JP2016006228A - NICKEL THIN FILM ON Si-SUBSTRATE BY CHEMICAL VAPOR DEPOSITION AND METHOD FOR MANUFACTURING NICKEL SILICIDE THIN FILM ON Si-SUBSTRATE - Google Patents
NICKEL THIN FILM ON Si-SUBSTRATE BY CHEMICAL VAPOR DEPOSITION AND METHOD FOR MANUFACTURING NICKEL SILICIDE THIN FILM ON Si-SUBSTRATE Download PDFInfo
- Publication number
- JP2016006228A JP2016006228A JP2015127262A JP2015127262A JP2016006228A JP 2016006228 A JP2016006228 A JP 2016006228A JP 2015127262 A JP2015127262 A JP 2015127262A JP 2015127262 A JP2015127262 A JP 2015127262A JP 2016006228 A JP2016006228 A JP 2016006228A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- film
- nickel
- vapor deposition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000010409 thin film Substances 0.000 title claims abstract description 72
- 239000000758 substrate Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 238000005229 chemical vapour deposition Methods 0.000 title claims description 18
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 title description 2
- 229910021334 nickel silicide Inorganic materials 0.000 title description 2
- 239000010408 film Substances 0.000 claims abstract description 93
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 40
- 239000012495 reaction gas Substances 0.000 claims description 11
- 239000012535 impurity Substances 0.000 abstract description 14
- 230000008021 deposition Effects 0.000 abstract description 8
- 229910005883 NiSi Inorganic materials 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 18
- 239000002243 precursor Substances 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- -1 nickel nitride Chemical class 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 229910021332 silicide Inorganic materials 0.000 description 4
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910005849 NiNx Inorganic materials 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229910004219 SiNi Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005468 ion implantation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000000392 cycloalkenyl group Chemical group 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 125000001162 cycloheptenyl group Chemical group C1(=CCCCCC1)* 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000004090 cyclononenyl group Chemical group C1(=CCCCCCCC1)* 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Abstract
Description
本発明は、化学蒸着法（化学気相蒸着法（ＣＶＤ法）、原子層蒸着法（ＡＬＤ法））により、Ｓｉ基板に直接、高品位のニッケル薄膜を製造するための方法に関する。また、このニッケル薄膜をシリサイド化してＮｉシリサイド薄膜を製造する方法に関する。 The present invention relates to a method for producing a high-quality nickel thin film directly on a Si substrate by chemical vapor deposition (chemical vapor deposition (CVD), atomic layer deposition (ALD)). The present invention also relates to a method for manufacturing a Ni silicide thin film by siliciding the nickel thin film.
近年、ＭＯＳＦＥＴ等の半導体デバイスにおける電極材料の低抵抗化を図るため、ニッケル薄膜をシリサイド化したニッケルシリサイド膜（ＮｉＳｉ）の適用が検討されている。このＮｉＳｉ膜の形成方法としては、Ｓｉ基板上にＮｉ薄膜を形成し、これを熱処理することでＳｉ基板からＳｉを拡散させてシリサイド化してＮｉＳｉを生成するのが一般的である。 In recent years, in order to reduce the resistance of an electrode material in a semiconductor device such as a MOSFET, application of a nickel silicide film (NiSi) obtained by siliciding a nickel thin film has been studied. In general, the NiSi film is formed by forming a Ni thin film on a Si substrate and heat-treating it to diffuse Si from the Si substrate to form a silicide to form NiSi.
上記のように、Ｓｉ基板にＮｉＳｉ薄膜を製造するためのＮｉ薄膜の製造方法としては、スパッタリング法等の物理蒸着法（ＰＶＤ）の適用例がこれまで多かったが、化学気相蒸着法（ＣＶＤ法）や原子層蒸着法（ＡＬＤ法）等の化学蒸着法の適用が着目されるようになっている。近年、半導体デバイスの３次元集積化が進んでおり、そこで用いられる電極も立体構造となってきている。そして、ＰＶＤ法では立体構造の薄膜形成は困難であることから、段差被覆能に優れる化学蒸着法の適用が好ましいとされている。 As described above, as a manufacturing method of the Ni thin film for manufacturing the NiSi thin film on the Si substrate, there have been many examples of physical vapor deposition (PVD) such as sputtering, but chemical vapor deposition (CVD) Method) and chemical vapor deposition methods such as atomic layer vapor deposition (ALD method) have attracted attention. In recent years, three-dimensional integration of semiconductor devices has progressed, and the electrodes used therein have also become three-dimensional structures. And since it is difficult to form a three-dimensional thin film by the PVD method, it is considered preferable to apply a chemical vapor deposition method having excellent step coverage.
