CN101471421B - Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory - Google Patents
Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory Download PDFInfo
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- CN101471421B CN101471421B CN2007103042203A CN200710304220A CN101471421B CN 101471421 B CN101471421 B CN 101471421B CN 2007103042203 A CN2007103042203 A CN 2007103042203A CN 200710304220 A CN200710304220 A CN 200710304220A CN 101471421 B CN101471421 B CN 101471421B
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- metallic oxide
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Abstract
The invention discloses a binary transition metal oxide nonvolatile resistance-transition memory based on ion implantation. The memory comprises an upper conductive electrode; a lower conductive electrode; a binary transition metal oxide film arranged between the upper conductive electrode and the lower conductive electrode, wherein ions are implanted in the binary transition metal oxide film. The binary transition metal oxide film with ions implanted therein can greatly improve the yield of the memory, increase the ratio of high resistance state to low resistance state of the device and reduce the discrete value of the resistance transition characteristics among the devices. The memory device has the advantages of simple structure, easy integration, and low cost, and is compatible to the conventional silicon planar CMOS process, which facilitates the extensive generalization and application of the memory.
Description
Technical field
The present invention relates to microelectronic component and memory technology field, relate in particular to a kind of Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion.
Background technology
In recent years, the growth rate of memory has surpassed logical circuit in the integrated circuit (IC), the ratio that memory accounts for chip area by 1999 20% increase to 2005 71%.According to the statistics of fourth quarter in 2005, IC makes in the world, and it is to be used for memory that 47% production capacity is arranged, and the logic class product only accounts for 29%.
The share that the whole storage market of present China accounts for semi-conductor market was near 40%, and expectation will reach 759.4 hundred million yuan in 2009.Simultaneously, be subjected to the influence of current 3C consumer electronics product market explosive growth, in various memory products, the market demand is fastest-rising to be nonvolatile memory (NVM).Flash memory (flash memory) is the non-volatility memorizer that dominates at present, and its output value also will approach dynamic random access memory.
The traditional flash memory is based on the silica-based non-volatility memorizer of polysilicon membrane floating gate structure, and this structure is being faced with the challenge how to continue to dwindle.From ITRS (ITRS) in 2005, traditional multi-crystal silicon floating bar memory can only be extended to the 65nm technology node, this mainly be because, polysilicon membrane can cause tunnel oxide to produce leak channel in the process that sassafras is write repeatedly, thereby to obtain high reliability, the tunnel oxide layer thickness must remain on more than the 9nm, reads and writes voltage accordingly and also will remain on higher level, and it is slower to make also that simultaneously programming/sassafras removes speed.
Following non-volatility memorizer (NVM) requires to possess lower program/erase (P/E) voltage, P/E speed, stronger data retention characteristics etc. faster.Recent years, the internal and international structure and material of going up at the nonvolatile memory of future generation of alternative multi-crystal silicon floating bar memory has carried out extensive studies, mainly comprises following several: nanocrystalline floating gate memory, phase transition storage, organic memory, electric resistance transition type memory.Wherein, electric resistance transition type memory because have simple device architecture (metal-insulator-metal type), very high device density, lower power consumption, programming/sassafras removes outstanding advantages such as speed faster, so come into one's own more.
As shown in Figure 1, Fig. 1 is the basic structure schematic diagram of electric resistance transition type memory device.Wherein, 101 is top electrode, and 102 is bottom electrode, and 103 is functional layer.Fig. 2 shows one pole type and the Utopian i-v curve schematic diagram of ambipolar electric resistance changing memory.The electric resistance changing memory technology is can realize the reversible basis that is converted under the control of voltage with the resistance of material between high-impedance state and low resistance state.
At present reported material, mainly can be divided into following three kinds with electric resistance changing characteristic:
1), organic polymer, as polyimides (PI), AIDCN and CuTCNQ etc.;
2), multi-element metal oxide, as magnetoresistance material Pr
0.7Ca
0.3MnO
3And La
0.7Ca
0.3MnO
3Deng, the SrTiO of doping
3And SrZrO
3Deng;
3), Dyadic transition group metallic oxide, as NiO, Nb
2O
5, CuO
x, ZrO
2, HfO
2, Ta
2O
5, TiO
2Deng.
