WO2013111592A1 - 半導体装置の製造方法 - Google Patents
半導体装置の製造方法 Download PDFInfo
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- WO2013111592A1 WO2013111592A1 PCT/JP2013/000348 JP2013000348W WO2013111592A1 WO 2013111592 A1 WO2013111592 A1 WO 2013111592A1 JP 2013000348 W JP2013000348 W JP 2013000348W WO 2013111592 A1 WO2013111592 A1 WO 2013111592A1
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- 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
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a technical field of forming a wiring by embedding copper in a recess for embedding formed in an insulating film which is a low dielectric constant film in a method for manufacturing a semiconductor device.
- a SiCOH film which is a low dielectric constant film made of silicon (Si), carbon (C), hydrogen (H), and oxygen (O)
- Si silicon
- C carbon
- H hydrogen
- O oxygen
- a concave portion including is formed.
- copper (Cu) is buried in the recess to form an upper layer side wiring connected to the lower layer side wiring.
- Ta tantalum
- TaN tantalum nitride
- a laminated film thereof is a so-called barrier between the copper wiring and the interlayer insulating film. Used as a membrane.
- Ti titanium
- TiN titanium nitride
- laminated film thereof is also known.
- the increase in wiring resistance and electrode resistance (via resistance) in the via hole affects the performance of the semiconductor device.
- FIG. 22 is a diagram showing how copper wiring is formed when Ru is used as a barrier film.
- an embedding recess 2 including a trench and a via hole is formed in an upper interlayer insulating film (SiCOH film) 1 (FIG.
- Reference numerals 61 to 63 denote an interlayer insulating film, a copper wiring, and a barrier layer on the lower layer side, respectively.
- Reference numeral 64 denotes an etch stopper film having a copper diffusion prevention function (a film that performs a stopper function during etching).
- the reason why the base film 3 is interposed between the interlayer insulating film 1 and the Ru film 4 is as follows.
- the SiCOH film that is the interlayer insulating film 1 is disconnected from the film by plasma during etching or ashing, and C is desorbed from the film, and moisture in the atmosphere is bonded to the dangling bonds generated by the desorption of C.
- Si—OH is formed, and the surface layer portion becomes a damaged layer. Since the damaged layer has a low C content, the relative dielectric constant increases. For this reason, the surface layer is removed with, for example, hydrofluoric acid. Therefore, the surface state of the interlayer insulating film 1 immediately before the barrier film is buried is hydrophobic.
- Japanese Patent Application Laid-Open No. 2005-347472 discloses that when a SiCOH film is plasma-etched, a part of the film is bonded into a recessed portion for embedding, and nucleation with a methyl group or the like as a nucleus. The problem that the film quality is deteriorated when the barrier film is formed as it is is described.
- a technique has been proposed in which a SiCOH film is treated with hydrogen plasma to remove methyl groups on the surface of the recesses and terminate the bond with H. This technique differs from the technique of the present invention in that the surface of the recess to be treated is hydrophilic.
- J.H. Vac. Sci. Technol. A 26 (4), Jul / Aug 2008 pp. 974-979 describes a method in which an amorphous alloy of Ru and phosphorus (P) is formed directly on an insulating film by a CVD (Chemical Vapor Deposition) method without passing through a base film.
- CVD Chemical Vapor Deposition
- the present invention has been made under such circumstances.
- the purpose of the present invention is to reduce the resistance of a conductive path when copper is buried in a recess for embedding formed in an insulating film made of a SiCOH film to form a conductive path. It is to provide a technique that can be lowered.
- a method for manufacturing a semiconductor device of the present invention includes: An insulating film containing silicon, carbon, hydrogen, and oxygen formed on a substrate, in which a recess for embedding in which a conductive path on the lower layer side is exposed is formed at the bottom, and its surface is hydrophobic Supplying boron compound gas to the insulating film to adsorb boron atoms on the surface of the insulating film; Directly forming an adhesion film made of a ruthenium film on the surface of the recess where the boron atoms are adsorbed; Thereafter, a step of embedding copper serving as a conductive path in the recess is included.
- Examples of the boron compound include monoborane (BH 3 ), diborane (B 2 H 6 ), trimethylborane (B (CH 3 ) 3 ), triethylborane (B (C 2 H 5 ) 3 ), and dicarbadodecaborane. (C 2 B 10 H 12 ) and decaborane (B 10 H 14 ).
