WO2022124199A1 - 絶縁膜の製造方法 - Google Patents
絶縁膜の製造方法 Download PDFInfo
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- WO2022124199A1 WO2022124199A1 PCT/JP2021/044334 JP2021044334W WO2022124199A1 WO 2022124199 A1 WO2022124199 A1 WO 2022124199A1 JP 2021044334 W JP2021044334 W JP 2021044334W WO 2022124199 A1 WO2022124199 A1 WO 2022124199A1
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- insulating film
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- 239000000758 substrate Substances 0.000 claims abstract description 87
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- 238000000034 method Methods 0.000 claims description 30
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- 239000012298 atmosphere Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- -1 hydrogen siloxane Chemical class 0.000 claims description 6
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 claims description 5
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- 230000001678 irradiating effect Effects 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 33
- 229910052814 silicon oxide Inorganic materials 0.000 description 32
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 27
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- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
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- 238000009413 insulation Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
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- 125000004429 atom Chemical group 0.000 description 1
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
- H01L21/0234—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour treatment by exposure to a plasma
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- 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
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- H—ELECTRICITY
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- 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
- H01L21/02205—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 the layer being characterised by the precursor material for deposition
- H01L21/02208—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- 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
- H01L21/02205—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 the layer being characterised by the precursor material for deposition
- H01L21/02208—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02219—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
- H01L21/02222—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
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- 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
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/02252—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by plasma treatment, e.g. plasma oxidation of the substrate
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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
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02345—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light
- H01L21/02348—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to radiation, e.g. visible light treatment by exposure to UV light
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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
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
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- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
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- 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
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- 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
- H01L21/02164—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 oxide, e.g. SiO2
Definitions
- the present invention relates to a method for producing an insulating film having good insulating properties, and particularly to a method for producing an insulating film that does not require high-temperature annealing treatment.
- a silicon oxide film may be formed as an insulating film on a substrate or a patterned substrate of a semiconductor device.
- the silicon oxide film is formed by plasma CVD (plasma-enhanced chemical vapor deposition) using silane gas (SiH 4 ) or TEOS (tetraethoxysilane) as a source, or SOG (Spin on Glass) is applied to the substrate and annealed. It is often formed by doing.
- the formation of a silicon oxide film by plasma CVD is a method in which monosilane gas or disilane gas and oxygen are plasma-formed by electromagnetic wave irradiation in a reaction chamber, whereby SiO 2 is deposited on a substrate kept at about 400 ° C.
- the silicon oxide film formed by this method tends to have a low dielectric breakdown electric field because hydrogen is contained in monosilane gas and disilane gas.
- a process of flattening at a temperature of about 900 ° C. may be required in order to maintain the uneven shape of the substrate.
- Patent Document 1 discloses a technique for physically condensing a film formed by SOG by annealing at a relatively low temperature after applying SOG and then surface-treating with accelerated high-density plasma. ..
- the gate oxide film or the like formed on the substrate before the formation of the silicon oxide film may be electrostatically destroyed by the electric charge brought to the silicon oxide film by plasma.
- the impact of an ionic species is used to densify the film formed by SOG, and only the surface of the film formed by SOG, specifically, about 50 nm from the surface. Only the surface layer up to the bottom is condensed. Therefore, it is not suitable for applications that require, for example, an insulating film of 100 nm or more.
- the film is densified by using the impact of ion species, it is necessary to increase the accelerating energy of the ions in order to thicken the insulating film, and as a result, the insulating property of the obtained dielectric layer is improved. However, it is not easy to increase the density.
- the present invention has been made in view of such circumstances, and an object of the present invention is to provide a method for manufacturing an insulating film that does not require heating at a high temperature.
- a method for producing an insulating film which comprises a step of binding with and has a product of irradiation time and density of a radical formed by plasma of 25 ⁇ 10 14 minutes / piece / cm3 or more.
- the hydrogen permeated inside by diffusion reacts with the components of the film-forming material layer.
- the hydrogen molecule can be separated. Since the hydrogen molecules thus generated are discharged to the outside of the film-forming material layer, the hydrogen concentration in the film can be extremely lowered, and the insulating property of the film-forming material layer can be improved.
- insulation is performed without deteriorating the characteristics of the substrate before the formation of the insulating film corresponding to the film-forming material layer after the plasma irradiation treatment or the device portion formed on the substrate. It is possible to improve the insulating characteristics of the film.
- the product of the irradiation time and the density of radicals contained in the plasma is 25 ⁇ 10 14 minutes / piece / cm3 or more, hydrogen should be diffused deeply into the structure of the film-forming material layer at a sufficient density. It is possible to obtain an insulating film having high insulating properties.
- radicals are supplied to the surface of the film-forming material layer by forming plasma under a pressure of 5 Pa or more and 50 Pa or less.
- the plasma density in contact with the film forming material layer increases, and it becomes easy to reduce the potential difference between the plasma and the film forming material layer to 10 V or less, and the plasma particles form the film forming material layer. It is possible to prevent the film-forming material layer from being driven and disturbing the structure of the film-forming material layer and reducing the density of the film-forming material layer.
- the plasma is set to 50 Pa or less, the mean free path of radicals is maintained for a relatively long time, and the generated radicals can be effectively utilized to reach the film forming material layer.