Binary oxide simultaneously can be compatible completely with current CMOS technology because made is fairly simple, thereby come into one's own more.
The electric resistance changing characteristic of common Dyadic transition group metallic oxide has very strong dependence to the growing method and the defect state of sull, though there are a variety of Dyadic transition group metallic oxide materials to be found the characteristic with electric resistance changing under extra electric field, they do not have a unified physical mechanism and explain.But any is arranged is sure, and the defect state in electric resistance changing characteristic and the Dyadic transition group metallic oxide material has very strong relation.
Because the defect state that self-sow forms is difficult to Artificial Control, thus cause at present based on the productive rate of the storage component part of Dyadic transition group metallic oxide material resistance conversion characteristic not high, electric resistance changing characteristic instability.If can total amount and the distribution of Artificial Control defect state in oxide layer, the productive rate of device will obtain bigger raising so, and the performance of device also can be more stable simultaneously.
Summary of the invention
(1) technical problem that will solve
At the above-mentioned existing deficiency that exists based on the memory of Dyadic transition group metallic oxide electric resistance changing characteristic, main purpose of the present invention is to provide that a kind of manufacturing process is simple, low cost of manufacture, device yield height, the stable electric resistance transition type memory device of conversion characteristic.
(2) technical scheme
For reaching an above-mentioned purpose, the invention provides a kind of Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion, this memory comprises:
Conductive electrode on one;
Conductive electrode once;
One on this Dyadic transition group metallic oxide film between conductive electrode and the following conductive electrode, be injected with ion in this Dyadic transition group metallic oxide film, the concentration that this ion injects is 1E8cm
-2To 1E15cm
-2, and the thickness of this Dyadic transition group metallic oxide film is 20 to 200nm.
In the such scheme, described conductive electrode and the following conductive electrode employing metal gone up.
In the such scheme, described Dyadic transition group metallic oxide film adopts binary oxide zirconia, nickel oxide, titanium oxide, hafnium oxide, cobalt oxide, vanadium oxide, niobium oxide or the cupric oxide of magnesium-yttrium-transition metal.
In the such scheme, the described ion that injects in the Dyadic transition group metallic oxide film comprises metallic Z r, Hf, V, Ni, Fe, Co, Mn, Cr, W, Al, Cu, Au, Ag, Pt, Sn, perhaps nonmetal O, P, B, Ge, Si.
(3) beneficial effect
From technique scheme as can be seen, the present invention has following beneficial effect:
1, utilizes the present invention, the processing technology of device and traditional cmos process compatibility.
2, this Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion provided by the invention, the role who serves as electron trap by artificial introducing ion, make that the distribution of defect state in Dyadic transition group metallic oxide is more controlled and even, thereby make the productive rate of device be improved, make that simultaneously the device resistance conversion characteristic is more stable.
3, this Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion provided by the invention, concentration by the injection of control ion, reach the ratio between the high and low resistance state of trim, be extensive integrated the laying the first stone of device.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples:
Fig. 1 is the basic structure schematic diagram of electric resistance transition type memory device; 101 is top electrode, and 102 is bottom electrode, and 103 is functional layer.
Fig. 2 is one pole type and the Utopian i-v curve schematic diagram of ambipolar electric resistance changing memory.
Fig. 3 is the structural representation of the Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion provided by the invention; 301 is top electrode, and 302 is bottom electrode, and 303 is transition group metallic oxide, 304 ions for injection.
Fig. 4 is the i-v curve of the ambipolar non-volatile resistor transition type memory of Dyadic transition group metallic oxide that injects based on ion provided by the invention.
Fig. 5 is the i-v curve of the Dyadic transition group metallic oxide one pole type non-volatile resistor transition type memory that injects based on ion provided by the invention.
Fig. 6 is the comparison schematic diagram that has or not the Dyadic transition group metallic oxide device yield of ion injection.
Fig. 7 is based on the tolerance performance schematic diagram of the Dyadic transition group metallic oxide non-volatilization electric resistance transition type storage component part of ion injection.