- Another method for manufacturing a semiconductor device of the present invention is as follows.
- Supplying a silicon compound gas to the insulating film to adsorb silicon atoms on the surface of the insulating film Directly forming an adhesion film made of a ruthenium (Ru) film on the surface of the insulating film on which the silicon atoms are adsorbed;
- a step of embedding copper serving as a conductive path in the recess is included.
- silicon compound examples include monosilane (SiH 4 ) and disilane (Si 2 H 6 ).
- Another method for manufacturing a semiconductor device of the present invention is as follows.
- Supplying an organic compound gas containing aluminum to the insulating film to adsorb aluminum atoms on the surface of the insulating film Directly forming an adhesion film made of a ruthenium (Ru) film on the surface of the insulating film on which the aluminum atoms are adsorbed;
- a step of embedding copper serving as a conductive path in the recess is included.
- organic compound containing aluminum is trimethylaluminum.
- a boron (B) atom, a silicon (Si) atom, or an aluminum (Al) atom is adsorbed on the surface of an insulating film made of a SiCOH film in which a recess for filling is formed and the surface is hydrophobic. I am letting. For this reason, a Ru film that is a metal can be directly formed on the surface of the recess through B atoms, Si atoms, or Al atoms.
- the base film of the Ru film is not required, the volume of copper in the recess can be increased, and as a result, the resistance of the conductive path formed by embedding copper in the recess can be reduced, This is suitable as a method for manufacturing a semiconductor device whose line width is reduced.
- FIG. 1 and 2 show a state in which an upper layer side wiring structure is formed on a lower layer side wiring structure as a manufacturing stage of a semiconductor device, and parts equivalent to those shown in FIG. Is attached.
- Reference numeral 65 denotes a barrier film, for example, a Ta film.
- an interlayer insulating film 1 that is a SiCOH film is formed on a substrate that is a semiconductor wafer, for example, on which a lower wiring structure is formed (FIG. 1A). This film formation is performed, for example, by plasma CVD using DEMS (Diethoxymethylsilane) as a processing gas.
- a recess 2 including a trench serving as a wiring groove and a via hole for forming an electrode which is a connection portion between the lower layer wiring is formed in the interlayer insulating film 1 (FIG. 1B).
- the step of forming the recess 2 can be performed by forming a resist pattern and combining a plurality of stages of plasma etching using a sacrificial film, for example.
- the line width of the trench is designed to be 20 to 50 nm, for example, and the diameter of the via hole is designed to be 20 to 50 nm, for example.
- the substrate is cleaned with a cleaning liquid to remove residues attached to the surface of the substrate during etching and ashing for forming the recesses 2.
- the surface layer portion of the interlayer insulating film (SiCOH film) 1 is damaged by the plasma as described above (the bond is broken), and C is desorbed from the film. As a result, Si—OH groups are formed.
- Reference numeral 10 in FIG. 1B indicates a damage layer.
- the damaged layer 10 has a high relative dielectric constant, and a polymer of etching residue remains on the surface of the interlayer insulating film 1 after etching. Therefore, the damaged layer 10 is removed by a method such as wet etching using a hydrofluoric acid solution, for example (FIG. 1C).
- the substrate subjected to the above processing is subsequently subjected to a series of copper embedding processes including a surface treatment using diborane gas as shown in FIG. 2, and a processing module for performing the surface treatment first. Will be described with reference to FIG.
- reference numeral 71 denotes a processing container comprising a vacuum chamber.
- a stage 72 having a heater (not shown) as a heating unit is provided on the bottom surface of the processing container 71, and an exhaust pipe 73 is connected to the bottom.
- a vacuum exhaust mechanism 74 is provided on the downstream side of the exhaust pipe 73.
- a gas shower head 75 is provided in the upper part of the processing container 71, and a number of gas discharge holes 75 a for discharging gas uniformly into the processing atmosphere are formed in the lower surface of the gas shower head 75.
- a gas supply path 79 is connected to the gas shower head 75 from the outside.
- the base end side of the gas supply path 79 is branched and connected to a processing gas supply source 76 and a carrier gas supply source 77.
- V1 to V3 are valves, and f1 and f2 are flow rate adjusting units.
- diborane (B 2 H 6 ) which is a B (boron) compound, is used as the processing gas
- helium (He) is used as the carrier gas, for example.
- a substrate S is placed on the stage 72 from the outside by elevating pins (not shown) and heated by a heater, and the processing container 71 is connected via a gas supply path 79 and a gas shower head 75.
