一な微細パターンを形成することができるＣｕ超微粒子独立分散液を提供することを課題としている。
【０００５】
【課題を解決するための手段】
本発明のＣｕ超微粒子独立分散液は、粘度が５０ｃＰ以下であり、室温で蒸発し難くかつ半導体基板上にＣｕ配線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と、粒径０．０１μｍ以下のＣｕ金属含有超微粒子とを混合して形成され、該超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ものである。該有機溶媒は、１５０℃以上で蒸発するものである。該有機溶媒は、ミネラルスピリット、トリデカン、ドデシルベンゼン若しくはそれらの混合物、又はそれらにα−テルピネオールを混合したものである。その他に、炭素数５以上の炭化水素（例えば、ピネン等）、アルコール（例えば、ｎ−ヘプタノール等）、エーテル（例えば、エチルベンジルエーテル等）、エステル（例えば、ｎ−ブチルステアレート等）、ケトン（例えば、ジイソブチルケトン等）、有機窒素化合物（例えば、トリイソプロパノールアミン等）、有機ケイ素化合物（シリコーン油等）、有機イオウ化合物若しくはそれらの混合物を、使用するＣｕ分散液の用途によって適宜混合する。前記Ｃｕ金属含有超微粒子は、Ｃｕ、ＣｕＯ又は該ＣｕとＣｕＯとの混合物からなる超微粒子である。また、前記Ｃｕ金属含有超微粒子の濃度は、５〜７０ｗｔ％、好ましくは１５〜５０ｗｔ％である。該粒子の濃度が７０ｗｔ％を超えると、粘度が高くなりすぎ、また、該粒子の濃度が５ｗｔ％未満だと膜厚が小さすぎるという問題がある。前記Ｃｕ超微粒子独立分散液の粘度は２０℃で５０ｃＰ以下、好ましくは１０ｃＰ以下である。前記Ｃｕ超微粒子独立分散液は、Ｃｕ金属含有超微粒子以外にＣｕへの溶解度が低く、かつ半導体基板の基材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密着性が向上する。このＣｕ金属元素以外の金属の具体的な例としては、例えば、Ｍｇ、Ａｌ、Ｂ、Ｔａ、Ｎｂ及びＶから選ばれる金属又はこれら金属を含む化合物が挙げられる。これらの金属を含む化合物には、例えば(Ｃ17Ｈ35ＣＯＯ)2Ｍｇ等が挙げられる。これらの金属又は金属含有化合物のＣｕ超微粒子独立分散液への添加量は、超微粒子の全重量基準で、０．５〜５ｗｔ％である。
【０００６】
【実施例】
以下、本発明のＣｕ超微粒子独立分散液の実施例をその分散液の使用例と共に説明する。
（実施例１）
ヘリウム圧力０．５Ｔｏｒｒの条件下でＣｕを蒸発させ、ガス中蒸発法によりＣｕの超微粒子を生成する際に、生成過程のＣｕ超微粒子にミネラルスピリットの蒸気を接触させて冷却回収し、溶媒中に独立した状態で分散している平均粒子径０．００８μｍのＣｕ超微粒子を２０ｗｔ％含有するＣｕ超微粒子独立分散液を作製した。この分散液は粘度が室温で５ｃＰであった。
【０００７】
次いで、上記Ｃｕ超微粒子独立分散液を用いて、Ｓｉ基板上に設けられたビアホールを処理した。このＳｉ基板に形成されている絶縁膜としてのＳｉＯ2 膜には孔径０．１５μｍ（アスペクト比５）、０．２５μｍ（アスペクト比４）のビアホールが開けられており、ビアホールの内表面を含む基板の表面にはスパッタにより、ＷＮのバリヤ膜が厚さ０．０２μｍで形成されており、またこのバリヤ膜の表面にはスパッタによりＣｕのシード膜が形成されている。
【０００８】
上記の基板をスピンコータにセットして５００ｒｐｍで回転させ、その上方から室温で上記のＣｕ超微粒子独立分散液を滴下することによって、スピンコーティングした。ビアホール内にはこの分散液が充填され、基板の表面には平坦な該分散液の液膜が形成された。この状態の基板を１０-2Torr以下の真空中、２５０℃の温度で、２分間加熱して有機溶媒を蒸発させ、次いで温度を３００℃に上げて、ＣＯ2 ガス７６０Ｔｏｒｒ雰囲気中で、６０分間焼成した。さらに、温度を４００℃に上げて、不活性ガス中で３０分間焼成した。かくして、Ｃｕ超微粒子が相互に融着して、ビアホール内がＣｕで空洞なく埋め込まれた縮みや割れのないＣｕ薄膜が形成された。次いで、該ビアホールの内部以外のＣｕ膜をＣＭＰ処理したところ、基板表面の余分なＣｕが除去され、ビアホール内に平坦な表面を有するＣｕ薄膜が形成された。その比抵抗は２．０μΩｃｍであった。
