CN110537255A - The manufacturing method and electro-resistance element of electro-resistance element - Google Patents
The manufacturing method and electro-resistance element of electro-resistance element Download PDFInfo
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- CN110537255A CN110537255A CN201880025658.4A CN201880025658A CN110537255A CN 110537255 A CN110537255 A CN 110537255A CN 201880025658 A CN201880025658 A CN 201880025658A CN 110537255 A CN110537255 A CN 110537255A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 78
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 78
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000758 substrate Substances 0.000 claims abstract description 40
- 238000004544 sputter deposition Methods 0.000 claims abstract description 13
- 239000004065 semiconductor Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 225
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 25
- 239000001301 oxygen Substances 0.000 description 25
- 229910052760 oxygen Inorganic materials 0.000 description 25
- 239000000463 material Substances 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 9
- 229910001936 tantalum oxide Inorganic materials 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000015654 memory Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000005546 reactive sputtering Methods 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001552 radio frequency sputter deposition Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910016553 CuOx Inorganic materials 0.000 description 1
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 206010058490 Hyperoxia Diseases 0.000 description 1
- 229910002244 LaAlO3 Inorganic materials 0.000 description 1
- 229910005855 NiOx Inorganic materials 0.000 description 1
- 229910006854 SnOx Inorganic materials 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000000222 hyperoxic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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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
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
- H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
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- H10B—ELECTRONIC MEMORY DEVICES
- H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
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Abstract
Problem of the present invention is that the manufacture of electro-resistance element at low cost and excellent electrical characteristics.The manufacturing method of electro-resistance element comprises the following steps: the first titanium nitride electrodes layer is formed on substrate.First metal oxide layer with first resistor rate is formed on above-mentioned first titanium nitride electrodes layer.Second metal oxide layer with the second resistance rate different from above-mentioned first resistor rate is formed on above-mentioned first metal oxide layer.While applying bias voltage to aforesaid substrate, the second titanium nitride electrodes layer is formed by sputtering method on above-mentioned second metal oxide layer.
Description
Technical field
The present invention relates to the manufacturing method of electro-resistance element and electro-resistance elements.
Background technique
Semiconductor memory includes DRAM (Dynamic Random Access Memory: dynamic random access memory)
Etc. the nonvolatile memories such as volatile memory and flash memory.As nonvolatile memory, the storage of NAND type flash
Device is mainstream, but the limit extremely having miniaturize in the design rule after 20nm, and as the device that can further miniaturize
Part, ReRAM (Resistance RAM: resistance-type RAM) attract attention.
Existing ReRAM is to be clamped by top platinum (Pt) electrode layer and lower part platinum (Pt) electrode layer with desired resistance
The structure of the metal oxide layer of value oxidizes metal the resistance variations of nitride layer, thus by applying voltage to top electrode layer
It carries out memory switching (for example, referring to patent document 1).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-207130 bulletin
Summary of the invention
Problem to be solved by the invention
But the Pt as used in the material as electrode layer is expensive metal, in order to reduce resistance variations
The cost of element simultaneously improves productivity, needs the electrode material that development cost is low and electrical characteristics are excellent.
In view of above-mentioned such situation, the object of the present invention is to provide a kind of resistance at low cost and excellent electrical characteristics
Change the manufacturing method and electro-resistance element of element.
The means used to solve the problem
To achieve the goals above, the manufacturing method of electro-resistance element involved in one embodiment of the present invention includes such as
Lower process: the first titanium nitride electrodes layer is formed on substrate.Being formed on above-mentioned first titanium nitride electrodes layer has first resistor
First metal oxide layer of rate.Being formed on above-mentioned first metal oxide layer has different from above-mentioned first resistor rate the
Second metal oxide layer of two resistivity.While applying bias voltage to aforesaid substrate, aoxidized in above-mentioned second metal
The second titanium nitride electrodes layer is formed by sputtering method in nitride layer.