- the radical is a hydrogen atom H.
- the film forming material is SOG, and SOG is applied and deposited on the substrate.
- SOG facilitates the formation of a flat insulating film.
- the SOG is one or more of a ladder-type hydrogen silsesquioxane, a hydrogen siloxane, and a silicate.
- the insulating film is a silicon oxide film.
- the heating is carried out in the atmosphere of N 2 or an inert gas. This causes a dehydration polycondensation reaction.
- the SOG is silazane.
- the insulating film is a silicon oxide film.
- heating is performed in any of the atmospheres of H 2 O, O 2 and H 2 O 2 .
- a polycondensation reaction that releases nitrogen by hydrolysis or oxidation is caused.
- the substrate is a semiconductor substrate or a patterned substrate of a semiconductor device.
- an insulating film can be formed on the semiconductor substrate, or an insulating film can be formed on the pattern of the semiconductor device.
- a circuit device including an insulating film formed on a substrate and having an insulating film having a hydrogen concentration in the film of 1% or less.
- the insulating film having a hydrogen concentration in the film of 1% or less is provided, the insulating performance can be improved.
- the circuit device has a characteristic of repeating a plurality of concentration patterns that are saturated on the substrate side and become substantially zero on the surface side with respect to the hydrogen concentration. In this case, it is possible to provide a thick insulating film having improved insulating properties as a whole.
- FIG. 1A is a conceptual diagram illustrating an outline of a method for manufacturing an insulating film
- FIGS. 1B to 1E are conceptual cross-sectional views illustrating each step.
- FIG. 2A is a conceptual cross-sectional view illustrating a substrate on which an insulating film is formed
- FIG. 2B is a diagram illustrating formation of a film forming material layer
- FIG. 2C illustrates a heating process.
- FIG. 2D is a conceptual cross-sectional view illustrating a precursor layer or the like obtained by a heating step.
- FIG. 3A is a diagram illustrating an exposure process
- FIG. 3B is a conceptual cross-sectional view illustrating an insulating film obtained by exposure.
- 4A and 4B are conceptual cross-sectional views illustrating a manufacturing process of a laminated insulating film. It is a chart explaining the relationship between the plasma output and the shrinkage rate of a SiO 2 film. It is a chart explaining the effect of the treatment using radicals formed by high-density plasma.
- 7A and 7B are charts illustrating shrinkage of the SiO 2 film due to radical treatment. It is a figure explaining the cross-sectional characteristic of a laminated type insulating film. It is a figure explaining the result of having measured the characteristic about a specific sample.
- 10A to 10C are charts showing the relationship between the shrinkage rate of the film-forming material layer and the insulating property during radical treatment. It is sectional drawing explaining an example of the circuit apparatus obtained by the manufacturing method of the insulating film of an embodiment.
- 12A and 12B are diagrams illustrating a modified example of a radical processing apparatus using high-density plasma.
- FIG. 1 is a conceptual diagram showing a flow of manufacturing an insulating film.
- 1A is a conceptual diagram illustrating an outline of a method for manufacturing an insulating film
- FIGS. 1B to 1D are conceptual cross-sectional views illustrating each step (S1 to S3) shown in FIG. 1A.
- the method for manufacturing the insulating film includes a deposition step (S1) of depositing a film-forming material on the substrate 11 to form a film-forming material layer 12, and a film-forming material layer 12 on the substrate 11 at 85 ° C. or higher and 450 ° C. or lower.
- the product of the irradiation time and the density of the radicals formed by the plasma 82 is 25 ⁇ 10 from the viewpoint of diffusing the hydrogen H for treatment deeply in the structural FS of the film forming material layer 12 with a sufficient density. It is desirable to set it to 14 minutes / piece / cm 3 or more.
- the method for producing the insulating film according to the embodiment will be described separately for the deposition step, the heating step, and the exposure step.
- a flat plate-shaped substrate 11 made of a semiconductor or other material is prepared.
- the substrate 11 may be, for example, a semiconductor substrate, or may be a substrate with a semiconductor device in which the pattern 11p of the device portion 11d is formed on the semiconductor substrate.
- the substrate 11 is not limited to the semiconductor substrate, but may be a ceramic substrate, a glass substrate, a heat-resistant resin substrate, a metal substrate, or the like, or may be a semiconductor device formed on them.
- the film-forming material is applied onto the surface 11s of the substrate 11 to form the film-forming material layer 12.
- the film-forming material is a precursor material of an insulating film such as SiO 2 , or a highly fluid material such as an inorganic SOG (Spin on Glass).
- SOG is used as the film-forming material
- the film-forming material layer 12 is formed by applying SOG and drying it so as to form a flat surface on the surface 11s of the substrate 11.
- the film-forming material layer 12 is deposited on the substrate 11.
- a spin coating method can be used as a method for applying the film forming material on the substrate 11.
- the film-forming material applied on the substrate 11 may be prebaked at a relatively low temperature.
- the SOG for forming the film-forming material layer 12 is, for example, a solution containing at least one of a ladder-type hydrogen silsesquioxysan, a hydrogen siloxane, and a silicate as a film component, and the film component is an organic solvent. It was adjusted by adding.
