WO2009096251A1 - アモルファスハイドロカーボン膜の後処理方法およびその方法を用いた電子デバイスの製造方法 - Google Patents
アモルファスハイドロカーボン膜の後処理方法およびその方法を用いた電子デバイスの製造方法 Download PDFInfo
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- WO2009096251A1 WO2009096251A1 PCT/JP2009/050634 JP2009050634W WO2009096251A1 WO 2009096251 A1 WO2009096251 A1 WO 2009096251A1 JP 2009050634 W JP2009050634 W JP 2009050634W WO 2009096251 A1 WO2009096251 A1 WO 2009096251A1
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- amorphous hydrocarbon
- film
- gas
- hydrocarbon film
- atmosphere
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- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 6
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 6
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- 238000000151 deposition Methods 0.000 claims description 2
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 47
- 229910000077 silane Inorganic materials 0.000 abstract description 46
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052710 silicon Inorganic materials 0.000 abstract description 18
- 125000000524 functional group Chemical group 0.000 abstract description 13
- 239000010703 silicon Substances 0.000 abstract description 11
- 239000007789 gas Substances 0.000 description 86
- 229910018540 Si C Inorganic materials 0.000 description 35
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
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- 238000007254 oxidation reaction Methods 0.000 description 7
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
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- 125000004429 atom Chemical group 0.000 description 5
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02115—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material being carbon, e.g. alpha-C, diamond or hydrogen doped carbon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
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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
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/3146—Carbon layers, e.g. diamond-like layers
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- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67155—Apparatus for manufacturing or treating in a plurality of work-stations
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- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76802—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics
- H01L21/76807—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing by forming openings in dielectrics for dual damascene structures
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- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
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- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
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Definitions
- the present invention relates to an amorphous hydrocarbon film post-processing method and an electronic device manufacturing method using the method, and more particularly, to an electronic device manufacturing method suitable for forming a mask or the like during device manufacturing.
- a silicon oxide film SiO 2 film
- a film having a lower dielectric constant low-k film
- a silicon (Si) -based organic material containing Si, O, and C is used.
- a low dielectric constant film mainly composed of silicon is expensive and has a problem that it is difficult to perform highly selective etching with other films.
- an amorphous hydrocarbon film added with hydrogen has attracted attention as a low dielectric constant film that does not cause such a problem (see, for example, Patent Document 1).
- the amorphous hydrocarbon film is formed by CVD (Chemical Vapor Deposition) using a hydrocarbon gas or the like as a processing gas.
- CVD Chemical Vapor Deposition
- the film is subjected to a heat treatment (annealing process, etc.) at a temperature of about 350 ° C. to 400 ° C. so as not to cause alteration or dimensional change of each layer. Is done.
- a heat treatment annealing process, etc.
- the relatively heat-sensitive part of the surface of the amorphous hydrocarbon film is broken and part of the film is detached, resulting in dangling bonds (unbonded atoms).
- the present invention provides an amorphous hydrocarbon film post-processing method executed for protecting the surface of the amorphous hydrocarbon film, and an electronic device manufacturing method including the post-processing method. . Furthermore, a computer-readable storage medium storing a control program for executing these methods and a processing system for executing these methods are provided.
- a method for post-processing an amorphous hydrocarbon film in which an amorphous hydrocarbon film is formed on a substrate and Si x H is formed at a desired timing.
- a post-processing method for an amorphous hydrocarbon film in which a heat treatment is performed in an atmosphere of a Si x H y- based gas while supplying the y- based gas while the y- type gas is supplied.
- a weakly bonded portion may be cut and an unbonded hand (dangling bond) may be generated (processing a in FIG. 2).
- an atmosphere such as the atmosphere where moisture and hydroxyl groups are present, the dangling bonds and hydroxyl groups are combined to oxidize the film surface (treatment b in FIG. 2).
- the heat treatment in the atmosphere of the Si x H y gas is performed on the amorphous hydrocarbon film.
- the vapor of Si x H y gas is brought into contact with the surface of the amorphous hydrocarbon film.
- the hydroxyl group on the film surface and the H atom of the Si x H y- based gas undergo a chemical reaction, whereby the OH group is replaced with a silicon atom to form a Si—C bond.
- a highly polar functional group such as a hydroxyl group present on the outermost surface of the amorphous hydrocarbon film is replaced with a Si—C bond that is a group containing silicon (see processing c and processing d in FIG. 2).
- the difference in electronegativity ⁇ of the Si—O bond is 1.54, which is more than twice the difference 0.65 in electronegativity ⁇ of the Si—C bond. This shows that more electrons flow from silicon atoms to oxygen atoms than electrons flow from silicon atoms to carbon atoms, that is, Si—O bonds are more polar (polarization, ionic) than Si—C bonds. Yes.