According to the manufacturing method of this electro-resistance element, due to while applying bias voltage to aforesaid substrate, above-mentioned
Highdensity second titanium nitride electrodes layer is formed on second metal oxide layer, therefore it is excellent to be capable of forming at low cost and electrical characteristics
Electro-resistance element.
In the manufacturing method of above-mentioned electro-resistance element, the process for forming above-mentioned second titanium nitride electrodes layer can also be with
Including applying 0.03W/cm to aforesaid substrate2Above and 0.62W/cm2The process of bias power below.
According to the manufacturing method of such electro-resistance element, due to applying 0.03W/cm to aforesaid substrate2Above and
0.62W/cm2While bias voltage below, highdensity second titanium nitride is formed on above-mentioned second metal oxide layer
Electrode layer, therefore it is capable of forming electro-resistance element at low cost and excellent electrical characteristics.
It also may include with 3nm or more and 11nm film thickness below in the manufacturing method of above-mentioned electro-resistance element
The process for forming above-mentioned second metal oxide layer.
According to the manufacturing method of this electro-resistance element, due to forming above-mentioned second with 3nm or more and 11nm film thickness below
Metal oxide layer, therefore it is capable of forming electro-resistance element at low cost and excellent electrical characteristics.
In the manufacturing method of above-mentioned electro-resistance element, the process for forming above-mentioned second titanium nitride electrodes layer be can wrap
Include: using the mixed gas of rare gas and nitrogen as sputter gas, and relative to the total flow of above-mentioned mixed gas and
The flow of the above-mentioned nitrogen of speech is 10% or more and 100% process below.
According to the manufacturing method of such electro-resistance element, due to while applying bias voltage to aforesaid substrate, by phase
The flow of above-mentioned nitrogen for the total flow of above-mentioned mixed gas be adjusted to 10% or more and 100% hereinafter, to
Highdensity second titanium nitride electrodes layer is formed on above-mentioned second metal oxide layer, therefore is capable of forming at low cost and electrical characteristics
Excellent electro-resistance element.
In the manufacturing method of above-mentioned electro-resistance element, the process for forming above-mentioned second titanium nitride electrodes layer can also be with
Including the temperature of aforesaid substrate is adjusted to 20 DEG C or more and 320 DEG C of processes below.
It, will be upper due to while applying bias voltage to aforesaid substrate according to the manufacturing method of such electro-resistance element
The temperature for stating substrate is adjusted to 20 DEG C or more and 320 DEG C hereinafter, to form high density on above-mentioned second metal oxide layer
The second titanium nitride electrodes layer, therefore be capable of forming electro-resistance element at low cost and excellent electrical characteristics.
In the manufacturing method of above-mentioned electro-resistance element, the pressure of above-mentioned mixed gas can also be adjusted to
0.1Pa or more and 1Pa or less.
It, will be upper due to while applying bias voltage to aforesaid substrate according to the manufacturing method of such electro-resistance element
The pressure for stating mixed gas is adjusted to 0.1Pa or more and 1Pa hereinafter, highly dense to be formed on above-mentioned second metal oxide layer
Second titanium nitride electrodes layer of degree, therefore it is capable of forming electro-resistance element at low cost and excellent electrical characteristics.
To achieve the goals above, electro-resistance element involved in one embodiment of the present invention has the first titanium nitride electricity
Pole layer, the second titanium nitride electrodes layer and oxide semiconductor layer.Above-mentioned oxide semiconductor layer is arranged in above-mentioned first titanium nitride
Between electrode layer and above-mentioned second titanium nitride electrodes layer.Above-mentioned oxide semiconductor layer includes the first metal oxide layer, tool
There is first resistor rate；And second metal oxide layer, there is the second resistance rate different from above-mentioned first resistor rate.It is above-mentioned
Second metal oxide layer is arranged between above-mentioned first metal oxide layer and above-mentioned second titanium nitride electrodes layer.Above-mentioned second
Titanium nitride electrodes layer has 4.8g/cm3Above and 5.5g/cm3Density below.
