WO2012073471A1 - 不揮発性記憶素子およびその製造方法 - Google Patents
不揮発性記憶素子およびその製造方法 Download PDFInfo
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- WO2012073471A1 WO2012073471A1 PCT/JP2011/006597 JP2011006597W WO2012073471A1 WO 2012073471 A1 WO2012073471 A1 WO 2012073471A1 JP 2011006597 W JP2011006597 W JP 2011006597W WO 2012073471 A1 WO2012073471 A1 WO 2012073471A1
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- electrode
- metal oxide
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- oxide layer
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- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 230000008859 change Effects 0.000 claims abstract description 90
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 79
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 76
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 76
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 30
- 239000007789 gas Substances 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000011261 inert gas Substances 0.000 claims description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 238000004544 sputter deposition Methods 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 5
- 230000009467 reduction Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims 2
- 239000010408 film Substances 0.000 description 155
- 239000010410 layer Substances 0.000 description 145
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 41
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 32
- 239000010936 titanium Substances 0.000 description 24
- 238000012545 processing Methods 0.000 description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 19
- 230000008569 process Effects 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 229910001882 dioxygen Inorganic materials 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- 230000008021 deposition Effects 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 238000001228 spectrum Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000001020 plasma etching Methods 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 229910052774 Proactinium Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910003070 TaOx Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 229910000449 hafnium oxide Inorganic materials 0.000 description 2
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 238000005546 reactive sputtering Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910005855 NiOx Inorganic materials 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 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
- 238000012864 cross contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000002245 particle Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Images
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- G11C13/0002—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements
- G11C13/0007—Digital stores characterised by the use of storage elements not covered by groups G11C11/00, G11C23/00, or G11C25/00 using resistive RAM [RRAM] elements comprising metal oxide memory material, e.g. perovskites
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- 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
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- C23C14/0042—Controlling partial pressure or flow rate of reactive or inert gases with feedback of measurements
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- 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
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
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- 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
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
- H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/821—Device geometry
- H10N70/826—Device geometry adapted for essentially vertical current flow, e.g. sandwich or pillar type devices
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/841—Electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
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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
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/883—Oxides or nitrides
- H10N70/8833—Binary metal oxides, e.g. TaOx
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- 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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- G11C2213/55—Structure including two electrodes, a memory active layer and at least two other layers which can be a passive or source or reservoir layer or a less doped memory active layer
Definitions
- the present invention relates to a nonvolatile memory element and a method for manufacturing the same, and more particularly to a technology relating to a resistance change type nonvolatile memory element and a method for manufacturing the same.
- a flash memory using a floating gate which is currently mainstream, has a problem that a threshold voltage (Vth) fluctuation occurs due to interference due to capacitive coupling between floating gates of adjacent cells as the memory cell becomes finer. .
- Vth threshold voltage
- variable resistance nonvolatile memory element in which a layer that causes a resistance change is sandwiched between electrodes is underway.
- This variable resistance nonvolatile memory element is characterized in that the electrical resistance of the resistance layer can be switched between two or more values by electrical stimulation.
- This element is expected as a nonvolatile memory element that can be miniaturized and reduced in cost because of the simplicity of the element structure and operation.
- Examples of the layer whose resistance varies depending on the applied voltage include an oxide of an element selected from a group formed of transition metals.
- oxides nickel oxide (NiO), vanadium oxide (V 2 O 5 ), zinc oxide (ZnO), niobium oxide (Nb 2 O 5 ), titanium oxide (TiO 2 ), tungsten Examples include oxide (WO3), titanium oxide (TiO 2 ), cobalt oxide (CoO), and tantalum oxide (Ta 2 O 5 ).
- a general ReRAM variable resistance nonvolatile memory element (memory element) 610 includes a variable resistance film (for example, a transition metal oxide film) between a lower electrode 612 and an upper electrode 614 formed on an interlayer insulating film 611. ) A parallel plate type laminated structure with 613 sandwiched therebetween. Reference numeral 618 denotes a contact hole for connection to an external wiring.
- the operation mechanism of the variable resistance nonvolatile memory element 610 first applies a forming voltage as an initial operation for enabling transition between two resistance states.
- the forming voltage By applying the forming voltage, the variable resistance film 613 is in a state in which a filament serving as a current path can be formed. Thereafter, the generation state of the filament is changed by application of operating voltages (set voltage and reset voltage), and set / reset operations, that is, writing and erasing are executed.
- Patent Document 1 proposes a nonvolatile memory element in which an amorphous insulating layer containing nickel oxide and a crystalline resistance change layer containing nickel oxide are stacked between upper and lower electrodes. It is stated that a dielectric breakdown occurs in the crystalline insulating film and a stable filament is formed in the variable resistance layer on the region where current flows.
- Patent Document 2 discloses a hafnium oxide film having a composition of HfOx (0.9 ⁇ x ⁇ 1.6) and a hafnium oxide film having a composition of HfOy (1.8 ⁇ y ⁇ 2.0) between upper and lower electrodes. And a non-volatile memory element having a rewriting characteristic that is reversibly stable at high speed.
- Non-Patent Document 1 proposes a nonvolatile memory element in which Pt is used as the upper and lower electrodes and the resistance change layer is made of NiO, and a current path called a filament is formed in the Ni oxide to change the resistance. It is said that.
- Non-Patent Document 2 proposes a nonvolatile memory element in which Pt is used as the upper and lower electrodes and the resistance change layer is made of TaOx. When the resistance changes due to the movement of oxygen atoms in the interface layer between the Pt electrode and TaOx. It is stated.
- Non-Patent Document 3 proposes a non-volatile memory element made of TiN as a resistance change layer using Pt as a lower electrode, HfOx or HfAlOx as a resistance change layer, and using HfAlOx as a resistance change layer. It is stated that voltage variations can be suppressed.
- Non-Patent Document 4 states that a resistance changing operation can be realized by forming a TiN / Ti / HfO 2 / TiN laminated structure by TiN / TiOx / HfOx / TiN by oxygen annealing. Yes.
- Non-Patent Document 1 and Non-Patent Document 2 in order to obtain good resistance change characteristics using NiOx or TaOx as the variable resistance layer as in Non-Patent Document 1 and Non-Patent Document 2, it is necessary to use Pt as the upper and lower electrodes.
- the technique using a Pt electrode as an electrode of a variable resistance nonvolatile memory element is effective in suppressing the operational instability of element characteristics by oxidation of the electrode, but is difficult to etch in the electrode processing process. There is a problem that it is difficult to reduce material costs.
