WO2018180869A1 - めっき処理方法、めっき処理システム及び記憶媒体 - Google Patents
めっき処理方法、めっき処理システム及び記憶媒体 Download PDFInfo
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- WO2018180869A1 WO2018180869A1 PCT/JP2018/011364 JP2018011364W WO2018180869A1 WO 2018180869 A1 WO2018180869 A1 WO 2018180869A1 JP 2018011364 W JP2018011364 W JP 2018011364W WO 2018180869 A1 WO2018180869 A1 WO 2018180869A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
Definitions
- the present invention relates to a technique for performing selective plating on the surface of a substrate such as a semiconductor wafer.
- a substrate such as a silane coupling agent is applied to the surface of the substrate in order to satisfactorily adhere a catalyst, for example, palladium (Pd), as a deposition nucleus of the plating film to the surface of the substrate. It is often performed to form a self-assembled monolayer (SAM) on the surface of the substrate.
- a silane coupling agent has an amino group (—NH 2 ) as a functional group (see, for example, Patent Document 1).
- a self-assembled monomolecular film having an amino group (—NH 2 ) on the side opposite to the substrate surface adsorbs the Pd catalyst well.
- a plating film is not formed on at least a first portion of a substrate having a first portion made of a silicon compound containing nitrogen and a second portion made of a material different from the first portion on the surface. It aims at providing the plating processing method which can do.
- a substrate having a first portion made of a silicon compound containing nitrogen and a second portion made of a material different from the first portion on the surface;
- a plating step of plating the substrate to which the catalyst is applied, and the SAM formation step is performed by supplying a SAM formation agent having no functional group containing nitrogen to the substrate.
- the SAM having no functional group containing nitrogen is firmly attached to the surface of the first portion made of the silicon compound containing nitrogen, and this SAM is the catalyst adsorption that the nitrogen in the silicon compound has. Interfere with ability. For this reason, the catalyst hardly adheres to the surface of the silicon compound containing nitrogen, and it is possible to prevent the plating film from growing on at least the first portion in the plating step.
- Selective plating can be performed by selecting a material that is difficult to attach a SAM and has a catalyst adsorptivity as a material constituting the second portion.
- FIG. 5 is a schematic plan view showing an example of a plating system including the apparatus shown in FIGS. 2 to 4 used for carrying out the plating method.
- a substrate 2 is formed on a surface of a silicon (hereinafter referred to as “Si”) layer 3 in which a trench (recess or groove) is formed and an inner wall surface of the trench of the Si layer 3.
- Si silicon
- a titanium silicide (hereinafter referred to as “TiSi”) layer 4 and a silicon nitride layer (hereinafter referred to as “SiN”) 5 formed on the upper surface of the columnar body between the trenches of the Si layer 3 are provided.
- a plating layer 8 (see FIG. 1D) is formed on the surface of the TiSi layer 4 without forming a plating film on the surface of the SiN layer 5.
- the plating method will be specifically described.
- Pre-cleaning treatment First, as a pre-cleaning process, an SC1 cleaning process and a rinsing process are performed, thereby removing particles, organic contaminants, and the like on the substrate surface.
- the pre-cleaning process can be performed using a spinner (rotary liquid processing apparatus) 40 schematically shown in FIG. Specifically, as shown in FIG. 2, the pre-cleaning process is performed by rotating the substrate 2 around the vertical axis while holding the substrate 2 in a horizontal posture by the spin chuck 41 and moving the nozzle toward the center of the surface of the rotating substrate 2.
- the SC1 liquid is supplied from the nozzle 42 for a predetermined time, and then a rinsing liquid such as DIW is supplied from the nozzle 42 for a predetermined time.
- SAM layer silane-based self-assembled monolayer (SAM) layer 6 (hereinafter referred to as “SAM layer”) that does not have a functional group containing N is formed on the surface of the substrate 2.
- SAM layer forming agent a SAM layer forming agent is supplied to the surface of the substrate 2.
- a drug called a silane coupling agent or a drug having a similar molecular structure can be used.
- the agent for forming the SAM layer the trade name “KBE-3033” which is an alkoxysilane agent commercially available from Shin-Etsu Chemical Co., Ltd. can be used.
- KBE-3033 is n-propylpropyltriethoxysilane, and the structural formula is (C 2 H 5 O) 3 Si (CH 2 ) 2 CH 3 .
