WO2001069673A1 - Dispositif de memoire flash et son procede de fabrication et procede de formation de pellicule dielectrique - Google Patents
Dispositif de memoire flash et son procede de fabrication et procede de formation de pellicule dielectrique Download PDFInfo
- Publication number
- WO2001069673A1 WO2001069673A1 PCT/JP2001/001967 JP0101967W WO0169673A1 WO 2001069673 A1 WO2001069673 A1 WO 2001069673A1 JP 0101967 W JP0101967 W JP 0101967W WO 0169673 A1 WO0169673 A1 WO 0169673A1
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- WIPO (PCT)
- Prior art keywords
- gas
- film
- electrode
- silicon
- polysilicon
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 114
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 57
- 239000007789 gas Substances 0.000 claims abstract description 239
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 164
- 229920005591 polysilicon Polymers 0.000 claims abstract description 164
- 238000012545 processing Methods 0.000 claims abstract description 142
- 150000004767 nitrides Chemical class 0.000 claims abstract description 47
- 230000015654 memory Effects 0.000 claims abstract description 43
- 239000001301 oxygen Substances 0.000 claims abstract description 40
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 230000005284 excitation Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 131
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 129
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 129
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 123
- 229910052710 silicon Inorganic materials 0.000 claims description 123
- 239000010703 silicon Substances 0.000 claims description 121
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 101
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 100
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 41
- 239000011261 inert gas Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 238000005121 nitriding Methods 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 description 44
- 230000003647 oxidation Effects 0.000 description 43
- 230000008569 process Effects 0.000 description 17
- 238000010586 diagram Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 6
- 229910021332 silicide Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000059 patterning Methods 0.000 description 3
- 230000005641 tunneling Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010893 electron trap Methods 0.000 description 1
- 239000002784 hot electron Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000002294 plasma sputter deposition Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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- 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
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- 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
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- H01L21/314—Inorganic layers
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- H01L21/31604—Deposition from a gas or vapour
- H01L21/31641—Deposition of Zirconium oxides, e.g. ZrO2
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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
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- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
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- 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
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- 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
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- H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
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Definitions
- the present invention generally relates to a semiconductor device and a method of manufacturing the same, and more particularly, to a method of forming a dielectric film, a nonvolatile semiconductor memory element including a flash memory element, and an electrically rewritable information element, and a method of manufacturing the same.
- Semiconductor memory devices include volatile memory devices such as DRAM and SRAM, and non-volatile memories such as mask ROM, PROM, EP ROM, and EEPROM.One transistor per memory cell.
- volatile memory devices such as DRAM and SRAM
- non-volatile memories such as mask ROM, PROM, EP ROM, and EEPROM.
- flash memory which is an EEPROM with features, is characterized by its small size, large capacity, and low power consumption, and a great deal of effort is being made to improve it.
- an insulating film with uniform and excellent film quality is indispensable.
- a flash memory device is formed on a silicon substrate 170, and a source region 1701 and a drain region 1702 formed in the silicon substrate 170.
- a tunnel gate oxide film 1703 formed between the source region 1701 and the drain region 1702 on the silicon substrate 170; and the tunnel gate oxide film 17
- a floating gate 170 formed on the silicon oxide film 1705, a silicon nitride film 1706, and a silicon oxide film on the floating gate 1704.
- a control gate 1708 is formed on the silicon oxide film 1707. That is, in the flash memory cell having such a laminated structure, as shown in FIG. 1, the floating gate 1704 and the control gate 1708 are formed of the insulating films 1705, 1706 and 1770. 7 sandwiching the insulation structure Are laminated.
- the insulating structure provided between the floating gate 1704 and the control gate 1705 suppresses a leak current between the floating gate 1704 and the control gate 1705.
- it is general to have a so-called ONO structure in which the nitride film 1706 is sandwiched between the enzyme films 1705 and 1707.
- the tunnel gate oxide film 1703 and the silicon oxide film 1705 are formed by a thermal oxidation method
- the silicon nitride film 1706 and the silicon oxide film 1707 are formed by a thermal oxidation method. It is formed by a CVD method.
- the silicon oxide film 175 may be formed by C VD in some cases.
- the thickness of the tunnel gate oxide film 1703 is about 8 nm, and the total thickness of the insulating films 1705, 1706 and 1707 is about 15 nm in terms of oxide film thickness .
- a low-voltage transistor having a gate oxide film having a thickness of about 3 to 7 nm and a high-voltage transistor having a gate oxide film having a thickness of 15 to 30 nm are provided. Are formed on the same silicon.
- a flash memory cell having a stacked structure configured as described above for example, about 5 to 7 V is applied to the drain 1702 when writing information, and 12 V is applied to the control gate 1708, for example.
- a high voltage of about the same level or more channel hot electrons generated in the vicinity of the drain region 1702 are accumulated in the floating gate through the tunnel insulating film 1703.
- the drain region 1702 is floated, the control gate 1708 is grounded, and the source region 1701 is about 12 V or more.
- the electrons accumulated in the floating gate 1704 are extracted to the source region 1701.
- the tunnel gate insulating film 1703 also had to be thick enough to withstand a high voltage. Disclosure of the invention
- a more specific object of the present invention is to reduce the thickness of a tunnel gate insulating film or an insulating film between a floating gate and a control gate without generating a leak current, and to perform writing at a low voltage.
- An object of the present invention is to provide a highly reliable and high-performance flash memory element having a high-quality insulating film formed at a low temperature and capable of erasing, and a method of manufacturing the same.
- Another object of the present invention is to provide a method for forming an insulating film that can form a high-quality insulating film on polysilicon.
- Another subject of the present invention is:
- a flash memory device comprising: a first electrode formed on the silicon substrate via a tunnel insulating film; and a second electrode formed on the first electrode with an insulating film interposed therebetween.
- the insulating film has a stacked structure including at least one silicon oxide film and one silicon nitride film, and at least a part of the silicon oxide film contains Kr having a surface density of 101 Q cm- 2 or more.
- an insulating film between a floating gate electrode and a control gate electrode is formed by efficiently forming atomic oxygen ⁇ * or nitrogen nitride radical NH *.
- the film quality of the insulating film is improved, and accordingly, the film thickness of the insulating film can be reduced without increasing a leak current.
- the flash memory device of the present invention can operate at high speed at a low voltage and has a long life.
