EP0685115A1 - Semiconductor device comprising deuterium atoms - Google Patents
Semiconductor device comprising deuterium atomsInfo
- Publication number
- EP0685115A1 EP0685115A1 EP94910119A EP94910119A EP0685115A1 EP 0685115 A1 EP0685115 A1 EP 0685115A1 EP 94910119 A EP94910119 A EP 94910119A EP 94910119 A EP94910119 A EP 94910119A EP 0685115 A1 EP0685115 A1 EP 0685115A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bonds
- silicon
- deuterium
- plus
- silicon dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000004065 semiconductor Substances 0.000 title claims description 20
- 125000004431 deuterium atom Chemical group 0.000 title description 5
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 64
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000010703 silicon Substances 0.000 claims abstract description 50
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 8
- 229920005591 polysilicon Polymers 0.000 claims abstract description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 19
- 229910008051 Si-OH Inorganic materials 0.000 claims description 17
- 229910006358 Si—OH Inorganic materials 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 3
- 239000012459 cleaning agent Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 7
- QAOWNCQODCNURD-ZSJDYOACSA-N Sulfuric acid-d2 Chemical compound [2H]OS(=O)(=O)O[2H] QAOWNCQODCNURD-ZSJDYOACSA-N 0.000 abstract 1
- 230000008569 process Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 235000012431 wafers Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052909 inorganic silicate Inorganic materials 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000005445 isotope effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000001975 deuterium Chemical group 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 239000002784 hot electron Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- -1 deuterium compound Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000005527 interface trap Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- AKQNYQDSIDKVJZ-UHFFFAOYSA-N triphenylsilane Chemical compound C1=CC=CC=C1[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 AKQNYQDSIDKVJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
- 238000003868 zero point energy Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28185—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
- H01L21/02052—Wet cleaning only
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—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
- H01L21/0223—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 oxidation, e.g. oxidation of the substrate
- H01L21/02233—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 oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
- H01L21/02236—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 oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor
- H01L21/02238—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 oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer group IV semiconductor silicon in uncombined form, i.e. pure silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—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
- H01L21/02255—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 thermal treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28035—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being silicon, e.g. polysilicon, with or without impurities
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- 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
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
Definitions
- the present invention relates to silicon-based electronic devices and methods of fabricating them.
- the present invention provides improved VLSI fabrication methods that minimize some of the detrimental effects associated with hydrogen in oxides.
- Oxide layers are used to isolate devices and device elements on an integrated circuit. They are also used to control leakage currents in junction devices and act as stable gate oxides in field effect devices.
- Hydrogen can also be introduced unintentionally by a variety of standard fabrication processes including thermal oxidation of the wafer, post-oxidation treatments of the wafer, and ambient oxidation of the silicon surface. All of these processes result in the formation of Si-H and Si-OH bonds.
- thermal oxidation of the wafer post-oxidation treatments of the wafer, and ambient oxidation of the silicon surface. All of these processes result in the formation of Si-H and Si-OH bonds.
- Some hydrogen is introduced in the form of water present in materials used to fabricate semiconductor devices. In wet thermal oxidation processes water is purposely employed to form oxides, usually isolation oxides. These processes are rapid, but result in a somewhat porous oxide film.
- the introduction of hydrogen has the beneficial result of tying up some dangling bonds at the silicon/silica interface.
- the resulting Si-H bonds (as well as other compensating bonds such as Si-OH) are weaker than Si-0 bonds formed with the bulk oxide layer.
- the density of silicon dangling bonding is increased because Si-H and Si-OH bonds break and the resulting hydrogen species migrate away.
- Hot electrons having energies over 3.2eV which surmount the barrier between silicon and silicon dioxide. These "hot" electrons (or the resulting holes) can become trapped in the silica layer and break some of the silicon-hydrogen and silicon-OH bonds at the silicon and silicon dioxide interface. Hot electrons are especially prevalent during avalanche breakdown of a P-N junction, since the energy of avalanching carriers has a mean value of about 3eV. Hot electrons can also be produced in the channel region of MOS transistors, resulting in a change in the threshold voltage.
- the present invention provides a method in which a silicon wafer is contacted with a deuterium containing material to form Si-D and Si-OD bonds in a silicon dioxide layer and on a silicon surface at an interface with the silicon dioxide layer.
- Typical silicon dioxide layers suitable for treatment according to the present invention include isolation oxides, gate oxides, and various other oxide layers commonly used with semiconductor devices.
- deuterium or a deuterium- containing material is directed onto the device by, for example, annealing in a deuterium containing atmosphere, and/or cleaning with a deuterium compound such as D 2 0, D 2 S0 4 , and DC1.
- any hydrogen containing material used in VLSI fabrication can be replaced with corresponding deuterium containing material.