- the SOG may be, for example, a solution containing silazane as a membrane component. Cilazan is polymerized into a polymer state.
- the ladder-type hydrogen silsesquioxysan is expressed by the following formula.
- Hydrogen siloxane is expressed by the following formula.
- the silicate is expressed by the following formula.
- the silazane polymer is represented by one of the following formulas.
- m1, m2, and m3 in the formula are numbers representing the degree of polymerization.
- the substrate 11 on which the film-forming material layer 12 is deposited is heated in an atmosphere.
- the heating temperature of the substrate 11 is 85 ° C. or higher and 450 ° C. or lower, preferably 100 ° C. or higher and 200 ° C. or lower.
- the film-forming material layer 12 is solidified, and as shown in FIG. 2D, the precursor layer 112 is formed on the substrate 11.
- the substrate 11 on which the film-forming material layer 12 is formed is heated by, for example, baking in a heating furnace 51, and the atmosphere is controlled by supplying the atmosphere gas AG into the heating furnace 51 during heating. Will be done.
- the film-forming material layer 12 is a ladder-type hydrogen silsesquioxane, hydrogensiloxane, silicate or the like
- the treatment target 14 is heated for 10 minutes or more in the atmosphere of N2 or an inert gas, and undergoes a dehydration polycondensation reaction. Causes.
- the substrate 11 is heated for 10 minutes or more in the atmosphere of H 2 O, O 2 or H 2 O 2 , and nitrogen is hydrolyzed or oxidized. Causes a polycondensation reaction that causes the water to escape.
- the substrate temperature was set to 85 ° C. for the treatment target 14 obtained by spin-coating polysilazane, steam was supplied by bubbling at atmospheric pressure, and then the substrate temperature was set to 150 ° C. Annealing was performed for 1 hour in a nitrogen gas atmosphere at atmospheric pressure.
- the heating temperature of the substrate 11 when the heating temperature of the substrate 11 is 85 ° C. or higher, not only the solvent can be reliably removed, but also the atom / molecule of the material such as SOG constituting the film forming material layer 12 is active. It is possible to give chemical energy, allow the polymerization to proceed to some extent, and increase the ratio of Si—O—Si bonds. Further, when the heating temperature of the substrate 11 is 450 ° C. or lower, it is possible to avoid deterioration of the substrate 11 itself and deterioration of the characteristics of the device portion 11d.
- the substrate 11 on which the precursor layer 112 is formed is exposed to plasma. More specifically, the surface 14a of the treatment target 14 is exposed to a high-density plasma PZ containing radicals having a density of, for example, 5 ⁇ 10 14 / cm 3 or more for, for example, 5 to 20 minutes.
- a high-density plasma PZ containing radicals having a density of, for example, 5 ⁇ 10 14 / cm 3 or more for, for example, 5 to 20 minutes.
- the product of the irradiation time and the density of the radical RD in the high-density plasma PZ used for the radical treatment of the treatment target 14 becomes 25 ⁇ 10 14 minutes / piece / cm 3 or more.
- the temperature of the substrate 11 is kept constant in the range of 0 ° C to 400 ° C.
- the potential difference between the plasma and the surface of the processing target 14 is preferably 10 V or less.
- the irradiation density of radical RD can be determined by a known method (T. Arai el al. (2016) "Selective Heating of Transition Metal Usings Hydrogen Plasma and Its Application to Formation of Nickel Silicide Electrodes for Silicon Ultralarge-Scale Integration”. Devices "Journal of Materials Science and Chemical Engineering, 2016, 4, 29-33). Although the irradiation density of radical RD changes according to the pressure of plasma, the irradiation density of radicals according to the plasma pressure and other conditions can be obtained in advance by an experiment.
- Radical exposure to the substrate 11 on which the precursor layer 112 is formed, that is, the treatment target 14, is performed by, for example, a high-density plasma processing apparatus 53 provided with a microwave supply source 53a, and radicals introduced from the intake port 53i which is an injection port.
- the source gas IG is radicalized by microwaves in a standing wave state in the chamber 53c.
- the radical source gas IG is at least one of H 2, NH 3 , and H 2 O, is introduced into the chamber 53c via the intake port 53i, and is introduced outside the chamber 53c via the exhaust port 53o provided at the bottom. It is discharged.
- the radicals in the high-density plasma PZ are obtained by being excited by microwaves, and the target is hydrogen, but other components may be contained.
- the inner surface of the chamber 53c is, for example, a quartz dielectric tube 53 g, and microwaves are injected into the dielectric tube 53 g, and the temperature of the substrate 11 is supported under the dielectric tube 53 g. Stages 53s are arranged to adjust.
- the high-density plasma processing apparatus 53 for example, the one disclosed in International Publication No. WO2003 / 0967669 can be used.
- unnecessary gas is discharged to the outside from the exhaust port 53o of the chamber 53c, and the state of the high-density plasma PZ formed in the dielectric tube 53g is maintained.
- the inside of the chamber 53c is maintained at 5 Pa to 50 Pa by the high-density plasma PZ.