- the inter-electrode insulating film is a method for manufacturing a flash memory device having a stacked structure including at least one silicon oxide film and one silicon nitride film, wherein the silicon oxide film is
- An object of the present invention is to provide a method for manufacturing a flash memory device characterized by being formed by exposure to O *.
- an oxide film having excellent leakage current characteristics can be obtained as the inter-electrode insulating film. Therefore, with a simple configuration, it is possible to stably hold charges in the floating gate electrode and to perform low-voltage driving. A possible flash memory can be realized.
- Other objects of the present invention are:
- the inter-electrode insulating film is a method of manufacturing a flash memory device having a laminated structure including at least one silicon oxide film and one silicon nitride film.
- the silicon nitride film is
- the silicon nitride film deposited by the CVD method is excited by a microwave in the form of a mixed gas consisting of NH 3 gas or a gas containing N 2 and H 2 and a gas mainly composed of Ar or Kr gas.
- An object of the present invention is to provide a method for manufacturing a flash memory device, which is formed by exposing to a hydrogen nitride radical NH * formed by the above method.
- a nitride film having excellent leak current characteristics can be obtained as the inter-electrode insulating film, charges can be stably held in the floating gate electrode with a simple configuration, and low-voltage driving is possible.
- a simple flash memory can be realized.
- a uniform and uniform silicon oxide film on a polysilicon film irrespective of the orientation of a silicon crystal by exposing it to atomic oxygen 0 *.
- Such a silicon oxide film has excellent leakage current characteristics comparable to a thermal oxide film, and causes Fowler-Nordheim type tunneling similar to that of a thermal oxide film.
- the surface of the polysilicon film is formed by exciting plasma by a microphone mouth wave into a mixed gas of a gas containing nitrogen and hydrogen as component elements and an inert gas mainly containing Ar or r gas. Forming a nitride film on the surface of the polysilicon film by exposing to a hydrogen nitride radical NH *.
- a nitride film having excellent characteristics can be formed on the surface of a polysilicon film. And become possible.
- the polysilicon layer was excited and formed by a microwave in a mixed gas of an inert gas mainly containing Ar or Kr, a gas containing oxygen as a component element, and a gas containing nitrogen as a component element.
- a method of forming a dielectric film comprising exposing the surface of the polysilicon film to a dielectric film by exposing to a plasma.
- a method for manufacturing a flash memory device comprising:
- an oxide film having excellent leak current characteristics can be obtained as the inter-electrode oxide film, so that a flash can be stably held in the floating gate electrode with a simple configuration and can be driven at a low voltage.
- a memory can be realized.
- a method of manufacturing a flash memory device comprising: Depositing a polysilicon film as the first electrode on the silicon substrate;
- the surface of the polysilicon film is formed by exciting plasma by a microphone mouth wave to a mixed gas of a gas containing nitrogen and hydrogen and an inert gas mainly containing Ar or Kr gas.
- An object of the present invention is to provide a method for forming a silicon nitride film, which is formed by exposing to a hydrogen radical NH *.
- a flash having excellent leak current characteristics can be obtained as the inter-electrode nitride film, a flash having a simple configuration, capable of stably retaining charges in the floating gate electrode, and capable of being driven at a low voltage.
- a memory element can be realized.
- Another subject of the present invention is:
- a silicon substrate, a first electrode made of polysilicon formed on the silicon substrate via an insulating film, and a second electrode formed on the first electrode with an inter-electrode oxynitride film interposed therebetween A method for manufacturing a flash memory device, comprising:
- the polysilicon layer is exposed to plasma excited by microwaves in a mixed gas of an inert gas mainly containing Ar or Kr and a gas containing oxygen and nitrogen, and Converting the surface of the film into a silicon oxynitride film.
- an oxynitride film having excellent leakage current characteristics can be obtained as an inter-electrode oxynitride film, so that a flash memory that can stably hold charges in a floating gate electrode and can be driven at a low voltage An element can be realized.
- a method for forming a silicon oxide film on a polysilicon film comprising:
- a microphone mouth wave radiating antenna that irradiates the microphone mouth wave into the processing vessel through the plate is placed inside the processing vessel of the microphone mouth wave processing device. Then, a gas mainly containing Kr and a gas containing oxygen are supplied from the shower plate into the processing container, and the microphone mouth-wave radiation antenna enters the processing container via the shower plate. Supplying a microphone mouth wave to form a plasma containing atomic oxygen ⁇ * in the processing container;
- Forming a silicon oxide film by oxidizing the surface of the polysilicon film formed on the substrate in the processing container with the plasma. It is in.
- a plasma gas uniformly supplied from a shower plate is excited by a microwave, whereby a high-density plasma having a low electron temperature can be formed in a processing chamber. Oxidizing atomic oxygen is efficiently formed.
- the silicon oxide film formed by the Kr plasma in this manner becomes a ground and does not depend on the orientation of the Si crystal, and is thus formed uniformly on the polysilicon film.
- Such a silicon oxide film has preferable characteristics in which the interface state is small and the leak current is small.
- the oxidation treatment of the polysilicon can be performed at a low temperature of 550 ° C. or less. As a result, even if the oxidation treatment is performed, substantial grain growth does not occur in the polysilicon film. Problems such as electric current applied to the oxide film due to grain growth are avoided.
- a method for forming a silicon nitride film on a polysilicon film comprising:
- a processing vessel of a microphone mouth wave processing device provided with a microphone mouth wave radiation antenna for irradiating a microphone mouth wave into the processing vessel via a plate, Ar or from the shower plate into the processing vessel.
- a gas containing Kr as a main component, a gas containing nitrogen and hydrogen are supplied, and a microphone mouth wave is supplied from the microwave radiating antenna through the shower plate into the processing vessel.
- a plasma gas uniformly supplied from a shower plate is excited by a microwave to form a high-density plasma having a low electron temperature in a processing chamber.
- the nitrogen radical NH * for nitriding the silicon film is efficiently formed.
- the silicon nitride film formed by the Kr plasma in this manner has a preferable characteristic of having a small leak current, despite being formed at a low temperature.
- Another subject of the present invention is:
- the silicon oxide film is formed by introducing a gas containing mainly oxygen-containing gas and Kr gas into a processing chamber and exciting plasma in the processing chamber by a microphone mouth wave. It is an object of the present invention to provide a method for manufacturing a flash memory device.