- diborane gas using He as a carrier is supplied.
- the temperature of the substrate S needs to be set to be equal to or higher than the temperature at which B atoms are adsorbed on the SiCOH film, and is set to 350 ° C., for example.
- the temperature of the substrate S may be equal to or higher than the temperature at which diborane is thermally decomposed.
- the pressure in the processing container 71 is set to 2667 Pa, for example.
- FIG. 2A shows the surface state of the substrate S after being surface-treated with diborane gas.
- FIG. 4 shows a processing module constituting a thermal CVD apparatus for forming the Ru film 4.
- 81 is a processing container which is a mushroom type vacuum chamber
- 82 is an exhaust pipe
- 83 is a vacuum exhaust mechanism
- 84 is a stage with a heater (not shown)
- 85 is for supplying a processing gas to the substrate S on the stage 84.
- It is a gas shower head.
- the gas shower head 85 includes a shower plate 851 provided with a large number of gas discharge holes 852 for supplying gas uniformly to the processing atmosphere.
- the shower plate 851 forms a temperature adjustment unit, for example, a temperature adjustment fluid.
- the flow path 853 is formed.
- a processing gas supply path 94 is connected to the gas shower head 85 from the outside, and a raw material bottle 91 is connected to the base end side of the processing gas supply path 94.
- a powder 90 made of, for example, Ru 3 (CO) 12, which is a precursor of Ru is accommodated, and one end side of a carrier gas supply pipe 93 is inserted into the powder 90.
- a carrier gas for example, CO gas supply source 92 is connected to the other end of the carrier gas supply pipe 93.
- CO gas as the carrier gas is supplied to the raw material bottle 91, Ru 3 (CO) 12 is sublimated and the gas is sent out to the gas shower head 85.
- Reference numerals 931 and 941 denote gas supply device groups such as valves and flow rate adjusting units.
- the substrate S is carried from the outside onto the stage 84 by elevating pins (not shown) and heated to 150 to 300 ° C., for example. Then, Ru 3 (CO) 12 gas is supplied from the raw material bottle 91 into the processing container 81 through the gas supply pipe 94 and the gas shower head 85 using CO gas as a carrier. Then, a CVD reaction occurs on the substrate S, and the Ru film 4 is formed.
- the film thickness of the Ru film 4 is set to 2 nm, for example.
- B atoms on the SiCOH film serve as Ru adsorption sites, that is, since B has a metal property, it can be bonded to Ru, which is a metal, through free electrons.
- This phenomenon is considered as follows. That is, when the Ru 3 (CO) 12 gas described above is supplied onto the substrate S to form a Ru film, CO gas is released as a by-product. In this reaction, free electrons in the SiCOH film move to Ru 3 (CO) 12 via B atoms, and at that time, Ru compounds are adsorbed on B atoms and decomposed to Ru atoms. It is presumed that CO gas was generated. The state of the SiCOH film surface at this time is shown in FIG.
- Ru nucleation at the initial stage of film formation is promoted, and a continuous film can be formed.
- Ru film 4 is formed using Ru 3 (CO) 12 gas and CO gas, it is possible to form the film while suppressing the reaction, so that there is an advantage that the film thickness can be accurately controlled.
- a Ru raw material for example, a Ru organic compound disclosed in Patent Document 2 other than the above-described raw materials may be used.
- the process for forming the Ru film is not limited to the CVD method.
- a gas that is a precursor of Ru and a reaction gas that reacts with this precursor are alternately supplied to the substrate, and when the gas is switched, a vacuum is drawn, and atomic layers or molecular layers are stacked one by one to obtain a stacked film.
- a so-called ALD (Atomic Layer Deposition) method may be used.
- a copper seed layer may be formed in the recess 2 by sputtering, and then copper may be embedded by plating.
- the substrate S is heated to 150 ° C. in a vacuum atmosphere and annealed to stabilize the grain size of the copper 5. This is for reducing the resistance value of the copper 5.
- reference numeral “5” is assigned to any of copper, copper wiring, and copper electrode.
- the surface of the substrate S is polished by CMP to remove excess copper.
- an upper layer copper wiring structure is formed (FIG. 2D).
- FIG. 8 shows a substrate processing system for performing the steps (a) to (c) shown in FIG.