- the plasma in the chamber 53c By setting the plasma in the chamber 53c to a plasma density of 5 Pa or more, it becomes easy to reduce the potential difference between the plasma and the precursor layer 112 to 10 V or less, and plasma particles are driven into the precursor layer 112 to cause a precursor. It is possible to prevent the structure of the body layer 112 from being disturbed and the density from being lowered.
- the plasma in the chamber 53c by setting the plasma in the chamber 53c to a plasma density of 50 Pa or less, the mean free path of radicals is maintained for a relatively long time, and the generated radicals can be effectively utilized to reach the precursor layer 112.
- the precursor layer 112 is condensed and the silicon-based insulating film 212 is formed on the substrate 11 by the step of exposing the processing target 14 to the high-density plasma PZ by the apparatus shown in FIG. 3A.
- the silicon-based insulating film 212 exposed to the high-density plasma PZ is condensed due to the influence of H radicals in the plasma, and its shrinkage is 5% to 25% with the untreated film thickness of 150 nm. Therefore, the film thickness d2 of the silicon-based insulating film 212 is reduced by about 5% to 20% as compared with the thickness dl of the precursor layer 112.
- FIG. 5 is a chart illustrating the relationship between the output of the high-density plasma processing apparatus 53 and the shrinkage rate of the precursor layer 112.
- the horizontal axis represents the microwave output of the high-density plasma processing apparatus 53
- the vertical axis represents the shrinkage rate of the precursor layer 112.
- the amount of H 2 gas supplied to the chamber was 10 sccm
- the pressure in the chamber was 20 Pa
- the treatment time with plasma, that is, radicals was 5 minutes.
- the film thickness of the untreated (initial) SiO 2 film was 155 nm.
- the microwave output for supplying plasma is 1000 W
- the radical density is 3 ⁇ 10 15 / cm 3 .
- the shrinkage rate of the precursor layer 112 is 15%.
- the shrinkage rate of the precursor layer 112 is substantially proportional to the microwave output of the high-density plasma processing apparatus 53. That is, if the supply amount of the H 2 gas, which is the radical source gas IG, is sufficient and not excessive, the plasma, that is, the plasma so as to have a positive correlation with the output of the high-density plasma processing apparatus 53. It can be seen that the density of hydrogen radicals can be increased and the precursor layer 112 can be shrunk according to the density of hydrogen radicals.
- FIG. 6 is a chart illustrating the temporal effect of radical treatment with high density plasma PZ.
- the precursor layer 112 specifically, the silicon oxide film
- the comparative sample and the chamber The supply amount of H 2 is 10 sccm
- the pressure in the chamber is 20 Pa
- the microwave output is 1500 W
- the sample subjected to the radical treatment for 5 minutes the sample subjected to the radical treatment for 10 minutes
- the sample for 15 minutes The FTIR spectrum was measured with respect to the radically treated sample. Almost no Si—H bond is already observed in the sample subjected to the radical treatment for 5 minutes, and no Si—H bond is observed in the sample subjected to the radical treatment for 10 minutes or 5 minutes.
- FIG. 7A is a chart illustrating the shrinkage of the precursor layer 112 (specifically, the silicon oxide film) due to radical treatment using plasma.
- the horizontal axis represents the radical treatment time, and the vertical axis represents the shrinkage rate of the precursor layer 112.
- the supply amount of H 2 gas to the chamber was 10 sccm
- the pressure in the chamber was 20 Pa
- the treatment time by radical was 1, 2, 3, 4, 5, 10, and 15 minutes.
- the film thickness of the untreated (initial) silicon oxide film was 155 nm.
- FIG. 7B shows the shrinkage of the silicon oxide film due to radical treatment as in FIG. 7A, but the horizontal axis is the square root of the radical treatment time. As shown in FIG.
- the shrinkage rate of the insulating film reaches 20% and is becoming saturated when the radical treatment is 5 minutes or longer.
- the shrinkage rate increases in proportion to the square root of the processing time up to about 5 minutes.
- the influence of radical treatment extends in the depth direction in proportion to the square root of the treatment time. This corresponds to the diffusion length of hydrogen radicals from the surface of the silicon oxide film being proportional to the supply time of hydrogen radicals, and it can be seen that this phenomenon is dominated by diffusion.
- the shrinkage rate is saturated in 5 minutes or more, but considering the FTIR signal described in FIG. 5, this saturation means that the dehydrogenation treatment of the entire SiO 2 membrane is completed.
- the radicals supplied by the high-density plasma PZ are from the surface of the precursor layer 112, that is, from the surface 14a to a depth of 600 nm.
- the thickness of the precursor layer 112 is 600 nm or less, the density of the entire precursor layer 112 can be increased, and a silicon-based insulating film 212 having an extremely high proportion of SiO 2 and excellent insulating properties can be obtained. ..
- the radicals supplied by the high density plasma PZ diffuse from the surface of the precursor layer 112, that is, the surface 14a to a depth of 1.5 ⁇ m. Therefore, if the thickness of the precursor layer 112 is 1.5 ⁇ m or less, the density of the entire precursor layer 112 can be increased, and a silicon-based insulating film 212 having an extremely high proportion of SiO 2 and excellent insulating properties can be obtained. Can be done.
- the silicon-based insulating film 212 may be laminated in multiple layers to form the target silicon-based insulating film.