（実施例２）
１Ｔｏｒｒのヘリウムガス中に０．０１ＴｏｒｒのＯ2 ガスを混合した雰囲気下でＣｕを蒸発させてＣｕＯの超微粒子を生成し、ドデシルベンゼンとフタル酸ジエチルとの混合蒸気に接触させて冷却し、平均粒径０．０１μｍのＣｕＯ超微粒子を２５ｗｔ％含有する粘度１０ｃＰ（２０℃）のＣｕＯ超微粒子独立分散液を作製した。また、このＣｕＯ超微粒子独立分散液と実施例１で作製したＣｕ超微粒子独立分散液とを混合して、粘度７ｃＰ（２０℃）のＣｕ、ＣｕＯ混合分散液を作製した。
【０００９】
次いで、上記分散液を用いて、実施例１と同様にして室温で基板のビアホールを埋め込み、Ｃｕ膜を形成したところ、得られた薄膜は、いずれも焼結後も縮みや割れが生じることもなく、その比抵抗は２．０μΩｃｍであった。
（実施例３）
実施例１におけるＣｕ超微粒子独立分散液の代わりに、トリデカンとフェネトールとの混合溶媒に５０ｗｔ％のＣｕ超微粒子を分散させたＣｕ超微粒子独立分散液にＭｇ、Ａｌ、Ｂ、Ｔａ、Ｎｂ又はＶの有機化合物の添加されたものを、実施例１と同様にして作製した。この分散液の粘度は２０℃で１０ｃＰであった。
【００１０】
次いで、これらの分散液を用いて、ＷＮのバリア膜とＣｕシード膜を形成する工程を省き、他は実施例１と同様にして基板のビアホールを埋め込み、Ｃｕ膜を形成したところ、得られた薄膜は、焼結後も及びＣＭＰによる平坦化処理工程中も縮みや割れが生じることもなく、基板との密着性も良好であり、その比抵抗は２．１μΩｃｍであった。
（実施例４）
実施例１のミネラルスピリットにα−テルピネオールを混合した溶媒中に分散させた粘度５０ｃＰ（２０℃）のＣｕ超微粒子独立分散液を作製し、これを用いて、Ｓｉ基板上に配線パターンを形成した。このＳｉ基板に形成されている絶縁膜としてのＳｉＯ2 膜には幅０．２５μｍ、深さ１μｍ（アスペクト比４）の溝がパターン状に形成されており、溝の内表面を含む基板の表面にはスパッタにより、ＷＮバリヤ膜が厚さ０．０２μｍで形成されており、またこのバリヤ膜の表面にはスパッタによりＣｕのシード膜が形成されている。
【００１１】
上記の基板をスピンコータにセットして５００ｒｐｍで回転させ、その上方から上記のＣｕ超微粒子独立分散液を滴下することによって、スピンコーティングした。パターン状の溝内にはこの分散液が充填され、基板の表面には平坦な該分散液の液膜が形成された。この状態の基板を１０-2Torr以下の真空中、２５０℃の温度で、２分間加熱して有機溶媒を蒸発させ、次いで温度を３００℃に上げて、不活性ガス雰囲気中で、Ｈ2Ｏガスの存在下（Ｈ2Ｏ分圧：１０Torr）、６０分間焼成した。さらに、温度を４００℃に上げて、Ｈ2Ｏを除去した不活性ガス中で３０分間焼成した。かくして、Ｃｕ超微粒子が相互に融着して、溝内がＣｕで空洞なく埋め込まれた縮みや割れのないＣｕ薄膜が形成された。次いで、該溝の内部以外のＣｕ膜をＣＭＰ処理したところ、基板表面の余分なＣｕが除去され、溝内に平坦な表面を有するＣｕ薄膜が形成された。その比抵抗は２．０μΩｃｍであった。
【００１２】
【発明の効果】
本発明のＣｕ超微粒子独立分散液によれば、ＬＳＩ基板の微細な配線溝、ビアホール、コンタクトホール等を完全に埋設することができ、導電性の均一な微細パターンを形成することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a Cu ultrafine particle independent dispersion used for forming fine wiring of a semiconductor substrate such as an LSI substrate and filling via holes and contact holes.