- the stability of oxide layers is improved in the present invention because the bond energy of the Si-H and Si-OH bonds is increased by replacing the hydrogen atoms with deuterium atoms.
- the Si-D and Si-OD bonds thus formed provide completed silicon dangling bonds that are less likely to break when exposed to electrical stresses. Therefore, the deuterium containing devices of the present invention have improved stability, quality, and reliability.
- VLSI fabrication flows employ deuterium contained compounds in many or all of the fabrication steps that would normally employ hydrogen or a hydrogen containing compound.
- a wet thermal oxidation step is performed with heavy water rather than normal water
- an annealing step is conducted in a deuterium atmosphere rather than a hydrogen atmosphere
- a polysilicon chemical vapor deposition step is performed with SiD 4 rather than silane, etc.
- Devices of this invention will preferably have substantial numbers of Si-H and/or Si-OH bonds replaced with Si-D and/or Si-OD bonds.
- Deuterium atoms represent a very small fraction of the atoms in naturally occurring hydrogen.
- the ratio of deuterated to hydrogenated silicon bonds is substantially greater than the naturally occurring fraction of deuterium atoms. In most preferred embodiments the ratio of Si-D plus Si-OD bond to Si-H plus Si-OH bonds in the oxide and oxide- silicon interfaces will be greater than about 95:5.
- Fig. 1 is a representation of a silicon-silicon dioxide interface having some desirable features of the present invention.
- the present invention provides a method for producing semiconductor devices in which hydrogen-containing bonds in silicon dioxide are replaced with deuterium containing bonds. Specifically Si-H bonds are replaced with Si-D bonds and Si-OH bonds are replaced with Si-OD bonds. Because the deuterium containing bonds are less likely to break on exposure to electrical stresses, devices prepared according to this invention have various advantages over conventional devices. For example, they have more stable gate threshold voltage in MOS devices and better control over leakage currents in junction devices. The formation of Si-D and Si-OD bonds is accomplished in the present invention by contacting a silicon wafer with deuterium or a deuterium containing compound before, during, and/or after formation a device oxide layer.
- deuterium refers to materials that include deuterium in a concentration above its naturally occurring level.
- pure gaseous D 2 as well as a gaseous mixture of 50% H 2 and 50% D 2 qualify as “deuterium.”
- any artificial gaseous mixture containing a ratio of D 2 to H 2 above the naturally occurring level constitutes “deuterium” as used herein.
- the naturally occurring concentration of deuterium is about one part in 6000 parts of hydrogen.
- deuterium containing compound is intended to refer to compositions containing deuterated compounds in a concentration above the naturally occurring level. Thus, a solution of 50% D 2 0 in H 2 0 would constitute a deuterium containing compound.
- compositions containing DC1, D 2 S0 4 , SiD 4 are "deuterium containing compounds” so long as the deuterium containing compounds are present at a concentration greater than that of naturally occurring deuterium in hydrogen.
- Silicon layer 10 may be, for example, a highly doped, conductive polysilicon gate contact or a single crystal silicon semiconductor.
- the bulk oxide layer consists of infinitely linked Si0 4 tetrahedra with an occasional oxygen vacancy or other fault. Ideally, all silicon atoms at the interface are bonded to an oxygen atom associated with the oxide network. For example, at positions 8 and 22, silicon atoms on the surface of the silicon layer are bonded to oxygen atoms that are incorporated into Si0 tetrahedra. However, not all surface silicon atoms are bonded with the oxide layer.
- Some silicon atoms at the interface have completed bonds with species other than the Si0 4 tetrahedra of the bulk oxide.
- These bonding arrangements include Si-H and Si- OH groups shown at positions 14 and 24, respectively. As noted, these bonds result from contact of hydrogen or hydrogen containing compounds during the device fabrication steps. Some of them may have even been formed intentionally by hydrogen annealing to saturate dangling silicon bonds.
- the bonding arrangements shown at positions 2 and 18 are favored for the present invention. At these positions, silicon atoms that would otherwise have dangling bonds are saturated by coupling with -0D and -D. These bonds are less likely than their hydrogen counterparts to break when subjected to electrical stresses. As shown below, the zero-point energy levels of deuterium containing bonds are lower than the corresponding hydrogen containing bonds and hence need a greater thermodyna ic driving force to break them.
- the ionic product of D 2 0 (i.e. [D + ][0D ⁇ ]) is smaller by about an order of magnitude than the corresponding ionic product of H 2 0.
- the ion product constant of D 2 0 is 1.1*10 -15 while the ion product constant for H 2 0 is 1.01*10 ⁇ 14 .
- the present invention can be implemented throughout the VLSI fabrication procedure.
- a typical fabrication procedure will include various doping, etching, annealing, deposition, cleaning, passivation, and oxidation steps.
- deuterium or a deuterium containing compound can be used in its place. This is particularly important in those fabrication steps in which a permanent oxide layer is being formed or treated.