- the surface of the first electrode can be oxidized at a low temperature in Kr plasma for efficiently forming atomic oxygen ⁇ *, and as a result, the silicon oxide film becomes an interface state It is possible to obtain an oxide film having a small amount and a small leak current.
- Another subject of the present invention is:
- An object of the present invention is to provide a method of manufacturing a flash memory device, which is formed by performing According to the present invention, the surface of the first electrode can be nitrided at a low temperature in an Ar or Kr plasma that efficiently forms hydrogen nitride radicals NH *, and as a result, the silicon nitride As the film, a nitride film having a small leak current can be obtained.
- FIG. 1 is a diagram showing a schematic cross-sectional structure of a conventional flash memory device
- FIG. 2 is a diagram showing the concept of a plasma device using a radial line slot antenna
- FIG. 3 is a diagram showing the relationship between the obtained oxide film thickness and the gas pressure in the processing chamber for the oxide film formed according to the first embodiment of the present invention
- FIG. 4 is a diagram showing the oxidation time dependence of the obtained oxide film thickness for the oxide film formed according to the first embodiment of the present invention
- FIG. 5 is a diagram showing the distribution of the Kr density in the silicon oxide film in the depth direction according to the first embodiment of the present invention.
- FIG. 6 is a diagram showing the interface state density of the silicon oxide film according to the first embodiment of the present invention
- FIG. 7 is a relationship between the interface state density in the silicon oxide film and the withstand voltage according to the first embodiment of the present invention.
- 8A and 8B are diagrams showing the relationship between the interface state density and the dielectric strength voltage in the silicon oxide film obtained in the first embodiment of the present invention and the total pressure in the processing chamber;
- FIG. 9 is a diagram showing the gas pressure dependency of the processing chamber on the nitride film thickness of the nitride film formed according to the second embodiment of the present invention.
- FIG. 10 shows the current-voltage characteristics of the silicon nitride film according to the second embodiment of the present invention.
- FIGS. 11A and 1IB are diagrams showing an oxidizing process, a nitriding process, and a nitriding process of a polysilicon film according to a third embodiment of the present invention
- FIG. 12 is a diagram showing the oxidation time dependency of the obtained oxide film thickness in the oxidation treatment of the polysilicon film according to the third embodiment of the present invention
- FIGS. 13A to 13C are diagrams showing changes in the surface state due to the oxidation treatment of the polysilicon film according to the third embodiment of the present invention.
- Figures 14A and 14B show the changes in surface state when a polysilicon film is thermally oxidized
- FIGS. 15A and 15B show transmission electron microscope images of the polysilicon film formed according to the third embodiment of the present invention.
- FIGS. 16 to 17 are diagrams showing electrical characteristics of an oxide film formed on polysilicon according to a third embodiment of the present invention in comparison with a thermal oxide film;
- FIG. 18 shows a cross-sectional structure of a flash memory device according to a fourth embodiment of the present invention.
- FIG. 19 is a view showing a cross-sectional structure of a flash memory device according to a fifth embodiment of the present invention.
- 20 to 23 are views showing a manufacturing process of a flash memory device according to a fifth embodiment of the present invention.
- FIG. 24 is a diagram showing a cross-sectional structure of a flash memory device according to a sixth embodiment of the present invention.
- FIG. 25 is a diagram showing a cross-sectional structure of a flash memory device according to a seventh embodiment of the present invention.
- FIG. 2 is a cross-sectional view showing an example of a microwave plasma processing apparatus using a radial line slot antenna for realizing the oxidation method of the present invention (see WO99Z333362). .
- This embodiment has a novel feature in that Kr is used as a plasma excitation gas for forming an oxide film.
- the microphone mouth-wave plasma processing apparatus includes a vacuum vessel (processing chamber) 101 having a sample stage 104 holding a substrate 103 to be processed. 0 1 was evacuated and the processing chamber 1 0 1 the pressure in the treatment chamber from the shower plate 1 0 2 formed on a part by introducing K r gas and 0 2 gas wall 1 T or r. ( i Set it to about 33P a).
- a circular substrate such as a silicon wafer is placed on the sample stage 104 having a heating mechanism as the substrate 103 to be processed, and the temperature of the sample is set to about 400 ° C.
- This temperature setting is preferably in the range of 200-550, within which the results described below are almost similar.
- 2.45 GHz The microphone mouth wave is supplied to generate high-density plasma in the processing chamber 101. If the frequency of the supplied microphone mouth wave is in the range from 900 MHz to 10 GHz, the results described below are almost the same.
- the distance between the shower plate 102 and the substrate 103 is 6 cm in this embodiment. The shorter the distance, the faster the film formation.
- Microphone port wave plasma processing apparatus of FIG. 2 it is possible to realize a plasma density exceeding surface odor T lx 1 0 12 c m-3 of the substrate to be processed 1 0 3. Further, the formed high-density plasma is excited by the microphone mouth wave, so that the electron temperature is low, and the plasma potential on the surface of the substrate 103 to be processed becomes 10 V or less. Therefore, the surface of the substrate 103 to be processed is not damaged by the plasma, and plasma sputtering of the processing chamber 101 does not occur, so that the substrate 103 to be processed is not contaminated.
- the reaction product quickly flows to the side in the space, and the reaction holding table 104 Since the gas is exhausted from a large volume of space formed around, very uniform treatment is possible.
- Mashi is Nozomu the higher pressure in the processing chamber 101 Iga, when too high, the generated ⁇ * comrade collide, intends island back to the 0 2 molecule . For this reason, of course, there is an optimal gas pressure.
- FIG. 3 shows the thickness of the oxide film obtained when the total pressure of the processing chamber 101 was changed while maintaining the pressure ratio between Kr and oxygen in the processing chamber 101 at Kr 97% and oxygen 3%. Is shown. However, in the experiment in Fig. 3, the silicon substrate temperature was set to 400 ° C and the oxidation treatment was performed for 10 minutes.
- the thickness of the oxide film obtained when the gas pressure in the processing chamber 101 is 1 Torr is maximized, and that this pressure or an oxidizing condition in the vicinity thereof is optimal. . Moreover, this optimum pressure is the same whether the plane orientation of the silicon substrate is 100 or 111.
- Figure 4 shows the relationship between the r / ⁇ 2 film thickness and oxidation time of oxide film obtained in the oxidation process the silicon substrate surface using a high-density plasma. However, FIG. 4 shows both the results when the silicon substrate has the (100) plane and the (111) plane. FIG. 4 also shows the dependence on the oxidation time due to the conventional 900 ° C. dry thermal oxidation.