- Non-Patent Document 3 and Non-Patent Document 4 a technique using a metal oxide containing Hf and Al as a resistance change layer and using TiN as an electrode material is the etching in the electrode processing process described above. Although effective in reducing the material cost, there is a problem that nothing is described about the range of the optimum oxygen composition in the metal oxide film for obtaining resistance change characteristics.
- the present invention has been made with respect to the above-described conventional problems, and an object thereof is to provide a variable resistance layer having a high resistance change ratio in a nonvolatile memory element having a variable resistance layer having a laminated structure.
- a non-volatile memory element and a manufacturing method thereof are provided.
- a first aspect of the present invention is a nonvolatile memory element, which is a first electrode, a second electrode, the first electrode, and the second electrode.
- a variable resistance layer whose resistance value changes in at least two different resistance states, the variable resistance layer including a first metal oxide layer containing Hf and O, and the first And a laminated structure having a second metal oxide layer containing Al and O, which is provided between the metal oxide layer and at least one of the first electrode and the second electrode.
- the second aspect of the present invention includes a first electrode, a second electrode, and a resistance value that is sandwiched between the first electrode and the second electrode and has at least two different resistance states.
- variable resistance layer wherein the variable resistance layer includes a first metal oxide layer containing Hf and O, and the first metal oxide layer.
- Hafnium is used as a metal target in a mixed atmosphere of reactive gas and inert gas.
- the second metal oxide layer is formed by using aluminum as a metal target in a mixed atmosphere of a reactive gas containing oxygen and an inert gas and having a molar ratio of Al to O (O / Al ratio). It has the 2nd magnetron sputtering process which sets the mixing ratio of the said reactive gas and the said inert gas so that the range of 1.0 to 2.2 may be satisfy
- variable resistance nonvolatile semiconductor element having a high resistance change ratio can be realized.
- FIG. It is a figure which shows the relationship between the resistance change ratio of the variable resistance nonvolatile memory element which concerns on embodiment of this invention, and an AlOx film thickness.
- the present invention includes a variable resistance layer having a stacked structure of a first metal oxide film containing Hf and O and a second metal oxide layer containing Al and O, and Ti and Ti as first and second electrodes. And a resistance variable nonvolatile semiconductor element (such as a resistance variable nonvolatile memory element) having an electrode including a metal nitride layer containing N and N.
- a resistance variable nonvolatile semiconductor element such as a resistance variable nonvolatile memory element having an electrode including a metal nitride layer containing N and N.
- the ratio (O / Hf ratio) is set to a composition range represented by 0.30 to 1.90, and the molar ratio of Al and O (O / Al in the second metal oxide layer containing Al and O) It was discovered that a variable resistance nonvolatile semiconductor element (nonvolatile memory element) having a high resistance change ratio can be realized by setting the ratio to a composition range represented by 1.0 to 2.2.
- the inventors of the present invention provide a method for manufacturing a nonvolatile memory element in which a variable resistance layer whose resistance value changes between at least two different resistance states is sandwiched between a first electrode and a second electrode.
- hafnium is used as a metal target in a mixed atmosphere of a reactive gas containing oxygen and an inert gas, and a molar ratio of Hf to O (O / Hf ratio) is 0.30 to 1.90.
- the first metal oxide layer containing Hf and O is formed by setting the mixing ratio of the reactive gas and the inert gas so as to satisfy the range, and performing the first magnetron sputtering process, and the inside of the vacuum vessel
- a mixed atmosphere of a reactive gas containing oxygen and an inert gas aluminum is used as the metal target so that the molar ratio of Al to O (O / Al ratio) satisfies the range of 1.0 to 2.2.
- Reactive gas and inert gas A high resistance change ratio can be obtained by forming a variable resistance layer by forming a second metal oxide layer containing Al and O by performing a second magnetron sputtering process. It has been found that a variable resistance nonvolatile semiconductor element (nonvolatile memory element) having the above can be realized.
- variable resistance layer and the titanium nitride electrode layer suitable for the variable resistance nonvolatile memory element will be described using the variable resistance nonvolatile memory element of FIG. 1 as an example.
- a variable resistance layer 5 which is a laminate of a first metal oxide film (HfOx) 3 containing Hf and O and a second metal oxide film (AlOx) 4 containing Al and O;
- a titanium nitride film 6 as a second electrode is formed.
- FIG. 2 shows an outline of a processing apparatus used in the process of forming a titanium nitride film constituting the first electrode and a variable resistance film (variable resistance layer 5) having a laminated structure in one embodiment of the present invention.
- the film formation processing chamber 100 is configured to be heated to a predetermined temperature by the heater 101.
- the substrate 102 to be processed can be heated to a predetermined temperature by the heater 105 through the susceptor 104 incorporated in the substrate support base 103. It is preferable that the substrate support 103 can be rotated at a predetermined rotational speed from the viewpoint of film thickness uniformity.
- a target 106 is installed at a position where the target substrate 102 is desired.
- the target 106 is installed on the target holder 108 via a back plate 107 made of a metal such as Cu.
- the outer shape of the target assembly in which the target 106 and the back plate 107 are combined may be made of a target material as a single component and attached as a target.
- the target may be installed on the target holder.
- a direct current power source 110 for applying power for sputtering discharge is connected to the target holder 108 made of metal such as Cu, and is insulated from the wall of the film formation processing chamber 100 at the ground potential by an insulator 109.
- a magnet 111 for realizing magnetron sputtering is disposed behind the target 106 as viewed from the sputtering surface.
- the magnet 111 is held by a magnet holder 112 and can be rotated by a magnet holder rotation mechanism (not shown). In order to make the erosion of the target uniform, the magnet 111 rotates during discharge.
- the target 106 is installed at an offset position obliquely above the substrate 102.
- the center point of the sputtering surface of the target 106 is at a position that is shifted by a predetermined dimension with respect to the normal line of the center point of the substrate 102.
- a shielding plate 116 is disposed between the target 106 and the substrate 102 to be processed, and the film formation on the processing substrate 102 by the sputtered particles emitted from the target 106 supplied with power is controlled.
- a Hf metal target may be used as the target 106.
- the deposition of the first metal oxide film containing Hf and O is performed by supplying electric power to the metal target 106 from the DC power source 110 via the target holder 108 and the back plate 107, respectively.
- an inert gas is introduced into the processing chamber 100 from the vicinity of the target from the inert gas source 201 through the valve 202, the mass flow controller 203, and the valve 204.