It is highdensity due to being formed on above-mentioned second metal oxide layer according to the manufacturing method of such electro-resistance element
Second titanium nitride electrodes layer, therefore it is capable of forming electro-resistance element at low cost and excellent electrical characteristics.
Invention effect
As previously discussed, in accordance with the invention it is possible to provide the manufacture of electro-resistance element at low cost and excellent electrical characteristics
Method and electro-resistance element.
Detailed description of the invention
Fig. 1 is the schematic sectional view for indicating the structure of electro-resistance element involved in present embodiment.
Fig. 2 is the case where top electrode layer and lower electrode layer have used TiN in electro-resistance element relating to the comparative example
Under I-E characteristic curve graph.
Fig. 3 is the curve graph of the I-E characteristic of electro-resistance element involved in present embodiment.
Fig. 4 is the curve graph for indicating the relationship between RF bias power and the density of titanium nitride electrodes layer.
Fig. 5 is to indicate nitrogen flow relative to the relationship between the ratio of mixed gas flow and the density of titanium nitride electrodes layer
Curve graph.
Fig. 6 is the curve graph for indicating the relationship between substrate temperature and the density of titanium nitride electrodes layer.
Fig. 7 is the film thickness for indicating the second metal oxide layer and the electricity for forming RF bias power of the TiN as top electrode layer when
The associated chart of characteristic.
Specific embodiment
Hereinafter, embodiments of the present invention will be described referring to attached drawing.In the drawings, XYZ axis is introduced sometimes to sit
Mark.
Fig. 1 is the schematic sectional view for indicating the structure of electro-resistance element involved in present embodiment.
Electro-resistance element 1 shown in FIG. 1 has: substrate 2, lower electrode layer 3 (the first titanium nitride electrodes layer), oxide
Semiconductor layer 4 and top electrode layer 5 (the second titanium nitride electrodes layer).
As substrate 2, typically using semiconductor substrates such as silicon wafers, but it is not limited to this, and glass base also can be used
The insulating ceramics substrate such as plate.
Oxide semiconductor layer 4 is arranged between lower electrode layer 3 and top electrode layer 5.Oxide semiconductor layer 4 has
First metal oxide layer 41 and the second metal oxide layer 42.First metal oxide layer 41 and the second metal oxide layer 42
It is made of, but can also be made of different types of material material of the same race respectively.The resistivity of first metal oxide layer 41
(first resistor rate) is different from resistivity (the second resistance rate) of the second metal oxide layer 42.
A side in first metal oxide layer 41 and the second metal oxide layer 42 is by the oxygen close to stoichiometric composition
Compound material (hereinafter also referred to " stoichiometric composition material ") is constituted, and another party is by the oxide material comprising a large amount of Lacking oxygen
Expect that (hereinafter also referred to as " Lacking oxygen material ") is constituted.In the present embodiment, the first metal oxide layer 41 is by Lacking oxygen material
It constitutes, the second metal oxide layer 42 is made of stoichiometric composition material.
First metal oxide layer 41 is formed on lower electrode layer 3, and contains tantalum (Ta) and oxygen (O).For example, the first gold medal
Belong to oxide skin(coating) 41 in the present embodiment by tantalum oxide (TaOx) formed.Tantalum oxide used in first metal oxide layer 41
Compared with the tantalum oxide for forming the second metal oxide layer 42, oxidizability is lower, and resistivity is greater than 1 Ω cm and is 1
×106Ω cm or less.
The material for constituting the first metal oxide layer 41 is not limited to above-mentioned material, such as zirconium oxide (ZrO can be usedx), oxygen
Change hafnium (HfOx), yttrium oxide (YOx), titanium oxide (TiOx), aluminium oxide (AlOx), silica (SiOx), iron oxide (FeOx), oxidation
Nickel (NiOx), cobalt oxide (CoOx), manganese oxide (MnOx), tin oxide (SnOx), zinc oxide (ZnOx), vanadium oxide (VOx), tungsten oxide
(WOx), copper oxide (CuOx)、Pr(Ca、Mn)O3、LaAlO3、SrTiO3、La(Sr、Mn)O3Etc. it is more than binary systems or ternary system
Oxide material.