- the method of this invention can be implemented, for example, by annealing in N 2 ambient with D 2 , by replacing HC1 and/or H 2 0 with DC1 and/or D 2 0 during cleaning, or by using deuterium containing compounds during chemical vapor deposition to form polysilicon layers.
- deuterium or deuterium containing compounds having a mole fraction of near 1 are employed in fabrication steps.
- lower concentrations of deuterated compounds may also be employed, but generally require a longer reaction or contact time to ensure formation of a substantial percentage of Si-D and/or Si-OD bounds.
- annealing atmospheres of the present invention includes a deuterium mole fraction of greater than about 0.90, and more preferably greater than about 0.95. In especially preferred embodiments, the annealing atmosphere includes a deuterium mole fraction of greater than about 0.99.
- the deuterium containing annealing atmosphere is preferably provided at a temperature of about 500°C and a pressure of about one atmosphere. These conditions are typically maintained for approximately 10 to 20 minutes. Of course, other acceptable conditions will be apparent to those of skill in the art.
- the semiconductor devices fabricated according to the present invention are preferably cleaned with a deuterium containing compound.
- preferred cleaning compounds include D 2 0, D 2 S0 4 , CDC1 3 , and DC1.
- any other common hydrogen containing cleaning compound can be replaced with the corresponding deuterium containing compound.
- Wet thermal oxidation of the silicon wafer can be conducted using heavy water. A suitable process is conducted by bubbling a carrier gas such as oxygen, nitrogen, or argon through a heavy water bath.
- Some of the heavy water will be vaporized in the process and transported with the carrier gas to the silicon surface where an oxide layer is formed.
- deuterium and oxygen gases are passed through a diffusion tube to form heavy water that is used to produce the oxide film.
- some of the deuterium atoms from the heavy water will bond with surface silicon atoms. Although such bonds are less preferred than Si-O bonds with the bulk oxide, they are an inevitable side product of any wet oxidation processes. Because heavy - rather than normal - water is employed, these less preferred bonds will be satisfied with deuterium or deuterium oxide groups.
- silanes such as SiH and Si(C 6 H 5 ) 3 H during chemical vapor deposition steps are another source of hydrogen in normal VLSI fabrication procedures. If deuterated silanes are substituted for their hydrogen counterparts, the density of Si-H and Si-OH bonds will be further reduced. In general, any of the organosilicon compounds widely used in VLSI technology can be replaced with the corresponding deuterium analogs.
- the semiconductor devices of this invention will have at this interface a ratio of Si-OD plus Si-D bonds to Si-OH plus Si-H bonds that is substantially greater than ratio of naturally occurring deuterium to hydrogen. Similar ratios will be found in the bulk oxide of the devices. Thus, the ratio will be substantially greater than 1:6000 deuterated to hydrogenated bonds at the interface and in the bulk oxide. In preferred embodiments, the ratio of deuterated to hydrogenated silicon bonds will be greater than about 95:5, and in more preferred embodiments, greater than about 99:1.
- Especially preferred devices of this invention are MOS transistors in which the gate oxide- silicon layer contains additional deuterium containing bonds.
- other devices such as bipolar junction transistors are also within the purview of this invention.
- the above description is intended to be illustrative and not restrictive. Many variations of the invention will become apparent to those of skill in the art upon review of this disclosure.
- the invention has been illustrated with regard to specific deuterium containing compounds, it should be clear that a wide variety of deuterium containing compounds may be used herein without departing from the scope of the inventions herein. The scope of the invention should, therefore be determined not with reference to the above description, but instead should be determined with reference to the appended claims along with their full scope of equivalents.