- a silicon oxide film having a desired thickness can be obtained by repeating the deposition step, the heating step, and the exposure step.
- the material of the precursor layer 112 is a ladder-type hydrogen silsesquioxane, hydrogen siloxane, silicate, etc., when it is desired to form a silicon oxide film corresponding to the precursor layer 112 having a film thickness of 600 nm or more, it is silicon-based.
- the insulating film 212 is laminated in multiple layers.
- the film-forming material is applied on the surface 12a of the silicon-based insulating film 212 formed on the substrate 11 to form the film-forming material layer 12.
- the film-forming material layer 12 on the silicon-based insulating film 212 is made into the precursor layer 112 by the heat treatment shown in FIG. 2C, and the first silicon is subjected to the exposure treatment shown in FIG. 3A, as in the case of FIG. 2D.
- the precursor layer 112 on the system insulating film 212 is used as the second silicon-based insulating film 212, and a laminated silicon-based insulating film 312 as shown in FIG. 4B is obtained.
- FIG. 8 is a diagram illustrating the hydrogen concentration distribution of the laminated silicon-based insulating film.
- the horizontal axis shows the distance from the surface 11s of the substrate 11 as a base toward the surface of the silicon-based insulating film 312, and the vertical axis shows the hydrogen concentration in the silicon-based insulating film 312.
- the distribution of the hydrogen concentration is repeated for each constituent layer EL.
- the hydrogen concentration saturates at the maximum value at a position close to the substrate 11, and the hydrogen concentration decreases to a value close to zero at a position near the inside of the interface IF or the surface of the silicon-based insulating film 312. There is.
- the laminated silicon-based insulating film 312 has a characteristic of repeating a plurality of concentration patterns that are saturated on the substrate 11 side and become substantially zero on the surface 312a side with respect to the hydrogen concentration.
- hydrogen radicals from the high-density plasma PZ efficiently diffuse into the constituent layer EL through the surface of each constituent layer EL to generate hydrogen.
- the Si—O bond is increased while reducing the Si—H bond, so that the hydrogen concentration can be lowered except for the bottom of each constituent layer EL, and the insulating property as the constituent layer EL. It is possible to increase the insulation characteristics of the plurality of constituent layers EL as a whole.
- the silicon-based insulating films 212 and 312 formed on the substrate 11 by the above steps are silicon oxide films, have a leakage current of 1 ⁇ 10-8 A / cm 2 or less, and have a dielectric breakdown electric field of 8 MV /. It is cm or more and 10 MV / cm or less. Further, this silicon oxide film has a density of 2.50 g / cm 3 or more and 2.65 g / cm 3 or less, and the ratio of Si—OH bond and Si—H bond contained therein is 1% or less.
- the silicon-based insulating film 212 manufactured by the manufacturing method of the present invention has a film thickness of 100 nm or more, and realizes a low leakage current at a film thickness that is not easy to manufacture by the conventional manufacturing method, and has a dielectric breakdown electric field strength. Is increasing.
- FIG. 9 is a chart illustrating the results of measuring the characteristics of a sample of a silicon oxide film, which is a specific silicon-based insulating film 212.
- the horizontal axis shows the applied voltage to the silicon oxide film, and the vertical axis shows the leakage current of the silicon oxide film.
- the “ ⁇ ” mark indicates that the output of the microwave supply source 53a is 1 kW, the chamber 53c having a capacity of 0.05 cubic meters is depressurized, the flow rate of H 2 is 5 sccm (scc / min), and the internal pressure is 20 Pa.
- the leak current of the obtained sample is shown.
- the “ ⁇ ” mark is the result obtained for the conventional silicon oxide film sample obtained by treating the film-forming material layer 12 at a high temperature of 900 ° C. and not performing the radical treatment with plasma, and the “+” mark is formed. This is the result obtained for a sample of a conventional silicon oxide film in which the film material layer 12 was treated at 400 ° C. and not subjected to radical treatment. It can be seen that the sample indicated by the “ ⁇ ” mark has insulation characteristics approaching those obtained by high temperature treatment at 900 ° C.
- FIGS. 10A to 10C are charts showing the relationship between the shrinkage rate of the precursor layer 112 and the insulating characteristics during radical treatment, which are measured for a silicon oxide film which is a specific silicon-based insulating film 212.
- FIG. 10A shows the insulating properties of the comparative example without radical treatment
- FIG. 10B shows the insulating properties of the example in which the precursor layer 112 was shrunk by 8% by radical treatment
- FIG. 10C shows the insulating properties of the precursor by radical treatment. Shows the insulating properties of the examples in which the body layer 112 is shrunk by 19%.
- the resistance is large and the current density can be suppressed to a low level, but dielectric breakdown occurs at 5 MV / cm.
- the shrinkage rate is 19% shown in FIG. 10C, the resistance is large and the current density can be suppressed to a low level, and dielectric breakdown does not occur even at an electric field strength close to 10 MV / cm.
- FIG. 11 is a cross-sectional view illustrating an example of a semiconductor device 10 which is a circuit device obtained by the method for manufacturing an insulating film.
- the semiconductor device 10 is a MOSFET which is a kind of power device.