Second metal oxide layer 42 is formed on the first metal oxide layer 41, and contains tantalum (Ta) and oxygen (O).Example
Such as, in the present embodiment, the second metal oxide layer 42 is by tantalum oxide (Ta2O5) formed.Second metal oxide layer 42 is made
Tantalum oxide has stoichiometric composition or therewith similar composition, such as with greater than 1 × 106(1E+06) Ω cm's
Resistivity.The material for constituting the second metal oxide layer 42 is without being limited thereto, can be using more than above-mentioned binary system or ternary system
Oxide material.
First metal oxide layer 41 and the second metal oxide layer 42 can for example pass through the reactive sputtering method with oxygen
It is formed.In the present embodiment, by being sputtered in the vacuum chamber for having imported oxygen to metal (Ta) target, thus in substrate 2
The metal oxide layer 41,42 being made of tantalum oxide is sequentially formed on (lower electrode layer 3).Each metal oxide layer 41,42
Oxidizability is controlled by the flow (partial pressure) for importeding into the oxygen of vacuum chamber.
Since the oxidizability of the second metal oxide layer 42 is higher than the oxidizability of the first metal oxide layer 41, thus second
The resistivity of the first metal oxide layer of resistivity ratio 41 of metal oxide layer 42 is high.Here, if applying to top electrode layer 5
Negative voltage, and electrode layer 3 applies positive voltage, the then oxygen in the second metal oxide layer 42 of high resistance (hyperoxia density) to the lower part
Ion (O2-) be diffused into low-resistance first metal oxide layer 41, the resistance of the second metal oxide layer 42 reduces.The shape
State is low resistance state.
On the other hand, from low resistance state, make the voltage reversal for being applied to lower electrode layer 3 and top electrode layer 5,
When electrode layer 3 applies negative voltage and applies positive voltage to top electrode layer 5 to the lower part, oxonium ion is from the first metal oxide layer 41
It is spread to the second metal oxide layer 42, the oxidizability of the second metal oxide layer 42 increases again, and resistance is got higher.The state is
High resistance state.
As described above, by the voltage between control lower electrode layer 3 and top electrode layer 5, thus oxide semiconductor
Layer 4 reversibly switches low resistance state and high resistance state.Even if moreover, because low resistance state and high resistance state do not apply
Voltage is also able to maintain, thus such as under high resistance state be written data, under low resistance state read data in this way, resistance become
Changing element 1 can be used as non-volatile memory device.
Since the noble metals such as Pt corrosion resistance is high and conductive, thus it is used as electro-resistance element sometimes
The material of top electrode layer and lower electrode layer.But the noble metals such as Pt are expensive, the microfabrications such as are in addition difficult to be etched,
Therefore it is not suitable for mass production.Therefore, in order to reduce the cost of electro-resistance element and improve productivity, need it is at low cost and
The good electrode layer of electrical characteristics.
On the other hand, TiN is cheap compared with the noble metals such as Pt.Moreover, TiN is also able to carry out, etching etc. is fine to be added
Work is consequently adapted to mass production.But since oxide semiconductor layer 4 is containing aerobic, thus the metal other than using noble metal
In the case where as electrode layer, the case where being diffused into electrode layer there are the oxygen of oxide semiconductor layer 4.
In the case that Fig. 2 is top electrode layer and lower electrode layer has used TiN in the electro-resistance element of comparative example
I-E characteristic curve graph.Fig. 2 shows the current-voltages carried out when being written and wiping to electro-resistance element
Curve.
Here, the horizontal axis of Fig. 2 indicates that the voltage for being applied to top electrode layer 5, the longitudinal axis are indicated in top electrode layer 5 and lower part
The current value flowed between electrode layer 3.Current value is low to mean that oxide semiconductor layer is in high resistance state, current value Gao Yi
Taste oxide semiconductor layer be in low resistance state.