[0002]
[Prior art]
Conventionally, when forming a multilayer wiring such as an LSI substrate, as a metal paste for forming a conductive fine pattern, a particle size of 1000 mm in an organic solvent containing alcohols having 5 or more carbon atoms or organic esters is used. It is known that metal ultrafine particles of (0.1 μm) or less are covered with the organic solvent and uniformly dispersed individually (for example, Japanese Patent No. 2561537).
[0003]
[Problems to be solved by the invention]
However, the conventional metal paste has the following problems. In other words, as the wiring width of the LSI substrate is becoming finer to 0.25 μm and 0.18 μm, the applied metal paste begins to dry before the wiring groove is sufficiently embedded, and the viscosity is high. Therefore, it has been difficult to completely bury the inside of the fine groove.
[0004]
The present invention has been made to solve the problems of the prior art, and can completely bury fine wiring grooves, via holes, contact holes, etc. of an LSI substrate, and has a uniform conductive fine pattern. It is an object of the present invention to provide an independent dispersion of Cu ultrafine particles capable of forming a Cu.
[0005]
[Means for Solving the Problems]
The Cu ultrafine particle independent dispersion of the present invention has an viscosity of 50 cP or less, an organic solvent that is difficult to evaporate at room temperature and evaporates in a drying / firing process when forming a Cu wiring on a semiconductor substrate, and a particle size It is formed by mixing with Cu metal-containing ultrafine particles of 0.01 μm or less, and the surface of the ultrafine particles is covered with the organic solvent and dispersed individually. The organic solvent evaporates at 150 ° C. or higher. The organic solvent is mineral spirit, tridecane, dodecylbenzene or a mixture thereof, or a mixture thereof with α-terpineol . In addition, hydrocarbons having 5 or more carbon atoms (eg, pinene), alcohols (eg, n-heptanol), ethers (eg, ethyl benzyl ether), esters (eg, n-butyl stearate), ketones (For example, diisobutyl ketone, etc.), organic nitrogen compound (for example, triisopropanolamine, etc.), organic silicon compound (silicone oil, etc.), organic sulfur compound, or a mixture thereof is appropriately mixed depending on the use of the Cu dispersion to be used . The Cu metal containing ultrafine particles, Cu, a ultrafine particles consisting of a mixture of CuO or the Cu and CuO. The concentration of the Cu metal-containing ultrafine particles is 5 to 70 wt%, preferably 15 to 50 wt%. When the concentration of the particles exceeds 70 wt%, the viscosity becomes too high, and when the concentration of the particles is less than 5 wt%, the film thickness is too small. The viscosity of the Cu ultrafine particle independent dispersion is 50 cP or less, preferably 10 cP or less at 20 ° C. In addition to the Cu metal-containing ultrafine particles, the Cu ultrafine particle independent dispersion may contain at least one metal having a low solubility in Cu and easily reacting with the substrate of the semiconductor substrate or a compound containing these metals. Thereby, adhesiveness with a base material improves. Specific examples of the metal other than the Cu metal element include, for example, a metal selected from Mg, Al, B, Ta, Nb and V or a compound containing these metals. Examples of the compound containing these metals include (C 17 H 35 COO) 2 Mg. The addition amount of these metals or metal-containing compounds to the Cu ultrafine particle independent dispersion is 0.5 to 5 wt% based on the total weight of the ultrafine particles.
[0006]
【Example】
Hereinafter, examples of the Cu ultrafine particle independent dispersion of the present invention will be described together with examples of use of the dispersion.
Example 1
When Cu is evaporated under the condition of helium pressure of 0.5 Torr and Cu ultrafine particles are produced by gas evaporation method, mineral spirit vapor is brought into contact with the Cu ultrafine particles in the production process and cooled and recovered. A Cu ultrafine particle independent dispersion containing 20 wt% Cu ultrafine particles having an average particle diameter of 0.008 μm dispersed in an independent state was prepared. This dispersion had a viscosity of 5 cP at room temperature.