The data that Fig. 8 is based on the Dyadic transition group metallic oxide non-volatilization electric resistance transition type storage component part of ion injection keep the performance schematic diagram.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
As shown in Figure 3, Fig. 3 is the structural representation of the Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion provided by the invention, this memory comprises conductive electrode 301, down conductive electrode 302, the Dyadic transition group metallic oxide film 303 on this between conductive electrode 301 and the following conductive electrode 302, is injected with ion 304 in this Dyadic transition group metallic oxide film 303.
Described conductive electrode and following conductive electrode employing metal or other the conductive electrode material gone up.
Described Dyadic transition group metallic oxide film adopts the binary oxide of magnesium-yttrium-transition metals such as zirconia, nickel oxide, titanium oxide, hafnium oxide, cobalt oxide, vanadium oxide, niobium oxide or cupric oxide, and the thickness of this Dyadic transition group metallic oxide film is 20 to 200nm.
The described ion that injects in the Dyadic transition group metallic oxide film comprises metallic particles such as Zr, Hf, V, Ni, Fe, Co, Mn, Cr, W, Al, Cu, Au, Ag, Pt, Sn, also comprise non-metallic particles such as O, P, B, Ge, Si, ion implantation concentration is 1E8cm
-2To 1E15cm
-2These artificial ions of introducing can serve as the role of electron trap, make that the distribution of defect state in Dyadic transition group metallic oxide is more controlled and even, thereby make the productive rate of device be improved, and make that simultaneously the device resistance conversion characteristic is more stable; The concentration of injecting by the control ion reaches the ratio between the high and low resistance state of trim in addition.
For the Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion provided by the invention shown in Figure 3, in one embodiment of the invention, can adopt the preparation of following method: at first by electron beam evaporation process, with heavily doped n N-type semiconductor N substrate as bottom electrode; The zirconia layer of deposit one deck 70nm on bottom electrode carries out the Zr ion to this zirconia layer then and injects then, and implantation concentration is 1E12cm
2, then under nitrogen environment and 800 ℃ of temperature conditions, carrying out the thermal anneal process of 30s, last deposit top electrode is finished the basic structure of entire device.
Fig. 4 shows the i-v curve of the ambipolar non-volatile resistor transition type memory of Dyadic transition group metallic oxide that injects based on ion provided by the invention.Fig. 4 is that the Zr ion is injected into ZrO in the explanation one embodiment of the invention
2The ratio of the high and low resistance state of formed ambipolar electric resistance transition type memory device increases greatly in the film.Illustrate that ion injects the ratio that can change based on the high and low resistance state of Dyadic transition group metallic oxide non-volatilization electric resistance transition type storage component part.
For the Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion provided by the invention shown in Figure 3, in another embodiment of the present invention, can adopt following method preparation: at first pass through electron beam evaporation process, with heavily doped n N-type semiconductor N substrate as bottom electrode, the zirconia layer of deposit one deck 70nm on bottom electrode then, and then under nitrogen environment and 800 ℃ of temperature conditions, carry out 2 minutes thermal anneal process, then this zirconia layer is carried out the Au ion and inject, implantation concentration is respectively 1E10cm
2, inject back 5 seconds of annealing under 400 ℃, nitrogen atmosphere; Last deposit top electrode is finished the basic structure of entire device.
Fig. 5,6,7, the 8th is used for illustrating the schematic diagram of another embodiment of the present invention.
Fig. 5 is the i-v curve of the Dyadic transition group metallic oxide one pole type non-volatile resistor transition type memory that injects based on ion provided by the invention.Fig. 5 is the i-v curve that gold ion is injected into formed one pole type electric resistance transition type memory device in the zirconia film in the explanation one embodiment of the invention.
Shown in Figure 4 and 5, in scandium oxide, mix different impurity and can form electric resistance transition type memory bipolar or the one pole type.
Fig. 6 is the comparison schematic diagram that has or not the Dyadic transition group metallic oxide device yield of ion injection.As shown in Figure 6, the Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory of ion injection can improve the productive rate of device greatly.