It is known by sputtering method formed TiN as top electrode layer when, by nitrogen plasma in TiN top electrode layer
Interface between oxide semiconductor layer will form the film (TiNO film) of high-insulativity.As the film for forming this high-insulativity
One of the main reason for, it is believed that in the case where the density of TiN top electrode layer is not high enough, in the crystalline substance of TiN top electrode layer
Oxygen diffusion is easy to happen at boundary.Here, in a comparative example, in a manner of not applying bias voltage to substrate 2 in sputtering process,
Form TiN top electrode layer.
In the case where foring the film of such high-insulativity, in order to as electro-resistance element come using, need into
The following element initialization processing (forming (forming)) of row: applying higher switching action voltage to oxide semiconductor layer,
To generate the phenomenon similar with insulation breakdown.It is considered that being referred to as filament by being formed in generate in oxide semiconductor layer
(filament) thus current path shows the switching action of oxide semiconductor layer.
But in the case where being formed with the film of high-insulativity in oxide semiconductor layer, due to that can not be fitted by forming
The size of locality control filament, position, therefore there is the case where forming voltage is got higher.Moreover, passing through high forming voltage shape
At filament there is thicker tendency, so that the resistance of oxide semiconductor layer is lower sometimes after shaping actions, resistance variations member
The on/off ratio of part becomes bad.For example, in the example in figure 2, in the oxide semiconductor to original state (high resistance state)
Forming voltage when layer is formed is about 2.5V.
On the other hand, it is believed that if the density of TiN top electrode layer is got higher, the crystal boundary meeting of TiN top electrode layer
Reduction or crystal boundary can narrow, and become to be not susceptible to spread from oxide semiconductor layer to the oxygen of TiN top electrode layer.Therefore, originally
The inventors of invention are it is found that pass through the density of control TiN top electrode layer, so that the oxygen in oxide semiconductor layer is not easy
The top electrode layer 5 being diffused into TiN top electrode layer.
As the method for forming the high TiN top electrode layer of density, for example, applying bias voltage to substrate 2
While, pass through RF (Radio Frequency: radio frequency) sputtering method or pulse DC (Direct Current: direct current) sputtering method
Come the method formed.Target in each sputtering method uses titanium (Ti) target, by reactive sputtering method, in the second metal oxide layer 42
Upper formation TiN top electrode layer.As reaction gas, nitrogen (N can be enumerated2) or nitrogen (N2) gaseous mixture with argon gas (Ar) etc.
Body.About the detailed content for the method for forming TiN top electrode layer, together with the manufacturing method of aftermentioned electro-resistance element 1
It is illustrated.
The density for being formed by TiN top electrode layer by above method is relatively high, is 4.8g/cm3Above and 5.5g/cm3
Below.For example, if the density of TiN top electrode layer is less than 4.8g/cm3, then oxygen is easy to spread from the second metal oxide layer 42
To the crystal boundary of TiN top electrode layer, the interface between TiN top electrode layer and oxide semiconductor layer forms high-insulativity
Film (TiNO film), therefore not preferably.
Fig. 3 is the curve graph of the I-E characteristic of electro-resistance element involved in present embodiment.
As shown in figure 3, shaping voltage quilt compared with comparative example in the electro-resistance element 1 involved in present embodiment
Inhibit, is about 1.5V.Moreover, on/off ratio also becomes compared with comparative example in the electro-resistance element involved in present embodiment
It obtains well.
In this way, electro-resistance element 1 involved according to the present embodiment, top electrode layer 5 are made of TiN, therefore with
The case where top electrode layer is made of precious metal materials such as Pt is compared, and can be realized the reduction of cost.Moreover, top electrode layer 5
That is the density of TiN top electrode layer is high, so that top electrode layer 5 is difficult to penetrate and absorb the oxygen in oxide semiconductor layer 4, by
This inhibits the extraction of the oxygen in oxide semiconductor layer 4.Thereby, it is possible to prevent the low resistance of oxide semiconductor layer 4.Its
As a result, the switching characteristic of electro-resistance element improves.
The manufacturing method of electro-resistance element 1 is illustrated.