化学蒸着によりＳｉ基板上にＮｉ膜を形成する方法としては、例えば、プリカーサ（原料化合物）としてニッケルアミジネートを用い、反応ガスとしてＮＨ３を適用する方法を基本としたものが知られている（特許文献１）。但し、ニッケルアミジネートを適用して生成されるＮｉ膜は、原料物質由来の窒素（Ｎ）や反応ガスであるＮＨ３由来のＮが膜中に取り込まれるため、膜中で窒化ニッケル（ＮｉＮｘ）が生成する。このような不純物は電極の低抵抗化の阻害要因となるが、特許文献１においては成膜後に熱処理を行いＮを除去することとしている。以上のＮｉ薄膜の成膜及び高純度化プロセスは、最終的にはＮ成分のない高純度で低抵抗のＮｉ薄膜を形成することができる。そして、Ｓｉ基板上に係る高純度のＮｉ薄膜を形成することでＮｉＳｉ膜の製造も可能となる。 As a method for forming a Ni film on a Si substrate by chemical vapor deposition, for example, a method based on a method using nickel amidinate as a precursor (raw material compound) and NH 3 as a reaction gas is known. (Patent Document 1). However, in the Ni film formed by applying nickel amidinate, nitrogen (N) derived from the raw material and N derived from NH 3 which is the reaction gas are taken into the film, so that nickel nitride (NiNx) is incorporated in the film. ) Is generated. Such an impurity becomes an obstacle to lowering the resistance of the electrode. However, in Patent Document 1, N is removed by heat treatment after film formation. The above-described Ni thin film formation and purification process can finally form a high-purity, low-resistance Ni thin film that does not contain an N component. Then, a NiSi film can be manufactured by forming a high-purity Ni thin film on the Si substrate.
しかし、このようなＮｉＮｘ膜の形成を経由する方法では、Ｎ除去に伴い膜の密度低下や形態（ラフネス）の変化が生じ、更に、Ｎの残留も懸念される。そのためバルクのＮｉに対して抵抗が高いＮｉ薄膜となっているという問題がある。そして、かかるＮｉ薄膜をシリサイド化しても好適な電極を形成することはできない。 However, in such a method that passes through the formation of the NiNx film, the density of the film is reduced and the form (roughness) is changed as N is removed, and there is also a concern that N may remain. Therefore, there is a problem that the Ni thin film has a high resistance to bulk Ni. A suitable electrode cannot be formed even if the Ni thin film is silicided.
ここで、不純物残留のない高品位のＮｉ薄膜を成膜するためには、プリカーサ及び反応ガスの構成元素として、Ｎｉ薄膜中に残留する可能性のあるＮ等の元素を排除することが適切な対応といえる。この観点から考えられる好適条件としては、プリカーサとして炭化水素系のＮｉ錯体を用い、反応ガスとして水素を適用するのが好ましい。炭化水素系Ｎｉ錯体であれば、錯体成分が炭化水素の形態で放出されることになり、薄膜中に不純物を残留させる懸念は少ないからである。 Here, in order to form a high-quality Ni thin film having no impurities remaining, it is appropriate to exclude elements such as N that may remain in the Ni thin film as constituent elements of the precursor and the reaction gas. It can be said that it corresponds. As preferable conditions considered from this viewpoint, it is preferable to use a hydrocarbon-based Ni complex as a precursor and to apply hydrogen as a reaction gas. This is because if the hydrocarbon-based Ni complex is used, the complex component is released in the form of hydrocarbon, and there is little concern that impurities remain in the thin film.
しかしながら、炭化水素系Ｎｉ錯体を用いてＳｉに直接Ｎｉ薄膜を製造することができるとの検討例はこれまでない。本発明者等によれば、これまでの炭化水素系Ｎｉ錯体を用いたＮｉ薄膜の成膜例としては、酸化皮膜（ＳｉＯ２）が形成されたＳｉ基板に対するものの報告例がいくつかあり、それらで好適なＮｉ皮膜を形成できるとされている。しかし、酸化皮膜のないＳｉ素地面については連続的なＮｉ薄膜を形成するのは困難であるとされており、この現象は本発明者等の実証試験でも確認されている。 However, there has been no examination example that a Ni thin film can be directly produced on Si using a hydrocarbon-based Ni complex. According to the present inventors, there have been several reports on Ni substrates with an oxide film (SiO 2 ) as examples of Ni thin film formation using hydrocarbon-based Ni complexes. Thus, a suitable Ni film can be formed. However, it is said that it is difficult to form a continuous Ni thin film on a Si base without an oxide film, and this phenomenon has been confirmed in the demonstration test by the present inventors.
そして、酸化皮膜を有するＳｉ基板にＮｉ皮膜を形成する場合、これをシリサイド化してＮｉＳｉとすることはできない。シリサイド化はＮｉ皮膜へＳｉが拡散することで進行するものであり、Ｎｉ皮膜とＳｉ基板との間に酸化皮膜があると、これが障壁となりＳｉのＮｉ膜への拡散が阻害されるからである。従って、ＮｉＳｉ薄膜形成のためには、Ｓｉ素地面のＮｉ薄膜の形成は必須の事項である。 When a Ni film is formed on a Si substrate having an oxide film, it cannot be converted into NiSi by silicidation. This is because silicidation proceeds by diffusion of Si into the Ni film, and if there is an oxide film between the Ni film and the Si substrate, this acts as a barrier and inhibits diffusion of Si into the Ni film. . Therefore, in order to form a NiSi thin film, the formation of a Ni thin film on a Si base is an essential matter.
そこで本発明は、ＮｉＳｉ皮膜の形成のために、Ｓｉ基板に直接Ｎｉ薄膜を形成することができ、且つ、形成されるＮｉ薄膜について不純物を残留させることのない方法を提供する。また、形成したＮｉ薄膜についてこれを的確にシリサイド化しＮｉＳｉ皮膜を製造する方法についても言及する。 Therefore, the present invention provides a method in which a Ni thin film can be directly formed on a Si substrate for forming a NiSi film and no impurities remain in the formed Ni thin film. In addition, a method for producing a NiSi film by appropriately silicidating the formed Ni thin film will also be described.