- This agent does not contain a functional group having N, and on the opposite side of the three O-ethoxy groups (groups involved in bonding to the surface of the substrate 2), a general formula C X H Y (specifically It has a functional group represented by (CH 2 ) 2 —CH 3 ).
- the formation of the SAM layer 6 can be performed by liquid treatment or vapor deposition treatment.
- a spinner 40 as a SAM forming portion having the configuration schematically shown in FIG. 2 can be used.
- the substrate 2 is held in a horizontal posture by the spin chuck 41 of the spinner 40 shown in FIG. 2 and rotated around the vertical axis, and the SAM layer is formed from the nozzle 42 toward the center of the surface of the rotating substrate 2.
- a forming drug is supplied, and a thin film of the drug is formed on the surface of the substrate 2. Thereafter, the thin film of the drug is fired.
- This baking treatment can be performed by heating the substrate in a low oxygen atmosphere, for example, a nitrogen gas atmosphere.
- baking device 50 having a configuration schematically shown in FIG. 4, an upper surface of a mounting table (hot plate) 52 provided in a processing chamber 51 in a nitrogen gas atmosphere.
- the substrate 2 is placed on the substrate 2, and the substrate 2 is heated to, for example, about 100 ° C. by a heater 53 provided inside the placement table 52.
- the SAM layer 6 is formed by this baking (baking) process.
- a vacuum vapor deposition apparatus 30 having a configuration schematically shown in FIG. 3 can be used.
- the substrate 2 is mounted on the mounting table 32 provided in the processing chamber 31 in a low oxygen atmosphere (for example, a nitrogen gas atmosphere or a reduced pressure atmosphere), and the substrate is provided by the heater 33 provided in the mounting table 32. 2 is heated to about 100 ° C., for example.
- the liquid SAM layer forming chemical stored in the tank 34 is heated by the heater 35 to be vaporized and placed on a carrier gas (for example, nitrogen gas) supplied from the carrier gas supply source 36. Supply into the chamber 31.
- a carrier gas for example, nitrogen gas
- a Pd nanocolloid solution obtained by dispersing Pd nanoparticles (Pd—NPs) as metal catalyst particles and polyvinylpyrrolidone (PVP) as a dispersant for coating Pd nanoparticles in a solvent, that is, a catalyst particle solution. Is supplied to the substrate 2 to perform a catalyst application process.
- Pd—NPs Pd nanoparticles
- PVP polyvinylpyrrolidone
- a spinner 40 as a catalyst application unit having a configuration schematically shown in FIG. 2 is used, and the substrate 2 is held in a horizontal posture by a spin chuck 41 and rotated around a vertical axis. It can be performed by discharging the catalyst-containing liquid from the nozzle toward the center of the surface of the substrate 2 to be performed.
- the catalyst-containing liquid is preferably adjusted to be acidic.
- the catalyst particle-containing layer 7 adheres to the surface of the TiSi layer 4 (here, the SAM layer 6 hardly adheres), while on the SAM layer 6 on the surface of the SiN layer 5.
- the catalyst-containing liquid is preferably acidic, so that the difference in the degree of adhesion of the catalyst becomes more prominent, and the plating selectivity can be improved.
- a rinsing process is performed.
- the substrate 2 is continuously held and rotated by the spin chuck 41, and pure water (DIW) as a rinsing liquid is discharged from the nozzle toward the center of the surface of the rotating substrate 2. This can be done. You may perform a baking process after a rinse process.
- DIW pure water
- a plating layer 8 made of copper (Cu), tungsten (W), cobalt (Co), nickel (Ni) or an alloy thereof is formed by electroless plating.
- a spinner 40 as a plating processing unit having a configuration schematically shown in FIG. 2 is used, and the substrate 2 is held in a horizontal posture by a spin chuck 41 and rotated around a vertical axis. 2 by discharging the plating solution from the nozzle toward the center of the surface.
- the plating layer 8 is selectively formed only on the surface of the TiSi layer 4 to which the catalyst particle-containing layer 7 is attached, and the SiN layer to which the catalyst particle-containing layer 7 is not attached. 5 is not formed on the surface of the SAM layer 6 on the upper surface.
- the plating layer 8 is formed bottom-up in the trench (recess). That is, the plating layer 8 is formed only inside the trench to be buried, and is not formed in a portion where the formation of the plating layer is not desired (the surface of the SiN layer 4). For this reason, it is not necessary to remove the extra plating layer after the plating process, or the number of steps for removing the extra plating layer can be greatly reduced.
- the plating layer 8 was selectively formed only on the TiSi layer 4 and not on the SiN layer 5.