Firstly, forming lower electrode layer 3 (the first titanium nitride electrodes layer) on the substrate 2 of wafer-like.Lower electrode layer 3 with
Identical condition is formed with aftermentioned top electrode layer 5 (the second titanium nitride electrodes layer).The density of lower electrode layer 3 for example with it is upper
The density of portion's electrode layer 5 is identical.The interface between lower electrode layer 3 and oxide semiconductor layer 4 is also not easy to be formed as a result,
TiNO, so as to obtain good electrical characteristics.The thickness of top electrode layer 5 is not particularly limited, for example, 50nm.
In lower electrode layer 3, preferably, crystal boundary is controlled, and is flat.The upper layer of lower electrode layer 3 becomes as a result,
It obtains more flat.In order to more be formed flatly lower electrode layer 3, such as control as room temperature or near room temperature by the temperature of substrate 2
Temperature while, formed lower electrode layer 3.
Then, oxide semiconductor layer 4 is formed on lower electrode layer 3.
Firstly, as the first metal oxide layer 41, for example, by vacuum vapour deposition, sputtering method, CVD (Chemical
Vapor Deposition: chemical vapor deposition) method, ALD (Atomic Layer Deposition: atomic layer deposition) method etc.,
Form the oxygen amount tantalum oxide layer fewer than stoichiometric composition.The thickness of oxide semiconductor layer 4 is not particularly limited, for example,
20nm.In the present embodiment, by the reactive sputtering with oxygen, the first metal oxide layer 41 is formed.
Then, the second metal oxide layer 42 is formed on the first metal oxide layer 41.In the present embodiment, as
Second metal oxide layer 42 forms the tantalum oxide layer of stoichiometric composition or close oxygen ratio of components.Second metal
The thickness of oxide skin(coating) 42 is not particularly limited, for example, 3nm or more and 11nm or less.Film build method is not particularly limited, example
Such as made by vacuum vapour deposition, sputtering method, CVD method, ALD method.In the present embodiment, it is splashed by the reactivity with oxygen
It penetrates, to form the second metal oxide layer 42.
Then, top electrode layer 5 is formed on oxide semiconductor layer 4.In the present embodiment, as top electrode layer
5, the TiN top electrode layer that forms a film is sputtered by RF sputtering or pulse DC.The thickness of TiN top electrode layer is not particularly limited,
For example, 50nm.
The condition of RF sputtering is not particularly limited, such as is implemented under the following conditions.
Gas flow: 50 [sccm]
Titanium target input power: 2 [W/cm2]
RF frequency: 13.56 [MHz]
The condition of pulse DC sputtering is not particularly limited, such as is implemented under the following conditions.
Gas flow: 50 [sccm]
Titanium target input power: 2 [W/cm2]
Pulse DC frequency: 20 [kHz]
In above-mentioned each sputtering method, uses the silicon wafer that diameter is 300mm as substrate 2, be by the control of RF bias power
0.03W/cm2Above and 0.62W/cm2Hereinafter, it is 10% or more that nitrogen flow is controlled relative to the ratio of mixed gas flow
And 100% hereinafter, be 20 DEG C or more and 320 DEG C by substrate temperature control hereinafter, film pressure is controlled as 0.1Pa or more and
Thus 1Pa is hereinafter, be adjusted to 4.8g/cm for the density of TiN top electrode layer3Above and 5.5g/cm3Below.It produces as a result,
Electro-resistance element 1 with good switching characteristic.
For example, Fig. 4 is the curve graph for indicating the relationship between RF bias power and the density of titanium nitride electrodes layer.Here,
Nitrogen flow is 26% relative to the ratio of mixed gas flow, and substrate temperature is 20 DEG C, film pressure 0.27Pa.
In the example in fig. 4, applying 20W (0.03W/cm as RF bias power2) when, titanium nitride electrodes layer it is close
Degree reaches 4.8g/cm3More than.Then, when keeping RF bias power further up, the density of titanium nitride electrodes layer gradually on
It rises, density reaches 5.4g/cm3Left and right.Accordingly, RF bias power is preferably controlled in 0.03W/cm2Above and 0.62W/cm2Below
In the range of, the second metal oxide layer is preferably set to 3nm or more and 11nm range below.