- a reactive gas containing oxygen is introduced from the oxygen gas source 205 to the vicinity of the substrate in the processing chamber 100 through the valve 206, the mass flow controller 207, and the valve 208.
- the introduced inert gas and reactive gas are exhausted by the exhaust pump 118 via the conductance valve 117.
- argon is used as the sputtering gas and oxygen is used as the reactive gas.
- the substrate temperature is appropriately determined in the range of 27 to 600 ° C., target power of 50 W to 1000 W, sputtering gas pressure of 0.2 Pa to 1.0 Pa, Ar flow rate of 0 sccm to 100 sccm, and oxygen gas flow rate of 0 sccm to 100 sccm. Can do.
- deposition is performed with a substrate temperature of 30 ° C., a Hf target power of 600 W (100 kHz, 1 us), a sputtering gas pressure of 0.24 Pa, an argon gas flow rate of 20 sccm, and an oxygen gas flow rate of 0 sccm to 30 sccm.
- Sputtering rate refers to the ratio of the number of sputtered atoms emitted per impact ion that bombards the sputter target.
- an Al metal target may be used as the target 106.
- the deposition of the second metal oxide film containing Al and O is performed by supplying electric power to the metal target 106 from the DC power source 110 via the target holder 108 and the back plate 107, respectively.
- an inert gas is introduced into the processing chamber 100 from the vicinity of the target from the inert gas source 201 through the valve 202, the mass flow controller 203, and the valve 204.
- a reactive gas containing oxygen is introduced from the oxygen gas source 205 to the vicinity of the substrate in the processing chamber 100 through the valve 206, the mass flow controller 207, and the valve 208.
- the introduced inert gas and reactive gas are exhausted by the exhaust pump 118 via the conductance valve 117.
- argon is used as the sputtering gas and oxygen is used as the reactive gas.
- the substrate temperature is appropriately determined in the range of 27 to 600 ° C., target power of 50 W to 1000 W, sputtering gas pressure of 0.2 Pa to 1.0 Pa, Ar flow rate of 0 sccm to 100 sccm, and oxygen gas flow rate of 0 sccm to 100 sccm. Can do.
- deposition is performed with a substrate temperature of 30 ° C., an Al target power of 200 W (100 kHz, 1 us), a sputtering gas pressure of 0.24 Pa, an argon gas flow rate of 20 sccm, and an oxygen gas flow rate of 0 sccm to 40 sccm.
- the molar ratio of Al element to O element in the metal oxide film is adjusted by the mixing ratio of argon and oxygen introduced during sputtering.
- “molar ratio” refers to the ratio of the number of moles which is the basic unit of the amount of substance.
- the molar ratio can be measured, for example, from X-ray photoelectron spectroscopy based on the binding energy of intrinsic electrons in the substance, the energy level and amount of electrons.
- the reason why the oxygen gas supply rate is set to 40 sccm or less is to maximize the reduction rate of the sputtering rate caused by the oxidation of the surface of the aluminum metal target.
- a Ti metal target may be used as the target 106 for forming the first electrode and the second electrode made of a titanium nitride film. This is performed by supplying power to the metal target 106 from the DC power source 110 via the target holder 108 and the back plate 107, respectively.
- an inert gas is introduced into the processing chamber 100 from the vicinity of the target from the inert gas source 201 through the valve 202, the mass flow controller 203, and the valve 204.
- a reactive gas containing nitrogen is introduced from the nitrogen gas source 205 to the vicinity of the substrate in the processing chamber 100 through the valve 206, the mass flow controller 207, and the valve 208.
- the introduced inert gas and reactive gas are exhausted by the exhaust pump 118 via the conductance valve 117.
- the deposition of the titanium nitride film in one embodiment of the present invention uses argon as the sputtering gas and nitrogen as the reactive gas.
- the substrate temperature is appropriately determined within the range of 27 ° C. to 600 ° C., target power of 50 W to 1000 W, sputtering gas pressure of 0.2 Pa to 1.0 Pa, Ar flow rate of 0 sccm to 100 sccm, and nitrogen gas flow rate of 0 sccm to 100 sccm. be able to.
- deposition is performed at a substrate temperature of 30 ° C., a Ti target power of 1000 W, an argon gas flow rate of 0 sccm, and a nitrogen gas flow rate of 50 sccm.
- the molar ratio of Ti element and N element in the titanium nitride film is adjusted by the mixing ratio of argon and nitrogen introduced during sputtering.
- the first electrode 2 made of a titanium nitride film is formed on the Si substrate 1 with a thermal oxide film using the film forming apparatus shown in FIG.
- the first metal oxide film 3 containing Hf and O contained in the variable resistance layer 5 is formed on the first electrode 2 by a film forming apparatus similar to the film forming apparatus shown in FIG. Form.
- a second metal oxide film containing Al and O contained in the variable resistance layer 5 is formed on the first metal oxide film 3 by a film formation apparatus similar to the film formation apparatus shown in FIG. 4 is formed.
- variable resistance layer 5 which is a laminated body of the first metal oxide film 3 and the second metal oxide film is formed.
- a titanium nitride film is formed as a second electrode 6 on the second metal oxide film 4 (that is, on the variable resistance layer 5) by a film formation apparatus similar to the film formation apparatus shown in FIG.
- the first electrode 2 is deposited by the same method as that for forming the electrode 2.
- the TiN film is processed into a desired size by using a lithography technique and a RIE (Reactive Ion Etching) technique to form an element.
- composition of the deposited first metal oxide film 3 containing Hf and O and the second metal oxide film 4 containing Al and O were analyzed by an X-ray photoelectron spectroscopy (XPS) method. .
- XPS X-ray photoelectron spectroscopy
- resistance change characteristics of the fabricated devices were evaluated by IV measurement.
- the O / Hf ratio increases from 0.30 to 1.90
- the set state resistance changes from a high resistance state to a low resistance state
- / reset state resistance changes from a low resistance state to a high resistance state
- the resistance change ratio increases from 1 digit to 6 digits.
- the switching operation was not confirmed when the O / Hf ratio was less than 0.30 and 1.90 or more.
- the negative voltage applied for the set operation is referred to as “set voltage”, and the positive voltage applied for the reset operation is referred to as “reset voltage”).
- set voltage the negative voltage applied for the set operation
- reset voltage the positive voltage applied for the reset operation
- 4A to 4D while the switching operation is not confirmed when the O / Al ratio is 0 (metal Al), the switching operation is obtained in the element having the AlOx layer with the O / Al ratio of 1.0 or more. Furthermore, it can be seen that a resistance change ratio of 4 digits or more can be realized in an element having an AlOx layer having an O / Al ratio of 1.5 or more.