[0007]
Subsequently, the via hole provided on the Si substrate was processed using the Cu ultrafine particle independent dispersion. A via hole having a hole diameter of 0.15 μm (aspect ratio 5) and 0.25 μm (aspect ratio 4) is formed in the SiO 2 film as an insulating film formed on the Si substrate, and the substrate includes the inner surface of the via hole. A WN barrier film having a thickness of 0.02 μm is formed by sputtering on the surface, and a Cu seed film is formed by sputtering on the surface of the barrier film.
[0008]
The above substrate was set on a spin coater, rotated at 500 rpm, and the above-mentioned Cu ultrafine particle independent dispersion was dropped from above at room temperature to perform spin coating. The via hole was filled with this dispersion, and a flat liquid film of the dispersion was formed on the surface of the substrate. The substrate in this state is heated in a vacuum of 10 −2 Torr or less at a temperature of 250 ° C. for 2 minutes to evaporate the organic solvent, and then the temperature is raised to 300 ° C. in a CO 2 gas 760 Torr atmosphere for 60 minutes. Baked. Furthermore, the temperature was raised to 400 ° C. and calcination was performed for 30 minutes in an inert gas. Thus, Cu ultrafine particles were fused to each other, and a Cu thin film free from shrinkage and cracking in which the via hole was filled with a cavity without Cu was formed. Next, when the Cu film other than the inside of the via hole was subjected to CMP, excess Cu on the substrate surface was removed, and a Cu thin film having a flat surface was formed in the via hole. Its specific resistance was 2.0 μΩcm.
(Example 2)
Cu is evaporated in an atmosphere in which 0.01 Torr O 2 gas is mixed with 1 Torr helium gas to form ultrafine CuO particles, which are cooled in contact with a mixed vapor of dodecylbenzene and diethyl phthalate. A CuO ultrafine particle independent dispersion having a viscosity of 10 cP (20 ° C.) and containing 25 wt% of CuO ultrafine particles having a particle diameter of 0.01 μm was prepared. Moreover, this CuO ultrafine particle independent dispersion and the Cu ultrafine particle independent dispersion prepared in Example 1 were mixed to prepare a Cu and CuO mixed dispersion having a viscosity of 7 cP (20 ° C.).
[0009]
Next, using the above dispersion, via holes in the substrate were filled at room temperature in the same manner as in Example 1 to form a Cu film. Any of the thin films obtained may shrink or crack after sintering. The specific resistance was 2.0 μΩcm.
(Example 3)
Instead of the Cu ultrafine particle independent dispersion in Example 1, Mg, Al, B, Ta, Nb or V was used in the Cu ultrafine particle independent dispersion in which 50 wt% Cu ultrafine particles were dispersed in a mixed solvent of tridecane and phenetole. A compound to which the organic compound was added was prepared in the same manner as in Example 1. The viscosity of this dispersion was 10 cP at 20 ° C.
[0010]
Next, using these dispersions, the process of forming the WN barrier film and Cu seed film was omitted, and the others were filled with via holes in the substrate in the same manner as in Example 1 to form a Cu film. The thin film did not shrink or crack after sintering and during the planarization treatment process by CMP, had good adhesion to the substrate, and had a specific resistance of 2.1 μΩcm.
(Example 4)
A Cu ultrafine particle independent dispersion liquid having a viscosity of 50 cP (20 ° C.) dispersed in a solvent in which α-terpineol was mixed with the mineral spirit of Example 1 was prepared, and a wiring pattern was formed on the Si substrate using this. . A groove having a width of 0.25 μm and a depth of 1 μm (aspect ratio 4) is formed in a pattern on the SiO 2 film as an insulating film formed on the Si substrate, and the surface of the substrate including the inner surface of the groove A WN barrier film having a thickness of 0.02 μm is formed by sputtering, and a Cu seed film is formed by sputtering on the surface of the barrier film.
[0011]
The above substrate was set on a spin coater, rotated at 500 rpm, and the above-mentioned Cu ultrafine particle independent dispersion was dropped from above to perform spin coating. The dispersion was filled in the pattern-shaped grooves, and a flat liquid film of the dispersion was formed on the surface of the substrate. Vacuum below 10 -2 Torr substrate in this state, at a temperature of 250 ° C., then heated for 2 minutes and the organic solvents were evaporated, then the temperature was raised to 300 ° C., in an inert gas atmosphere, H 2 O Firing was performed for 60 minutes in the presence of gas (H 2 O partial pressure: 10 Torr). Furthermore, the temperature was raised to 400 ° C. and calcination was performed for 30 minutes in an inert gas from which H 2 O had been removed. Thus, Cu ultrafine particles were fused to each other, and a Cu thin film without shrinkage or cracking was formed in which the inside of the groove was filled with Cu without a cavity. Subsequently, when the Cu film other than the inside of the groove was subjected to CMP, excess Cu on the substrate surface was removed, and a Cu thin film having a flat surface was formed in the groove. Its specific resistance was 2.0 μΩcm.