In addition, Fig. 5 be indicate nitrogen flow relative to mixed gas flow ratio and titanium nitride electrodes layer density it
Between relationship curve graph.Here, substrate temperature is 20 DEG C, film pressure 0.27Pa.
In the example of fig. 5, by by nitrogen flow relative to mixed gas flow ratio control 10% or more and
100% hereinafter, so that be adjusted to 4.8g/cm for the density of titanium nitride electrodes layer3Above and 5.5g/cm3Below.Accordingly, nitrogen stream
It measures and is preferably controlled in 10% or more and 100% or less relative to the ratio of mixed gas flow.It is especially opposite in nitrogen flow
When the ratio of mixed gas flow is 26%, the density of titanium nitride electrodes layer becomes very big.
In addition, Fig. 6 is the curve graph for indicating the relationship between substrate temperature and the density of titanium nitride electrodes layer.Here, nitrogen
Throughput is 26% relative to the ratio of mixed gas flow, film pressure 0.27Pa.
In the example of fig. 6, by being 20 DEG C or more and 320 DEG C by substrate temperature control hereinafter, to which titanium nitride is electric
The density of pole layer is adjusted to 4.8g/cm3Above and 5.5g/cm3Below.Accordingly, substrate temperature be preferably controlled to 20 DEG C or more and
320 DEG C or less.But when substrate temperature is more than 275 DEG C, the surface of titanium nitride electrodes layer has and becomes coarse tendency, institute
It is preferably 20 DEG C or more and 275 DEG C or less with substrate temperature.
RF bias power when the film thickness and formation TiN that Fig. 7 is the second metal oxide layer of expression are as top electrode layer
Electrical characteristics associated chart.
Here, ◎ indicates that switching is good and do not need forming voltage substantially, zero indicates that switching and forming voltage are good, △
Indicate that switching is good, × indicate that switching is bad.
That is, in the case where the film thickness of the second metal oxide layer 42 is 3nm or more and 11nm situation below, if substrate bias
Value is 0.03W/cm2Above and 0.62W/cm2Hereinafter, can then obtain switching and the forming good characteristic of voltage.In addition, In
The film thickness of second metal oxide layer 42 is in 5nm or more and 11nm situation below, if substrate bias value is 0.43W/cm2
Above and 0.62W/cm2Hereinafter, can then hardly need forming.
This can be presumed as follows: if the density of TiN top electrode layer is got higher, the crystal boundary of TiN top electrode layer is reduced
Or crystal boundary narrows, and is not susceptible to spread from oxide semiconductor layer to the oxygen of TiN top electrode layer, and due to by given
Ion bombardment caused by substrate bias and the defect that is generated in the second metal oxide layer 42 and form filament, from without
It shapes.
The electro-resistance element 1 for being formed in the substrate 2 of wafer-like is formed as given component size.For the pattern of each layer
It is formed, photoetching and dry etching technology can be used, photoetching and wet etch techniques also can be used, it can also be across Etching mask
Deng the film forming for carrying out each layer.It, can also be between lower wiring layers and top wiring layer using etching technique
Interlayer dielectric makes the electro-resistance element 1.In addition, becoming since top electrode layer 5 is formed as high density in resistance
In the manufacturing process for changing element, top electrode layer 5 can also be applied as mask.
According to above-mentioned manufacturing method, not due to the interface between top electrode layer 5 and the second metal oxide layer 42
The film of high-insulativity is formed, therefore can reduce the required voltage of forming or do not need to shape.Thereby, it is possible to prevent element
Operating current rise.In addition, inhibiting oxide semiconductor layer 4 since top electrode layer 5 is not easy to transmit and absorb oxygen
In oxygen extraction, thus, it is possible to prevent the low resistance of oxide semiconductor layer 4.Therefore, can produce makes with electrode layer
With the case where noble metal compared to it is at low cost and with good switching characteristic electro-resistance element.