- a substrate temperature of 400 ° C the processing rate of oxidation by KrZ ⁇ 2 high density plasma oxidation treatment in the chamber pressure Iotatauomikuron rr, oxidation during the atmospheric dry ⁇ 2 oxidation at a substrate temperature of 900 ° C It turns out that it is faster than the speed.
- Oxidation of the silicon substrate surface using K r / 0 2 high-density plasma is as expected, and the (111) plane is as dense as the (100) plane. It is considered that an oxide film was formed.
- the oxidation rate of the (111) plane is higher than that of the (100) plane. Indicates that the density is lower than that of the oxide film formed on the (100) plane.
- Fig. 5 shows the depth distribution of the Kr density in the silicon oxide film formed by the above procedure, which was examined using a total reflection X-ray fluorescence spectrometer.
- the silicon oxide film was formed by setting the oxygen partial pressure in Kr to 3%, the pressure in the processing chamber to 1 Torr (about 133 Pa), and the substrate temperature to 400 ° C. ing.
- the surface density of Kr decreases as it approaches the silicon / silicon oxide interface, but is included at a density of about 2 ⁇ 10 11 cm ⁇ 2 on the silicon oxide film surface. That is, FIG. 5, the silicon oxide film formed by the silicon substrate surface oxidation using Kr / ⁇ 2 high density plasma, the K r concentration in the case the film thickness is more than 4 nm with a constant real qualitatively, silicon This indicates that the Kr concentration decreases toward the interface of the silicon oxide film. According to the silicon oxide film forming method of the present invention, 10 10 cm- Kr of two or more surface density is contained in the silicon oxide film. The result of FIG. 5 is similarly obtained on the (100) plane and also on the (111) plane.
- Figure 6 shows the results of low-frequency CV measurements of the interface state density of the oxide film.
- the silicon oxide film was formed at a substrate temperature of 400 ° C. using the apparatus shown in FIG.
- the partial pressure of oxygen in the rare gas was fixed at 3%, and the pressure in the processing chamber was fixed at 1 Torr (about 133 Pa).
- the interface state density of the thermal oxide film formed in an atmosphere of 900% oxygen and 100% oxygen is also shown.
- the interface state density of the oxide film formed using Kr gas is low on both the (100) plane and the (111) plane, and the oxide film was formed in a dry oxidation atmosphere at 900 ° C. It can be seen that the interface state density is the same as that of the thermal oxide film formed on the () plane. In contrast, the interface state density of the thermal oxide film formed on the (111) plane is one order of magnitude higher.
- the relationship between the partial pressure of oxygen in Kr in the silicon oxide film deposition atmosphere, the dielectric strength of the silicon oxide film, and the interface order density in the formed silicon oxide film was determined by the pressure in the processing chamber. When the film was measured at (133 Pa), the same results were obtained for both the (100) and (111) planes. A value equivalent to the interface order density in the oxide film is obtained. Also, the withstand voltage of the silicon oxide film becomes maximum near the oxygen partial pressure of 3%. This et al., When performing Sani ⁇ with KrZ_ ⁇ 2 mixed gas, the oxygen partial pressure is 2 to 4% is good suitable.
- FIG. 7 shows the relationship between the pressure at the time of forming the silicon oxide film, the withstand voltage of the silicon oxide film, and the interface order density. At this time, the partial pressure of oxygen is 3%.
- the dielectric strength of the silicon oxide film becomes maximum and the interface order density becomes minimum when the pressure during film formation is around 1 Torr.
- the pressure in the case of forming the oxide film using the K r / 0 2 mixed gas 800- 1200 m the To rr is found to be optimal.
- the results shown in FIG. 7 are similarly obtained on the (100) plane and also on the (111) plane.
- the oxide film obtained by oxidizing the silicon substrate surface using K r ⁇ 2 high-density plasma had the same good characteristics as the thermal oxidation at 900 ° C.
- Figures 8A and 8B show the stress current-induced leakage current characteristics of the obtained silicon oxide film in comparison with the case of the conventional thermal oxide film. However, in FIGS. 8A and 8B, the thickness of the oxide film is 3.2 nm.
- K r / ⁇ 2 oxide films grown with a high density plasma even though oxidized at a low temperature of 4 0 0 ° C, (1 0 0) plane, (1 1 1) plane
- Kr is contained in the oxide film. Since Kr is contained in the oxide film, stress in the film and at the Si / Si 2 interface is reduced, the charge and interface state density in the film are reduced, and the electrical conductivity of the silicon oxide film is reduced. It is considered that the characteristics were greatly improved.
- r with a density of 101 (1 cm- 2 or more) contributes to the improvement of the electrical and reliability characteristics of the silicon oxide film.
- the apparatus used for forming the nitride film is the same as the apparatus in FIG. 2, and uses Ar or Kr as a plasma excitation gas for forming the nitride film.
- the inside of the processing chamber 101 is evacuated to a high vacuum state by introducing the Ar gas and NH 3 gas from the shower plate 102 as an example.
- Set the pressure to about 10 O mT orr (about 13 Pa).
- a circular substrate 103 such as a silicon wafer is placed on the sample stage 104, and the substrate temperature is set to about 550 ° C.
- the substrate temperature is within the range of 400-550 ° C, almost the same results can be obtained.
- a microwave aperture of 2.45 GHz is supplied into the processing chamber through the coaxial waveguide 105, the radial line slot antenna 106 and the dielectric plate 107, and the processing chamber To generate high density plasma.
- the frequency of the supplied microwave is in the range from 900 MHz to 10 GHz.
- the interval between the shower plate 102 and the substrate 103 is set to 6 em. The shorter the distance, the faster the film formation.
- a microwave may be introduced into a processing chamber using another method.
- Ar is used as the plasma excitation gas, but the same result can be obtained by using Kr.
- NH 3 is used as the plasma process gas, but a mixed gas such as N 2 and H 2 may be used.
- the nitride film has been formed by plasma CVD or other methods.However, such a method can provide a high-quality nitride film that can be used as a gate film of a transistor. I didn't.
- a high-quality nitride film can be formed at a low temperature on the (100) plane or the (111) plane regardless of the plane orientation of silicon. Becomes
- the presence of hydrogen is one important requirement. Due to the presence of hydrogen in the plasma, dangling pounds in the silicon nitride film and at the interface are terminated by forming Si_H, NH bonds, and as a result, electron traps at the silicon nitride film and the interface are eliminated.