- the “resistance change ratio” refers to the ratio of change in resistance at a certain voltage value.
- the resistance R can be in the range of 10 3 to 1 ⁇ 10 7 and a four-digit resistance change ratio can be realized.
- FIG. 5 shows an element ( ⁇ in FIG. 5) made of an HfO single layer film in which the resistance change layer has a composition with an O / Hf ratio of 0.30, and a second element having a composition with an O / Al ratio of 2.2.
- the current-voltage characteristics of an element ( ⁇ in FIG. 5) composed of an AlO / HfO laminated film of a metal oxide film and a first metal oxide film having a composition with an O / Hf ratio of 0.30 are shown.
- the resistance change ratio is about 10 in the range of 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 4 in the case of the HfO single layer structure.
- the resistance R can only be achieved by a single digit resistance change ratio in the range of 10 3 to 1 ⁇ 10 4 .
- the variable resistance layer has a stacked structure of a first metal oxide layer containing Hf and O and a second metal oxide layer containing Al and O.
- the resistance change ratio is improved by about 4 digits as compared with the case of the HfO single layer structure.
- the forming voltage (voltage applied to generate a conduction path in the oxide film in the initial stage) becomes high, and the set voltage It has been confirmed that the reset voltage increases.
- the resistance change ratio can be improved without causing a significant increase in forming voltage by using the laminated film of AlOx and HfOx in one embodiment of the present invention as the variable resistance layer.
- positive and negative pulses are alternately and continuously applied to a resistance change type nonvolatile memory element, even when the resistance change phenomenon is evaluated for rewrite endurance (endurance characteristics), a phenomenon that causes breakdown and causes no operation. showed that.
- FIG. 6 shows current-voltage characteristics of an element in which an AlOx layer is inserted at the interface between the HfOx layer and the lower TiN electrode, and an element in which an AlOx layer is inserted at the interface between the HfOx layer, the upper TiN electrode, and the lower TiN electrode.
- ⁇ indicates an element made of a HfO single layer film in which the resistance change layer has a composition with an O / Hf ratio of 0.30
- ⁇ indicates a second element having a composition with an O / Al ratio of 2.2.
- 2 shows current-voltage characteristics of an element composed of an AlO / HfO laminated film of a metal oxide film and a first metal oxide film having a composition with an O / Hf ratio of 0.30.
- the resistance change ratio at an applied voltage of 0.2 V is found to be improved by about four orders of magnitude when the resistance change layer is laminated, compared to the case of the HfO single layer structure. did.
- FIG. 7 is a diagram showing the relationship between the resistance change ratio of the element and the AlO film thickness as the second metal oxide film at a voltage of 0.2 V.
- the HfO film thickness as the first metal oxide film at that time is 20 nm. Fixed with.
- the resistance change ratio at the time of setting / resetting from an AlO film thickness of 1 nm or more is 1 ⁇ 10 4 when the AlO film thickness is 1 nm, and 1 ⁇ 10 6 when the AlO film thickness is 5 nm.
- the resistance change ratio at the time of set / reset increases from 4 digits to 6 digits.
- the resistance variable layer including the laminated film of the first metal oxide film containing Hf and O and the second metal oxide containing Al and O in one embodiment of the present invention.
- the molar ratio of Al and O in the second metal oxide film for obtaining the resistance change operation is preferably 1.0 to 2.2. In order to realize the change ratio, it is more preferably 1.5 to 2.2.
- the film thickness is preferably 1 nm or more.
- the molar ratio of Hf and O in the first metal oxide film is preferably 0.30 to 1.90.
- the molar ratio of Hf and O, Al and O in the variable resistance layer is adjusted by the mixing ratio of argon and oxygen introduced during sputtering, but the present invention is not limited to this.
- a method of adjusting the molar ratio of Hf and O and Al and O by heat treatment in an oxygen atmosphere after continuously forming a Hf metal film and an Al metal film as the variable resistance layer may be used.
- the heat treatment temperature in the oxygen atmosphere is desirably in the range of 300 ° C. to 600 ° C. from the viewpoint of suppressing oxidation of the electrode layer.
- FIG. 8 shows the relationship between the film composition (N / Ti ratio: corresponding to ⁇ in the figure) and the film composition (O / Ti ratio: corresponding to ⁇ in the figure) and film density in one embodiment of the present invention.
- the film density shown in the figure is 4.7 g / cc or more
- the film composition N / Ti ratio is 1.15 or more. It was confirmed that the switching operation by the resistance change was obtained in the region of.
- the film density is smaller than 4.7 g / cc and the film composition O / Ti ratio is smaller than 1.15, switching operation due to resistance change was not obtained.
- the film composition O / Ti ratio shown in the figure is smaller than the film density 4.7 g / cc and the film composition N / Ti ratio is smaller than the film density 4.7 g / cc
- the film composition O / Ti This is thought to be due to the increase in the ratio. That is, it is suggested that when the film composition O / Ti ratio increases and oxygen in the variable resistance change layer moves to some extent in the titanium nitride film, the resistance change due to voltage application does not occur.
- condition A argon gas flow rate 10 sccm, nitrogen gas flow rate 10 sccm
- condition B argon gas flow rate 0 SCCM, nitrogen gas flow rate 50 SCCM
- condition C argon gas flow rate 13.5 sccm, nitrogen gas flow rate
- C (111), C (200), and C (220) in FIG. 9 represent the crystal plane, (111) plane, (200) plane, and (220) plane of the titanium nitride film, respectively.
- the titanium nitride film capable of changing the resistance in one embodiment of the present invention has a crystal structure with high crystal orientation on the (200) plane.
- FIG. 10 shows the film composition (N / Ti ratio) of the titanium nitride film in the present invention and the peak intensity ratio C (200) / C (111) between the (111) plane and the (200) plane in the XRD spectrum shown in FIG. The relationship is shown.
- the titanium nitride film having a film composition N / Ti ratio of 1.15 or more that can obtain the resistance changing operation in the present invention has a peak intensity ratio of 1.2 or more.
- the morphology of the titanium nitride film having a high peak intensity ratio was evaluated by cross-section and surface observation by SEM.
- FIG. 11 shows an observation image of the titanium nitride film deposited under the condition A by SEM (scanning electron microscope).
- the titanium nitride film in the present invention has a columnar structure having a grain size of 20 nm or less and is excellent in surface flatness.