- the SAM material (material for forming the SAM layer 6) once adheres to the surfaces of the TiSi layer 4 and the SiN layer 5. However, for at least one of the following (1) and (2), the SAM material on the TiSi layer 4 is removed by the end of the rinsing process at the latest, and only the SAM material on the SiN layer 5 is removed. Remain. (1)
- the bonding force of the SAM material to the TiSi layer 4 which is a metal layer is weaker than the bonding force of the SAM material to the SiN layer 5. For this reason, when the catalyst-containing liquid or the rinse liquid is supplied to the substrate 2, the SAM material on the TiSi layer 4 is easily removed by a physical force due to the flow of the liquid.
- SAM material that does not have a functional group containing N (nitrogen) atoms hardly adsorbs catalytic metal (here, Pd particles). Furthermore, the adsorptivity of the Pd particles of the SiN layer 5 underlying the SAM layer 6 is substantially lost when the surface is covered with a SAM material that does not have a functional group containing N (nitrogen) atoms. For this reason, even if Pd particles adhere to the SAM layer 6, the Pd particles are removed from the SAM layer 6 by the time when the rinsing process is completed at the latest.
- the metal catalyst contained in the catalyst-containing liquid is palladium (Pd).
- the metal catalyst is not limited to this.
- gold (Au), platinum (Pt), and ruthenium (Ru) May be.
- the dispersant contained in the catalyst particle solution is polyvinyl pyrrolidone (PVP), but is not limited to this.
- PVP polyvinyl pyrrolidone
- PAA polyacrylic acid
- PEI polyethyleneimine
- TMA tetramethyl Ammonium
- citric acid may be used.
- a drug called a silane coupling agent having a functional group having the above general formula C X H Y specifically, represented by (CH 2 ) 2 —CH 3 ) or a drug having a similar molecular structure (in detail)
- the above-mentioned n-propylpropyltriethoxy group having an O-methoxy group or an O-ethoxy group as a group involved in binding to the substrate on one end side and a C X H Y group on the other end side in addition to silane (KBE-3033), for example, the following can be used.
- Vinyltrimethoxysilane (KBM-1003), vinyltriethoxysilane (KBE-1003), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303), 3-gridoxypropylmethyldimethoxysilane (KBM) -402) 3-Glydoxypropyltrimethoxysilane (KBM-403), 3-Glydoxypropylmethyldiethoxysilane (KBE-402) and 3-Gridoxypropyltriethoxysilane (KBE-403).
- These agents are commercially available from Shin-Etsu Chemical Co., Ltd. under product names in parentheses.
- a drug called a silane coupling agent having an amino group that is not suitable for use in the above embodiment or a drug having a similar molecular structure (specifically, a group involved in binding to the substrate on one end side) examples of those having an O-methoxy group or an O-ethoxy group and having an amino group on the other end are as follows.
- KBM-602 N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane
- KBM-603 N-2- (aminoethyl) -3-aminopropyltrimethoxysilane
- KBM-903 3-aminopropyltrimethoxy Silane
- KBE-903 3-aminopropyltriethoxysilane
- the layer desired not to be plated by the plating method includes N such as SiCN (silicon carbonitride), SiON (silicon oxynitride), and SiOCN (silicon oxycarbonitride).
- N such as SiCN (silicon carbonitride), SiON (silicon oxynitride), and SiOCN (silicon oxycarbonitride).
- SiCN silicon carbonitride
- SiON silicon oxynitride
- SiOCN silicon oxycarbonitride
- TEOS is often exposed on the surface of the substrate, it has been confirmed that the formation of a plating layer on TEOS can be prevented by applying the above plating method.
- Examples of the layer desired to be plated by the plating method include a layer made of a conductive material such as Si doped with TiN, Si, B or P in addition to TiSi.
- a material constituting the layer to which the plating layer is attached any material can be used as long as it does not easily attach a SAM having a functional group containing nitrogen and has a catalyst adsorptivity.
- the plating method is not limited to the method in which the plating metal is embedded in the trench structure shown in FIG. 1A.
- the plating method can also be used when a plating layer is selectively provided on the surface of a flat substrate where different materials are exposed.
- the plating layer can be used as a hard mask for dry etching.
- the series of processes described above, that is, the pre-cleaning process, the SAM forming process, the baking (baking) process, the catalyst applying process, the rinsing process, and the plating process can be executed by, for example, the plating processing system schematically shown in FIG. it can.