本発明者等は、上記課題を解決すべくプリカーサとして炭化水素系Ｎｉ錯体を用いつつもＳｉ基板へ直接Ｎｉを成膜するための条件について検討した。この検討においては、まず炭化水素系Ｎｉ錯体においてＳｉへの直接成膜が可能となる範囲（Ｎｉ錯体の種類）を模索するとともに、各種成膜条件について検討を行った。また、この検討において留意したのは、炭化水素系Ｎｉ錯体といえどもＮｉ薄膜中に不純物残留が常に生じないとはいえない点である。即ち、炭化水素系Ｎｉ錯体は、ニッケルアミジネートに比べると不純物残留の懸念は低いものの、その構成元素故に炭素（Ｃ）がＮｉ膜中に取り込まれる可能性がある。本発明者等の検討でも、成膜条件の設定によっては、Ｎｉ膜（基板とＮｉ膜との境界部）に炭素の残留が懸念されている。そして、本発明者等は、鋭意検討の結果、Ｓｉ基板への好適なＮｉ薄膜の成膜条件を見出し、本発明に想到した。 In order to solve the above-mentioned problems, the present inventors have examined conditions for directly forming Ni on a Si substrate while using a hydrocarbon-based Ni complex as a precursor. In this study, first, a range (type of Ni complex) in which a hydrocarbon-based Ni complex can be directly deposited on Si was sought and various deposition conditions were examined. Also, it was noted in this examination that even if it is a hydrocarbon-based Ni complex, it cannot be said that impurities remain in the Ni thin film. That is, hydrocarbon-based Ni complexes are less likely to have impurities compared to nickel amidinate, but carbon (C) may be incorporated into the Ni film because of its constituent elements. Even in the study by the present inventors, there is a concern that carbon remains in the Ni film (the boundary between the substrate and the Ni film) depending on the setting of the film forming conditions. As a result of intensive studies, the present inventors have found a suitable Ni thin film forming condition on the Si substrate and have arrived at the present invention.
即ち、本発明は、化学蒸着法により、酸化皮膜のないＳｉ基板上に直接ニッケル薄膜を製造する方法であって、前記Ｓｉ基板として、表面にＢ、Ｐ、ＡｓのいずれかをドープしたＳｉ基板を用い、原料化合物として、次式で示される、ニッケルに、シクロペンタジエニル基（Ｃｐ）又はその誘導体、及び、３〜９個の炭素原子から成る鎖状あるいは環状のアルケニル基又はその誘導体が配位するニッケル錯体であって、炭素と水素以外の元素を構造中に含まない炭化水素系ニッケル錯体を用い、反応ガスとして水素を用い、更に、成膜条件として、成膜圧力１〜１５０ｔｏｒｒ、成膜温度８０〜２５０℃としてニッケル薄膜を製造する方法である。 That is, the present invention is a method for producing a nickel thin film directly on a Si substrate without an oxide film by a chemical vapor deposition method, wherein the Si substrate is doped with any of B, P, and As on the surface. As a raw material compound, nickel represented by the following formula is a cyclopentadienyl group (Cp) or a derivative thereof, and a chain or cyclic alkenyl group consisting of 3 to 9 carbon atoms or a derivative thereof. Coordinating nickel complex, using a hydrocarbon-based nickel complex that does not contain elements other than carbon and hydrogen in its structure, using hydrogen as a reaction gas, and further, as film formation conditions, film formation pressure of 1 to 150 torr, This is a method for producing a nickel thin film at a film forming temperature of 80 to 250 ° C.
以下、本発明についてより詳細に説明する。本発明に係るＮｉ薄膜の製造方法は、基本的な工程は通常の化学蒸着法に準じる。化学蒸着法による薄膜製造工程は、プリカーサとなる金属錯体を気化し、これを反応ガスと共に基板表面に輸送し、基板表面で金属錯体から金属を析出させる。本発明に係るＮｉ薄膜の製造方法もこの工程に沿うものであるが、適用するプリカーサの種類と成膜条件（成膜圧力、成膜温度）において規定することを特徴とする。以下の説明ではこれらの特徴部分について詳説する。 Hereinafter, the present invention will be described in more detail. In the method for producing a Ni thin film according to the present invention, the basic process conforms to a normal chemical vapor deposition method. The thin film manufacturing process by chemical vapor deposition vaporizes a metal complex to be a precursor, transports it to the substrate surface together with a reaction gas, and deposits the metal from the metal complex on the substrate surface. The method for producing a Ni thin film according to the present invention also follows this step, but is characterized in that it is defined by the type of precursor to be applied and film formation conditions (film formation pressure and film formation temperature). In the following description, these characteristic portions will be described in detail.