- the small grain size and excellent surface flatness are considered to suppress the leakage current caused by the crystal grain boundary and obtain a high resistance change ratio necessary for the resistance change nonvolatile memory element. Further, it is considered that the fact that the grain size is small and the crystal structure is dense leads to the improvement of the film density.
- a titanium nitride film suitable for an element having a variable resistance layer preferably has a Ti / N molar ratio of 1.15 or more and a film density of 4.7 g / cc or more.
- the peak intensity ratio X of C [220] / C [111] in the XRD spectrum representing the crystal orientation of the metal nitride layer is preferably 1.2 or more.
- crystal orientation means the ratio of (200) peak intensity to (111) peak intensity in the X-ray diffraction spectrum of a metal nitride layer containing Ti and N (C (200) / C (111)).
- the titanium nitride film deposition step in one embodiment of the present invention is shown in FIG. 2 in order to suppress deterioration of device characteristics due to plasma damage to the variable resistance layer and to control composition and crystal orientation.
- the Ti target is magnetron sputtered in a mixed atmosphere of a reactive gas containing nitrogen and an inert gas in a vacuum vessel in which the target is installed at an offset position obliquely above the substrate.
- the mixing ratio of nitrogen gas and inert gas is set so that the molar ratio of Ti and N in the metal nitride layer is 1.15 or more and the crystal orientation X1 satisfies the range of 1.2 ⁇ X. It is preferable to set.
- the resistance operation in the element having the stacked variable resistance layer of the first metal oxide containing Hf and O and the second metal oxide containing Al and O in one embodiment of the present invention Therefore, it is necessary to control the composition of Hf and O and the composition of Al and O. Moreover, it is desirable to suppress oxidation at the interface between the resistance change layer and the electrode (first electrode and second electrode) sandwiching the resistance change layer. Therefore, in order to manufacture the variable resistance nonvolatile memory element according to an embodiment of the present invention, after forming the first electrode on the substrate to be processed, the variable resistance layer is formed without exposing the substrate to be processed to the atmosphere.
- the first electrode, the variable resistance layer, and the second electrode may be formed in the same processing apparatus. However, the cross-contamination between the metal element constituting the electrode layer and the element constituting the variable resistance layer is prevented.
- the electrode for forming the electrode connected to the transfer device that prevents the substrate to be processed from being exposed to the atmosphere is used. It is desirable to perform processing using a manufacturing apparatus that includes a processing apparatus, a processing apparatus that deposits a metal film, and a processing apparatus that performs heat treatment in an oxygen atmosphere. Also, when a thin film diode layer with a metal film or silicon formed on the surface is exposed as a substrate to be processed, a process for removing the metal film or the oxide film on the silicon surface for the purpose of reducing contact resistance Is required. In that case, you may connect a pre-processing apparatus to the manufacturing apparatus mentioned above.
- FIG. 12 shows a variable resistance nonvolatile memory element manufacturing apparatus 300 of the best mode used for carrying out an embodiment of the present invention.
- the manufacturing apparatus 300 is an apparatus that can perform the following first to sixth steps without exposing the substrate to be processed to the atmosphere.
- the first step is a step of carrying out the pretreatment by carrying the substrate 11 carried into the transfer chamber 306 from the load lock chamber 307 to the pretreatment / Pre-etch chamber 301
- the second step is a pretreatment.
- the substrate 11 is transferred from the pretreatment / Pre-etch chamber 301 to the first electrode (lower electrode) formation chamber 302 to form the titanium nitride film 12 based on the film formation conditions.
- the substrate 11 of the first electrode (lower electrode) forming chamber 302 is transferred to the variable resistance layer forming chamber 303 to form the first variable resistance layer 13.
- the substrate 11 of the first variable resistance layer forming chamber 303 is transferred to the second variable resistance layer forming chamber 304, and 2 is a step of forming the variable resistance layer 14.
- the substrate 11 of the second variable resistance layer forming chamber 304 is transferred to the second electrode (upper electrode) forming chamber 305 to form the film.
- the sixth process transports the substrate 11 of the second electrode (upper electrode) forming chamber 305 to the load lock chamber 307 when the variable resistance element is formed. This is a step of unloading the substrate 11.
- FIG. 13 is a diagram showing a process flow for producing a variable resistance element according to an embodiment of the present invention using the manufacturing apparatus 300 shown in FIG.
- Step 701 is a pre-processing step, and may be implemented by Degas or by removing the surface oxide film.
- a titanium nitride film is formed as a first electrode on the substrate (step 702).
- a variable resistance layer resistance change layer HfOx
- a variable resistance layer resistance change layer AlOx
- the first A titanium nitride film of the second electrode is formed by the same method as the electrode (step 705).
- FIG. 14 is a schematic cross-sectional view of an element structure according to the first embodiment.
- An electrode layer and a variable resistance layer were formed using a manufacturing apparatus 300 shown in FIG. 12 on a silicon substrate 11 having a 100 nm-thickness silicon oxide film on the surface as a substrate to be processed.
- the molar ratio of Ti and N is 1.15 or more at an argon gas flow rate of 0 sccm and a nitrogen gas flow rate of 50 sccm, and the crystal orientation X1 is 1.
- a titanium nitride film 12 having a range of .2 ⁇ X was deposited to 10 nm.
- variable resistance layer forming chamber 303 using a Hf metal target, the molar ratio of O to Hf is 1.30 to 1.90 at an argon gas flow rate of 20 sccm and an oxygen gas flow rate of 10 sccm.
- a resistance layer HfOx13 was deposited to 20 nm.
- variable resistance layer forming chamber 304 using an Al metal target, an argon gas flow rate of 20 sccm and an oxygen gas flow rate of 40 sccm, the molar ratio of O and Al is 1.
- a variable resistance layer AlOx14 of 0 to 2.2 was deposited to 2.5 nm.
- the titanium nitride film 15 was deposited on the variable resistance layer AlOx 14 by the same method as the titanium nitride film 12 using the upper electrode processing chamber 305 provided in the manufacturing apparatus 300.
- the TiN film was processed into a desired size using a lithography technique and an RIE (Reactive Ion Etching) technique to form an element.
- the composition of the deposited HfOx film and AlOx was analyzed by an X-ray photoelectron spectroscopy (XPS) method. The resistance changing operation of the fabricated element was evaluated by current-voltage measurement.
- XPS X-ray photoelectron spectroscopy
- FIG. 15 shows current-voltage characteristics of the produced resistance variable nonvolatile memory element.