- Reference numeral 101 denotes a loading / unloading port for loading / unloading the transfer container 100, 102 an atmospheric transfer chamber, 103 an atmospheric transfer arm, and 104 an alignment module for adjusting the center position and orientation of the substrate (semiconductor wafer) S.
- the container 100 is a FOUP
- a FOUP lid opening / closing mechanism or the like is interposed between the carry-in / out port 101 and the atmospheric transfer chamber 102.
- a processing block is airtightly connected to the inner side of the atmospheric transfer chamber 102 via load lock chambers 105 and 106.
- the substrate S is stored in the transfer container 100 that is carried into the carry-in / out port 101. At this time, the substrate S is in a state after the damage layer 10 of the interlayer insulating film 1 is removed (the state shown in FIG. 1C).
- the processing block includes a first vacuum transfer chamber 200 in which processing modules 202, 203, 204, and 205 are connected to the periphery and a first substrate transfer arm 201 is provided, and processing modules 302, 303, 304, 305, and 204. , 205 are connected to the periphery, and a second vacuum transfer chamber 300 provided with a second substrate transfer arm 301 is provided.
- the processing modules 204 and 205 are pre-processing modules that process the substrate S shown in FIG. 1C into a state where the processing shown in FIG. 2 can be performed, and the entrance and the exit are the first vacuum transfer chamber 200 and the first one, respectively. 2 vacuum transfer chambers 300.
- Reference numerals 304 and 305 denote surface treatment modules for performing surface treatment of the substrate S using diborane as shown in FIG. 302 and 303 are thermal CVD modules for forming the Ru film 4 shown in FIG. 2B, and 202 and 203 are sputter modules for copper embedding.
- the load lock chamber 105 (or 106) and the first substrate transfer chamber 200 are moved. Via the preprocessing module 204 (or 205). In the pretreatment module 204 (205), moisture on the surface of the insulating film and residues at the time of etching and ashing are removed. Thereafter, the substrate S is carried into the diborane surface treatment module 304 (or 305) through the second vacuum transfer chamber 300, and B atoms are adsorbed onto the SiCOH film. Then, the substrate S is again carried into the CVD module 302 (or 303) through the second vacuum transfer chamber 300, and the Ru film 4 is formed.
- the substrate S is then filled with copper 5 in the recesses 2 by copper sputtering. After that, it is returned to the transfer container 100 through the first vacuum transfer chamber 200, the load lock chamber 105 (or 106), and the atmospheric transfer chamber 102.
- the B compound used for adsorbing B atoms on the surface of the interlayer insulating film 1 is not limited to the above-mentioned diborane, but monoborane (BH 3 ), trimethylborane (B (CH 3 ) 3 ), triethylborane (B ( C 2 H 5) 3), radical Bud decaborane (C 2 B 10 H 12) , and the like decaborane (B 10 H 14).
- Examples of the carrier gas for the B compound include H 2 and argon in addition to He.
- the SiCOH film surface is treated by using a silane-based gas instead of the B compound gas in the first embodiment.
- a module for performing this surface treatment a module using a silane compound gas as a treatment gas in the surface treatment module 304 (or 305) in FIG. 8 of the first embodiment can be exemplified.
- Si atoms on the SiCOH film become Ru adsorption sites. That is, since Si has a metallic property, it can be bonded to Ru, which is a metal, through free electrons.
- Ru 3 (CO) 12 gas described above when supplied onto the substrate S to form a Ru film, CO gas is released as a byproduct. In this reaction, free electrons in the SiCOH film move to Ru 3 (CO) 12 through Si atoms, and at that time, Ru compounds are adsorbed on Si atoms and decomposed into Ru atoms. It is presumed that CO gas was generated.
- Ru nucleation in the initial stage of film formation is promoted, and a continuous film can be formed.
- the Si compound used for adsorbing Si atoms on the surface of the interlayer insulating film 1 is not limited to the above-mentioned monosilane, but includes disilane (Si 2 H 6 ), dichlorosilane (SiH 2 Cl 2 ), and the like. .
- the surface of the SiCOH film is treated with trimethylaluminum (TMA) gas instead of the B compound gas in the first embodiment or the silane-based gas in the second embodiment.
- TMA gas is carried by, for example, a carrier gas that is an inert gas, and is supplied into the processing container 71 from, for example, the shower head 75 shown in FIG.
- Al atoms on the SiCOH film become Ru adsorption sites. That is, since Al is a metal, it can be bonded to Ru, which is a metal, via free electrons.