- the presence of the Si-H bond and the NH bond in the nitride film of the present invention has been confirmed by measuring the infrared absorption spectrum and the X-ray photoelectron spectrum, respectively.
- FIG. 9 shows the pressure dependency of the silicon nitride film thickness formed by the above-described procedure.
- the partial pressure ratio of Ar: NH 3 was 98: 2
- the deposition time was 30 minutes.
- the growth rate of the nitride film is higher when the pressure in the processing chamber 101 is reduced to increase the energy given by the rare gas (Ar or Kr) to NH 3 (or N 2 ZH 2 ). It turns out that it becomes.
- the gas pressure is preferably 50-10 OmTorr (about 7-13 Pa).
- the partial pressure of NH 3 (or N 2 / H 2 ) in the rare gas is preferably in the range of 1 to 10%, more preferably 2 to 6%.
- the dielectric constant of the silicon nitride film of this example was 7.9, which was about twice that of the silicon oxide film.
- FIG. 10 shows the current-voltage characteristics of the silicon nitride film of this example.
- Ar N 2: the partial pressure ratio 93 H 2: 5: 2 is set to a thickness of 4. 2 nm of silicon nitride film ( (Equivalent to a dielectric constant-equivalent oxide film of 2.1 nm). This result is shown in Fig. 10 in comparison with a thermal oxide film with a thickness of 2.1 nm.
- a leak current characteristic that is at least four orders of magnitude lower than that of the silicon oxide film can be obtained when an IV voltage is applied.
- the obtained silicon nitride film is an insulating film suitable for suppressing a leakage current between the floating gate electrode and the control gate electrode in the flash memory device.
- the film formation conditions, physical properties, and electrical characteristics described above are the same for the (100) plane and the (111) plane regardless of the plane orientation of silicon.
- a silicon nitride film having excellent film quality can be obtained.
- the effect of the present invention relates to the fact that not only Si—H bonds and N—H bonds but also Ar or Kr are contained in the oxide film.
- the above-described method of forming an oxide film and a nitride film is similarly applied to the oxidation and nitridation of polysilicon, and a high-quality oxide film and nitride film can be formed on polysilicon.
- a polysilicon film 203 is deposited on a silicon substrate 201 covered with an insulating film 202. Therefore, the polysilicon silicon slag 203 is subjected to the process of FIG. 11 (B) in the processing vessel 101 of the microwave plasma processing apparatus described in FIG. 2 in a high-density mixed gas of Kr or Ar and oxygen.
- a silicon oxide film 204 having excellent film quality that is, a small interface state density and a small leak current can be obtained on the surface of the polysilicon film 203.
- the polysilicon film 203 is exposed to a high-density mixed gas plasma of Kr or Ar and NH 3 or N 2 and H 2 , whereby the polysilicon film 203 is exposed.
- a similar excellent nitride film 205 can be obtained on the surface of No. 3.
- the polysilicon film 203 is exposed to a high-density mixed gas plasma of Kr or Ar and oxygen and NH 3 , or N 2 and H 2 , thereby An oxynitride film 206 having excellent film quality can be obtained on the surface of the polysilicon film 203.
- Polysilicon formed on an insulating film is stable when the (1 1 1) plane orientation is perpendicular to the insulating film, and is dense, has good crystallinity, and has high quality. Actually, crystal grains having another plane orientation also exist in polysilicon. According to the method for forming an oxide film, a nitride film, or an oxynitride film according to the present embodiment, as described above, a high-quality oxide film, a nitride film, or an oxynitride film is formed regardless of the plane orientation of silicon. Can be. For this reason, the processes shown in FIGS.
- 11A and 11B are performed on a thin high-quality oxide film, nitride film, and oxide film on a polysilicon film such as a first polysilicon gate electrode, which is a floating electrode of flash memory.
- a polysilicon film such as a first polysilicon gate electrode, which is a floating electrode of flash memory.
- a polysilicon film such as a first polysilicon gate electrode, which is a floating electrode of flash memory.
- the oxide film, nitride film and oxynitride film of the present invention can be formed at a low temperature of 550 ° C. or less, so that the polysilicon surface is not roughened.
- Figure 12 shows a thermal oxide film with a thickness of 100 nm formed on a Si substrate having a (100) plane orientation, and an additional 200 nm thick n-type polysilicon film formed on the thermal oxide film.
- the results of an oxide film formation experiment performed on the Si substrate are shown in comparison with the case where the (100) and (111) planes of the Si substrate were directly oxidized.
- the vertical axis represents the thickness of the formed oxide film
- the horizontal axis represents time. Further in FIG.
- ⁇ it is the case in this way to form polysilicon film surface is treated with K r / 0 2 plasma to form an oxide film
- ⁇ indicates the case where the (100) plane of the Si substrate was thermally oxidized
- the opening indicates the case where the (111) plane of the Si substrate was thermally oxidized
- ⁇ indicates the case where the surface of the polysilicon film was thermally oxidized. The following shows the case.
- the heat treatment step is performed in a 100% oxygen atmosphere at 900 ° C.
- the polysilicon film is de-loop to a carrier concentration of greater than 10 2 ° cm- 3.
- FIG. 12 when using the Kr / ⁇ 2 plasma oxidation process may be a single crystal surface of any surface orientation S i table surface being oxidized and also shall apply polycrystalline surfaces containing grain boundary It can be seen that almost the same oxidation rate can be obtained.
- FIG. 13A shows the result of inspecting the surface of the polysilicon film thus formed with an atomic force microscope before performing the oxidation treatment.
- FIG. 1 3 B shows a state in which the surface of FIG. 1 3 A was treated with K r / ⁇ 2 plasma, namely the state of the polysilicon surface Sani ⁇ is formed on the surface.
- FIG. 13C shows the surface of the polysilicon surface in a state where the oxide film has been removed from the surface of FIG. 13B by HF treatment.
- the K r / ⁇ 2 for oxidation using plasma to be efficiently effective even at a low temperature of about 4 0 0 ° C, the crystalline Te polysilicon film odor It can be seen that almost no grain growth occurred, the surface roughness was suppressed, and the formed oxide film had a substantially uniform thickness.
- Fig. 148 shows the surface state including the oxide film when the polysilicon film of Fig. 13A was thermally oxidized at 900 ° C
- Fig. 14B shows the oxide film in Fig. 14A. This shows the surface condition after removing.