- the titanium nitride film 12 of the element was grounded, and a voltage of 0 V to ⁇ 2.7 V was applied to the titanium nitride film 15 to perform a forming operation for generating a conduction path in the oxide film. Thereafter, measurement was performed by applying voltages of 0V ⁇ 3.0V, 3.0V ⁇ 0V, 0V ⁇ ⁇ 2.7V, and ⁇ 2.7V ⁇ 0V, respectively.
- the On / 0ff resistance change ratio in the low resistance state and the high resistance state is 10 3 or more. It is shown that a variable resistance nonvolatile memory element having a value of can be formed.
- variable resistance layer a reactive sputtering method using an Hf metal target as a mixed gas of a reactive gas containing oxygen and an inert gas, and an Al metal target as a reactive gas containing oxygen.
- Hf metal target as a mixed gas of a reactive gas containing oxygen and an inert gas
- Al metal target as a reactive gas containing oxygen.
- a method is used in which an Hf metal film is deposited in the chamber 303 and then an Al metal film is deposited in the chamber 304, and then an annealing process is performed at 300 ° C. to 600 ° C. in an oxygen atmosphere.
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Abstract
Description
第1に、特許文献1のように非晶質の絶縁層と結晶質の抵抗変化層とが積層された積層構造を用いた技術は素子の動作電圧のバラツキを抑制するため、および安定して情報を記憶させるためには効果的であるが、抵抗変化層の組成に関して具体的に述べられていないため、抵抗変化比の向上ができないという課題がある。
また、本発明の第2の態様は、第1の電極と、第2の電極と、前記第1の電極と前記第2の電極との間に挟持され、少なくとも2つの異なる抵抗状態に抵抗値が変化する可変抵抗層とを備える不揮発性記憶素子の製造方法であって、前記可変抵抗層は、HfとOを含有する第1の金属酸化物層と、該第1の金属酸化物層と前記第1の電極および前記第2の電極の少なくとも一方との間に設けられ、AlとOを含有する第2の金属酸化物層を有する積層構造を持ち、前記可変抵抗層を形成する工程が、前記第1の金属酸化物層を形成することと、前記第2の金属酸化物層を形成することと、を有し、前記第1の金属酸化物層を形成することは、酸素を含む反応性ガスと不活性ガスの混合雰囲気下において、金属ターゲットとしてハフニウムを用いHfとOのモル比率(O/Hf比)が0.30から1.90の範囲を満たすように前記反応性ガスと前記不活性ガスの混合比を設定する第1のマグネトロンスパッタ工程を有し、前記第2の金属酸化物層を形成することは、酸素を含む反応性ガスと不活性ガスの混合雰囲気下において、金属ターゲットとしてアルミニウムを用いAlとOのモル比率(O/Al比)が1.0から2.2の範囲を満たすように前記反応性ガスと前記不活性ガスの混合比を設定する第2のマグネトロンスパッタ工程を有すること特徴とする。
本発明は、HfとOを含有する第1の金属酸化膜とAlとOを含有する第2の金属酸化物層との積層構造を有する可変抵抗層と、第1および第2の電極としてTiとNを含有する金属窒化物層を含む電極を有する抵抗変化型不揮発性半導体素子(抵抗変化型の不揮発性記憶素子等)に指向する。本発明者らは、これら抵抗変化型不揮発性半導体素子において、抵抗変化に適した金属酸化膜構造を鋭意検討した結果、HfとOを含有する第1の金属酸化物層のHfとOのモル比率(O/Hf比)を0.30から1.90で表される組成範囲に設定し、かつAlとOを含有する第2の金属酸化物層のAlとOのモル比率(O/Al比)を1.0から2.2で表される組成範囲に設定することにより、高い抵抗変化比を有する抵抗変化型の不揮発性半導体素子(不揮発性記憶素子)を実現できることを発見した。
はじめに、図2に示した成膜装置を用い、熱酸化膜付きSi基板1上に窒化チタン膜からなる第1の電極2を形成する。
次に、図2に示した成膜装置と同様の成膜装置にて、第1の電極2上に、可変抵抗層5に含まれる、HfとOを含有する第1の金属酸化膜3を形成する。
次に、図2に示した成膜装置と同様の成膜装置にて、第1の金属酸化膜3上に、可変抵抗層5に含まれる、AlとOを含有する第2の金属酸化膜4を形成する。これにより、第1の金属酸化膜3と第2の金属酸化膜との積層体である可変抵抗層5が形成されることになる。
次に、図2に示した成膜装置と同様の成膜装置にて、第2の金属酸化膜4上(すなわち、可変抵抗層5上)に、第2の電極6として窒化チタン膜を第1の電極2の形成工程と同様の方法により堆積する。
次に、リソグラフィー技術とRIE(Reactive Ion Etching)技術とを用いてTiN膜を所望の大きさに加工し素子を形成する。
堆積したHfとOを含有する第1の金属酸化膜3およびAlとOを含有する第2の金属酸化膜4の組成は、X線光電子分光(XPS:X-ray Photoelectron Spectroscopy)法により分析した。また、作製した素子の抵抗変化特性をI-V測定により評価した。
図3は電圧0.2VにおいてのHfOx抵抗変化層からなる素子の抵抗変化比とO/Hf比(O/Hf=0.16~O/Hf=2.0)の関係を示す図であり、特にO/Hf比が0.30から1.90に増加するにつれてセット状態(高抵抗状態から低抵抗状態に抵抗が変化)/リセット状態(低抵抗状態から高抵抗状態に抵抗が変化)時の抵抗変化比が1桁から6桁まで増加している様子が分かる。一方、O/Hf比が0.30未満、1.90以上ではswitching動作が確認されなかった。