本発明においてＮｉ薄膜製造のためのプリカーサは、炭素と水素以外の元素を構造中に含まない炭化水素系のＮｉ錯体である。上述の通り、成膜されたＮｉへの不純物の残留を抑制するためである。そして、本発明で適用される炭化水素系Ｎｉ錯体は、上記した特定の炭化水素系Ｎｉ錯体である。炭化水素系Ｎｉ錯体の中でこのＮｉ錯体を適用するのは、水素ガスとの適度な反応性と優れた気化特性を有するからである。 In the present invention, a precursor for producing a Ni thin film is a hydrocarbon-based Ni complex that does not contain elements other than carbon and hydrogen in its structure. As described above, it is for suppressing the residue of impurities in the deposited Ni. And the hydrocarbon type Ni complex applied by this invention is an above-mentioned specific hydrocarbon type Ni complex. The reason why this Ni complex is applied among hydrocarbon-based Ni complexes is that it has moderate reactivity with hydrogen gas and excellent vaporization characteristics.
この炭化水素系Ｎｉ錯体は、シクロペンタジエニル基又はその誘導体と、鎖状あるいは環状のアルケニル基又はその誘導体が配位するＮｉ錯体である。アルケニル基の炭素数を３〜９とするのは、Ｎｉ錯体の気化・分解特性を考慮したものである。好ましいのは環状のアルケニル基（シクロアルケニル基）であり、次式で示される、シクロブテニル、シクロペンテニル、シクロヘキセニル、シクロヘプテニル、シクロオクテニル、シクロノネニル、又はこれらの誘導体のうち、いずれか１種が特に好ましい。これらが配位するＮｉ錯体は、気化段階では安定的に気化しつつ、成膜段階では低温で分解しやすく、化学蒸着用原料として好適である。 This hydrocarbon Ni complex is a Ni complex in which a cyclopentadienyl group or a derivative thereof and a chain or cyclic alkenyl group or a derivative thereof are coordinated. The reason why the number of carbon atoms in the alkenyl group is 3 to 9 is in consideration of the vaporization / decomposition characteristics of the Ni complex. A cyclic alkenyl group (cycloalkenyl group) is preferable, and any one of cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclononenyl, and derivatives thereof represented by the following formula is particularly preferable. Ni complexes coordinated with these are suitable for chemical vapor deposition because they are stably vaporized in the vaporization stage and easily decomposed at a low temperature in the film formation stage.
また、このＮｉ錯体でＮｉに配位するもう一つの配位子であるシクロペンタジエニル（Ｃｐ）は、置換基（Ｒ１〜Ｒ５）が全て水素原子であるものの他、アルキル基を置換した誘導体であっても良い。シクロペンタジエニル誘導体としては、置換基（Ｒ１〜Ｒ５）のうち、１つがアルキル基、残り４つの置換基が水素原子である誘導体が好ましい。また、置換基（Ｒ１〜Ｒ５）として、とりうる炭素数は０〜６であるが、好ましくは４以下である。シクロペンタジエニルの置換基が長すぎると、有機ニッケル化合物の融点上昇、分子量増加に伴う蒸気圧の低下、蒸発しにくくなり成膜の際に膜中に不純物が混入する、等の傾向があり、化学蒸着用原料として好適な特性を維持しにくい。 In addition, cyclopentadienyl (Cp), which is another ligand coordinated to Ni in this Ni complex, substitutes for an alkyl group in addition to all of the substituents (R 1 to R 5 ) being hydrogen atoms. It may be a derivative. The cyclopentadienyl derivative is preferably a derivative in which one of the substituents (R 1 to R 5 ) is an alkyl group and the remaining four substituents are hydrogen atoms. Further, as the substituent (R 1 ~R 5), the number of carbon atoms which can be taken is 0 to 6, preferably 4 or less. If the substituent of cyclopentadienyl is too long, the melting point of the organic nickel compound will increase, the vapor pressure will decrease with increasing molecular weight, and it will be difficult to evaporate and impurities will be mixed into the film during film formation. It is difficult to maintain characteristics suitable as chemical vapor deposition materials.
化学蒸着法によるＮｉ成膜に当たっては、上記のプリカーサを気化してＳｉ基板に供給する。このとき、気化したプリカーサは反応ガスと共に基板上に輸送される。この反応ガスは水素を適用する。Ｎｉ膜中に不純物を残留させないためである。 In the Ni film formation by chemical vapor deposition, the above precursor is vaporized and supplied to the Si substrate. At this time, the vaporized precursor is transported onto the substrate together with the reaction gas. This reaction gas applies hydrogen. This is to prevent impurities from remaining in the Ni film.
基板は、Ｓｉ基板が適用されるが、これは単結晶Ｓｉ、多結晶Ｓｉのいずれでも良く、高純度のものが好ましい。Ｓｉ基板に対しては、Ｎｉ成膜前に酸化皮膜の除去がなされたものが適用される。 As the substrate, a Si substrate is applied, which may be either single crystal Si or polycrystalline Si, and preferably has a high purity. For the Si substrate, one obtained by removing the oxide film before forming the Ni film is applied.