- Figure 1 5 A, 1 5 B is, the polysilicon film surface, shows the results of the K r Z0 2 plasma treated sample of a cross section forming a more acid I arsenide film was observed by a transmission electron microscope.
- Figure 15B is an enlarged view of a part of Figure 15A.
- an A1 layer is formed on the oxide film (denoted as polyoxide), but the oxide film is formed with a uniform thickness on the surface of the polysilicon film. I understand. Also, referring to the enlarged view of FIG. 15B, it can be seen that the oxide film is uniform.
- FIG. 16 shows the relationship between the current density of the silicon oxide film thus obtained on the polysilicon film and the applied electric field in comparison with the thermal oxide film.
- FIG. 17 is a diagram showing FIG. 16 as a Fowler-Nordheim plot.
- the tunneling current is applied electric field the 5 M VZ cm super
- the plots in Fig. 17 show that the tunnel current flowing in the film is a Fowler-Nordheim type tunnel current as in the case of the thermal oxide film.
- K r Z_ ⁇ is ⁇ Baria height of the tunneling current ⁇ in oxidation film formed by oxidation treatment with 2 plasma, greater than that of the thermal oxide film and the breakdown voltage conventional thermal It can be seen that it is larger than the oxide film.
- the flash memory device is formed on a silicon substrate 1.001, and a tunnel oxide film 1002 formed on the silicon substrate 1001, and the tunnel oxide film.
- illustration of a source region, a drain region, a contact hole, a wiring pattern, and the like is omitted.
- the flash memory device of such a configuration in the polysilicon gate electrode 1 0 0 3 in microphone port wave plasma processing apparatus of FIG. 2, by exposure to high-density plasma in which the K r / ⁇ 2 plasma gas, the oxidizing Since an excellent film having a small leakage current can be obtained as the film 104, the thickness of the oxide film 104 can be reduced, and the flash memory element can be driven at a low voltage. Become. Note that, in the flash memory device of FIG. 18, instead of the oxide film 104, the nitride film 1005 formed by the above-described Kr / NH 3 plasma processing step, It is also possible to use the oxynitride film 109 described in the above.
- a flash memory device which includes a high-voltage transistor and a low-voltage transistor having a gate electrode of a polysilicon / silicide laminated structure using a semiconductor device, will be described.
- FIG. 19 shows a schematic cross-sectional structure of a flash memory device 100 according to the present embodiment.
- the flash memory device 100 is formed on a silicon substrate 1001, and a tunnel oxide film 1002 formed on the silicon substrate 1001,
- a first polysilicon gate electrode formed on the tunnel oxide film and serving as a gate electrode; and a silicon nitride film on the polysilicon gate electrode.
- 100 4 a silicon oxide film 100 5, a silicon nitride film 100 6, and a silicon oxide film 100 7 are sequentially formed, and a control is provided on the silicon nitride film 100 7.
- a second polysilicon gate electrode 108 serving as a gate electrode is formed.
- illustration of a source region, a drain region, a contact hole, a wiring pattern, and the like is omitted.
- the silicon oxide films 100, 100, and 107 are formed by the silicon oxide film forming method described above.
- 06 is formed by the silicon nitride film forming method described above, so that even if the film thickness of these films is reduced to about half that of the conventional oxide film and nitride film, good electrical characteristics can be obtained. Guaranteed.
- a flash memory cell area A, a high-voltage transistor area B, and a low-voltage transistor area C are formed on a silicon substrate 1101 by a field oxide film 1102.
- a silicon oxide film 1103 is formed in each of the regions A to C.
- the field oxide film 1102 can be formed by a selective oxidation method (LOCOS method), a shallow trench isolation method, or the like.
- Kr is used as a plasma excitation gas for forming an oxide film and a nitride film.
- the microwave plasma shown in Fig. 2 is used to form the oxide and nitride films. Use processing equipment.
- the silicon oxide film 1103 is removed in the memory cell region A, and a tunnel oxide film 110 is formed in the memory cell region A to a thickness of about 5 nm. .
- the inside of the vacuum chamber (processing chamber) 101 is evacuated, and Kr gas and O 2 gas are introduced from the shower plate 102.
- the pressure was set to about 1 Torr (about 1333 Pa)
- the temperature of the silicon wafer was set to 450 ° C
- the frequency supplied from the coaxial waveguide 105 was 2.56 GHz.
- the waves are supplied into the processing chamber through the radial line slot antenna 106 and the dielectric plate 107 to generate high-density plasma.
- a first polysilicon layer 110 5 is further deposited so as to cover the tunnel oxide film 110.
- the surface of the deposited polysilicon layer 1105 is flattened by hydrogen radical treatment.
- the first polysilicon layer 1105 is removed by patterning from the high-voltage transistor region B and the low-voltage transistor region C, and only on the tunnel oxide film 110 in the memory cell region A. The first polysilicon 110 is left.
- a lower nitride film 110 A, a lower oxide film 110 B, an upper nitride film 110 C, and an upper oxide film 111 are formed on the structure of FIG. 6D are sequentially formed, and an insulating film 110 having a NONO structure is formed using the microwave plasma processing apparatus of FIG.
- the inside of the vacuum chamber (processing chamber) 101 is evacuated to a high vacuum state in the microphone mouth-wave plasma processing apparatus shown in FIG. 2, and the Kr gas, N 2 gas, H Two gases are introduced, the pressure inside the processing chamber is set at about 10 OmTorr (about 13 Pa), and the temperature of the silicon wafer is set at 500 ° C. Then, in this state, a microwave having a frequency of 2.45 GHz from the coaxial waveguide 105 is supplied into the processing chamber through the radial line slot antenna 106 and the dielectric plate 107 to perform processing. Generates high-density plasma in the room.
- a silicon nitride film having a thickness of about 2 nm is formed as the lower nitride film 110 A on the surface of the polysilicon.
- introduction of the Kr gas, N 2 gas, and H 2 gas is stopped, and the inside of the vacuum chamber (processing chamber) 101 is evacuated.
- introduced and K r gas and 0 2 gas from the shower plates 1 0 2 in a state where the pressure in the treatment chamber was set at l T orr (about 1 3 3 P a) extent, again 2. 4 5 GH z
- a high-density plasma is generated in the processing chamber 101, and a silicon oxide film having a thickness of about 2 nm is formed on the lower oxide film 110. Formed as B.
- the insulating film 1106 having the N ⁇ N ⁇ structure can be formed to a thickness of 9 nm.
- the orientation of the polysilicon does not depend, and the thickness and quality of each oxide film and nitride film are extremely uniform.
- the insulating film 1106 thus formed is further patterned and selectively removed in the high-voltage transistor region B and the low-voltage transistor region C.
- ion implantation for threshold voltage control is performed on the high-voltage transistor region B and the low-voltage transistor region C, and the oxide film 110 3 on the regions B and C is further implanted. Is removed. Further, in the high-voltage transistor region B, Forms a gate oxide film 1107 with a thickness of 7 nm, and then forms a gate oxide film 1108 with a thickness of 3.5 nm in the low voltage transistor region C.
- a second polysilicon layer 1109 and a silicide layer 111 are sequentially formed on the entire structure including the field oxide film 1102, and furthermore, The gate electrodes 1 1 1 1 B and 1 1 1 1 C are formed in the high-voltage and low-voltage transistor regions B and C, respectively, by performing these processes.
- the polysilicon layer 1109 and the silicide layer 111 are patterned to form a gate electrode 111A.
- the device is completed by forming the source and drain, forming the insulating film, forming the contact, and forming the wiring according to standard semiconductor processes.
- a flash memory integrated circuit device formed by two-dimensionally arranging a plurality of flash memory elements of the present invention can perform information writing and erasing operations at a low voltage, suppress generation of a substrate current, and reduce the tunnel insulating film. Inferiority is suppressed, and the characteristics of the element are stabilized.
- the flash memory device of the present invention has excellent low-leakage characteristics, can operate for writing and erasing at a voltage of about 7 V, increases the memory retention time by one digit or more, and increases the number of rewritable times by about one digit or more. be able to.
- a flash memory according to a sixth embodiment of the present invention having a gate electrode of a polysilicon / silicide laminated structure using a technique of forming an oxide film and a nitride film at a low temperature using the high-density microphone mouth-wave plasma at a low temperature.
- the element will be described.
- FIG. 24 shows a schematic sectional structure of a flash memory device 1500 according to the present embodiment.
- the flash memory element 150 A tunnel nitride film 1502 formed on the silicon substrate 1501, and a first polysilicon gate formed on the tunnel nitride film 1502 and serving as a floating gate electrode.
- a second polysilicon electrode 1507 serving as a control gate electrode is formed on the silicon oxide film 1506.
- illustration of a source region, a drain region, a contact hole, a wiring pattern, and the like is omitted.
- the silicon oxide films 1502, 1504 and 1506 are the silicon oxide film forming method using the high-density microwave plasma described above.
- the silicon nitride film 1505 is formed by the silicon nitride film forming method using the high-density microphone mouth-wave plasma described above.
- the steps up to patterning the first polysilicon layer 1503 are the same as the steps in FIGS. 20 and 21 described above.
- the tunnel nitride film 1 5 0 2 after evacuating the vacuum vessel (processing chamber) 1 0 in 1, A r gas from the shower plate 1 0 2, New 2 gas, Eta 2 gas And set the pressure in the processing chamber to about 10 OmTorr (about 13 Pa), supply a 2.45 GHz microphone mouth wave, and generate high-density plasma in the processing chamber. It has a thickness of about 4 nm.
- a lower silicon oxide film 1504 and a silicon nitride film 150 are formed on the first polysilicon layer in the region A.
- 05 and an upper silicon oxide film 1506 are sequentially formed, and an insulator film having an ONO structure is formed.
- evacuating the vacuum vessel (processing chamber) 1 0 1 of the microwave plasma processing device described above in FIG. 2 in a high vacuum state K r gas from the shower plate 1 0 2 0 2 Gas is introduced, and the pressure in the processing chamber 101 is set to about l Torr (about 133 Pa).
- a microphone mouth wave of 2.45 GHz is supplied into the processing chamber 101 to generate a high-density plasma, whereby the first polysilicon is produced.
- a silicon oxide film having a thickness of about 2 nm is formed on the surface of the silicon layer 1503.
- the inside of the vacuum chamber (processing chamber) 101 was evacuated. N 2 gas and H 2 gas are introduced, and the pressure in the processing chamber is set to about 1 Torr (about 133 Pa).
- high-density plasma is generated in the processing chamber 101 by supplying a microwave of 2.445 GHz again, and the silicon nitride film is converted into a hydrogen nitride radical NH * accompanying the high-density plasma. Exposure to a dense silicon nitride film.
- a silicon oxide film was formed to a thickness of about 2 nm on the dense silicon nitride film by the CVD method, and again from the shower plate 102 using a microwave plasma apparatus, Kr gas, 0 2 gas was introduced and to set the pressure of the processing chamber 1 0 1 the degree 1 T orr (about 1 3 3 P a).
- a microwave of 2.45 GHz is supplied again into the processing chamber 101 to generate high-density plasma in the processing chamber 101.
- the CVD silicon oxide film is converted into a dense silicon oxide film.
- an ONO film having a thickness of about 7 nm is formed on the polysilicon film 1503, but the formed ⁇ N ⁇ film does not depend on the plane orientation of the polysilicon.
- the ONO film has a very uniform thickness.
- the ONO film is then subjected to a patterning process for removing the portions corresponding to the high-voltage and low-voltage transistor regions B and C, and subsequently to the same steps as in the fourth embodiment, and Complete the device.
- This flash memory device has excellent low leakage characteristics and can operate at a write / erase voltage of about 6 V.
- the memory retention time is one digit higher than that of the conventional flash memory.
- the number of rewritable times can be increased by about one digit or more.
- a technology for forming a low-temperature oxide film and a nitride film using the microphone mouth-wave high-density plasma A description will be given of a flash memory device 160 according to a seventh embodiment of the present invention having a gate electrode of a polysilicon Z-silicide laminated structure using the same.
- FIG. 25 shows a schematic sectional structure of the flash memory device 160.
- the flash memory device 160 of this embodiment is formed on a silicon substrate 1601, and a tunnel oxide film formed on the silicon substrate 1601.
- a first polysilicon gate electrode 163 formed on the tunnel oxide film 162 and constituting a floating gate electrode, wherein the first polysilicon gate electrode 166 is provided.
- a silicon nitride film 1604 and a silicon oxide film 1605 are sequentially formed on 03.
- a second polysilicon gate electrode 166 serving as a control gate electrode is formed on the silicon oxide film 1605.
- FIG. 25 illustration of a source region, a drain region, a contact hole, a wiring pattern, and the like is omitted.
- the silicon oxide films 1602 and 1605 are formed by the silicon oxide film forming method described above, and the silicon nitride film 1604 is described above. Formed by the silicon nitride film forming method described above.
- the first polysilicon layer 163 is formed in the region A until the first polysilicon layer 163 is patterned.
- a silicon nitride film and a silicon nitride film are sequentially formed on the first polysilicon layer 163 to form an insulator film having an NO structure.
- the NO film is formed as follows using the microwave plasma processing apparatus of FIG.
- the inside of the vacuum chamber (processing chamber) 101 is evacuated, 1 ⁇ 1 "gas, N 2 gas, and H 2 gas are introduced from the shower plate 102, and the pressure in the processing chamber is adjusted to 10 O mT orr (approx. In this state, a microwave of 2.45 GHz is supplied to generate high-density plasma in the processing chamber, and the nitrogen of the polysilicon layer 1603 is reduced.
- a silicon nitride film with a thickness of about 3 nm is formed by the arsenic reaction.
- a silicon oxide film is formed to a thickness of about 2 nm by the CVD method, and the mask is formed again.
- high-density plasma is generated in the processing chamber, and the oxide film formed by the CVD method is converted into an atom accompanying the high-density plasma. Exposure to oxygen O *.
- the CVD oxide film is converted into a dense silicon oxide film.
- the NO film thus formed had a thickness of about 5 nm, but did not depend on the plane orientation of polysilicon, and was extremely uniform. After the N ⁇ film is formed in this manner, it is patterned, and portions formed in the high-voltage and low-voltage transistor regions B and C are selectively removed.
- the flash memory device thus formed has excellent low-leakage characteristics, and can perform writing and erasing at a low voltage of about 5 V.
- the retention time can be increased by one digit or more, and the number of rewritable times can be increased by approximately one digit or more.
- the method of forming the memory cell, the high-voltage transistor, and the low-voltage transistor described in the above embodiments is merely an example, and the present invention is not limited to these.
- Ar may be used in place of Kr in forming the nitride film of the present invention.
- polysilicon / silicide, polysilicon Z high melting point metal / amorphous It is also possible to use a film having a laminated structure such as silicon or polysilicon.
- the oxide film ⁇ ⁇ nitride film of the present invention in addition to the microwave plasma processing apparatus shown in FIG. 2, another plasma processing apparatus capable of forming a low-temperature oxide film using plasma is used. May be used.
- the example in which the film is formed by using the plasma apparatus using the radial line slot antenna is described.
- the microphone mouth wave may be introduced into the processing chamber by using another method.
- a plasma gas such as Kr gas or Ar gas is discharged from the first shower plate, and the processing gas is discharged from a second gas discharge unit different from the first gas discharge unit.
- shower from the shower plate It is also possible to use a plate type plasma processing apparatus. In this case, for example, oxygen gas may be released from the second shower plate.
- a process is performed such that a floating gate electrode of a flash memory element is formed by the first polysilicon electrode and a gate electrode of a high-voltage transistor is formed by the same first polysilicon electrode. It is also possible to design.
- the film can be formed at a high temperature of about 100 ° C.
- Silicon oxide film, silicon nitride film or silicon oxynitride film is equivalent to or better than silicon thermal oxide film and silicon nitride film deposited by CVD.
- a high-quality, high-performance flash memory device with excellent charge retention characteristics that can be rewritten at a low voltage can be realized.
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Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
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DE60140179T DE60140179D1 (de) | 2000-03-13 | 2001-03-13 | Verfahren zur herstellung eines flash-speicherbausteins |
EP01912317A EP1265279B1 (en) | 2000-03-13 | 2001-03-13 | Method of fabricating a flash memory device |
JP2001567036A JP4987206B2 (ja) | 2000-03-13 | 2001-03-13 | フラッシュメモリ素子の製造方法 |
US09/867,699 US6551948B2 (en) | 2000-03-13 | 2001-05-31 | Flash memory device and a fabrication process thereof, method of forming a dielectric film |
US10/359,592 US7026681B2 (en) | 2000-03-13 | 2003-02-07 | Flash memory device and fabrication process thereof, method of forming a dielectric film |
US10/359,714 US6998354B2 (en) | 2000-03-13 | 2003-02-07 | Flash memory device and fabrication process thereof, method of forming a dielectric film |
US10/359,701 US7001855B2 (en) | 2000-03-13 | 2003-02-07 | Flash memory device and fabrication process thereof, method of forming a dielectric film |
US10/721,513 US6838394B2 (en) | 2000-03-13 | 2003-11-26 | Flash memory device and a fabrication process thereof, method of forming a dielectric film |
US10/721,473 US6846753B2 (en) | 2000-03-13 | 2003-11-26 | Flash memory device and a fabrication process thereof, method of forming a dielectric film |
US10/762,522 US7109083B2 (en) | 2000-03-13 | 2004-01-23 | Flash memory device and a fabrication process thereof, method of forming a dielectric film |
US10/762,520 US6998355B2 (en) | 2000-03-13 | 2004-01-23 | Flash memory device and a fabrication process thereof, method of forming a dielectric film |
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PCT/JP2001/001966 WO2001069665A1 (fr) | 2000-03-13 | 2001-03-13 | Procede de formation de pellicule dielectrique |
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EP (3) | EP1265276B1 (ja) |
JP (6) | JP4987206B2 (ja) |
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AT (1) | ATE514181T1 (ja) |
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Cited By (9)
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US6551948B2 (en) | 2000-03-13 | 2003-04-22 | Tadahiro Ohmi | Flash memory device and a fabrication process thereof, method of forming a dielectric film |
JP2005530341A (ja) * | 2002-06-12 | 2005-10-06 | アプライド マテリアルズ インコーポレイテッド | 基板を処理するためのプラズマ方法及び装置 |
WO2006025363A1 (ja) * | 2004-08-31 | 2006-03-09 | Tokyo Electron Limited | シリコン酸化膜の形成方法、半導体装置の製造方法およびコンピュータ記憶媒体 |
JP2006310393A (ja) * | 2005-04-26 | 2006-11-09 | Toshiba Corp | 半導体記憶装置及びその製造方法 |
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