- Ru 3 (CO) 12 gas described above when supplied onto the substrate S to form a Ru film, CO gas is released as a byproduct. In this reaction, free electrons in the SiCOH film move to Ru 3 (CO) 12 through Al atoms, and at that time, the Ru compound is adsorbed to Al atoms and decomposed into Ru atoms. It is presumed that CO gas was generated. For this reason, as in the first embodiment, Ru nucleation in the initial stage of film formation is promoted, and a continuous film can be formed.
- the Ru film and the Al film are stacked one molecule at a time using the above-described ALD method or the like, so that the copper embedded in the recesses of the interlayer insulating film 1 in a later step.
- the improvement of the barrier effect against 5 can be expected.
- TMA gas is used as the processing gas for the substrate surface.
- a gas containing an organic compound containing Al other than TMA is used, the effect of adsorbing Al on the substrate surface can be obtained.
- the substrate on which the SiO 2 film was formed was heated to 350 ° C., and surface treatment using diborane was performed in the same manner as in the first embodiment, and then a Ru film was formed on the surface of the SiO 2 film.
- This process is referred to as Example 1.
- the substrate on which the SiO 2 film is formed is heated to 350 ° C., and a surface treatment using silane is performed in the same manner as in the second embodiment, and then a Ru film is formed on the surface of the SiO 2 film. It was.
- This process is referred to as Example 2.
- the Ru film was formed directly on the SiO 2 film surface. This process is referred to as Comparative Example 1.
- FIG. 13 is a photograph of the surface of the film formation sample taken from an oblique direction
- FIG. 14 is a photograph of the surface of the film formation sample taken in a plane.
- the place where the Ru film is formed is white and formed.
- the areas that are not displayed are black.
- the numbers are the percentage of the area of the white area relative to the whole.
- Ru nuclei grow around the Ru atoms that are first bonded to the B and Si atoms adsorbed on the SiO 2 film surface. Then, as the reaction proceeds, a plurality of Ru nuclei that have grown are combined to form a uniform Ru film.
- FIG. 15 is a graph in which the amount of Ru analyzed by fluorescent X-ray analysis (XRF) in Examples 1 and 2 and Comparative Example 1 is plotted on the horizontal axis, and the coverage with the Ru film on the substrate surface is plotted on the vertical axis.
- the solid line (1) indicates the case where the Ru film is formed after the SiO 2 film surface is treated with diborane gas
- the dashed line (2) indicates the case where the Ru film is formed after the SiO 2 film surface is treated with silane gas.
- FIG. 16 is a photograph of the surface of the film formation sample taken from an oblique direction
- FIG. 17 is a photograph of the surface of the film formation sample taken in a plane as in FIG. 13, where the Ru film is formed. Is white and black areas are not formed. The numbers are the percentage of the area of the white area relative to the whole.
- Example 3 and Comparative Example 2 the relationship between the elapsed time from the start of the Ru film formation process and the film thickness of the Ru film was also examined. The results are shown in FIG. The horizontal axis of the graph is the elapsed time, and the vertical axis is the film thickness of the Ru film.
- the relationship between the elapsed time and the film thickness is linearly approximated based on the plot, and is considered based on the obtained straight line.
- Ru immediately after the start of the film forming process. Film deposition has begun.
- Comparative Example 2 Ru film deposition started a while after the start of film formation, and a time delay occurred.
- Example 3 the relationship between the elapsed time and the deposition rate of the Ru film was examined.
- the results are shown in FIGS.
- the graphs of FIGS. 19 and 20 represent the relationship at the center of the substrate and the average value of the entire substrate, respectively.
- the result of Example 3 is indicated by a solid line
- the result of Comparative Example 2 is indicated by a dotted line.
- Comparative Example 2 it can be seen that the deposition rate of the Ru film is low in the initial stage and increases with time.
- Example 3 it can be seen that the deposition rate of the Ru film is substantially constant over time. Considering this change in the deposition rate of the Ru film, in Comparative Example 2, there is unevenness in the Ru deposition on the surface of the substrate, and in Example 3, the Ru film is uniformly deposited on the surface of the substrate. I can hear that.
- FIG. 21 is a graph in which the horizontal axis represents the amount of Ru analyzed by fluorescent X-ray analysis (XRF) in Example 3 and Comparative Example 2, and the vertical axis represents the coverage with the Ru film on the substrate surface.
- XRF fluorescent X-ray analysis
- the SiO 2 film was used as the evaluation target, but the same result can be obtained by using the SiCOH film.
