CN106784308A - A kind of Nonvolatile resistance variation memory part and preparation method thereof - Google Patents
A kind of Nonvolatile resistance variation memory part and preparation method thereof Download PDFInfo
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- CN106784308A CN106784308A CN201611072653.6A CN201611072653A CN106784308A CN 106784308 A CN106784308 A CN 106784308A CN 201611072653 A CN201611072653 A CN 201611072653A CN 106784308 A CN106784308 A CN 106784308A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000002346 layers by function Substances 0.000 claims abstract description 7
- WFPQISQTIVPXNY-UHFFFAOYSA-N niobium strontium Chemical compound [Sr][Nb] WFPQISQTIVPXNY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 238000000151 deposition Methods 0.000 claims description 35
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 29
- 230000008021 deposition Effects 0.000 claims description 19
- 238000005137 deposition process Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000000608 laser ablation Methods 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004549 pulsed laser deposition Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 239000010409 thin film Substances 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000004627 transmission electron microscopy Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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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
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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
- H10N70/011—Manufacture or treatment of multistable switching devices
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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
- H10N70/011—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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- 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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Abstract
The invention discloses a kind of Nonvolatile resistance variation memory part and preparation method thereof, belong to semiconductor memory technologies field.The resistive memory includes bottom electrode layer niobium strontium titanate doping, top electrode layer Ta metals and the resistance-change memory functional layer between the hearth electrode and top electrode, wherein, resistance-change memory functional layer material is by the ultra-thin CeO of hearth electrode Epitaxial growth2Film and one layer of binary metal oxide HfOxFilm is constituted.The invention also discloses the preparation method of Nonvolatile resistance variation memory part.The present invention uses HfOxFilm and the ultra-thin CeO of epitaxial growth2Film bilayer film as resistive functional layer, the resistive memory of acquisition have low in energy consumption, device job stability it is high, it is non-volatile the characteristics of.
Description
Technical field
The invention belongs to semiconductor memory technologies field, and in particular to a kind of Nonvolatile resistance variation memory part and its system
Preparation Method.
Background technology
At present, so that high storage density, low-power consumption, erasable number of times be fast etc., that advantage occupies flash chip memory technology is non-volatile
Property storage chip monopoly position, but continuing to develop with semiconductor technology, flash chip memory technology encounters technology bottle
Neck.Resistance-variable storing device (RRAM) with its material and simple structure, cellar area be small, preparation cost is low and traditional cmos process and
Hold, can miniature ability it is strong, while having, read or write speed is fast, the operation low advantage of power consumption again, increasingly paid attention to by industry, turn into
The contenders of non-volatility memorizer of future generation.Certainly, from practical on a large scale also there is a certain distance in RRAM, for
Products application, at the aspect such as device performance regulation and control, parameter uniformity and reliability, in addition it is also necessary to deeper into research.
The content of the invention
The present invention is difficult to the deficiency of large-scale application for existing memory, there is provided a kind of Nonvolatile resistance variation memory
Part and preparation method thereof, it is characterised in that：
The resistive memory, including bottom electrode layer niobium strontium titanate doping NSTO, top electrode layer Ta metals and positioned at institute
The resistance-change memory functional layer between hearth electrode and top electrode is stated, resistance-change memory functional layer is by ultra-thin in hearth electrode Epitaxial growth
CeO2Film and one layer of binary metal oxide HfOxFilm is constituted.The bottom electrode layer niobium strontium titanate doping NSTO is simultaneously device
Part substrate.
The preparation method of above-mentioned resistive memory, comprises the following steps：
(1) NSTO substrates cleaning, and shield portions region is used as hearth electrode；
(2) using pulsed laser deposition technique in one layer of ultra-thin CeO of NSTO Epitaxial growths2Film, thickness is 3~5nm,
Depositing operation is：Before deposition, the vacuum of chamber is 1 × 10-8Pa；Laser pulse frequency 1Hz in deposition process, target base spacing is
80mm, the vacuum in deposition process is 3 × 10-8Pa, underlayer temperature is 800 DEG C, and laser ablation energy is 1Jcm-2；
(3) using magnetron sputtering technique in CeO2HfO is deposited on filmxFilm, thickness is 10nm~50nm, depositing operation
For：Before deposition, Chamber vacuum degree is 1 × 10-5Pa；In deposition process, chamber pressure is maintained at 2Pa, and partial pressure of oxygen is controlled 5%,
25 DEG C of depositing temperature, deposition power 60W；
(4) using mask plate in HfOxTop electrode figure is formed on film；
(5) using magnetron sputtering technique in HfOxTa metal electrode layers are deposited on film, thickness is 10~500nm, deposition
Technique is：Before deposition, Chamber vacuum degree is 2 × 10-4Pa；In deposition process, chamber pressure is maintained at 1Pa, 25 DEG C of depositing temperature,
Deposition power 60W.