また、本発明者等によれば、Ｓｉ基板の表面について、Ｂ、Ｐ、Ａｓのいずれかを適当量ドープしたものを適用した場合、連続的なＮｉ皮膜を高速で形成することができる。Ｂ、ＰあるいはＡｓのドープによりＮｉの成膜速度が向上する理由については明確ではないが、本発明者等は基板表面状態の変化がＮｉ化合物の吸着と分解を促進したと考察している。Ｂ、ＰあるいはＡｓのドーズ量は、最大で１０１８ａｔｍｓ／ｃｍ３とする。１０１８ａｔｍｓ／ｃｍ３を超えても成膜速度に変化がないからである。より好ましくは、１０１３〜１０１６ａｔｍｓ／ｃｍ３とする。Ｓｉ基板に対するＢ、ＰあるいはＡｓのドープの方法は特に限定されることはなく、イオン注入法、熱拡散法等を適用することができる。 Further, according to the present inventors, a continuous Ni film can be formed at a high speed when the surface of the Si substrate is doped with an appropriate amount of any of B, P, and As. Although the reason why the Ni film formation rate is improved by doping with B, P or As is not clear, the present inventors consider that the change in the substrate surface state promoted the adsorption and decomposition of the Ni compound. The dose amount of B, P, or As is 10 18 atms / cm 3 at the maximum. This is because there is no change in the film formation rate even if it exceeds 10 18 atms / cm 3 . More preferably, it is 10 13 to 10 16 atms / cm 3 . The method for doping B, P, or As on the Si substrate is not particularly limited, and an ion implantation method, a thermal diffusion method, or the like can be applied.
本発明における炭化水素系Ｎｉ錯体によるＮｉ成膜の条件について、規定されるのは、成膜圧力、成膜温度である。これらの成膜条件は、Ｓｉへ直接Ｎｉを成膜する上で重要な条件となる。 The conditions for Ni film formation by the hydrocarbon-based Ni complex in the present invention are defined by the film formation pressure and the film formation temperature. These film forming conditions are important conditions for forming Ni directly on Si.
成膜圧力は、成膜に必要なプリカーサの供給量のために規定される。成膜圧力が１５０ｔｏｒｒを超えるとプリカーサが気化されにくく供給不足となる。また、１ｔｏｒｒよりも低い場合も供給量が不足する。好ましい成膜圧力は５０〜１２０ｔｏｒｒであり、膜の連続性と平滑性が得られやすい。 The film formation pressure is defined for the amount of precursor supply required for film formation. When the film forming pressure exceeds 150 torr, the precursor is hardly vaporized and the supply becomes insufficient. Further, the supply amount is insufficient even when it is lower than 1 torr. A preferable film forming pressure is 50 to 120 torr, and it is easy to obtain continuity and smoothness of the film.
また、本発明者等によれば、炭化水素系Ｎｉ錯体によるＮｉ薄膜は、不純物残留の可能性は低いものの、成膜温度が高温となることによって炭素の残留が懸念されることが確認されている。そして、成膜温度が２５０℃を超えることで炭素残留量が増大する。そのため、本発明においては成膜温度を８０〜２５０℃とする。８０℃未満では、成膜反応が進行し難く必要な膜厚が得られ難い。好ましい成膜温度は１００〜２２０℃である。尚、成膜温度とは、基板の加熱温度の意義である。 Further, according to the present inventors, it has been confirmed that the Ni thin film by the hydrocarbon-based Ni complex has a low possibility of residual impurities, but there is a concern that carbon remains due to the high film formation temperature. Yes. And carbon deposition amount increases because film-forming temperature exceeds 250 degreeC. Therefore, in the present invention, the film forming temperature is set to 80 to 250 ° C. If it is less than 80 degreeC, a film-forming reaction will not advance easily and it will be difficult to obtain a required film thickness. A preferable film forming temperature is 100 to 220 ° C. The film forming temperature means the heating temperature of the substrate.
次に、本発明に係るＮｉシリサイド（ＮｉＳｉ）薄膜の製造方法について説明する。上記のＮｉ薄膜の製造工程で、成膜直後の段階で純度が高く形態性にも優れる。そして、Ｓｉに直接接触していることから、シリサイド化によりＮｉＳｉ膜を形成することも容易である。シリサイド化は、不活性ガス（窒素、アルゴンが好ましい）又は水素雰囲気で、基板を加熱してＮｉ膜を３００〜６００℃で加熱することで可能となる。 Next, a method for manufacturing a Ni silicide (NiSi) thin film according to the present invention will be described. In the Ni thin film manufacturing process, the purity is high and the formability is excellent immediately after the film formation. Since it is in direct contact with Si, it is easy to form a NiSi film by silicidation. Silicidation is possible by heating the substrate at 300 to 600 ° C. by heating the substrate in an inert gas (preferably nitrogen or argon) or hydrogen atmosphere.
本発明によれば、基板となるＳｉに直接接触した状態でＮｉ薄膜を製造することができる。本発明により形成されるＮｉ薄膜は、Ｃ、Ｎ、Ｏ等の不純物を含有することもなく、適宜の熱処理によりシリサイド化が容易でありＮｉＳｉ膜を形成することが可能である。 According to the present invention, a Ni thin film can be produced in a state of being in direct contact with Si serving as a substrate. The Ni thin film formed according to the present invention does not contain impurities such as C, N, and O, can be easily silicided by an appropriate heat treatment, and can form a NiSi film.
以下、本発明における最良の実施形態について説明する。
第１実施形態：この実施形態は、炭化水素系Ｎｉ錯体によるＳｉ基板へのＮｉ成膜の形成及びそのシリサイド化の可否を検討するために行ったものである。ここでは、複数の高純度Ｓｉ基板を用意してそれぞれについて成膜試験を行った。Ｓｉ基板は、酸洗により酸化皮膜を除去したＳｉ基板、酸洗を行わずに酸化皮膜をそのままにしたＳｉ基板を用意した。酸洗は、希フッ酸（０．５％）に基板を５分間浸漬し、表面の酸化皮膜を除去した。
Hereinafter, the best embodiment of the present invention will be described.