図4A~4Dは積層型抵抗変化層におけるAlOx層の各O/Al比(O/Al=0~O/Al=2.2)において、抵抗変化型不揮発性記憶素子の電流-電圧特性を示す(O/Hf比は0.30に固定している)。抵抗変化層のO/Al比が1.0以上から抵抗変化型不揮発性記憶素子においてバイポーラ型のswitching動作が得られることを確認した。つまり、抵抗変化型不揮発性記憶素子に負の電圧を印加すると高抵抗状態から低抵抗状態(セット)に、正の電圧を印加すると低抵抗状態から高抵抗状態(リセット)に抵抗が変化することが示される(以下、セット動作のために印加した負の電圧を“セット電圧”、リセット動作のために印加した正の電圧を"リセット電圧"と言う)。図4A~4Dより、O/Al比が0(メタルAl)ではswitching動作が確認されないのに対して、O/Al比が1.0以上のAlOx層を有する素子において、switching動作が得られ、更にO/Al比が1.5以上のAlOx層を有する素子においては、4桁以上の抵抗変化比が実現できることがわかる。
なお、本明細書において、「抵抗変化比」とは、ある電圧値における抵抗の変化の比率をいう。例えば、O/Al比が1.5以上のAlOx層を有する素子においては、印加電圧Vが約2Vの場合、電流Iは1×10-3から1×10-7の範囲で変化している。従って、V=I×Rより、抵抗Rは103から1×107の範囲で、4桁の抵抗変化比が実現できる。
印加電圧Vが0.2Vにおいての抵抗変化比はHfO単層構造の場合、電流Iは1×10-3から1×10-4の範囲で約10変化している。従って、V=I×Rより、抵抗Rは103から1×104の範囲で、1桁の抵抗変化比しか実現できない。これに対して、印加電圧Vが0.2Vにおいての抵抗変化比は、AlO/HfO積層構造の場合、電流は1×10-3から1×10-8の範囲で約105変化している。従って、V=I×Rより、抵抗Rは103から1×108の範囲で、5桁の抵抗変化比を実現できる。本発明の一実施形態のように、抵抗変化層を、HfとOとを含有する第1の金属酸化物層とAlとOとを含有する第2の金属酸化物層との積層構造とすることにより、HfO単層構造の場合と比較して、抵抗変化比が4桁程度向上することが判明した。
HfO単層構造を有する抵抗変化層において、AlO/HfO積層構造の場合と同程度の高い抵抗変化比を得るためにはO/Hf比を増加させる方法がある。しかし、その方法ではAlO/HfO積層構造と同一な抵抗変化比が得られるものの、フォーミング電圧(初期に酸化膜中に伝導パスを生成させるために印加する電圧)が高くなることと、セット電圧とリセット電圧が高くなることとを確認している。従って、可変抵抗層として本発明の一実施形態におけるAlOxとHfOxの積層膜を用いることでフォーミング電圧の大幅な増加を招くことなく、抵抗変化比の向上を実現できることが示された。
なお、抵抗変化型不揮発性記憶素子に正負のパルスを交互に連続して印加し、抵抗変化現象の書き換え耐性(エンデュランス特性)の評価においても印加回数が数回で絶縁破壊を起こし動作しなくなる現象を示した。
また、ここではHfOx層と上部TiN電極界面にAlOx層を挿入した素子について述べたが、HfOx層と下部TiN電極界面にAlOx層を挿入した素子ならびにHfOx層と上部TiN電極および下部TiN電極界面にAlOx層を挿入した素子においても同様の効果が得られることを確認した。すなわち、HfOx層と上部TiN電極界面、およびHfOx層と下部TiN電極界面の少なくとも一方にAlOx層を挿入することにより、フォーミング電圧の増加を低減しつつ、抵抗変化比を高くすることができる。
図6はHfOx層と下部TiN電極界面にAlOx層を挿入した素子とHfOx層と上部TiN電極および下部TiN電極界面にAlOx層を挿入した素子の電流-電圧特性を示す。なお、図6において、□は抵抗変化層がO/Hf比が0.30の組成を有するHfO単層膜からなる素子を示し、■はO/Al比が2.2の組成を有する第2の金属酸化膜とO/Hf比が0.30の組成を有する第1の金属酸化膜とのAlO/HfO積層膜からなる素子の電流-電圧特性を示す。図5と同様、印加電圧0.2Vにおいての抵抗変化比は、抵抗変化層を積層構造することにより、HfO単層構造の場合と比較して、抵抗変化比が4桁程度向上することが判明した。
図7は電圧0.2Vにおいての素子の抵抗変化比と第2の金属酸化膜としてのAlO膜厚の関係を示す図であり、そのときの第1の金属酸化膜としてのHfO膜厚は20nmで固定した。AlO膜厚1nm以上からセット/リセット時の抵抗変化比は、AlO膜厚1nmの場合、1×104であり、AlO膜厚5nmの場合、1×106であること示している。これにより、セット/リセット時の抵抗変化比が4桁から6桁まで増加している様子が分かる。
次に、本発明の一実施形態に係るHfとOを含有する第1の金属酸化物とAlとOを含有する第2の金属酸化物とを積層させた積層型抵抗変化層を挟持する電極として最適な窒化チタン膜を用いた場合において、抵抗変化動作を得るための窒化チタン膜の構造(組成・結晶性)について説明する。
上述の説明より、本発明の一実施形態におけるHfとOを含有する第1の金属酸化物とAlとOを含有する第2の金属酸化物の積層型抵抗変化層を有する素子において抵抗化動作を得るには、HfとOの組成、AlとOの組成を制御する必要がある。また、抵抗変化層と抵抗変化層を挟持する電極(第1の電極と第2の電極)との界面の酸化を抑制することが望ましい。従って、本発明の一実施形態における抵抗変化型不揮発性記憶素子を作製するには、被処理基板上に第1の電極を形成した後、被処理基板を大気暴露させることなく可変抵抗層を形成し、その後、被処理基板を大気に暴露させることなく、第2の電極を形成することが望ましい。
尚、第1の電極、可変抵抗層および第2の電極の形成は、同一処理装置内で処理しても良いが、電極層を構成する金属元素と可変抵抗層を構成する元素の相互汚染を防止ないしは低減するため、被処理基板の大気暴露を阻止する搬送装置に接続された電極形成用の処理装置と可変抵抗層形成用の処理装置とを備える製造装置を用いて処理することが望ましい。また、可変抵抗層の形成工程として、HfとAlの金属膜を連続に堆積した後に酸素雰囲気中の熱処理を行う場合、被処理基板の大気暴露を阻止する搬送装置に接続された電極形成用の処理装置と金属膜を堆積する処理装置と酸素雰囲気中で熱処理を行う処理装置とを備える製造装置を用いて処理することが望ましい。また、被処理基板として表面に金属膜やシリコン等が形成された薄膜ダイオード層が露出している場合には、コンタクト抵抗を低減することを目的として金属膜やシリコン表面の酸化膜を除去する処理が必要となる。その場合、上述した製造装置に前処理装置を接続しても良い。
図14は、実施例1に関わる素子構造の断面の概略である。被処理基板として表面に膜厚100nmのシリコン酸化膜を有するシリコン基板11に、図12に示す製造装置300を用いて電極層と可変抵抗層の形成を行った。
製造装置300が備える下部電極処理チャンバ302において、Ti金属ターゲットを用いてアルゴンガス流量0sccmと窒素ガス流量50sccmにてTiとNのモル比率が1.15以上であり、かつ結晶配向性X1が1.2<Xの範囲を有する窒化チタン膜12を10nm堆積した。