(6) mask plate is removed, resistive memory Ta/HfO is obtainedx/CeO2/NSTO。
The advantage of the invention is that：
The resistive memory store function layer choosing of the invention mainstay material HfO of current CMOSxIt is super with one layer rich outer
Prolong monocrystalline CeO2Film is collectively as resistive memory function layer material so that device passes through epitaxy single-crystal CeO2Film obtains height
Resistance states, reduce device power consumption.Simultaneously as CeO2The regulation and control of film layer so that HfOxThe resistive memory of film base
Transformation uniformity is improve, job stability higher is obtained.Compare with existing resistive memory, the resistance-change memory utensil
There is significant technical advantage, can be suitably used for the memory unit in super large-scale integration.
Brief description of the drawings
Fig. 1 is comparative example resistive memory Ta/HfOxThe structural representation of/NSTO；
Fig. 2 is Nonvolatile resistance variation memory part Ta/HfOx/CeO2The structural representation of/NSTO；
Fig. 3 is comparative example resistive memory Ta/HfOxThe transmission electron microscopy structure chart of/NSTO devices；
Fig. 4 is Nonvolatile resistance variation memory part Ta/HfOx/CeO2The transmission electron microscopy structure chart of/NSTO；
Fig. 5 is comparative example resistive memory Ta/HfOxThe resistive characteristic curve of/NSTO devices；
Fig. 6 is comparative example resistive memory Ta/HfOxThe voltage of/NSTO devices-cycle-index curve；
Fig. 7 is Nonvolatile resistance variation memory part Ta/HfOx/CeO2The resistive characteristic curve of/NSTO；
Fig. 8 is Nonvolatile resistance variation memory part Ta/HfOx/CeO2/ NSTO voltages-cycle-index curve；
Fig. 9 is Nonvolatile resistance variation memory part Ta/HfOx/CeO2/ NSTO and comparative example resistive memory Ta/HfOx/
The power dissipation ratio of NSTO devices is relatively schemed；
Figure 10 is Nonvolatile resistance variation memory part Ta/HfOx/CeO2The rate of transformation test chart of/NSTO devices；
Figure 11 is Nonvolatile resistance variation memory part Ta/HfOx/CeO2The device data holding capacity test chart of/NSTO.
Specific embodiment
The invention provides a kind of Nonvolatile resistance variation memory part and preparation method thereof, below in conjunction with drawings and Examples
The present invention is described in detail, but the present invention is not limited thereto.
Each layer film thickness and area size shape do not reflect actual proportions in figure, and purpose is in the schematically illustrate present invention
Hold.
Fig. 1 is comparative example resistive memory Ta/HfO of the present inventionxThe structural representation of/NSTO, the structure bottom is
Backing material NSTO, NSTO are the strontium titanate materials (doping mass fraction is 0.7%) of niobium doping, simultaneously as device after doping
Hearth electrode material.It is HfO to be deposited on NSTOx, due to depositing operation control, the HfO of acquisitionxThin-film material is for non-chemically
Metering ratio.It is deposited on HfOxOn be top electric metal thin-film material Ta, Ta/HfOx/ NSTO constitutes the resistive of comparative example of the present invention
Memory construction unit.
Fig. 2 is embodiment of the present invention Nonvolatile resistance variation memory part Ta/HfOx/CeO2The structural representation of/NSTO, should
Structure bottom is backing material NSTO, and NSTO is the strontium titanate material (doping mass fraction is 0.7%) of niobium doping, after doping
Simultaneously as the hearth electrode material of device.It is one layer of monocrystalline CeO to be deposited on NSTO2Film, for reducing whole device
Power consumption is deposited and reduces devices transition parameter discrete, in CeO2On be HfOx, due to depositing operation control, the HfO of acquisitionx
Thin-film material is non-stoichiometric, is deposited on HfOxOn be top electric metal thin-film material Ta, Ta/HfOx/CeO2/ NSTO structures
Into the resistance variation memory structure unit of the embodiment of the present invention.