- the substrate 11 is, for example, SiC
- the back surface side of the substrate 11 is the drain layer 11a of n + SiC
- the drain electrode 39 is formed on the back surface
- the front surface side of the substrate 11 is the drift layer 11b of n - SiC.
- a pair of pSiC body regions 24 and a pair of n + SiC source regions 25 are formed so as to be embedded in the drift layer 11b.
- a gate oxide film (insulating film) 33 is formed so as to cover the local region of the drift layer 11b sandwiched between the pair of source regions 25, and the gate electrode 35 is formed on the gate oxide film (insulating film) 33.
- Wiring 31 is connected to the pair of source regions 25.
- the body region 24, the source region 25, the gate oxide film 33, the gate electrode 35, etc. correspond to the device portion 11d shown in FIG. 2A and are covered with the silicon-based insulating film 212.
- an insulating layer can be formed in advance between the wiring 31 and the surface of the substrate 11.
- the hydrogen radicals formed by the high-density plasma PZ include a step of exposing the surface of the layer 112 to a high-density plasma PZ containing hydrogen radicals, and the hydrogen radicals have a density of 5 ⁇ 10 14 / cm 3 or more and hydrogen.
- the product of the radical irradiation time and the density is 25 ⁇ 10 14 minutes / piece / cm3 or more.
- the insulation of the silicon-based insulating film 212 is not deteriorated without deteriorating the characteristics of the substrate 11 or the device portion 11d formed on the substrate 11 before the formation of the silicon-based insulating film 212.
- the characteristics can be improved.
- the present invention has been described above in accordance with the embodiments, the present invention is not limited to the above-described embodiments, and can be implemented in various embodiments without departing from the gist thereof.
- the target for incorporating the insulating film is not limited to the MOSFET shown in FIG. 5, but may be an IGBT or other power device, and may be various LSIs other than the power device, and may be elements constituting each part of the display. You can also.
- the insulating film is not limited to the one used as an interlayer insulating film, and may be a functional layer such as a gate insulating film constituting a circuit device.
- the insulating film of the present application or a silicon-based insulating film can be used as the insulating film adjacent to the floating gate constituting the flash memory.
- the insulating film can be incorporated as an insulating layer constituting each circuit element or an insulating layer for separating the elements, and insulates necessary parts inside and outside the element in a laminated body of a large number of circuit elements. It can be a functional multi-layer structure.
- the film-forming material forming the film-forming material layer 12 is not limited to the above-mentioned inorganic silicon compound such as hydrogen silsesquioxysan, and may be an organosilicon compound such as organic SOG.
- the exposure step as described above is also performed on the film-forming material formed by CVD or the like using tetraethoxysilane (TEOS) or the film-forming material formed by CVD or the like using silane (SiH 4 ). This makes it possible to obtain a silicon oxide film having excellent insulating properties.
- the deposition process and the heating process are performed collectively. That is, the substrate is placed on the substrate stage maintained at 150 ° C. or higher and 400 ° C. or lower, and the SiO 2 film is deposited.
- the insulating film is not limited to the SiO 2 film, and may be silicon nitride (Si 3 N 4 ). Silicon nitride is formed, for example, by plasma CVD. The reaction formula is shown below, and the treatment temperature is, for example, about 600 ° C. 3SiH 4 + 4NH 3 ⁇ Si 3 N 4 + 12H 2 3SiCl 2 H 2 + 4NH 3 ⁇ Si 3 N 4 + 6HCl + 6H 2
- the silicon nitride precursor layer 112 is exposed to, for example, a high density plasma PZ containing radicals having a density of 5 ⁇ 10 14 / cm 3 or higher, more preferably the radicals formed by the high density plasma PZ.
- the precursor layer 112 can be condensed and a silicon nitride film is formed on the substrate 11 by radical treatment so that the product of the irradiation time and the density is 25 ⁇ 10 14 minutes / piece / cm 3 or more. Radical.
- a high-density plasma PZ containing a radical of H is used to reduce the hydrogen concentration.
- the silicon nitride film obtained from the precursor layer 112 exposed to the high-density plasma PZ is condensed by the influence of radicals and the insulating property is enhanced.
- the insulating film is not limited to the SiO 2 film, but may be aluminum oxide (Al 2 O 3 ).
- the aluminum oxide precursor layer 112 is exposed to, for example, a high density plasma PZ containing H radicals having a density of 5 ⁇ 10 14 / cm 3 or higher, more preferably radicals formed by the high density plasma PZ.
- the precursor layer 112 can be condensed and an aluminum oxide film is formed on the substrate 11 by radical treatment so that the product of the irradiation time and the density of the plasma is 25 ⁇ 10 14 minutes / piece / cm 3 or more. Will be done.
- a high-density plasma PZ containing a radical of H is used to reduce the hydrogen concentration.
- the aluminum oxide film exposed to the high-density plasma PZ is condensed by the influence of radicals and the insulating property is enhanced.
- the high-density plasma processing device 53 is not limited to the one shown in the figure, and various modifications are possible.
- the processing target 14 is supported on the rotation stage 153s and rotates at a predetermined speed.