- the substrate transport device 13 provided in the carry-in / out station 200 takes out the substrate 2 from the carrier C placed on the carrier placement unit 11 and transfers the taken-out substrate 2 to the delivery unit 14.
- the processing unit 16 provided in the processing station is configured to execute at least one of the series of processes described above. That is, some of the processing units 16 are the devices 30, 40, 50 shown in FIGS. 2A-2C.
- the substrate 2 placed on the delivery unit 14 is taken out from the delivery unit 14 by the substrate transfer device 17 of the processing station 300, and sequentially carried into the processing unit 16 corresponding to the above-described processing. Is processed. After the series of processing is completed, the substrate 2 is unloaded from the processing unit 16 and placed on the delivery unit 14. Then, the processed substrate 2 placed on the delivery unit 14 is returned to the carrier C of the carrier placement unit 11 by the substrate transport device 13.
- the plating system 100 includes a control device 400.
- the control device 400 is a computer, for example, and includes a control unit 401 and a storage unit 402.
- the storage unit 402 stores a program for controlling various processes executed in the plating system 100.
- the control unit 401 controls the operation of the plating processing system 100 by reading and executing a program stored in the storage unit 402. That is, the control device 400 controls the operation of each processing unit 16 and the transport operation of the substrate 2 by the substrate transport devices 13 and 17 in order to perform the above-described series of processing related to plating.
- Such a program may be recorded on a computer-readable storage medium and may be installed in the storage unit 19 of the control device 400 from the storage medium.
- Examples of the computer-readable storage medium include a hard disk (HD), a flexible disk (FD), a compact disk (CD), a magnetic optical disk (MO), and a memory card.
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Abstract
Description
まず、前洗浄処理として、SC1洗浄処理、続いてリンス処理を行い、これにより、基板表面のパーティクル、有機系汚染物質等を除去する。前洗浄処理は、図2に概略的に構成を示したスピナー(回転式液処理装置)40を用いて行うことができる。具体的には、前洗浄処理は、図2に示すように、スピンチャック41により基板2を水平姿勢に保持して鉛直軸線周りに回転させ、この回転する基板2の表面中央部に向けてノズル42からSC1液を所定時間供給し、その後、ノズル42からリンス液例えばDIWを所定時間供給することにより行うことができる。
次に、Nを含む官能基を有しないシラン系の自己組織化単分子膜(SAM)の層6(以下、「SAM層」と記す)を基板2の表面に形成するSAM形成処理が行われる。SAM層6の形成にあたって、SAM層形成用の薬剤が、基板2の表面に供給される。SAM層形成用の薬剤としては、シランカップリング剤と呼ばれる薬剤あるいはこれに類する分子構造を有する薬剤を用いることができる。ここでは、SAM層形成用の薬剤として、信越化学工業株式会社から商業的に入手可能なアルコキシシラン系薬剤である商品名「KBE-3033」を用いることができる。KBE-3033の化学名はn-プロピルプロピルトリエトキシシラン、構造式は(C2H5O)3Si(CH2)2CH3である。この薬剤は、Nを有する官能基を含んでおらず、3つのO-エトキシ基(基板2の表面への結合に関与する基)の反対側に、一般式CXHY(具体的には(CH2)2-CH3)で示される官能基を有している。