Comparative example 1
Resistive memory Ta/HfOxThe preparation method of/NSTO, comprises the following steps：
Step 1：NSTO substrates are cleaned, and shield portions region is used as hearth electrode；
Step 2：Using magnetron sputtering technique HfO is deposited on NSTO filmsxFilm, thickness is 20nm, and depositing operation is：
Before deposition, Chamber vacuum degree is 1 × 10-5Pa；In deposition process, chamber pressure is maintained at 2Pa, and partial pressure of oxygen control is in 5%, deposition
25 DEG C of temperature, deposition power 60W, sedimentation time 20 minutes；
Step 3：Using mask plate in HfOxTop electrode figure is formed on film；
Step 4：Using magnetron sputtering technique in HfOxTa metal electrode layers are deposited on film, thickness is 80nm, deposit work
Skill is：Before deposition, Chamber vacuum degree is 2 × 10-4Pa；In deposition process, chamber pressure is maintained at 1Pa, and 25 DEG C of depositing temperature sinks
Product power 60W, sedimentation time 4 minutes.
Step 5：Removal mask plate, obtains resistive memory Ta/HfOx/CeO2/NSTO。
Embodiment 1
Resistive memory Ta/HfOx/CeO2The preparation method of/NSTO, comprises the following steps：
Step 1：NSTO substrates are cleaned, and shield portions region is used as hearth electrode；
Step 2：Using pulsed laser deposition technique on NSTO one layer of ultra-thin CeO of extension2Film, thickness is 4nm, deposition
Technique is：Before deposition, the vacuum of chamber is~1 × 10-8Pa；Laser pulse frequency 1Hz in deposition process, target base spacing is
80mm, the vacuum in deposition process is~3 × 10-8Pa, underlayer temperature is 800 DEG C, and laser ablation energy is 1Jcm-2；
Step 3：Using magnetron sputtering technique in CeO2HfO is deposited on filmxFilm, thickness is 20nm, and depositing operation is：
Before deposition, Chamber vacuum degree is 1 × 10-5Pa；In deposition process, chamber pressure is maintained at 2Pa, and partial pressure of oxygen control is in 5%, deposition
Temperature room temperature, deposition power 60W, sedimentation time 20 minutes；
Step 4：Using mask plate in HfOxTop electrode figure is formed on film；
Step 5：Using magnetron sputtering technique in HfOxTa metal electrode layers are deposited on film, thickness is 80nm, deposit work
Skill is：Before deposition, Chamber vacuum degree is 2 × 10-4Pa；In deposition process, chamber pressure is maintained at 1Pa, and depositing temperature room temperature is sunk
Product power 60W, sedimentation time 4 minutes.
Step 6：Removal mask plate, obtains resistive memory Ta/HfOx/CeO2/NSTO。
Fig. 3 is comparative example resistive memory Ta/HfO of the present inventionxThe transmission electron microscopy structure chart of/NSTO devices.From
Interface and the thickness between three-layer thin-film can must be clearly found out in figure, and is existed without obvious boundary layer, NSTO is single
Crystalline state, HfOxIt is amorphous state, Ta is polycrystalline state.
Fig. 4 is resistive memory Ta/HfO of the present inventionx/CeO2The transmission electron microscopy structure chart of/NSTO.Can from figure
Must clearly find out interface and the thickness between four-level membrane, and exist without obvious boundary layer, NSTO is monocrystalline state,
CeO2It is monocrystalline state, there is phase relation, HfO with NSTOxIt is amorphous state, Ta is polycrystalline state.
Fig. 5 comparative example resistive memory Ta/HfO of the present inventionxThe resistive characteristic curve of/NSTO devices, shows good
Good resistance transformation characteristic, can be used for memory device.
Fig. 6 comparative example resistive memory Ta/HfO of the present inventionxThe voltage of/NSTO devices-cycle-index curve, from figure
It can be seen that, although comparative example of the present invention also shows preferable resistive characteristic, but its transition parameters is discrete, increases outer
Enclose the degree of difficulty of circuit design.
Fig. 7 is resistive memory Ta/HfO of the present inventionx/CeO2The resistive characteristic curve of/NSTO, shows good
Resistance transformation characteristic, can be used for memory device, and compared with comparative example, with lower current value that is, lower
Power consumption.
Fig. 8 is resistive memory Ta/HfO of the present inventionx/CeO2The device voltage of/NSTO-cycle-index curve, from figure
It can be seen that compared with comparative example of the present invention 1, transition parameters discrete type substantially weakens, illustrate that the present invention significantly inhibits resistive
The discrete problem of memory device transition parameters.
Fig. 9 is resistive memory Ta/HfO of the present inventionx/CeO2/ NSTO and comparative example resistive memory Ta/ of the present invention
HfOxThe power dissipation ratio of/NSTO devices is relatively schemed, and as can be seen from the figure has lower power consumption number compared with comparative example of the present invention 1,
Suitable for embedded device.