- the high-density plasma processing unit 53A is arranged at a position displaced from the position directly above the rotation stage 153s. In this case, even if a high-density plasma PZ or a radical density distribution occurs in each part on the rotation stage 153s, the radicals can be uniformly supplied to the entire surface of the precursor layer 112 and irradiated by the rotation of the processing target 14. ..
- the high-density plasma processing apparatus 453 shown in FIG. 12B has a structure in which two high-density plasma processing units 53A and 53B are combined. Also in this case, radicals can be uniformly supplied and irradiated on the entire surface of the precursor layer 112 by the rotation of the processing target 14 supported on the rotation stage 153s.
- the method of applying the film-forming material on the substrate 11 is not limited to the spin coating method, and a brush or a roller can be used.
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Abstract
Description
図1は、絶縁膜の製造の流れを示す概念図である。図1Aは、絶縁膜の製造方法の概要を説明する概念図であり、図1B~1Dは、図1Aに示す各段階(S1~S3)を説明する概念的な断面図である。絶縁膜の製造方法は、基板11上に成膜材料を堆積させて成膜材料層12を形成する堆積工程(S1)と、基板11上の成膜材料層12を85℃以上450℃以下の加熱環境81で加熱する加熱工程(S2)と、基板11上の成膜材料層12又は前駆体層の表面SA2に対して水素のラジカルを含むプラズマ82を照射する暴露工程(S3)とを含む。この暴露工程(S3)により、例えばシリコン酸化膜を製造する場合について説明すると、図1Eに示すように、成膜材料層12の構造FSに衝撃を与えないでネットワーク的な構造FS中に水素Hを拡散させ成膜材料層の成分である水素と結合させる。これによって形成された水素分子H2は成膜材料層12中を移動して成膜材料層12外に排出される。この際、成膜材料層12の構造FS中に処理用の水素Hを十分な密度で深くまで拡散させるという観点で、プラズマ82により形成されるラジカルの照射時間と密度との積は25×1014分・個/cm3以上とすることが望ましい。
図2Aに示すように、半導体その他の材料で形成された平板状の基板11を準備する。基板11は、例えば半導体基板であり、或いは半導体基板に対して装置部分11dのパターン11pを形成した半導体装置付き基板であってもよい。基板11は、半導体基板に限らず、セラミック基板、ガラス基板、耐熱樹脂基板、金属基板等であってもよく、それらの上に半導体装置を形成したものであってもよい。
図2Cに示すように、成膜材料層12が堆積された基板11を雰囲気下で加熱する。基板11の加熱温度は、85℃以上450℃以下、好ましくは100℃以上200℃以下とする。この加熱により、成膜材料層12が固化され、図2Dに示すように、基板11上に前駆体層112が形成された状態となる。
図3Aに示すように、前駆体層112が形成された基板11、つまり処理対象14の表面14aをプラズマに暴露する。より具体的には、処理対象14の表面14aを、密度が例えば5×1014/cm3以上のラジカルを含む高密度プラズマPZに例えば5分から20分暴露する。これにより、処理対象14のラジカル処理に用いられる高密度プラズマPZ中のラジカルRDの照射時間と密度との積が25×1014分・個/cm3以上となる。このとき、基板11の温度は、0℃~400℃の範囲で一定に保持される。また、プラズマと処理対象14の表面との間の電位差は、10V以下であることが好ましい。ラジカルRDの照射密度は、公知の手法によって決定することができる(T. Arai el al. (2016) "Selective Heating of Transition Metal Usings Hydrogen Plasma and Its Application to Formation of Nickel Silicide Electrodes for Silicon Ultralarge-Scale Integration Devices" Journal of Materials Science and Chemical Engineering, 2016, 4, 29-33参照)。なお、プラズマの圧力に応じてラジカルRDの照射密度も変化するが、プラズマ圧力その他の条件に応じたラジカル照射密度を、予め実験によって求めておくことができる。
以上の工程により基板11上に形成されたシリコン系絶縁膜212,312は、シリコン酸化膜であり、リーク電流が1×10-8A/cm2以下であり、かつ、絶縁破壊電界が8MV/cm以上10MV/cm以下である。また、このシリコン酸化膜は、密度が2.50g/cm3以上2.65g/cm3以下であり、含有されるSi-OH結合及びSi-H結合の割合が1%以下である。