次に、金属触媒粒子としてのPdナノ粒子(Pd-NPs)と、Pdナノ粒子を被覆する分散剤としてのポリビニルピロリドン(PVP)を溶媒中に分散させてなるPdナノコロイド溶液、すなわち触媒粒子溶液を基板2に供給して、触媒付与処理を行う。
次に、リンス処理を行う。このリンス処理は、触媒付与処理の後、引き続きスピンチャック41により基板2を保持して回転させ、この回転する基板2の表面中央部に向けてノズルからリンス液としての純水(DIW)を吐出することにより行うことができる。リンス処理後にベーク処理を行ってもよい。
次に、無電解めっきにより、銅(Cu)、タングステン(W)、コバルト(Co)、ニッケル(Ni)またはその合金からなるめっき層8を形成する。このめっき処理は、図2に概略的に示した構成を有するめっき処理部としてのスピナー40を用い、スピンチャック41により基板2を水平姿勢に保持して鉛直軸線周りに回転させ、この回転する基板2の表面中央部に向けてノズルからめっき液を吐出することにより行うことができる。
(1)金属層であるTiSi層4へのSAM材の結合力は、SiN層5へのSAM材の結合力よりも弱い。このため、触媒含有液またはリンス液が基板2に供給されるときに、液の流れによる物理的な力によりTiSi層4上のSAM材が除去されやすい。
(2)金属層であるTiSi層4の表面は、酸性またはアルカリ性に調整される触媒含有液により侵され、これに伴い、TiSi層4の表面に一旦付着したSAM材がTiSi層4から除去される。一方で、SiN層5の表面は酸性またはアルカリ性に調整される触媒含有液により侵されることはないため、SiN層5上のSAM材は触媒含有液を基板2に供給した後でもSiN層5上に残留する。
4 第2部分(TiSi層)
5 窒素を含むシリコン化合物からなる第1部分(SiN層)
6 自己組織化単分子膜(SAM層)
7 触媒(触媒粒子含有層)
8 めっき(めっき層)
Claims (8)
- 表面に、窒素を含むシリコン化合物からなる第1部分と、前記第1部分とは異なる材料からなる第2部分とを有する基板を準備する工程と、
前記基板の表面にSAM(自己組織化単分子膜)を形成するSAM形成工程と、
前記SAMが形成された前記基板に触媒含有液を供給して、前記基板に触媒を付与する触媒付与工程と、
前記触媒が付与された前記基板にめっきを施すめっき工程と、
を備え、
前記SAM形成工程は、窒素を含む官能基を有しないSAM形成用の薬剤を前記基板に供給することにより行われる、めっき処理方法。 - 前記第2部分は導電性材料からなる、請求項1記載のめっき処理方法。
- 窒素を含む前記シリコン化合物が、SiN、SiCN、SiONまたはSiOCNであり、前記導電性材料が、TiSi、TiN、Si、またはB若しくはPでドープされたSiである、請求項2記載のめっき処理方法。
- 前記触媒含有液は酸性である、請求項1記載のめっき処理方法。
- 前記触媒付与工程の後であって前記めっき工程の前に、前記基板の表面にリンス液を供給するリンス工程をさらに備えた、請求項1記載のめっき処理方法。
- 前記SAM形成工程は、前記SAM形成用の薬剤として薬液を前記基板に供給した後に、前記基板を非酸化性雰囲気でベークすることにより行われる、請求項1記載のめっき処理方法。
- めっき処理システムの動作を制御するためのコンピュータにより実行されたときに、前記コンピュータが前記めっき処理システムを制御して請求項1記載のめっき処理方法を実行させるプログラムが記録された記憶媒体。
- めっき処理システムであって、
窒素を含む官能基を有しないSAM形成用の薬剤を基板に供給することにより、前記基板の表面にSAM(自己組織化単分子膜)を形成するSAM形成部と、
前記SAMが形成された前記基板に触媒液を供給して、前記基板に触媒を付与する触媒付与部と、
前記触媒が付与された前記基板にめっきを施すめっき処理部と、
を備えためっき処理装置。
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JP2006291284A (ja) * | 2005-04-11 | 2006-10-26 | Alps Electric Co Ltd | 部分めっき方法及び回路基板の製造方法 |
WO2010029635A1 (ja) * | 2008-09-11 | 2010-03-18 | パイオニア株式会社 | 金属配線の形成方法、及び金属配線を備えた電子部品 |
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JP2022504574A (ja) * | 2018-10-10 | 2022-01-13 | 東京エレクトロン株式会社 | 半導体デバイス内の凹状特徴部を低抵抗率金属で充填する方法 |
JP7406684B2 (ja) | 2018-10-10 | 2023-12-28 | 東京エレクトロン株式会社 | 半導体デバイス内の凹状特徴部を低抵抗率金属で充填する方法 |
WO2021166709A1 (ja) * | 2020-02-20 | 2021-08-26 | 東京エレクトロン株式会社 | 基板液処理方法及び基板液処理装置 |
JPWO2021166709A1 (ja) * | 2020-02-20 | 2021-08-26 | ||
JP7451676B2 (ja) | 2020-02-20 | 2024-03-18 | 東京エレクトロン株式会社 | 基板液処理方法及び基板液処理装置 |
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JP6801089B2 (ja) | 2020-12-16 |
KR20190132473A (ko) | 2019-11-27 |
TW201843347A (zh) | 2018-12-16 |
KR102617193B1 (ko) | 2023-12-26 |
US20210108316A1 (en) | 2021-04-15 |
JPWO2018180869A1 (ja) | 2020-02-06 |
TWI750352B (zh) | 2021-12-21 |
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