[0012]
【The invention's effect】
According to the Cu ultrafine particle independent dispersion of the present invention, fine wiring grooves, via holes, contact holes and the like of an LSI substrate can be completely buried, and a conductive fine pattern can be formed.
Claims (2)
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| JP22646499A JP4362173B2 (en) | 1998-08-10 | 1999-08-10 | Cu ultrafine particle independent dispersion |
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| JP4578755B2 (en) * | 2000-05-02 | 2010-11-10 | 日揮触媒化成株式会社 | Integrated circuit manufacturing method |
| EP1662020B1 (en) * | 2003-07-03 | 2008-05-14 | Mec Company Ltd. | Method for producing a copper thin film |
| JP4918994B2 (en) | 2005-05-30 | 2012-04-18 | 住友電気工業株式会社 | Method for forming metal coating and metal wiring |
| US8083972B2 (en) | 2005-07-25 | 2011-12-27 | Sumitomo Metal Mining Co., Ltd. | Copper particulate dispersions and method for producing the same |
| US7521710B2 (en) | 2006-02-16 | 2009-04-21 | Idemitsu Kosan Co., Ltd. | Organic thin film transistor |
| US7535626B2 (en) | 2006-06-06 | 2009-05-19 | Konica Minolta Opto, Inc. | Shape-variable optical element, optical device and image pickup apparatus |
| WO2008044695A1 (en) | 2006-10-12 | 2008-04-17 | Idemitsu Kosan Co., Ltd. | Organic thin film transistor device and organic thin film light-emitting transistor |
| KR20090080522A (en) | 2006-11-14 | 2009-07-24 | 이데미쓰 고산 가부시키가이샤 | Organic thin film transistor and organic thin film light emitting transistor |
| WO2008059816A1 (en) | 2006-11-14 | 2008-05-22 | Idemitsu Kosan Co., Ltd. | Organic thin film transistor and organic thin film light-emitting transistor |
| WO2009041254A1 (en) | 2007-09-26 | 2009-04-02 | Idemitsu Kosan Co., Ltd. | Organic thin film transistor |
| WO2009060803A1 (en) | 2007-11-05 | 2009-05-14 | Sumitomo Metal Mining Co., Ltd. | Copper fine particle, method for producing the same, and copper fine particle dispersion |
| WO2020116003A1 (en) * | 2018-12-03 | 2020-06-11 | 太陽誘電株式会社 | Method and system for treating volatile organic compound |
| JP6687822B1 (en) * | 2018-12-03 | 2020-04-28 | 太陽誘電株式会社 | Method and system for treating volatile organic compounds |
| JP6808882B1 (en) * | 2020-07-22 | 2021-01-06 | 有限会社 ナプラ | A method of forming a conductor in a fine space provided on a semiconductor substrate |
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| JPS59215367A (en) * | 1983-05-23 | 1984-12-05 | Tdk Corp | Electrically conductive paste composition |
| JP2561537B2 (en) * | 1989-03-30 | 1996-12-11 | 真空冶金株式会社 | Metal paste and manufacturing method thereof |
| JPH05114306A (en) * | 1991-10-18 | 1993-05-07 | Nippon Cement Co Ltd | Low viscosity copper ink composite for metallizing ceramics |
| JPH0786128A (en) * | 1993-09-13 | 1995-03-31 | Fujitsu Ltd | Method for forming electrical characteristic film and spin coater used during formation |
| JPH0786737A (en) * | 1993-09-20 | 1995-03-31 | Fujitsu Ltd | Method for manufacturing thin film multilayer circuit board |
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| JPH09134891A (en) * | 1995-09-06 | 1997-05-20 | Vacuum Metallurgical Co Ltd | Formation of thin film of semiconductor substrate |
| JPH10195350A (en) * | 1996-12-25 | 1998-07-28 | Clariant Internatl Ltd | Coating composition |
| JPH1166957A (en) * | 1997-08-12 | 1999-03-09 | Tanaka Kikinzoku Kogyo Kk | Conductor composition. |
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