図11は、上記絶縁膜の製造方法によって得られる回路装置である半導体装置10の一例を説明する断面図である。半導体装置10は、パワーデバイスの一種であるMOSFETである。この場合、基板11は、例えばSiCであり、基板11の裏面側がn+SiCのドレイン層11aとなっており、裏面にドレイン電極39が形成され、基板11の表面側がn-SiCのドリフト層11bとなっており、ドリフト層11bに埋め込まれるようにpSiCの一対のボディ領域24や、n+SiCの一対のソース領域25が形成されている。一対のソース領域25に挟まれたドリフト層11bの局所領域を覆うようにゲート酸化膜(絶縁膜)33が形成され、その上にゲート電極35が形成されている。一対のソース領域25には、配線31が接続されている。ボディ領域24、ソース領域25、ゲート酸化膜33、ゲート電極35等は、図2Aに示す装置部分11dに相当し、シリコン系絶縁膜212で覆われている。なお、図示を省略しているが、配線31と基板11の表面との間には予め絶縁層を形成することができる。
以上実施形態に即して本発明を説明したが、本発明は、上記の実施形態に限られるものではなく、その要旨を逸脱しない範囲において種々の態様において実施することが可能である。例えば絶縁膜を組み込む対象は、図5に示すMOSFETに限らずIGBTその他のパワーデバイスとすることができ、さらにパワーデバイス以外の各種LSIとすることができ、ディスプレイの各部を構成する要素とすることもできる。
3SiH4+4NH3→Si3N4+12H2
3SiCl2H2+4NH3→Si3N4+6HCl+6H2
この場合も、窒化シリコンの前駆体層112を、例えば密度が5×1014/cm3以上のラジカルを含む高密度プラズマPZに暴露すること、より好ましくは高密度プラズマPZにより形成されるラジカルの照射時間と密度との積が25×1014分・個/cm3以上となるようにラジカル処理することにより、前駆体層112を凝縮させることができ、基板11上に窒化シリコン膜が形成される。ここで、高密度プラズマPZとしてHのラジカルを含むものを用いて水素濃度を低下させる。高密度プラズマPZに暴露された前駆体層112から得た窒化シリコン膜は、ラジカルの影響で凝縮し絶縁性が高まる。
Claims (9)
- 絶縁膜の製造方法であって、
堆積工程と、加熱工程と、暴露工程とを含み、
前記堆積工程では、基板上に成膜材料を堆積させて成膜材料層を形成し、
前記加熱工程では、前記基板上の前記成膜材料層を85℃以上450℃以下で加熱し、
前記暴露工程では、前記基板上の前記成膜材料層の表面に対して水素のラジカルを含むプラズマを照射することによって、前記成膜材料層の構造中に水素を拡散させ前記成膜材料層の成分と結合させ、
前記プラズマにより形成されるラジカルの照射時間と密度との積が25×1014分・個/cm3以上である
絶縁膜の製造方法。 - 請求項1に記載の絶縁膜の製造方法において、
前記ラジカルは、5Pa以上50Pa以下の圧力下でプラズマを立てることにより前記成膜材料層の表面に供給される
絶縁膜の製造方法。 - 請求項1及び2のいずれか一項に記載の絶縁膜の製造方法において、
前記ラジカルは、水素原子Hである
絶縁膜の製造方法。 - 請求項1~3のいずれか一項に記載の絶縁膜の製造方法において、
前記成膜材料は、SOGであり、
前記SOGを前記基板上に塗布して堆積させる
絶縁膜の製造方法。 - 請求項4に記載の絶縁膜の製造方法において、
前記SOGは、はしご型ハイドロゲンシルセスキオキサンと、ハイドロゲンシロキサンと、シリケートとのうちの1つ以上である
絶縁膜の製造方法。 - 請求項5に記載の絶縁膜の製造方法において、
前記加熱は、N2又は不活性ガスの雰囲気中で行われる
絶縁膜の製造方法。 - 請求項6に記載の絶縁膜の製造方法において、
前記SOGは、シラザンである
絶縁膜の製造方法。 - 請求項7に記載の絶縁膜の製造方法において、
前記加熱は、H2O、O2と、H2O2のいずれかの雰囲気中で行われる
絶縁膜の製造方法。 - 請求項1~7のいずれか一項に記載の絶縁膜の製造方法において、
前記基板は、半導体基板又は半導体装置のパターン付き基板である
絶縁膜の製造方法。
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JPH04116825A (ja) * | 1990-09-06 | 1992-04-17 | Fujitsu Ltd | 半導体装置の製造方法 |
JP2000332010A (ja) * | 1999-03-17 | 2000-11-30 | Canon Sales Co Inc | 層間絶縁膜の形成方法及び半導体装置 |
JP2006222171A (ja) * | 2005-02-09 | 2006-08-24 | Fujitsu Ltd | 絶縁膜の形成方法、多層構造の形成方法および半導体装置の製造方法 |
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JPH07115136A (ja) * | 1993-10-20 | 1995-05-02 | Hitachi Ltd | 半導体集積回路装置およびその製造方法 |
JP2001085420A (ja) * | 1999-09-09 | 2001-03-30 | Toshiba Corp | 半導体装置およびその製造方法 |
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JP2009010043A (ja) * | 2007-06-26 | 2009-01-15 | Tokyo Electron Ltd | 基板処理方法,基板処理装置,記録媒体 |
KR101523358B1 (ko) * | 2009-12-04 | 2015-05-27 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | 표시 장치 |
US20130288485A1 (en) | 2012-04-30 | 2013-10-31 | Applied Materials, Inc. | Densification for flowable films |
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JPH04116825A (ja) * | 1990-09-06 | 1992-04-17 | Fujitsu Ltd | 半導体装置の製造方法 |
JP2000332010A (ja) * | 1999-03-17 | 2000-11-30 | Canon Sales Co Inc | 層間絶縁膜の形成方法及び半導体装置 |
JP2006222171A (ja) * | 2005-02-09 | 2006-08-24 | Fujitsu Ltd | 絶縁膜の形成方法、多層構造の形成方法および半導体装置の製造方法 |
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