- the electronegativity ⁇ (H) of the hydrogen atom is 2.20
- the electronegativity ⁇ (O) of the oxygen atom (O) is 3.44.
- the difference in electronegativity ⁇ of —H bond is 1.24, which is also about twice the difference in electronegativity ⁇ of Si—C bond. Therefore, the O—H bond has a higher polarity than the Si—C bond.
- amorphous hydrocarbon film of process a in FIG. 10 is heat-treated, as shown in process b of FIG. 10, it is exposed to the atmosphere and OH groups are attached to the film surface.
- treatment c even when the film is subjected to silylation treatment with a silylating agent such as DMSDMA, the OH groups on the film surface are reduced and replaced with Si—O bonds.
- treatment d when moisture (H 2 O) or hydroxyl group (OH) approaches the Si—O bond, the Si—O bond is more polar than the Si—C bond. Similarly to the case of bonding, it is likely to cause a chemical reaction with moisture and hydroxyl groups having high polarity, and the film surface may be oxidized again.
- the amorphous hydrocarbon film is heated (not in a silane atmosphere) (process a in FIG. 2), in the atmosphere.
- treatment b in FIG. 2 After exposure to water (treatment b in FIG. 2) and heat treatment (in a silane atmosphere) (treatment c in FIG. 2), even if highly polar moisture and hydroxyl groups approach the film surface, they are shown as treatment d in FIG.
- the film surface layer having Si—C bonds prevents the film deterioration due to moisture more effectively than the Si—O bond, and the electrical characteristics such as dielectric constant and adhesion of the amorphous hydrocarbon film.
- the physical characteristics such as can be kept in a better state.
- the Si x H desired timing to be supplied with y based gas may be a heat treatment simultaneously, or even in the middle of the heat treatment.
- heat treatment in the atmosphere of the Si x H y based gas may be performed immediately after the heat treatment non atmosphere advance the Si x H y based gas into the amorphous hydrocarbon layer is performed.
- Si x H y gas is supplied at the same time as the heat treatment, the surface of the film becomes Si—C bonds without oxidizing the surface of the film with a hydroxyl group or the like, as shown in processes a to c of FIG. Can be protected. Thereby, the oxidation of the amorphous hydrocarbon film surface can be more effectively prevented.
- the Si x H y- based gas may contain any of monomethylsilane, dimethylsilane, and trimethylsilane.
- the heat treatment in the atmosphere of the Si x H y gas may be performed at a temperature of 200 ° C. to 400 ° C.
- the heat treatment in the atmosphere of the second Si x H y gas is preferably performed on an amorphous hydrocarbon film having a thickness of 10 nm or less. This is because if the amorphous hydrocarbon film has a thickness of 10 nm or more, the dielectric constant increases and the speed of the electronic device cannot be increased.
- the step of forming an amorphous hydrocarbon film on a substrate and the film formation while supplying a Si x H y gas at a desired timing are performed. And a step of subjecting the amorphous hydrocarbon film to a heat treatment in an atmosphere of a Si x H y gas, an electronic device manufacturing method is provided.
- the heat treatment is performed in an atmosphere of Si x H y gas while supplying the Si x H y gas at a desired timing. That is, in the heat treatment, the vapor of the Si x H y gas is brought into contact with the surface of the amorphous hydrocarbon film at a desired timing. Therefore, even when a weakly bonded portion is broken by heat treatment and becomes a dangling bond, a Si—C bond can be formed on the film surface by the dangling bond and the silicon atom. As a result, it is possible to prevent hydroxyl groups and moisture from adsorbing on the surface of the amorphous hydrocarbon film and increasing functional groups such as hydroxyl groups over time. Thereby, the electrical characteristics and physical characteristics of the amorphous hydrocarbon film can be maintained in a good state.
- a step of forming a predetermined film on the amorphous hydrocarbon film may be included after the step of performing the heat treatment in the atmosphere of the Si x H y gas.
- the predetermined film include a SiO 2 film, a SiN film, a SiCN film, a SiCO film, and a Cu, Ti, Ta, and W as a metal film that function as a cap film and a hard mask.
- the step of performing the heat treatment in the atmosphere of the Si x H y gas may be performed at a temperature of 200 ° C. to 400 ° C.
- the amorphous hydrocarbon film may be an interlayer insulating film.
- a computer-readable storage medium storing a control program for causing a computer to implement the post-processing method of the amorphous hydrocarbon film.
- a computer-readable storage medium storing a control program for causing a computer to implement the method for manufacturing an electronic device.
- a processing system for manufacturing an electronic device which includes an amorphous hydrocarbon film forming apparatus and a heat processing apparatus.
- the amorphous hydrocarbon layer is deposited on a substrate using a film processing apparatus, desired while supplying Si x H y based gas to the timing, the amorphous hydrocarbon layer using the heat treatment apparatus Si x
- a processing system for performing heat treatment in an atmosphere of a Hy- based gas is provided.
- Si—C bonds can be formed on the film surface by chemically reacting dangling bonds generated on the film surface during the heat treatment with silicon atoms. Thereby, the characteristic of an electronic device can be kept favorable irrespective of a subsequent process.
- Si—C bonds can be formed on the surface of the amorphous hydrocarbon film, and oxidation of the film surface can be prevented.
- the semiconductor wafer W is carried into the amorphous hydrocarbon film forming apparatus.
- a SiCO-based low dielectric constant film (Low-k film 105) is formed on the semiconductor wafer W as a base film on the silicon substrate Sub.
- an amorphous hydrocarbon film 110 is formed on the low-k film 105 in step b of FIG.
- a method for forming the amorphous hydrocarbon film 110 it is preferable to perform the film forming process by CVD, but the method is not limited to this.
- propylene (C 3 H 6 ), propyne (C 3 H 4 ), propane (C 3 H 8 ), butane (C 4 H 10 ), butylene (C 4 H 8 ), butadiene ( Hydrocarbon gases such as C 4 H 6 ) and acetylene (C 2 H 2 ), and those mainly composed of these compounds can be used.
- a processing gas for example, a film can be formed by the method described in JP-A-2002-12972. Further, by containing oxygen as a processing gas, a strong carbon network can be formed even at a relatively low temperature.
- a heat treatment such as an annealing treatment (not in a silane gas atmosphere) is performed as shown in step c of FIG.
- This treatment is performed under appropriate conditions depending on the electronic device (semiconductor element) to be obtained.
- the treatment is performed in a non-oxidizing atmosphere (vacuum or an inert gas atmosphere such as Ar gas, N 2 gas, etc.) It is performed at a temperature of about 400 ° C.
- the amorphous hydrocarbon film 110 immediately after the film formation has a healthy surface state and does not change with time even when taken out into the atmosphere. However, after the heat treatment such as the annealing process is performed, the amorphous hydrocarbon film 110 110, a relatively heat-sensitive portion on the surface is broken and a part of the film is detached, and dangling bonds are formed on the surface layer of the amorphous hydrocarbon film 110 as shown in process a of FIG. Arise.
- a functional group having a polarity such as a carbonyl group or a hydroxyl group is formed in the film, and such a functional group increases with time.
- Such a functional group adsorbs moisture or greatly changes electrical characteristics such as dielectric constant and other characteristics.
- the heat treatment step in the silane gas atmosphere is performed immediately after the heat treatment not in the silane gas atmosphere.
- a functional group having a polarity such as a hydroxyl group formed on the surface of the amorphous hydrocarbon film 110 is reacted with silane gas to produce silicon (Si).
- Substitution (reduction, Si—C bond) is performed on the containing group. Thereby, the surface of the amorphous hydrocarbon film 110 is protected, and it can be prevented that the functional group such as a hydroxyl group increases with time and the characteristics are changed.
- the value of the dielectric constant k slightly increases, but the value hardly changes even if it is left in the atmosphere after that.
- the refractive index even if it is left in the air after the silylation treatment, its value hardly changes.
- immediate after the heat treatment that is not in the silane gas atmosphere is performed may be within a period in which the characteristics of the amorphous hydrocarbon film hardly deteriorate after the heat treatment.
- the electronegativity ⁇ (Si) of the silicon atom (Si) is 1.90.
- the electronegativity ⁇ (C) of the carbon atom (C) is 2.55, and the electronegativity ⁇ (O) of the oxygen atom (O) is 3.44. Therefore, although the Si—C bond and the Si—O bond are both covalent bonds, the carbon atom and the oxygen atom have a greater force to draw electrons than the silicon atom, and in any bond, the carbon element and the oxygen atom In this state, a small amount of electrons flow into the polar bond.
- the difference in electronegativity ⁇ of the Si—O bond is 1.54, which is more than twice the difference 0.65 in electronegativity ⁇ of the Si—C bond. This shows that more electrons flow from silicon atoms to oxygen atoms than electrons flow from silicon atoms to carbon atoms, that is, Si—O bonds are more polar (polarization, ionic) than Si—C bonds. Yes.
- the electronegativity ⁇ (H) of the hydrogen atom is 2.20
- the electronegativity ⁇ (O) of the oxygen atom (O) is 3.44.
- the difference in electronegativity ⁇ of —H bond is 1.24, which is also about twice the difference in electronegativity ⁇ of Si—C bond. Therefore, the O—H bond has a higher polarity than the Si—C bond.
- process a of FIG. 10 after the amorphous hydrocarbon film is heated, as shown in process b of FIG. 10, it is exposed to the atmosphere so that OH groups adhere to the film surface.
- process c of FIG. 10 the film was subjected to silylation treatment with a silylating agent such as DMSDMA to reduce OH groups on the film surface and replace them with Si—O bonds.
- a silylating agent such as DMSDMA
- moisture (H 2 O) or a hydroxyl group (OH) approaches the Si—O bond
- the Si—O bond is more polar than the Si—C bond. Therefore, a chemical reaction with moisture and hydroxyl groups having the same polarity as in the case of Si—C bonds is likely to occur, and the film surface may be oxidized again.
- the Si—C bond has a low polarity and the state of the covalent bond is close to a nonpolar bond
- the amorphous hydrocarbon film is heated (not in a silane gas atmosphere) (process a in FIG. 2), in the atmosphere.
- process d of FIG. 2 even if highly polar moisture and hydroxyl groups approach after exposure to (treatment b in FIG. 2) and heat treatment (in a silane gas atmosphere) (treatment c in FIG. 2) It is difficult to cause a chemical reaction (reduction reaction), thereby preventing oxidation of the film.
- having a Si—C bond in the surface layer of the film prevents deterioration of the film due to moisture more than having a Si—O bond, and physical properties such as electrical properties such as dielectric constant and adhesion of the amorphous hydrocarbon film.
- the mechanical characteristics can be kept in a better state.
- a cap film or a hard mask is formed on the amorphous hydrocarbon film 110.
- a predetermined film 115 made of Cu, Ti, Ta, W or the like is formed as a SiO 2 film, a SiN film, a SiCN film, a SiCO film, or a metal film.
- the film characteristics are not deteriorated over time, and a series of subsequent treatments. An electronic device having good characteristics can be manufactured.
- a hard mask is formed as the film 115 to be in the state of step e in FIG. 1, from which holes 120, amorphous hydrocarbons are formed in the low-k film 105.
- a trench 125 is formed in the film 110 by etching, and then a barrier film 130 and a Cu film 135 are formed (FIG. 3).
- This processing system Sys is a cluster type apparatus group, and includes an amorphous hydrocarbon film forming processing apparatus PM1, a heat processing apparatus PM2, a heat processing apparatus PM3, a film forming processing apparatus PM4, and an etching processing apparatus PM5.
- the amorphous hydrocarbon film formation processing apparatus PM1 forms an amorphous hydrocarbon film on a predetermined film formed on a semiconductor wafer, for example, a SiCO-based low dielectric constant film (Low-k film).
- the heat treatment apparatus PM2 performs heat treatment not in a silane gas atmosphere on the semiconductor wafer on which the amorphous hydrocarbon film is formed.
- An example of heat treatment that is not in a silane gas atmosphere is annealing.
- the heat treatment apparatus PM3 heat-treats the amorphous hydrocarbon film after the heat treatment in a silane gas atmosphere.
- the film forming apparatus PM4 forms a predetermined film on the amorphous hydrocarbon film after the heat treatment in the silane gas atmosphere.
- the etching processing apparatus PM5 forms holes and trenches in desired portions with an etching gas.
- the processing system Sys carries in the semiconductor wafer from the load lock chamber LLM in a desired reduced pressure state, and transfers between the processing apparatuses using the arm Arm arranged in the transfer chamber TM.
- a process controller 200 having a microprocessor (CPU 200a), a memory (ROM 200b and RAM 200c) and an interface (internal interface 200d, external interface 200e).
- CPU 200a microprocessor
- ROM 200b and RAM 200c memory
- interface 200d external interface 200e
- the process controller 200 is connected with a keyboard through which an operation manager inputs commands to manage each device, and a display that visualizes and displays the operating status of each device through an interface.
- a recipe in which a control program that defines a process to be executed by each processing apparatus, processing condition data, and the like is recorded is stored in a storage area such as the ROM 200b and the RAM 200c.
- the CPU 200a controls a process executed by each processing apparatus while using a control program and related data stored in an arbitrary storage area.
- the recipe may be stored in a readable storage medium such as a CD-ROM, a hard disk, a flexible disk, or a nonvolatile memory, and may be available from an external device connected via a network. .
- FIG. 5 shows a longitudinal section of a heat treatment apparatus PM3 that performs heat treatment in a silane atmosphere. Note that description of other processing apparatuses is omitted in this specification, but known apparatuses can be used.
- the heat treatment apparatus PM3 includes a container 300 and a lid 305.
- first shield rings 310 are provided on the inner peripheral side and the outer peripheral side, respectively.
- second shield rings 315 are provided on the inner peripheral side and the outer peripheral side on the lower outer peripheral surface of the lid 305, respectively.
- the first shield ring 310 and the second shield ring 315 are in close contact with each other on the inner peripheral side and the outer peripheral side, and further, the first shield ring 310 and the second shield ring 315 are in close contact with each other.
- an airtight process chamber U is formed.
- the container 300 is provided with a hot plate 320.
- a heater 320a is embedded in the hot plate 320, and the temperature in the processing chamber U is adjusted to a desired temperature by the heater 320a.
- a pin 320b for supporting the glass substrate G is provided on the upper surface of the hot plate 320 so as to be able to move up and down, thereby facilitating the conveyance of the substrate and preventing the back surface of the substrate from being contaminated.
- Silane gas is vaporized by the vaporizer 325, becomes vaporized molecules, passes through the gas flow path 330 using argon (Ar) gas as a carrier gas, and is supplied from the periphery of the hot plate 320 to the inside of the processing chamber U.
- the supply of silane gas is controlled by opening and closing the electromagnetic valve 335.
- An exhaust port 340 is provided at substantially the center of the upper portion of the lid 305, and the silane gas and the argon gas supplied to the processing chamber U are exhausted to the outside using the pressure adjusting device 345 and the vacuum pump P. Yes.
- silane gas is supplied from the periphery of the hot plate 320 to the lower side in the processing chamber U using argon gas as a carrier gas, and the pressure is adjusted from an exhaust port provided on the bottom surface of the apparatus. You may make it exhaust outside using the apparatus 345 and the vacuum pump P.
- argon gas as a carrier gas
- the hot plate 320 is controlled to a predetermined temperature so that the temperature of the vaporizer 325 becomes a temperature in the range of 200 to 400 ° C.
- the gas flow rate and the exhaust amount of the vacuum pump P are controlled so that the pressure of the gas is about 20 mTorr.
- the semiconductor wafer W is placed on the pin 320b of the hot plate 320, and the silane gas flow rate is controlled to, for example, 50 sccm and the argon gas flow rate is, for example, 50 sccm.
- the amorphous hydrocarbon film 110 is subjected to a heat treatment in a silane gas atmosphere for 10 to 30 minutes.
- the vapor of the silane gas is brought into contact with the surface of the amorphous hydrocarbon film 110 to cause a chemical reaction between the silane gas and the OH group.
- functional groups such as OH groups attached to the surface of the amorphous hydrocarbon film 110 can be reduced and replaced with stable Si—C bonds.
- the inventor introduced silane gas and argon gas in a ratio of 1: 1 at a rate of 50 sccm during the experiment. Under the conditions, the inventor performed heat treatment (post-treatment of the amorphous hydrocarbon film) in a silane gas atmosphere under the following two pattern temperature conditions. (1) Temperature 350 ° C (2) Temperature 400 ° C
- the outermost layer a 1 of the amorphous hydrocarbon film had a high strength in the vicinity of 102 (eV) which is the binding energy of the Si—O bond.
- the inventor conducted the heat treatment in the silane gas atmosphere described above, and the silane gas proceeded to dissociate at the above temperature, chemically reacted with the hydroxyl group (OH) present on the surface of the amorphous hydrocarbon film, and reduced. It was clarified that the OH—C bond was replaced with the Si—C bond.
- the strength was higher when the amorphous hydrocarbon film was formed or post-treated at 400 ° C. than at 350 ° C. That is, the inventor has clarified that, in a temperature range of about 300 to 400 ° C., the higher the temperature, the more the Si—C bond can be promoted and the film surface can be protected more firmly.
- the inventor measured the silicon concentration in order to confirm the state of the surface layer of the amorphous hydrocarbon film by another method.
- ESCA Electron Spectroscopy for Chemical Analysis
- the results of the temperature conditions (1) and (2) are shown in FIGS. 7A and 7B, respectively. Each graph shows the state of the film closer to the surface toward the left.
- the silicon concentration in the surface layer with a film depth of about 1 nm was high when the temperature shown in FIG. 7B was as high as 400 ° C.
- the inventor has replaced the hydroxyl groups (OH) present on the surface of the amorphous hydrocarbon film with silicon atoms by the heat treatment in the silane gas atmosphere described above, even by the silicon concentration of the surface layer of the amorphous hydrocarbon film. Proved.
- the appropriate temperature range of about 300 to 400 ° C. it was proved that the higher the temperature, the more dissociation of the silane gas progressed, the chemical reaction was promoted, and the substitution to the Si—C bond was further promoted.
- the post-treatment method of the amorphous hydrocarbon film according to the present embodiment by replacing the polar hydroxyl group (functional group) with a stable Si—C covalent bond, Therefore, the deterioration of the film due to moisture adsorption or the like can be prevented, and the characteristics of the manufactured electronic device can be kept good.
- the heat treatment divided into two steps in the first embodiment is one step shown in step c of FIG.
- the desired timing for supplying the silane gas may be simultaneous with the start of the heat treatment or in the middle of the heat treatment. If silane gas is supplied simultaneously with the start of the heat treatment, as shown in treatment a to treatment c in FIG. 9, the dangling bonds and silicon atoms are directly bonded without oxidizing the film surface with a hydroxyl group, etc. The film surface can be protected by Si—C bonds. Thereby, the oxidation of the amorphous hydrocarbon film surface can be more effectively prevented.
- monosilane gas (SiH 4 ) is used for the heat treatment in the silane gas atmosphere.
- the heat treatment in the silane gas atmosphere is not limited to this, and the above effect can be obtained even if Si x H y gas is used. It can be obtained sufficiently.
- the Si x H y gas contains any of monomethylsilane (CH 3 SiH 3 ), dimethylsilane ((CH 3 ) 2 SiH 2 ), and trimethylsilane ((CH 3 ) 3 SiH). Is preferred. Since trimethylsilane, dimethylsilane, and monomethylsilane are easily dissociated in this order, the use of trimethylsilane or dimethylsilane can lower the process temperature. For example, monomethylsilane has an appropriate temperature of about 300 to 400 ° C., while dimethylsilane and trimethylsilane have an appropriate temperature of about 200 to 300 ° C.
- the heat treatment in the silane gas atmosphere is preferably performed on an amorphous hydrocarbon film having a thickness of 10 nm or less. This is because if the amorphous hydrocarbon film has a thickness of 10 nm or more, the dielectric constant increases and the speed of the electronic device cannot be increased.
- the above effect can be obtained even when the heat treatment in the silane gas atmosphere is performed at a pressure of atmospheric pressure to 1 Torr. Further, the heat treatment in the silane gas atmosphere may be 10 minutes to 30 minutes.
- the flow rates of the silane gas and the argon gas are 1: 1, but the present invention is not limited to this, and the concentration of the silane gas with respect to the inert gas may be 10% to 100%.
- the inert gas nitrogen gas or the like can be used in addition to argon gas.
- the operations of the respective units are related to each other, and can be replaced as a series of operations in consideration of the relationship between each other. And by substituting in this way, embodiment of the post-processing method of the said amorphous hydrocarbon film can be made into embodiment of the manufacturing method of an electronic device.
- the embodiment of the electronic device manufacturing method can be made the embodiment of the control program for controlling the electronic device manufacturing method.
- an amorphous hydrocarbon film is applied as an interlayer insulating film.
- the present invention can also be applied to other uses such as an antireflection film.
- the antireflective film has a specific refractive index.
- the refractive index tends to increase with time by leaving it in the air after the heat treatment not in the silane gas atmosphere. For this reason, the temporal change of the refractive index can be prevented by the post-processing method of the present invention. As a result, stable characteristics as an antireflection film can be obtained.
- the amorphous carbon film is left in the air after being subjected to a heat treatment such as annealing.
- the present invention is not limited to the air, but is effective in a case where the amorphous carbon film is left in an atmosphere containing oxygen and hydrogen to some extent. Can be obtained.
- the semiconductor wafer is exemplified as the object to be processed.
- the present invention is not limited to this, and a glass substrate for a flat panel display (FPD: Flat Panel Display) typified by a liquid crystal display device (Liquid Crystal Display) or the like. It can also be applied to other substrates.
- FPD Flat Panel Display
- liquid crystal display device Liquid Crystal Display
- Low-k film 110 Amorphous hydrocarbon film 200
- Process controller 200a CPU 200b ROM 200c RAM
- PM1 Amorphous hydrocarbon film-forming treatment device
- PM2 Heat treatment device
- PM3 Heat treatment device (silane atmosphere)
- PM4 Deposition System Sub Silicon Substrate Sys Processing System
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Abstract
Description
まず、本発明の第1実施形態にかかるアモルファスハイドロカーボン膜の後処理方法を含んだ電子デバイスの製造工程について、工程断面図及びその手順を示した図1を参照しながら説明する。
つぎに、本実施形態にかかるアモルファスハイドロカーボン膜の後処理方法の効果を実証するために、実際に発明者が行った実験及びその実験結果について、図6A、図6B、図7A及び図7Bを参照しながら説明する。
(1)温度 350℃
(2)温度 400℃
次に、本発明の第2実施形態に係るアモルファスハイドロカーボン膜の後処理方法を含んだ電子デバイスの製造工程について、工程断面図及びその手順を示した図8を参照しながら説明する。
110 アモルファスハイドロカーボン膜
200 プロセスコントローラ
200a CPU
200b ROM
200c RAM
PM1 アモルファスハイドロカーボン成膜処理装置
PM2 加熱処理装置
PM3 加熱処理装置(シラン雰囲気)
PM4 成膜処理装置
Sub シリコン基板
Sys 処理システム
Claims (17)
- アモルファスハイドロカーボン膜の後処理方法であって、
基板上にアモルファスハイドロカーボン膜を成膜し、
所望のタイミングにSixHy系ガスを供給しながら、前記成膜されたアモルファスハイドロカーボン膜にSixHy系ガスの雰囲気中にて加熱処理を施すアモルファスハイドロカーボン膜の後処理方法。 - 前記SixHy系ガスの雰囲気中の加熱処理は、SixHy系ガスの蒸気を前記アモルファスハイドロカーボン膜の表面に接触させる請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法。
- 前記SixHy系ガスは、モノメチルシラン、ジメチルシラン、トリメチルシランのいずれかを含む請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法。
- 前記SixHy系ガスの雰囲気中の加熱処理は、200℃~400℃の温度で実行される請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法。
- 前記SixHy系ガスの雰囲気中の加熱処理は、前記アモルファスハイドロカーボン膜に前もって前記SixHy系ガスの雰囲気中でない加熱処理が実行された直後に行われる請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法。
- 前記SixHy系ガスの雰囲気中の加熱処理は、大気圧~1Torrの圧力で実行される請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法。
- 前記SixHy系ガスの雰囲気中の加熱処理は、10分~30分間実行される請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法。
- 前記アモルファスハイドロカーボン膜は、10nm以下の膜厚である請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法。
- 前記SixHy系ガスの雰囲気中でない加熱処理は、アニール処理である請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法。
- 基板上にアモルファスハイドロカーボン膜を形成する工程と、
所望のタイミングにSixHy系ガスを供給しながら、前記成膜されたアモルファスハイドロカーボン膜にSixHy系ガスの雰囲気中にて加熱処理を施す工程と、を含む電子デバイスの製造方法。 - 前記SixHy系ガスの雰囲気中にて加熱処理を施す工程後、前記アモルファスハイドロカーボン膜上に所定の膜を成膜する工程を含む請求項10に記載された電子デバイスの製造方法。
- 前記SixHy系ガスの雰囲気中にて加熱処理を施す工程は、SixHy系ガスの蒸気を前記アモルファスハイドロカーボン膜の表面に接触させる請求項10に記載された電子デバイスの製造方法。
- 前記SixHy系ガスの雰囲気中にて加熱処理を施す工程は、200℃~400℃の温度で実行される請求項10に記載された電子デバイスの製造方法。
- アモルファスハイドロカーボン膜は、層間絶縁膜である請求項10に記載された電子デバイスの製造方法。
- 請求項1に記載されたアモルファスハイドロカーボン膜の後処理方法をコンピュータに実現させるための制御プログラムが記憶されたコンピュータ読取可能な記憶媒体。
- 請求項10に記載された電子デバイスの製造方法をコンピュータに実現させるための制御プログラムが記憶されたコンピュータ読取可能な記憶媒体。
- アモルファスハイドロカーボン膜の成膜処理装置と加熱処理装置とを含み、電子デバイスを製造する処理システムであって、
前記成膜処理装置を使用して基板上にアモルファスハイドロカーボン膜を成膜し、
所望のタイミングにSixHy系ガスを供給しながら、前記加熱処理装置を使用して前記アモルファスハイドロカーボン膜にSixHy系ガスの雰囲気中にて加熱処理を施す処理システム。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2009551466A JP5296714B2 (ja) | 2008-01-30 | 2009-01-19 | アモルファスハイドロカーボン膜の後処理方法およびその方法を用いた電子デバイスの製造方法 |
US12/864,606 US8936829B2 (en) | 2008-01-30 | 2009-01-19 | Method of aftertreatment of amorphous hydrocarbon film and method for manufacturing electronic device by using the aftertreatment method |
KR1020107016154A KR101130065B1 (ko) | 2008-01-30 | 2009-01-19 | 어모퍼스 하이드로 카본막의 후처리 방법 및 그의 방법을 사용한 전자 디바이스의 제조 방법, 및 관련 기억 매체 및 관련 처리 시스템 |
CN2009801036506A CN101971322A (zh) | 2008-01-30 | 2009-01-19 | 非晶碳氢膜的后处理方法以及使用了该方法的电子器件的制造方法 |
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US (1) | US8936829B2 (ja) |
JP (1) | JP5296714B2 (ja) |
KR (1) | KR101130065B1 (ja) |
CN (1) | CN101971322A (ja) |
TW (1) | TWI464804B (ja) |
WO (1) | WO2009096251A1 (ja) |
Cited By (1)
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US20110195580A1 (en) * | 2010-02-05 | 2011-08-11 | Tokyo Electron Limited | Method for forming laminated structure including amorphous carbon film |
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CN102892706B (zh) * | 2010-03-03 | 2015-08-12 | 太阳化学工业株式会社 | 在由非晶质碳膜构成的层的固定化方法及层叠体 |
KR101565042B1 (ko) | 2014-01-10 | 2015-11-03 | 국제엘렉트릭코리아 주식회사 | 하부막 전처리 방법 및 이를 이용한 박막 형성 방법 |
CN105244254B (zh) * | 2014-07-09 | 2018-10-16 | 中芯国际集成电路制造(上海)有限公司 | 半导体结构的形成方法 |
CN105990237B (zh) * | 2015-02-04 | 2019-01-22 | 中芯国际集成电路制造(上海)有限公司 | 一种半导体器件及其制造方法、电子装置 |
US11694902B2 (en) * | 2021-02-18 | 2023-07-04 | Applied Materials, Inc. | Methods, systems, and apparatus for processing substrates using one or more amorphous carbon hardmask layers |
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JPH11297686A (ja) * | 1998-04-08 | 1999-10-29 | Nec Corp | 半導体装置の製造方法 |
WO2008004584A1 (fr) * | 2006-07-05 | 2008-01-10 | Tokyo Electron Limited | Procédé de post-traitement destiné à un film de carbone amorphe |
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US6030904A (en) * | 1997-08-21 | 2000-02-29 | International Business Machines Corporation | Stabilization of low-k carbon-based dielectrics |
US6423384B1 (en) * | 1999-06-25 | 2002-07-23 | Applied Materials, Inc. | HDP-CVD deposition of low dielectric constant amorphous carbon film |
JP5121090B2 (ja) * | 2000-02-17 | 2013-01-16 | アプライド マテリアルズ インコーポレイテッド | アモルファスカーボン層の堆積方法 |
US6573030B1 (en) | 2000-02-17 | 2003-06-03 | Applied Materials, Inc. | Method for depositing an amorphous carbon layer |
US6562735B1 (en) * | 2001-12-11 | 2003-05-13 | Lsi Logic Corporation | Control of reaction rate in formation of low k carbon-containing silicon oxide dielectric material using organosilane, unsubstituted silane, and hydrogen peroxide reactants |
US6936551B2 (en) | 2002-05-08 | 2005-08-30 | Applied Materials Inc. | Methods and apparatus for E-beam treatment used to fabricate integrated circuit devices |
US6900002B1 (en) * | 2002-11-19 | 2005-05-31 | Advanced Micro Devices, Inc. | Antireflective bi-layer hardmask including a densified amorphous carbon layer |
JP2006013190A (ja) | 2004-06-28 | 2006-01-12 | Rohm Co Ltd | 半導体装置の製造方法 |
DE102004057997A1 (de) * | 2004-12-01 | 2006-06-08 | Wacker Chemie Ag | Metalloxide mit einer in einem weiten pH-Bereich permanenten positiven Oberflächenladung |
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2009
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- 2009-01-19 JP JP2009551466A patent/JP5296714B2/ja not_active Expired - Fee Related
- 2009-01-19 CN CN2009801036506A patent/CN101971322A/zh active Pending
- 2009-01-19 KR KR1020107016154A patent/KR101130065B1/ko not_active IP Right Cessation
- 2009-01-23 TW TW098103126A patent/TWI464804B/zh not_active IP Right Cessation
Patent Citations (2)
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JPH11297686A (ja) * | 1998-04-08 | 1999-10-29 | Nec Corp | 半導体装置の製造方法 |
WO2008004584A1 (fr) * | 2006-07-05 | 2008-01-10 | Tokyo Electron Limited | Procédé de post-traitement destiné à un film de carbone amorphe |
Cited By (2)
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US20110195580A1 (en) * | 2010-02-05 | 2011-08-11 | Tokyo Electron Limited | Method for forming laminated structure including amorphous carbon film |
US8592324B2 (en) * | 2010-02-05 | 2013-11-26 | Tokyo Electron Limited | Method for forming laminated structure including amorphous carbon film |
Also Published As
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CN101971322A (zh) | 2011-02-09 |
JP5296714B2 (ja) | 2013-09-25 |
US20100304014A1 (en) | 2010-12-02 |
TWI464804B (zh) | 2014-12-11 |
US8936829B2 (en) | 2015-01-20 |
JPWO2009096251A1 (ja) | 2011-05-26 |
KR101130065B1 (ko) | 2012-03-29 |
TW200949940A (en) | 2009-12-01 |
KR20100088716A (ko) | 2010-08-10 |
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