Figure 10 is resistive memory Ta/HfO of the present inventionx/CeO2The rate of transformation test chart of/NSTO devices, can from figure
To agree device of the present invention with the data rate memory less than 50ns, it is adaptable to high speed storing technology of future generation.
Figure 11 is resistive memory Ta/HfO of the present inventionx/CeO2The device data holding capacity test chart of/NSTO, from figure
Middle data can be seen that prepared device by 106Low resistance state high shows that the device has without significant change after the reading of s
It is non-volatile, and can be inferred that resistive device of the present invention has the data retention characteristics more than 10 years by extrapolation.
Finally illustrate, the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although by ginseng
According to the preferred embodiments of the present invention, invention has been described, it should be appreciated by those of ordinary skill in the art that can
To make various changes to it in the form and details, without departing from the present invention that appended claims are limited
Spirit and scope.
Claims (3)
1. a kind of Nonvolatile resistance variation memory part, including bottom electrode layer niobium strontium titanate doping NSTO, top electrode layer Ta metals with
And the resistance-change memory functional layer between the hearth electrode and top electrode, it is characterised in that：Resistance-change memory functional layer is by the bottom of at
The ultra-thin CeO of electrode Epitaxial growth2Film and one layer of binary metal oxide HfOxFilm is constituted.
2. a kind of Nonvolatile resistance variation memory part according to claim 1, it is characterised in that：The bottom electrode layer niobium is mixed
Miscellaneous strontium titanates NSTO is simultaneously device substrate.
3. a kind of preparation method of Nonvolatile resistance variation memory part described in claim 1, it is characterised in that including following step
Suddenly：
(1) NSTO substrates cleaning, and shield portions region is used as hearth electrode；
(2) using pulsed laser deposition technique in one layer of ultra-thin CeO of NSTO Epitaxial growths2Film, thickness is 3~5nm, deposition
Technique is：Before deposition, the vacuum of chamber is 1 × 10-8Pa；Laser pulse frequency 1Hz in deposition process, target base spacing is
80mm, the vacuum in deposition process is 3 × 10-8Pa, underlayer temperature is 800 DEG C, and laser ablation energy is 1Jcm-2；
(3) using magnetron sputtering technique in CeO2HfO is deposited on filmxFilm, thickness is 10nm~50nm, and depositing operation is：It is heavy
Before product, Chamber vacuum degree is 1 × 10-5Pa；In deposition process, chamber pressure is maintained at 2Pa, and partial pressure of oxygen control is in 5%, deposition temperature
25 DEG C of degree, deposition power 60W；
(4) using mask plate in HfOxTop electrode figure is formed on film；
(5) using magnetron sputtering technique in HfOxTa metal electrode layers are deposited on film, thickness is 10~500nm, depositing operation
For：Before deposition, Chamber vacuum degree is 2 × 10-4Pa；In deposition process, chamber pressure is maintained at 1Pa, 25 DEG C of depositing temperature, deposition
Power 60W.
(6) mask plate is removed, resistive memory Ta/HfO is obtainedx/CeO2/NSTO。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623634A (en) * | 2012-03-29 | 2012-08-01 | 杭州电子科技大学 | Zinc oxide-doped film based resistance type memorizer and preparation method thereof |
| CN104393172A (en) * | 2014-11-27 | 2015-03-04 | 浙江理工大学 | Interface oxygen vacancy based stable-storage resistive random access memory achieving method |
| CN104752609A (en) * | 2013-12-26 | 2015-07-01 | 北京有色金属研究总院 | RRAM (Resistive Random Access Memory) and preparation method thereof |
| CN105264682A (en) * | 2013-04-19 | 2016-01-20 | 苏黎世联邦理工学院 | Strained multilayer resistive-switching memory elements |
-
2016
- 2016-11-28 CN CN201611072653.6A patent/CN106784308A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102623634A (en) * | 2012-03-29 | 2012-08-01 | 杭州电子科技大学 | Zinc oxide-doped film based resistance type memorizer and preparation method thereof |
| CN105264682A (en) * | 2013-04-19 | 2016-01-20 | 苏黎世联邦理工学院 | Strained multilayer resistive-switching memory elements |
| CN104752609A (en) * | 2013-12-26 | 2015-07-01 | 北京有色金属研究总院 | RRAM (Resistive Random Access Memory) and preparation method thereof |
| CN104393172A (en) * | 2014-11-27 | 2015-03-04 | 浙江理工大学 | Interface oxygen vacancy based stable-storage resistive random access memory achieving method |
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