First Embodiment : This embodiment was carried out in order to examine the formation of a Ni film on a Si substrate by a hydrocarbon-based Ni complex and the possibility of silicidation thereof. Here, a plurality of high-purity Si substrates were prepared, and a film formation test was performed for each. As the Si substrate, an Si substrate from which the oxide film was removed by pickling and an Si substrate in which the oxide film was left as it was without pickling were prepared. In pickling, the substrate was immersed in dilute hydrofluoric acid (0.5%) for 5 minutes to remove the oxide film on the surface.
成膜試験は、プリカーサとして、（η３−シクロヘキセニル）（η５−シクロペンタジエニル）ニッケル（ＩＩ）を用いた。そして、コールドウォール式の成膜装置を用い、ＣＶＤ法によりニッケル薄膜を形成させた。成膜試験後、基板表面についてＳＥＭ観察を行い、Ｎｉ成膜の可否を評価した。成膜条件は、次の通りである。 In the film formation test, (η 3 -cyclohexenyl) (η 5 -cyclopentadienyl) nickel (II) was used as a precursor. Then, a nickel thin film was formed by a CVD method using a cold wall type film forming apparatus. After the film formation test, SEM observation was performed on the substrate surface to evaluate the possibility of Ni film formation. The film forming conditions are as follows.
プリカーサ加熱温度：９０℃
基板加熱温度：２００℃
キャリアガス：アルゴン６０ｓｃｃｍ
反応ガス：水素、１００ｃｃｍ
圧力：１００ｔｏｒｒ
成膜時間：２０分
Precursor heating temperature: 90 ° C
Substrate heating temperature: 200 ° C
Carrier gas: Argon 60sccm
Reaction gas: Hydrogen, 100 ccm
Pressure: 100 torr
Deposition time: 20 minutes
次に、成膜したＮｉ薄膜について、シリサイド化の熱処理を行った。熱処理条件は、基板温度を５００℃とし、１０ｓｃｃｍの水素ガス＋１０ｓｃｃｍのアルゴンの雰囲気中で基板を加熱した。加熱時間はいずれも１０分間とした。 Next, the formed Ni thin film was subjected to silicidation heat treatment. As the heat treatment conditions, the substrate temperature was set to 500 ° C., and the substrate was heated in an atmosphere of 10 sccm of hydrogen gas + 10 sccm of argon. All heating times were 10 minutes.
図１は、各基板におけるＮｉ薄膜及び熱処理後の薄膜のＳＥＭ写真である。図１から、本実施形態で適用したプリカーサ及び成膜条件によってＳｉ基板上に直接Ｎｉが成膜していることがわかる。そして、これを熱処理したことでシリサイド化が進行し、Ｓｉ基板上にＳｉＮｉ薄膜が形成されたのが確認できる。一方、酸化皮膜（ＳｉＯ２）を有するＳｉ基板でもＮｉ薄膜は形成される。しかし、これを熱処理してもＳｉＮｉ薄膜に変化は見られない。これは、Ｎｉ薄膜とＳｉ基板との境界のＳｉＯ２層がバリア層となってＳｉの拡散を阻害しシリサイド化されなかったことによると考えられる。 FIG. 1 is a SEM photograph of the Ni thin film and the heat-treated thin film on each substrate. From FIG. 1, it can be seen that Ni is directly formed on the Si substrate according to the precursor and film forming conditions applied in the present embodiment. And it can confirm that silicidation advances by heat-processing this, and the SiNi thin film was formed on the Si substrate. On the other hand, a Ni thin film is also formed on a Si substrate having an oxide film (SiO 2 ). However, no change is seen in the SiNi thin film even when this is heat-treated. This is presumably because the SiO 2 layer at the boundary between the Ni thin film and the Si substrate became a barrier layer and inhibited the diffusion of Si and was not silicided.
第２実施形態：ここでは、Ｓｉ基板表面についてＢをドープした状態でＮｉ薄膜を製造した。基板へのＢドープは、イオン注入後９００℃で３０分間のアニール処理により、Ｂを１０１５ａｔｍｓ／ｃｍ３ドープし、成膜前に上記と同様に酸洗した。本実施形態の成膜試験では、第１実施形態と同様のプリカーサ（（η3−シクロヘキセニル）（η5−シクロペンタジエニル）ニッケル（ＩＩ））を用いてＮｉ成膜を行い、成膜速度を評価した。成膜条件は下記の通りとし、成膜時間１分、２分、５分、１５分におけるＮｉ薄膜の膜厚を測定した。 Second Embodiment : Here, a Ni thin film was manufactured in a state where B was doped on the surface of the Si substrate. The substrate was doped with B by 10 15 atms / cm 3 of B by annealing at 900 ° C. for 30 minutes after ion implantation, and pickled in the same manner as described above before film formation. In the film formation test of this embodiment, Ni film formation was performed using the same precursor ((η 3 -cyclohexenyl) (η 5 -cyclopentadienyl) nickel (II)) as in the first embodiment. The speed was evaluated. The film forming conditions were as follows, and the film thickness of the Ni thin film was measured at film forming times of 1, 2, 5, and 15 minutes.