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Abstract
Description
このような観点からバリア膜として上述の材料に代えて、埋め込み特性が良好で、抵抗の小さなRu(ルテニウム)を用いることが米国公開公報US2008/237860A1(図1)に提案されている。図22は、Ruをバリア膜として用いた場合の銅配線の形成の様子を示す図である。先ず上層側の層間絶縁膜(SiCOH膜)1にトレンチ及びビアホールを含む埋め込み用の凹部2を形成した後(図22(a))、上述のTaやTaNなどの下地膜3を凹部2内に成膜し(図22(b))、次いで下地膜3の上にRu膜4を成膜する(図22(c))。しかる後に凹部2内に銅(銅からなる埋め込み材料)5を埋め込み(図22(d))、余分な銅5をCMP(Chemical Mechanical Polishing)により除去して上層側の配線構造を構築する(図22(e))。61~63は夫々下層側の層間絶縁膜、銅配線及びバリア層であり、64は銅の拡散防止機能を備えたエッチストッパ膜(エッチング時にストッパ機能を果たす膜)である。
基板上に成膜されたシリコン、炭素、水素及び酸素を含む絶縁膜であって、その底部に下層側の導電路が露出している埋め込み用の凹部が形成され、その表面が疎水性である絶縁膜に対して、ホウ素化合物ガスを供給して前記絶縁膜の表面にホウ素原子を吸着させる工程と、
前記ホウ素原子が吸着された前記凹部の表面にルテニウム膜からなる密着膜を直接形成する工程と、
しかる後、前記凹部内に導電路となる銅を埋め込む工程と、を含むことを特徴とする。
基板上に成膜されたシリコン、炭素、水素及び酸素を含む絶縁膜であって、その底部に下層側の導電路が露出している埋め込み用の凹部が形成され、その表面が疎水性である絶縁膜に対して、シリコン化合物ガスを供給して前記絶縁膜の表面にシリコン原子を吸着させる工程と、
前記シリコン原子が吸着された前記絶縁膜の表面にルテニウム(Ru)膜からなる密着膜を直接形成する工程と、
しかる後、前記凹部内に導電路となる銅を埋め込む工程と、を含むことを特徴とする。
基板上に成膜されたシリコン、炭素、水素及び酸素を含む絶縁膜であって、その底部に下層側の導電路が露出している埋め込み用の凹部が形成され、その表面が疎水性である絶縁膜に対して、アルミニウムを含む有機化合物のガスを供給して前記絶縁膜の表面にアルミニウム原子を吸着させる工程と、
前記アルミニウム原子が吸着された前記絶縁膜の表面にルテニウム(Ru)膜からなる密着膜を直接形成する工程と、
しかる後、前記凹部内に導電路となる銅を埋め込む工程と、を含むことを特徴とする。
本発明の半導体装置の製造方法の第1の実施形態を図面を参照しながら説明する。図1及び図2は、半導体装置の製造段階として下層側の配線構造の上に上層側の配線構造を形成する様子を示しており、既述の図22に示す部分と同等部分については同符号を付してある。なお65は、バリア膜であり、例えばTa膜である。
凹部2を形成するときに層間絶縁膜(SiCOH膜)1の表層部がプラズマにより既述のように損傷を受けて(結合が切断されて)Cが膜から脱離し、その後大気中の水分などによりSi-OH基が形成される。図1(b)における符号10はダメージ層を示している。このダメージ層10は比誘電率が高く、またエッチング後の層間絶縁膜1の表面にはエッチング残渣のポリマーも残っている。よってダメージ層10は、例えばフッ酸溶液によるウエットエッチングなどの方法で除去される(図1(c))。
ガスシャワーヘッド75には外部からガス供給路79が接続されている。ガス供給路79の基端側は分岐されて処理ガス供給源76及び、キャリアガス供給源77に接続されている。V1~V3はバルブ、f1、f2は流量調整部である。処理ガスとしては例えばB(ホウ素)化合物であるジボラン(B2H6)が用いられ、キャリアガスとしては例えばヘリウム(He)が用いられる。
図2(a)は、ジボランガスを用いて表面処理された後の基板Sの表面状態を示している。
銅の埋め込み工程の後は、基板Sの表面をCMPにより研磨して余分な銅を除去する。こうして上層側の銅配線構造が構成される(図2(d))。