次に、可変抵抗層HfOx13の上に製造装置300が備える可変抵抗層形成チャンバ304を用いてAl金属ターゲットを用いてアルゴンガス流量20sccmと酸素ガス流量40sccmにてOとAlのモル比率が1.0~2.2である可変抵抗層AlOx14を2.5nm堆積した。
次に、可変抵抗層AlOx14の上に製造装置300が備える上部電極処理チャンバ305を用いて窒化チタン膜12と同様の方法で窒化チタン膜15を堆積した。
次に、リソグラフィー技術とRIE(Reactive Ion Etching)技術を用いてTiN膜を所望の大きさに加工し素子を形成した。
堆積したHfOx膜とAlOxの組成は、X線光電子分光(XPS:X-ray Photoelectron Spectroscopy)法により分析した。また、作製した素子の抵抗変化動作は、電流-電圧測定により評価した。
また、上記実施例では、被処理基板として表面に膜厚100nmのシリコン酸化膜を有するシリコン基板を用いた場合を述べた。しかしながら、被処理基板として基板表面の一部にWが露出した基板を用い、製造装置300において、前処理チャンバ301においてWの表面酸化物を除去した後、電極層および可変抵抗層を形成しても上記実施例と同様の効果が得られることを確認した。
Claims (9)
- 第1の電極と、
第2の電極と、
前記第1の電極と前記第2の電極との間に挟持され、少なくとも2つの異なる抵抗状態に抵抗値が変化する可変抵抗層とを備え、
前記可変抵抗層が、HfとOを含有する第1の金属酸化物層と、該第1の金属酸化物層と前記第1の電極および前記第2の電極の少なくとも一方との間に設けられ、AlとOを含有する第2の金属酸化物層を有する積層構造を持っていること特徴とする不揮発性記憶素子。 - 前記第1の金属酸化物層のHfとOのモル比率(O/Hf比)が0.30から1.90で表される組成範囲を有しており、かつ前記第2の金属酸化物層のAlとOのモル比率(O/Al)が1.0から2.2で表される組成範囲を有していることを特徴とする請求項1に記載の不揮発性記憶素子。
- 前記第2の金属酸化物層のAlとOのモル比率(O/Al)は1.5から2.2で表される組成範囲を有していることを特徴とする請求項1に記載の不揮発性記憶素子。
- 前記第2の金属酸化物層の膜厚が少なくとも1nm以上であることを特徴とする請求項1に記載の不揮発性記憶素子。
- 前記不揮発性記憶素子が抵抗変化型のメモリであることを特徴とする請求項1に記載の不揮発性記憶素子。
- 第1の電極と、
第2の電極と、
前記第1の電極と前記第2の電極との間に挟持され、少なくとも2つの異なる抵抗状態に抵抗値が変化する可変抵抗層とを備える不揮発性記憶素子の製造方法であって、
前記可変抵抗層は、HfとOを含有する第1の金属酸化物層と、該第1の金属酸化物層と前記第1の電極および前記第2の電極の少なくとも一方との間に設けられ、AlとOを含有する第2の金属酸化物層を有する積層構造を持ち、
前記可変抵抗層を形成する工程が、
前記第1の金属酸化物層を形成することと、
前記第2の金属酸化物層を形成することと、を有し、
前記第1の金属酸化物層を形成することは、
酸素を含む反応性ガスと不活性ガスの混合雰囲気下において、金属ターゲットとしてハフニウムを用いHfとOのモル比率(O/Hf比)が0.30から1.90の範囲を満たすように前記反応性ガスと前記不活性ガスの混合比を設定する第1のマグネトロンスパッタ工程を有し、
前記第2の金属酸化物層を形成することは、
酸素を含む反応性ガスと不活性ガスの混合雰囲気下において、金属ターゲットとしてアルミニウムを用いAlとOのモル比率(O/Al比)が1.0から2.2の範囲を満たすように前記反応性ガスと前記不活性ガスの混合比を設定する第2のマグネトロンスパッタ工程を有すること特徴とする不揮発性記憶素子の製造方法。 - 前記第1の金属酸化物層を形成することにおいて、該第1の金属酸化物層を形成することが実行される真空容器内に供給する酸素を含む反応性ガスの供給量をハフニウム金属ターゲットの表面が酸化することにより生じるスパッタ率の低下率が最大となる供給量以下に設定し、
前記第2の金属酸化物層を形成することにおいて、該第2の金属酸化物層を形成することが実行される真空容器内に供給する酸素を含む反応性ガスの供給量をアルミニウム金属ターゲットの表面が酸化することにより生じるスパッタ率の低下率が最大となる供給量以下に設定することを特徴とする請求項6に記載の不揮発性記憶素子の製造方法。 - 前記可変抵抗層を形成する工程の前に、前記第1の電極を形成する工程と、
前記可変抵抗層を形成する工程の後に、前記第2の工程を形成する工程とをさらに備え、
前記第1の電極を形成する工程と、前記可変抵抗層を形成する工程と、前記第2の電極を形成する工程とを、被処理基板を大気暴露させることなく実施することを特徴とする請求項6に記載の不揮発性記憶素子の製造方法。 - 前記2つの異なる抵抗状態が、低抵抗から高抵抗に変化するリセット状態と高抵抗から低抵抗に変化するセット状態であることを特徴とする請求項6に記載の不揮発性記憶素子の製造方法。
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JPWO2018193759A1 (ja) * | 2017-04-18 | 2019-11-07 | 株式会社アルバック | 抵抗変化素子の製造方法及び抵抗変化素子 |
KR20190137875A (ko) * | 2017-04-18 | 2019-12-11 | 가부시키가이샤 아루박 | 저항 변화 소자의 제조 방법 및 저항 변화 소자 |
KR102228548B1 (ko) * | 2017-04-18 | 2021-03-16 | 가부시키가이샤 아루박 | 저항 변화 소자의 제조 방법 및 저항 변화 소자 |
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Also Published As
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TWI485776B (zh) | 2015-05-21 |
TW201241922A (en) | 2012-10-16 |
US9391274B2 (en) | 2016-07-12 |
US20160079530A1 (en) | 2016-03-17 |
KR20130107336A (ko) | 2013-10-01 |
JPWO2012073471A1 (ja) | 2014-05-19 |
JP5390715B2 (ja) | 2014-01-15 |
US20130256623A1 (en) | 2013-10-03 |
KR101492139B1 (ko) | 2015-02-10 |
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