プリカーサ加熱温度：９０℃
基板加熱温度：１７５℃
キャリアガス：アルゴン１００ｓｃｃｍ
反応ガス：水素、１００ｃｃｍ
圧力：１００ｔｏｒｒ
成膜時間：１分、２分、５分、１５分
Precursor heating temperature: 90 ° C
Substrate heating temperature: 175 ° C
Carrier gas: Argon 100 sccm
Reaction gas: Hydrogen, 100 ccm
Pressure: 100 torr
Deposition time: 1 minute, 2 minutes, 5 minutes, 15 minutes
図２は、この成膜試験の結果を示す。図２から、ＢドープＳｉ基板におけるＮｉ薄膜の成膜過程ではインキュベーションタイムもほとんど見られず、成膜開始から速やかに成長を開始する。また、成膜時間に対してリニアに膜厚は増大する。本実施形態では、８．２ｎｍ／ｍｉｎの比較的良好な成膜速度を示す。 FIG. 2 shows the results of this film formation test. From FIG. 2, almost no incubation time is observed in the film formation process of the Ni thin film on the B-doped Si substrate, and the growth starts promptly from the start of film formation. Further, the film thickness increases linearly with the film formation time. In this embodiment, a relatively good deposition rate of 8.2 nm / min is shown.
また、本実施形態の成膜時間１分、２分でＮｉ薄膜を製造した基板について、熱処理を行いＮｉ薄膜をＮｉＳｉ薄膜にシリサイド化した。熱処理条件は、基板温度を５００℃とし、１０ｓｃｃｍの水素ガス＋１０ｓｃｃｍのアルゴンの雰囲気中で基板を加熱した。加熱時間はいずれも１０分間とした。 In addition, the Ni thin film was formed into a NiSi thin film by performing a heat treatment on the substrate on which the Ni thin film was manufactured in 1 minute and 2 minutes in the present embodiment. As the heat treatment conditions, the substrate temperature was set to 500 ° C., and the substrate was heated in an atmosphere of 10 sccm of hydrogen gas + 10 sccm of argon. All heating times were 10 minutes.
図３は、各Ｎｉ薄膜の熱処理前後のＳＥＭ写真である。いずれのＮｉ薄膜も熱処理によりその上部にＮｉＳｉ薄膜が形成されている。Ｎｉ薄膜が薄い場合（成膜時間１分）のものであっても、ムラ無く均一なシリサイド化が確認できた。 FIG. 3 is an SEM photograph of each Ni thin film before and after heat treatment. Each Ni thin film has a NiSi thin film formed thereon by heat treatment. Even when the Ni thin film was thin (film formation time 1 minute), uniform silicidation was confirmed without unevenness.
また、図４には、ＮｉＳｉ薄膜（Ｎｉの成膜時間２分）のＸＰＳ分析の結果を示す。本実施形態で成膜したＮｉＳｉ薄膜には、Ｃ、Ｎ、Ｏのいずれの不純物も計測されなかった。また、ＮｉとＳｉの組成比もほぼ１：１であり、良好な品質のＮｉシリサイド薄膜を得ることができたことが確認できる。 FIG. 4 shows the results of XPS analysis of a NiSi thin film (Ni film formation time of 2 minutes). In the NiSi thin film formed in this embodiment, no impurities of C, N, and O were measured. Further, the composition ratio of Ni and Si is almost 1: 1, and it can be confirmed that a Ni silicide thin film having a good quality could be obtained.
本発明に係る方法は、Ｓｉ基板に直接Ｎｉ薄膜を製造することができるものあり、Ｃ、Ｎ、Ｏ等の不純物の残留のない高品位のＮｉ薄膜を得ることができる。また、このＮｉ薄膜は、熱処理によりそのままＮｉＳｉ膜とすることができる。本発明に係る方法は、化学蒸着法という段差被覆能に優れた薄膜製造プロセスを基本とし、各種半導体デバイスの３次元構造を有する立体電極の製造に好適である。 The method according to the present invention can produce a Ni thin film directly on a Si substrate, and can obtain a high-quality Ni thin film free from residual impurities such as C, N, and O. Moreover, this Ni thin film can be made into a NiSi film as it is by heat treatment. The method according to the present invention is based on a thin film manufacturing process having excellent step coverage called chemical vapor deposition and is suitable for manufacturing a three-dimensional electrode having a three-dimensional structure of various semiconductor devices.
Claims (1)
前記Ｓｉ基板として、表面にＢ、Ｐ、ＡｓのいずれかをドープしたＳｉ基板を用い、
原料化合物として、次式で示される、ニッケルに、シクロペンタジエニル基（Ｃｐ）又はその誘導体、及び、３〜９個の炭素原子から成る鎖状あるいは環状のアルケニル基又はその誘導体が配位するニッケル錯体であって、炭素と水素以外の元素を構造中に含まない炭化水素系ニッケル錯体を用い、
反応ガスとして水素を用い、
更に、成膜条件として、成膜圧力１〜１５０ｔｏｒｒ、成膜温度８０〜２５０℃としてニッケル薄膜を製造する方法。
As the Si substrate, a Si substrate doped with any of B, P and As on the surface is used.