Fig. 7 is based on the tolerance performance schematic diagram of the Dyadic transition group metallic oxide non-volatilization electric resistance transition type storage component part of ion injection.As shown in Figure 7, after through more than 200 times repetitive operation, the ratio of the high and low resistance state of device has the good window distinguished greater than 70 times.
The data that Fig. 8 is based on the Dyadic transition group metallic oxide non-volatilization electric resistance transition type storage component part of ion injection keep the performance schematic diagram.As shown in Figure 8, for high resistant or low resistive state, the resistance value after through 10000 seconds does not significantly change, and has proved the non-volatile performance of device.
From the above, in each embodiment of the present invention,, carry out ion then and inject and the activator impurity of annealing by electron beam evaporation Dyadic transition group metallic oxide film.The ion of these injections can improve the productive rate of device and the stability that device changes performance greatly as the artificial defect state of introducing, and simultaneously, can increase the ratio of the high and low resistance state of device.This Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion, its manufacturing process is simple, low cost of manufacture, compatible very good with traditional silicon planar CMOS technology.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion is characterized in that this memory comprises:
Conductive electrode on one;
Conductive electrode once;
One on this Dyadic transition group metallic oxide film between conductive electrode and the following conductive electrode, be injected with ion in this Dyadic transition group metallic oxide film, the concentration that this ion injects is 1E8cm
-2To 1E15cm
-2, and the thickness of this Dyadic transition group metallic oxide film is 20 to 200nm.
2. the Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion according to claim 1 is characterized in that, described conductive electrode and the following conductive electrode employing metal gone up.
3. the Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion according to claim 1, it is characterized in that described Dyadic transition group metallic oxide film adopts binary oxide zirconia, nickel oxide, titanium oxide, hafnium oxide, cobalt oxide, vanadium oxide, niobium oxide or the cupric oxide of magnesium-yttrium-transition metal.
4. the Dyadic transition group metallic oxide non-volatilization electric resistance transition type memory that injects based on ion according to claim 1, it is characterized in that, the described ion that injects in the Dyadic transition group metallic oxide film comprises metallic Z r, Hf, V, Ni, Fe, Co, Mn, Cr, W, Al, Cu, Au, Ag, Pt, Sn, perhaps nonmetal O, P, B, Ge, Si.
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| CN102738387B (en) * | 2011-04-12 | 2014-12-03 | 中国科学院微电子研究所 | Memristor based on TiOx structure and manufacturing method of memristor |
| CN102623638B (en) * | 2012-04-19 | 2014-07-02 | 北京大学 | Resistance random access memory and preparation method thereof |
| CN103227284A (en) * | 2013-05-09 | 2013-07-31 | 北京大学 | High-consistency high-speed resistive random access memory (RRAM) and producing method thereof |
| CN103972386B (en) * | 2014-05-23 | 2017-02-08 | 中国科学院微电子研究所 | Method for preparing high-memory-density multi-value nanocrystalline memorizer |
| CN105088166B (en) | 2015-08-24 | 2017-12-15 | 中国科学院上海微系统与信息技术研究所 | A kind of inversion of phases vanadium oxide material and preparation method thereof |
| CN106887519B (en) * | 2017-03-20 | 2020-07-21 | 中国科学院微电子研究所 | Preparation method of resistive random access memory for realizing multi-value storage |
| US20210296579A1 (en) * | 2018-08-02 | 2021-09-23 | Institute of Microelectronics, Chinese Academy of Sciences | Resistive random access memory and method for preparing the same |
| CN109065712A (en) * | 2018-08-02 | 2018-12-21 | 中国科学院微电子研究所 | Resistance-variable storing device and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5923056A (en) * | 1996-10-10 | 1999-07-13 | Lucent Technologies Inc. | Electronic components with doped metal oxide dielectric materials and a process for making electronic components with doped metal oxide dielectric materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5923056A (en) * | 1996-10-10 | 1999-07-13 | Lucent Technologies Inc. | Electronic components with doped metal oxide dielectric materials and a process for making electronic components with doped metal oxide dielectric materials |
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