Additionally, there are use method of the DLC (diamond-like-carbon) as the material of top electrode layer 5.In present embodiment
In, by using TiN as top electrode layer 5, compared with DLC, fugitive dust is inhibited, and can form low-resistance top electricity
Pole layer.
Only embodiments of the present invention are illustrated above, it is clear that the present invention is not limited to
The embodiment stated, but it is able to carry out various changes.
Symbol description
1 ... electro-resistance element
2 ... substrates
3 ... lower electrode layers
4 ... oxide semiconductor layers
41 ... first metal oxide layers
42 ... second metal oxide layers
5 ... upper electrodes.
Claims (7)
1. a kind of manufacturing method of electro-resistance element, comprises the following steps:
The first titanium nitride electrodes layer is formed on substrate；
First metal oxide layer with first resistor rate is formed on the first titanium nitride electrodes layer；
Second gold medal with the second resistance rate different from the first resistor rate is formed on first metal oxide layer
Belong to oxide skin(coating)；And
While applying bias voltage to the substrate, second is formed by sputtering method on second metal oxide layer
Titanium nitride electrodes layer.
2. the manufacturing method of electro-resistance element according to claim 1, wherein
The process for forming the second titanium nitride electrodes layer includes applying 0.03W/cm to the substrate2Above and 0.62W/cm2With
Under bias power process.
3. the manufacturing method of electro-resistance element according to claim 1 or 2, wherein
The process for forming the second titanium nitride electrodes layer includes forming second gold medal with 3nm or more and 11nm film thickness below
Belong to the process of oxide skin(coating).
4. the manufacturing method of electro-resistance element according to any one of claim 1 to 3, wherein
The process for forming the second titanium nitride electrodes layer includes: to use the mixed gas of rare gas and nitrogen as sputtering gas
Body, and the flow of the nitrogen for the total flow of the mixed gas is 10% or more and 100% below
Process.
5. the manufacturing method of electro-resistance element according to any one of claim 1 to 4, wherein
The process for forming the second titanium nitride electrodes layer include the temperature of the substrate is adjusted to 20 DEG C or more and 320 DEG C with
Under process.
6. the manufacturing method of electro-resistance element according to claim 4 or 5, wherein
Including the pressure of the mixed gas is adjusted to 0.1Pa or more and 1Pa process below.
7. a kind of electro-resistance element, has:
First titanium nitride electrodes layer；
Second titanium nitride electrodes layer；And
Oxide semiconductor layer is arranged between the first titanium nitride electrodes layer and the second titanium nitride electrodes layer, and
With the first metal oxide layer and the second metal oxide layer, first metal oxide layer has first resistor rate, institute
It states the second metal oxide layer to be arranged between first metal oxide layer and the second titanium nitride electrodes layer, and has
The second resistance rate different from the first resistor rate,
The second titanium nitride electrodes layer has 4.8g/cm3Above and 5.5g/cm3Density below.
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| JP2012059995A (en) * | 2010-09-10 | 2012-03-22 | Toshiba Corp | Semiconductor device and method of manufacturing the same |
| JP6180700B2 (en) * | 2011-09-09 | 2017-08-16 | ルネサスエレクトロニクス株式会社 | Nonvolatile semiconductor memory device and manufacturing method thereof |
| CN103907187B (en) * | 2012-09-05 | 2016-04-13 | 株式会社爱发科 | Electric resistance changing element and preparation method thereof |
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| US20130256623A1 (en) * | 2010-12-01 | 2013-10-03 | Canon Anelva Corporation | Nonvolatile memory element and method of manufacturing the same |
| WO2013054515A1 (en) * | 2011-10-12 | 2013-04-18 | パナソニック株式会社 | Non-volatile semiconductor storage device and method of manufacture thereof |
| CN103250253A (en) * | 2011-10-12 | 2013-08-14 | 松下电器产业株式会社 | Non-volatile semiconductor storage device and method of manufacture thereof |
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