この実施形態では、第1の実施形態におけるB化合物ガスの代わりにシラン系ガスを用いて、SiCOH膜表面を処理するようにしている。この表面処理を行うモジュールとしては、第1の実施形態の図8における表面処理モジュール304(あるいは305)において、処理ガスとしてシラン化合物ガスを用いたモジュールを挙げることができる。
Pもまた金属の性質を持つため、自由電子を介してRuと結合しやすい。よって絶縁膜の表面におけるP原子をRuの吸着サイトとして、Ru膜を層間絶縁膜1表面に形成できるので、同様の結果を得ることができる。
この実施形態では、第1の実施形態におけるB化合物ガス、あるいは第2の実施形態におけるシラン系ガスの代わりに、トリメチルアルミニウム(TMA)ガスを用いて、SiCOH膜表面を処理するようにしている。TMAガスは、例えば不活性ガスであるキャリアガスに運ばれて、例えば図3に示すシャワーヘッド75から処理容器71内へ供給される。
熱酸化膜であるSiO2膜を絶縁膜素材として用い、SiCOH膜に対する処理についての評価試験を行った。
一方、SiO2膜表面上にRu膜の成膜処理を直接行った。このプロセスを比較例1とする。
SiO2膜が形成された基板(シリコンウエハ)を350℃に加熱し、第3の実施形態と同様にしてTMAを用いた表面処理を行い、その後当該SiO2膜表面にRu膜の成膜処理を行った。このプロセスを実施例3とする。
一方、熱酸化により形成されたシリコン酸化膜上にRu膜の成膜処理を行った。このプロセスを比較例2とする。
Claims (7)
- 基板上に成膜されたシリコン、炭素、水素及び酸素を含む絶縁膜であって、その底部に下層側の導電路が露出している埋め込み用の凹部が形成され、その表面が疎水性である絶縁膜に対して、ホウ素化合物ガスを供給して前記絶縁膜の表面にホウ素原子を吸着させる工程と、
前記ホウ素原子が吸着された前記絶縁膜の表面にルテニウム(Ru)膜からなる密着膜を直接形成する工程と、
しかる後、前記凹部内に導電路となる銅を埋め込む工程と、を含むことを特徴とする半導体装置の製造方法。 - 前記ホウ素化合物は、モノボラン(BH3)、ジボラン(B2H6)、トリメチルボラン(B(CH3)3)、トリエチルボラン(B(C2H5)3)、ジカルバドデカボラン(C2B10H12)及びデカボラン(B10H14)から選択されたものであることを特徴とする請求項1記載の半導体装置の製造方法。
- 基板上に成膜されたシリコン、炭素、水素及び酸素を含む絶縁膜であって、その底部に下層側の導電路が露出している埋め込み用の凹部が形成され、その表面が疎水性である絶縁膜に対して、シリコン化合物ガスを供給して前記絶縁膜の表面にシリコン原子を吸着させる工程と、
前記シリコン原子が吸着された前記絶縁膜の表面にルテニウム(Ru)膜からなる密着膜を直接形成する工程と、
しかる後、前記凹部内に導電路となる銅を埋め込む工程と、を含むことを特徴とする半導体装置の製造方法。 - 前記シリコン化合物は、モノシラン(SiH4)及びジシラン(Si2H6)から選択されたものであることを特徴とする請求項3記載の半導体装置の製造方法。
- 基板上に成膜されたシリコン、炭素、水素及び酸素を含む絶縁膜であって、その底部に下層側の導電路が露出している埋め込み用の凹部が形成され、その表面が疎水性である絶縁膜に対して、アルミニウムを含む有機化合物のガスを供給して前記絶縁膜の表面にアルミニウム原子を吸着させる工程と、
前記アルミニウム原子が吸着された前記絶縁膜の表面にルテニウム(Ru)膜からなる密着膜を直接形成する工程と、
しかる後、前記凹部内に導電路となる銅を埋め込む工程と、を含むことを特徴とする半導体装置の製造方法。 - 前記アルミニウムを含む有機化合物は、トリメチルアルミニウムであることを特徴とする請求項5記載の半導体装置の製造方法。
- 前記絶縁膜の表面に前記ホウ素原子、シリコン原子あるいはアルミニウム原子を吸着させる工程の前に行なわれる工程であって、プラズマエッチングにより凹部を形成するときに炭素が脱落して親水性となった当該絶縁膜の表層部分を除去する工程を含むことを特徴とする請求項1に記載の半導体装置の製造方法。
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