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Insulated Gate Type Field-Effect Transistor (AREA)
- Formation Of Insulating Films (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US1993493A | 1993-02-19 | 1993-02-19 | |
US19934 | 1993-02-19 | ||
PCT/US1994/001669 WO1994019829A1 (en) | 1993-02-19 | 1994-02-17 | Semiconductor device comprising deuterium atoms |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0685115A1 true EP0685115A1 (en) | 1995-12-06 |
Family
ID=21795845
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94910119A Withdrawn EP0685115A1 (en) | 1993-02-19 | 1994-02-17 | Semiconductor device comprising deuterium atoms |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0685115A1 (ja) |
JP (1) | JPH08507175A (ja) |
KR (1) | KR960701477A (ja) |
WO (1) | WO1994019829A1 (ja) |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20020031920A1 (en) | 1996-01-16 | 2002-03-14 | Lyding Joseph W. | Deuterium treatment of semiconductor devices |
US5872387A (en) * | 1996-01-16 | 1999-02-16 | The Board Of Trustees Of The University Of Illinois | Deuterium-treated semiconductor devices |
US6077791A (en) * | 1996-12-16 | 2000-06-20 | Motorola Inc. | Method of forming passivation layers using deuterium containing reaction gases |
US6252270B1 (en) | 1997-04-28 | 2001-06-26 | Agere Systems Guardian Corp. | Increased cycle specification for floating-gate and method of manufacture thereof |
US5982020A (en) | 1997-04-28 | 1999-11-09 | Lucent Technologies Inc. | Deuterated bipolar transistor and method of manufacture thereof |
US6025280A (en) * | 1997-04-28 | 2000-02-15 | Lucent Technologies Inc. | Use of SiD4 for deposition of ultra thin and controllable oxides |
US5972765A (en) * | 1997-07-16 | 1999-10-26 | International Business Machines Corporation | Use of deuterated materials in semiconductor processing |
US6328801B1 (en) | 1997-07-25 | 2001-12-11 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Method and system for recovering and recirculating a deuterium-containing gas |
JPH11274489A (ja) | 1998-03-26 | 1999-10-08 | Toshiba Corp | 電界効果トランジスタ及びその製造方法 |
JP3250527B2 (ja) * | 1998-09-01 | 2002-01-28 | 日本電気株式会社 | 半導体記憶装置の製造方法 |
KR20000067657A (ko) * | 1999-04-30 | 2000-11-25 | 김효근 | 사중수소실리콘을 이용한 반도체 소자용 폴리실리콘 게이트 증착방법 |
US6365511B1 (en) | 1999-06-03 | 2002-04-02 | Agere Systems Guardian Corp. | Tungsten silicide nitride as a barrier for high temperature anneals to improve hot carrier reliability |
US7125768B2 (en) * | 1999-08-25 | 2006-10-24 | Micron Technology, Inc. | Method for reducing single bit data loss in a memory circuit |
WO2001094662A1 (fr) * | 2000-06-07 | 2001-12-13 | Commissariat A L'energie Atomique | Procede de preparation d'un revetement sur un substrat par le procede ald utilisant un reactant deutere |
FR2809973B1 (fr) * | 2000-06-07 | 2003-09-05 | Commissariat Energie Atomique | Procede de preparation d'un revetement comprenant au moins une couche d'oxyde de metal deutere ou de nitrure de metal isolant deutere, sur un substrat comprenant un silicium |
US6797644B2 (en) * | 2000-08-01 | 2004-09-28 | Texas Instruments Incorporated | Method to reduce charge interface traps and channel hot carrier degradation |
US6576522B2 (en) | 2000-12-08 | 2003-06-10 | Agere Systems Inc. | Methods for deuterium sintering |
US6740603B2 (en) | 2001-02-01 | 2004-05-25 | Texas Instruments Incorporated | Control of Vmin transient voltage drift by maintaining a temperature less than or equal to 350° C. after the protective overcoat level |
US6605529B2 (en) | 2001-05-11 | 2003-08-12 | Agere Systems Inc. | Method of creating hydrogen isotope reservoirs in a semiconductor device |
KR20030090868A (ko) * | 2002-05-22 | 2003-12-01 | 동부전자 주식회사 | 게이트 옥사이드 형성을 위한 실리콘 기판 세정방법 |
KR100500698B1 (ko) * | 2002-11-20 | 2005-07-12 | 광주과학기술원 | 고유전율 게이트 절연막 형성시 댕글링 본드 감소방법 |
US7302812B2 (en) | 2003-09-02 | 2007-12-04 | Air Products And Chemicals, Inc. | Process for production of isotopes |
US7087507B2 (en) | 2004-05-17 | 2006-08-08 | Pdf Solutions, Inc. | Implantation of deuterium in MOS and DRAM devices |
JP4225249B2 (ja) | 2004-07-21 | 2009-02-18 | セイコーエプソン株式会社 | 絶縁膜の評価方法 |
JP6132290B2 (ja) | 2012-04-30 | 2017-05-24 | トゥビタク | シリコン光源およびそれを応用したデバイス |
CN114207822A (zh) * | 2021-11-03 | 2022-03-18 | 长江存储科技有限责任公司 | 用于增强可靠性的三维存储器件和制造方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02218128A (ja) * | 1989-02-17 | 1990-08-30 | Fujitsu Ltd | 半導体表面清浄化方法 |
-
1994
- 1994-02-17 EP EP94910119A patent/EP0685115A1/en not_active Withdrawn
- 1994-02-17 JP JP6519103A patent/JPH08507175A/ja active Pending
- 1994-02-17 WO PCT/US1994/001669 patent/WO1994019829A1/en not_active Application Discontinuation
- 1994-02-17 KR KR1019950703467A patent/KR960701477A/ko not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO9419829A1 * |
Also Published As
Publication number | Publication date |
---|---|
JPH08507175A (ja) | 1996-07-30 |
WO1994019829A1 (en) | 1994-09-01 |
KR960701477A (ko) | 1996-02-24 |
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