As a raw material compound, a cyclopentadienyl group (Cp) or a derivative thereof and a chain or cyclic alkenyl group consisting of 3 to 9 carbon atoms or a derivative thereof are coordinated to nickel represented by the following formula: Use a nickel-complex hydrocarbon-based nickel complex that does not contain elements other than carbon and hydrogen in its structure,
Using hydrogen as the reaction gas,
Further, a method for producing a nickel thin film under film formation conditions of a film formation pressure of 1 to 150 torr and a film formation temperature of 80 to 250 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015127262A JP6091023B2 (en) | 2015-06-25 | 2015-06-25 | Nickel thin film on Si substrate by chemical vapor deposition and method for producing Ni silicide thin film on Si substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015127262A JP6091023B2 (en) | 2015-06-25 | 2015-06-25 | Nickel thin film on Si substrate by chemical vapor deposition and method for producing Ni silicide thin film on Si substrate |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2013207669A Division JP5770806B2 (en) | 2013-10-02 | 2013-10-02 | Nickel thin film on Si substrate by chemical vapor deposition and method for producing Ni silicide thin film on Si substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016006228A true JP2016006228A (en) | 2016-01-14 |
| JP6091023B2 JP6091023B2 (en) | 2017-03-08 |
Family
ID=55224797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2015127262A Active JP6091023B2 (en) | 2015-06-25 | 2015-06-25 | Nickel thin film on Si substrate by chemical vapor deposition and method for producing Ni silicide thin film on Si substrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6091023B2 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005093732A (en) * | 2003-09-17 | 2005-04-07 | Tri Chemical Laboratory Inc | Film formation material, film formation method, film, and element |
| JP2005109504A (en) * | 2003-09-30 | 2005-04-21 | Samsung Electronics Co Ltd | Semiconductor device having silicide thin film and manufacture method therefor |
| US20080248648A1 (en) * | 2007-04-06 | 2008-10-09 | Thompson David M | Deposition precursors for semiconductor applications |
-
2015
- 2015-06-25 JP JP2015127262A patent/JP6091023B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005093732A (en) * | 2003-09-17 | 2005-04-07 | Tri Chemical Laboratory Inc | Film formation material, film formation method, film, and element |
| JP2005109504A (en) * | 2003-09-30 | 2005-04-21 | Samsung Electronics Co Ltd | Semiconductor device having silicide thin film and manufacture method therefor |
| US20080248648A1 (en) * | 2007-04-06 | 2008-10-09 | Thompson David M | Deposition precursors for semiconductor applications |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6091023B2 (en) | 2017-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI648421B (en) | CVD Mo deposition using MoOC1<sub>4</sub> | |
| US9583348B2 (en) | Silane and borane treatments for titanium carbide films | |
| KR102472965B1 (en) | Fluorine-containing conductive films | |
| JP5725454B2 (en) | NiSi film forming method, silicide film forming method, silicide annealing metal film forming method, vacuum processing apparatus, and film forming apparatus | |
| TW201142946A (en) | NMOS metal gate materials, manufacturing methods, and equipment using CVD and ALD processes with metal based precursors | |
| JP2015021175A (en) | Film production method of metallic thin film | |
| WO2011156705A2 (en) | Selective formation of metallic films on metallic surfaces | |
| TWI661080B (en) | Selective formation of metal silicides | |
| JP5770806B2 (en) | Nickel thin film on Si substrate by chemical vapor deposition and method for producing Ni silicide thin film on Si substrate | |
| Kogut et al. | Magnesium silicide thin film formation by reactive diffusion | |
| Kim et al. | Remote plasma enhanced atomic layer deposition of titanium nitride film using metal organic precursor (C12H23N3Ti) and N2 plasma | |
| TW201201278A (en) | Chemical vapor deposition of ruthenium films containing oxygen or carbon | |
| Yuan et al. | Role of NH3 feeding period to realize high-quality nickel films by hot-wire-assisted atomic layer deposition | |
| TWI671422B (en) | Thin film formation method | |
| JP6091023B2 (en) | Nickel thin film on Si substrate by chemical vapor deposition and method for producing Ni silicide thin film on Si substrate | |
| JP2001110750A5 (en) | ||
| JP6797068B2 (en) | Method for manufacturing titanium carbide-containing thin film by atomic layer deposition method | |
| TWI791586B (en) | Ge-CONTAINING Co-FILM FORMING MATERIAL, Ge-CONTAINING Co FILM AND FILM FORMING METHOD THEREOF | |
| JP3894010B2 (en) | Solution raw material for metalorganic chemical vapor deposition containing titanium complex and method for producing titanium-containing thin film using the raw material | |
| JP2003017437A (en) | Copper material charging plug and manufacturing method of the copper material charging plug | |
| You et al. | WNx Film Prepared by Atomic Layer Deposition using F-Free BTBMW and NH3 Plasma Radical for ULSI Applications | |
| KR100872799B1 (en) | Manufacturing method of metal silicide by plasma-enhanced atomic layer deposition for contact application in semiconductor devices | |
| JP3894016B2 (en) | Solution raw material for metalorganic chemical vapor deposition containing titanium complex and method for producing titanium-containing thin film using the raw material | |
| Jung et al. | Thermal stability of N2–H2 plasma-treated metal-organic-vapor-deposition TiN in a W/TiN/Ti/Si system | |
| KR20070097188A (en) | Method for fabricating semiconductor device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160622 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170130 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170203 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170206 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6091023 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |