WO2006043433A1 - プラズマcvd装置 - Google Patents
プラズマcvd装置 Download PDFInfo
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- WO2006043433A1 WO2006043433A1 PCT/JP2005/018615 JP2005018615W WO2006043433A1 WO 2006043433 A1 WO2006043433 A1 WO 2006043433A1 JP 2005018615 W JP2005018615 W JP 2005018615W WO 2006043433 A1 WO2006043433 A1 WO 2006043433A1
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- Prior art keywords
- film
- substrate
- plasma
- reaction vessel
- compound
- Prior art date
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- 239000000758 substrate Substances 0.000 claims abstract description 60
- BGECDVWSWDRFSP-UHFFFAOYSA-N borazine Chemical group B1NBNBN1 BGECDVWSWDRFSP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 238000005229 chemical vapour deposition Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 14
- 238000010438 heat treatment Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000003254 radicals Chemical class 0.000 description 13
- 239000012159 carrier gas Substances 0.000 description 9
- -1 hydride carbon Chemical compound 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000008016 vaporization Effects 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 235000011470 Adenanthera pavonina Nutrition 0.000 description 2
- 240000001606 Adenanthera pavonina Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000010943 off-gassing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical compound B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000005596 ionic collisions Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
Classifications
-
- 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
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/38—Borides
-
- 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
- C23C16/44—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 method of coating
- C23C16/50—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 method of coating using electric discharges
- C23C16/505—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 method of coating using electric discharges using radio frequency discharges
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/02123—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 containing silicon
- H01L21/0217—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 containing silicon the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
- H01L21/318—Inorganic layers composed of nitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
Definitions
- the present invention relates to a plasma CVD (Chemical Vapor Deposition) apparatus.
- the signal delay is expressed as the product of the wiring resistance and the capacitance between the wirings and between the layers.
- the dielectric resistance of the interlayer insulating film is reduced along with lowering the wiring resistance. Lowering the rate is an effective means.
- an interlayer insulating layer containing BCN bonds is formed on the surface of the object by plasma CVD in an atmosphere containing a hydride carbon-based gas, borazine and a plasma-based gas.
- a method of forming a film is disclosed. Further, it is also disclosed that the interlayer insulating film has a low dielectric constant (see, for example, Japanese Patent Laid-Open No. 2000-058538 (Patent Document 1)).
- Patent Document 1 JP 2000-058538 A
- the present invention has been made to solve the above-mentioned problems of the prior art, and the object thereof is to stably obtain a low dielectric constant and high mechanical strength over a long period of time and to heat a film.
- the object is to provide a plasma CVD apparatus capable of producing a film that reduces the amount of gas components (outgas) released to the substrate and does not cause problems in the device production process.
- the plasma CVD apparatus of the present invention comprises means for supplying a compound having a borazine skeleton, a plasma generator for generating plasma, and means for applying a negative charge to an electrode on which a substrate is placed. It is characterized by.
- the compound having a borazine skeleton is represented by the following chemical formula (1).
- R to R may be the same or different from each other, a hydrogen atom and a carbon number of 1
- alkyl groups, alkenyl groups or alkyl groups are each independently selected, and at least one of R to R is not a hydrogen atom
- the plasma CVD apparatus of the present invention includes a reaction vessel for forming a film on a substrate by plasma chemical vapor deposition and a plasma generator provided outside the reaction vessel, or a plasma chemistry on the substrate. It is preferable to provide a reaction vessel for forming a film by chemical vapor deposition and a plasma generator provided in the reaction vessel.
- the plasma generator is provided in a reaction vessel, it is preferable that the plasma generator is provided on an electrode on which a substrate is provided.
- a low dielectric constant film and high mechanical strength can be stably provided over a long period of time, and the amount of outgas generated during device production of the obtained film can be reduced. Can do.
- FIG. 1 is a diagram schematically showing a preferred example of a PCVD apparatus of the present invention.
- FIG. 2 is a graph showing TDS data of the film formed in Example 1.
- FIG. 3 is a graph showing TDS data of the film formed in Comparative Example 1.
- FIG. 4 is a graph showing an example of the FT-IR vector shape of the film formed on the feeding electrode side (solid line) and the counter electrode side (dotted line), respectively.
- reaction vessel 1 reaction vessel, 2 high frequency power supply, 3 matching unit, 4 vacuum pump, 5 gas inlet, 6 caro heat Z cooling device, 7 feeding electrode, 8 substrate, 9 counter electrode.
- the plasma CVD apparatus (PCVD apparatus) of the present invention is a means for supplying a compound having a borazine skeleton, a plasma generator for generating plasma, and a means for applying a negative charge to an electrode on which a substrate is placed. It is characterized by providing. According to the plasma CVD apparatus of the present invention, by applying a negative charge to the portion of the substrate during the CVD, the outgas released when the film manufactured by the method is heated is reduced. There is no problem when manufacturing the used device.
- the PCVD apparatus of the present invention is a method of introducing and vaporizing into a device having a vaporization mechanism for heating a borazine compound at room temperature, or heating the container itself storing the borazine compound. After the borazine compound is vaporized, the vaporized borazine compound is introduced into the apparatus using the pressure increased by the vaporization of the borazine compound, or Ar, He, nitrogen and other gases. It is realized to supply a compound having a borazine skeleton, for example, by mixing it with a vaporized borazine compound and introducing it into the apparatus.
- an appropriate plasma generator such as a capacitive coupling method (parallel plate type) or an inductive coupling method (coil method) can be used. Practical film deposition rate (lOnmZ min to 5000nmZ min) is easily obtained From the viewpoint of V, a capacitively coupled (parallel plate) plasma generator is preferred.
- the PCVD apparatus of the present invention for example, in the case of generating a plasma between electrodes using a capacitively coupled plasma generator, a method of applying a high frequency to an electrode on which a substrate is installed, or a plasma generation Therefore, a negative charge is applied to the electrode on which the substrate is installed by applying a direct current other than the high frequency, or a high frequency or alternating current to the electrode on which the substrate is installed.
- a direct current other than the high frequency, or a high frequency or alternating current to the electrode on which the substrate is installed.
- any conventionally known appropriate compound can be used as long as it has a borazine skeleton.
- a film having improved dielectric constant, thermal expansion coefficient, heat resistance, thermal conductivity, mechanical strength, etc. it is preferable to use a compound represented by the following chemical formula (1) as a raw material. ,.
- alkenyl groups or alkyl groups can be used independently.
- the carbon number is 1 or 2.
- CVD method a chemical vapor deposition method used for film formation on a substrate using the PCVD apparatus of the present invention.
- the CVD method since the film is formed while the above-mentioned raw material gases are sequentially crosslinked, the crosslink density can be increased, so that the mechanical strength of the film is expected to increase.
- the source gas of the compound (1) having a borazine skeleton represented by the chemical formula (1) is moved to the vicinity of the substrate on which the film is formed. .
- the characteristics of a film formed by mixing the carrier gas with a compound of methane, ethane, ethylene, acetylene, ammonia or an alkylamine can be controlled to a desired value.
- the flow rate of the carrier gas is 100 to 1000 sccm
- the flow rate of the compound gas having a borazine skeleton is 1 to 300 sccm
- the flow rate of methane, ethane, ethylene, acetylene, ammonia or alkylamines is 0 to: LOOsccm It can be set arbitrarily.
- the flow rate of the carrier gas is less than lOOsccm, the time for obtaining a desired film thickness becomes extremely slow, and the film formation may not proceed.
- lOOOsccm the film thickness uniformity in the substrate surface tends to be poor. More preferably, it is 20 sccm or more and 800 sccm or less.
- the gas flow rate of the compound having a borazine skeleton is less than lsccm, the time for obtaining a desired film thickness becomes extremely slow, and the film formation may not proceed. Also, if it exceeds 300 SC cm, the film has a low crosslink density, so the mechanical strength decreases. More preferably, it is 5 SC cm or more and 200 sccm or less.
- the dielectric constant of the obtained film increases. More preferably, it is 5 sccm or more and 100 sccm or less.
- the source gas carried in the vicinity of the substrate as described above is deposited on the substrate with a chemical reaction to form a film.
- the chemical reaction is efficiently caused.
- plasma is used.
- the gas and substrate temperatures are controlled between room temperature and 450 ° C.
- the time for obtaining a desired film thickness becomes extremely slow, and the film formation may not proceed. More preferably, it is 50 ° C or higher and 400 ° C or lower.
- the substrate When plasma is used to heat the substrate, for example, the substrate is placed in a parallel plate type plasma generator, and the source gas is introduced into the substrate.
- the RF frequency used at this time is 13.56MHz or 400kHz, and the power can be set arbitrarily within the range of 5 to: LOOOW. It is also possible to use a mixture of these different frequencies.
- the RF power used for plasma CVD exceeds 1000 W, the frequency of decomposition of the compound having a borazine skeleton represented by the chemical formula (1) by plasma increases, and the desired borazine structure is obtained. It becomes difficult to obtain a film. More preferably, it is 10W or more and 800W or less.
- the pressure in the reaction vessel is preferably 0. OlPa or more and lOPa or less. If it is less than OlPa, the frequency of decomposition of the compound having a borazine skeleton by plasma increases, and it is difficult to obtain a film having a desired borazine structure. On the other hand, if it exceeds lOPa, the film has a low crosslinking density, so that the mechanical strength decreases. More preferably, it is 5 Pa or more and 6.7 Pa or less.
- the pressure can be adjusted by a pressure regulator such as a vacuum pump or a gas flow rate.
- the PCVD apparatus of the present invention preferably further includes a reaction vessel for forming a film on the substrate by PCVD.
- the plasma generator may take a configuration provided either inside or outside the reaction vessel.
- a plasma generator is provided outside the reaction vessel, plasma does not act directly on the substrate, so the film formed on the substrate is excessively applied to electrons, ions, radicals, etc. in the plasma.
- a practical film formation rate (lOnmZ min. 5000nmZ) is easy to obtain.
- FIG. 1 is a diagram schematically showing a preferred example of the PCVD apparatus of the present invention.
- a PCVD apparatus according to the present invention has a configuration in which a plasma generator is provided in the reaction vessel, and a plasma generator is provided on an electrode on which a substrate is installed using a capacitive coupling method. It is particularly preferable that this is realized with the PCVD apparatus.
- a film is formed on the applied electrode side (negative bias), so that borazine molecules or carriers generated in the plasma are compared with borazine molecules deposited on the substrate. It is considered that a new active site is generated by collision of He, Ar, etc. used as gas, and the crosslinking reaction can be further advanced.
- a reaction vessel 1 is provided with a power supply electrode 7 via a heating Z cooling device 6, and a substrate 8 to be deposited is placed on the power supply electrode 7. To do.
- the heating Z cooling device 6 can heat or cool the substrate 8 to a predetermined process temperature.
- the feeding electrode 7 is connected to the high frequency power source 2 via the matching unit 3, and can be adjusted to a predetermined potential.
- a counter electrode 9 is provided on the side facing the substrate 8, and a gas introduction port 5 and a vacuum pump 4 for discharging the gas in the reaction vessel 1 are provided. It is installed.
- the substrate 8 to be grown in the reaction vessel 1 for generating plasma is formed by placing the substrate 8 on the feeding electrode 7 for inducing plasma and performing film formation. A film can be formed.
- the potential on the substrate 8 to be deposited can be arbitrarily adjusted by applying a potential from another high frequency power source to the counter electrode 9 facing the power supply electrode 7.
- the present invention is characterized in that the power supply electrode 7 on the substrate 8 side has a negative potential.
- a desired film may be formed by applying a negative charge to the substrate using a power source independent of the RF source 2 of the plasma source.
- the counter electrode 9 is disposed on the upper side of the apparatus, and the force configured to dispose the feeding electrode 7 on the lower side of the apparatus.
- the board 8 can be supported by board fixing parts such as plate panels, screws, pins, etc.
- the susceptor substrate can be directly installed on the electrode power supply 7, but the substrate 8 is fixed to the power supply electrode 7 through a jig for transporting the substrate. It is also possible.
- the substrate 8 is placed on the power supply electrode 7 and the reaction vessel 1 is evacuated.
- the raw material gas, the carrier gas, and other gases as described above are supplied into the reaction vessel 1 from the gas inlet 5 if necessary.
- the flow rate at the time of supply is as described above.
- the pressure in the reaction vessel 1 is evacuated by the vacuum pump 4 to maintain a predetermined process pressure.
- the substrate 8 is set to a predetermined process temperature by the heating Z cooling device 6.
- a negative charge is applied to the power supply 7 from the high frequency power source 2 to generate plasma in the gas in the reaction vessel 1.
- the raw material and carrier gas force S ions, Z or radicals are formed and are deposited on the substrate 8 one after another to form a film.
- ions are attracted to electrodes having a potential opposite to that of their own charges, and react by repeatedly causing collisions on the substrate.
- the positive ions are attracted to the feeding electrode 7 side and the negative ions are attracted to the counter electrode 9 side due to the electric charge.
- radicals are uniformly distributed in the plasma field. For this reason, when film formation is performed on the feeding electrode 7 side, many reactions mainly involving cations occur, and the contribution of radical species to film formation decreases.
- the amount of radicals remaining in the formed film can be reduced by adjusting the potential of the electrode as described above, and therefore, after being taken out from the PCVD apparatus. Substances that are active against radicals such as oxygen and water in the air and remain in the film The reaction between the radicals is suppressed.
- the power frequency to be applied may be, for example, a force HF (several tens to several hundreds kHZ) or microwave (2.45 GHz). ) 30MHz to 300MHz ultra high frequency may be used.
- a force HF severe tens to several hundreds kHZ
- microwave 2.45 GHz
- 30MHz to 300MHz ultra high frequency may be used.
- a microwave a method of exciting a reaction gas and forming a film in an afterglow, or an ECR plasma CVD in which a microwave is introduced into a magnetic field that satisfies the ECR condition can be used.
- a film having a lower dielectric constant can be realized as compared with a film using a conventional compound having a borazine skeleton as a raw material.
- “low dielectric constant” means that a constant dielectric constant can be stably maintained over a long period of time. Specifically, it is about 3.0 to 1.8 for a film produced by a conventional manufacturing method.
- the present invention can maintain the dielectric constant for at least several years. This low dielectric constant can be confirmed, for example, by measuring the dielectric constant by the same method as that immediately after forming a film stored for a certain period.
- the film formed using the PCVD apparatus of the present invention can achieve a higher cross-linking density than the film obtained by the conventional PCVD apparatus, is denser, and has higher mechanical strength. It is a film with improved (modulus, strength, etc.).
- This improvement in crosslink density can be confirmed, for example, from the spectrum shape of FT-IR because the peak near 1400 cm 1 is shifted to the low wavenumber side.
- Figure 4 shows an example of this FT-IR spectrum.
- the FT-IR spectral shape of the membrane on the counter electrode side shown by the dotted line in the figure
- the FT- of the membrane on the feed electrode side In the IR spectral shape (shown by the solid line in the figure), it can be seen that the peak is shifted to the lower wavenumber side.
- the following film formation was performed using the parallel plate type plasma CVD apparatus of the example shown in FIG.
- Helium was used as a carrier gas, and the flow rate was set to 200 sccm, and the reaction vessel was charged.
- B, B, B, N, N, N-hexamethylborazine gas as a source gas is introduced into a reaction vessel in which a substrate is placed through a heated gas inlet with a flow rate set to 10 sccm. did.
- the vapor temperature of B, B, B, N, N, N-hexamethylborazine gas was 150 ° C.
- the substrate temperature was heated to 100 ° C, and a high frequency current of 13.56 MHz was applied to 150 W from the feeding electrode side where this substrate was installed.
- the pressure inside the reaction vessel was maintained at 2 Pa. Thereby, a film was formed on the substrate.
- the amount of outgas was measured while raising the temperature of the film on the obtained substrate at a rate of 60 ° CZ using a temperature programmed desorption gas analyzer (TDS).
- TDS temperature programmed desorption gas analyzer
- FIG. 2 shows the degree of vacuum when the film formed on the supply electrode side is heated using the method of the present invention.
- the vertical axis indicates the degree of vacuum (Pa)
- the horizontal axis indicates the temperature (° C).
- FIG. 2 shows that the outgas from the film is released as the degree of vacuum increases. Until 400 ° C, there is no clear change in vacuum, indicating that no outgassing occurs due to heating.
- FIG. 3 shows TDS data of a film formed on the counter electrode side for comparison.
- the vertical axis represents the degree of vacuum (Pa) and the horizontal axis represents the temperature (° C).
- Pa degree of vacuum
- ° C temperature
- outgassing occurs when the film is formed on the counter electrode side because the degree of vacuum increases when the temperature exceeds 100 ° C. From these facts, it was found that a film with less outgas could be formed by placing the substrate to be deposited on the feeding electrode and making it negative potential.
- TDS measurement is performed on a film prepared by changing the type of source gas in the same way as in Example 1. It was.
- Table 1 shows the results for Examples 2 to 9 (when the film is formed on the feeding electrode side), and Table 2 shows the results for Comparative Examples 2 to 9 (when the film is formed on the counter electrode side).
- Table 3 shows the results for Examples 10 to 13 (when the film is formed on the feeding electrode side), and Table 10 shows the results for Comparative Examples 10 to 13 (when the film is formed on the counter electrode side). Shown in 4.
- Example 9 Example 9
- Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 ⁇ , ⁇ . ⁇ —Trimet ⁇ , ⁇ , ⁇ -Tolechi ⁇ , ⁇ , ⁇ - ⁇ 1 JI ⁇ , ⁇ , ⁇ -Trivi ⁇ , ⁇ , ⁇ -Tori I ⁇ , ⁇ , ⁇ , ⁇ - ⁇ , ⁇ , ⁇ , ⁇ , ⁇ , ⁇ -Holashin Raw material gas Ruphorasin Luholachin Luo ⁇ , ⁇ , ⁇ Trinyl- ⁇ ⁇ -Toil- ⁇ , ⁇ . ⁇ -Tramethylho 'Lashi' Ngenta Methylho
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Abstract
Description
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US11/577,008 US20080029027A1 (en) | 2004-10-19 | 2005-10-07 | Plasma Cvd Device |
JP2006542326A JPWO2006043433A1 (ja) | 2004-10-19 | 2005-10-07 | プラズマcvd装置 |
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PCT/JP2005/018615 WO2006043433A1 (ja) | 2004-10-19 | 2005-10-07 | プラズマcvd装置 |
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JP (2) | JPWO2006043433A1 (ja) |
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Cited By (3)
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FR2923221A1 (fr) * | 2007-11-07 | 2009-05-08 | Air Liquide | Procede de depot par cvd ou pvd de composes de bore |
US20100181654A1 (en) * | 2007-06-18 | 2010-07-22 | Mitsubishi Heavy Industries, Ltd. | Manufacturing method of semiconductor device, insulating film for semiconductor device, and manufacturing apparatus of the same |
US8404314B2 (en) | 2006-03-29 | 2013-03-26 | Mitsubishi Electric Corporation | Plasma CVD apparatus, method for forming thin film and semiconductor device |
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US20080029027A1 (en) * | 2004-10-19 | 2008-02-07 | Mitsubishi Electric Corporation | Plasma Cvd Device |
JP2009102234A (ja) * | 2007-10-20 | 2009-05-14 | Nippon Shokubai Co Ltd | 放熱材料形成用化合物 |
WO2011127258A1 (en) | 2010-04-07 | 2011-10-13 | Massachusetts Institute Of Technology | Fabrication of large-area hexagonal boron nitride thin films |
RU2482121C1 (ru) * | 2012-03-23 | 2013-05-20 | ФЕДЕРАЛЬНОЕ ГОСУДАРСТВЕННОЕ БЮДЖЕТНОЕ УЧРЕЖДЕНИЕ НАУКИ ИНСТИТУТ ОРГАНИЧЕСКОЙ ХИМИИ им. Н.Д. ЗЕЛИНСКОГО РОССИЙСКОЙ АКАДЕМИИ НАУК (ИОХ РАН) | Способ получения в-триаллилборазола (варианты) |
CN106211763B (zh) * | 2014-03-25 | 2019-08-27 | 住友金属矿山株式会社 | 包覆焊料材料及其制造方法 |
JP6347705B2 (ja) * | 2014-09-17 | 2018-06-27 | 株式会社日立国際電気 | 半導体装置の製造方法、基板処理装置およびプログラム |
CN108220922B (zh) * | 2016-12-15 | 2020-12-29 | 东京毅力科创株式会社 | 成膜方法、硼膜以及成膜装置 |
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- 2005-10-07 CN CNB2005800312182A patent/CN100464395C/zh not_active Expired - Fee Related
- 2005-10-07 KR KR1020077011258A patent/KR20070057284A/ko not_active Application Discontinuation
- 2005-10-07 CN CNA2005800359047A patent/CN101044603A/zh active Pending
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- 2005-10-07 JP JP2006542325A patent/JP4986625B2/ja not_active Expired - Fee Related
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US20080029027A1 (en) | 2008-02-07 |
WO2006043432A1 (ja) | 2006-04-27 |
US20080038585A1 (en) | 2008-02-14 |
TWI295072B (en) | 2008-03-21 |
CN101023516A (zh) | 2007-08-22 |
TW200633063A (en) | 2006-09-16 |
CN101044603A (zh) | 2007-09-26 |
TW200620426A (en) | 2006-06-16 |
KR20070057284A (ko) | 2007-06-04 |
JPWO2006043432A1 (ja) | 2008-05-22 |
JP4986625B2 (ja) | 2012-07-25 |
KR20070065443A (ko) | 2007-06-22 |
JPWO2006043433A1 (ja) | 2008-05-22 |
CN100464395C (zh) | 2009-02-25 |
TWI280622B (en) | 2007-05-01 |
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