CN103227284A - High-consistency high-speed resistive random access memory (RRAM) and producing method thereof - Google Patents
High-consistency high-speed resistive random access memory (RRAM) and producing method thereof Download PDFInfo
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- CN103227284A CN103227284A CN2013101695380A CN201310169538A CN103227284A CN 103227284 A CN103227284 A CN 103227284A CN 2013101695380 A CN2013101695380 A CN 2013101695380A CN 201310169538 A CN201310169538 A CN 201310169538A CN 103227284 A CN103227284 A CN 103227284A
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- 238000000034 method Methods 0.000 title claims description 24
- 239000000463 material Substances 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 54
- 239000002184 metal Substances 0.000 claims abstract description 54
- 150000002739 metals Chemical class 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims abstract 9
- 238000005468 ion implantation Methods 0.000 claims abstract 2
- 239000010409 thin film Substances 0.000 claims abstract 2
- 229910000314 transition metal oxide Inorganic materials 0.000 claims description 10
- 229910003070 TaOx Inorganic materials 0.000 claims description 7
- 238000005240 physical vapour deposition Methods 0.000 claims description 7
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000059 patterning Methods 0.000 claims 2
- 239000007943 implant Substances 0.000 claims 1
- 230000008569 process Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
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- 239000002019 doping agent Substances 0.000 description 3
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- -1 oxonium ion Chemical class 0.000 description 3
- 230000009471 action Effects 0.000 description 2
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- 238000009413 insulation Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- SYHGEUNFJIGTRX-UHFFFAOYSA-N methylenedioxypyrovalerone Chemical compound C=1C=C2OCOC2=CC=1C(=O)C(CCC)N1CCCC1 SYHGEUNFJIGTRX-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
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Abstract
本发明涉及一种高一致性的高速阻变存储器及其制备方法，阻变存储器包括：底电极、阻变材料薄膜和顶电极，底电极在衬底上，阻变材料薄膜有金属掺杂，掺杂的金属同时满足低导热率和高吉布斯自由能。通过离子注入方法在阻变材料薄膜中注入相应的掺杂金属；本发明中掺杂的金属需要同时满足两个条件：1）金属氧化物对应的金属与氧反应生成氧化物的吉布斯自由能低于掺杂金属对应的吉布斯自由能；2）掺杂金属及对应氧化物的导热率低于阻变材料薄膜的导热率。本发明通过选择符合条件的阻变材料、掺杂材料，用RRAM常用工艺即可制备高一致性的高速阻变存储器，较好提高阻变存储器的性能。
The invention relates to a highly consistent high-speed resistive variable memory and a preparation method thereof. The resistive variable memory comprises: a bottom electrode, a resistive material film and a top electrode, the bottom electrode is on a substrate, and the resistive material film is doped with metal. Doped metals satisfy both low thermal conductivity and high Gibbs free energy. The corresponding doped metal is implanted into the resistive material film by ion implantation; the doped metal in the present invention needs to meet two conditions at the same time: 1) the Gibbs freedom of the metal corresponding to the metal oxide to react with oxygen to form an oxide The energy is lower than the Gibbs free energy corresponding to the doped metal; 2) The thermal conductivity of the doped metal and the corresponding oxide is lower than that of the resistive material thin film. The present invention can prepare high-consistency and high-speed resistive memory by selecting qualified resistive materials and doping materials, and can improve the performance of resistive memory.
Description
Technical field
The present invention relates to resistance-variable storing device (RRAM), be specifically related to a kind of high conforming high speed resistance-variable storing device and preparation method thereof, belong to nonvolatile memory (Nonvolatile memory) and manufacturing technology field thereof in the cmos vlsi (ULSI).
Background technology
Since the transistor invention, the development of semiconductor and IC technology is promoting the progress of whole information industry and even science and technology.Since nearly half a century, followed the prediction of Moore's Law, increase fast with per speed that doubled in 18 months based on the memory device integrated level of CMOS technology.Yet along with characteristic size is constantly dwindled, especially enter the nano-scale node after, at present the scaling of main flow memory will reach capacity.Especially non-volatility memorizer, the random fluctuation of its parameter significantly increases, and integrity problem is increasingly serious.On this basis, people have proposed multiple novel non-volatility memorizer technology, comprise charge trap memory (CTM), ferroelectric memory (FeRAM), magnetic memory (MRAM), phase transition storage (PRAM), resistance-variable storing device (RRAM) etc.Wherein, RRAM is with its excellent memory property parameter,, technology simple as device architecture realize simple and with CMOS process compatible, operating voltage is low, power consumption is little, read or write speed is fast, integration density is high, good integrated potentiality of 3D etc.Become the consistent main flow non-volatility memorizer of having an optimistic view of of future generation of industry.But the present technical development of RRAM also has certain gap from practical application, and its technological challenge that faces mainly comprises: device consistency problem, switching speed optimization etc.The present invention promptly proposes solution at above problem.
The resistance-variable storing device of main flow is made of top electrode (TE), hearth electrode (BE) and middle resistive material film at present, and transition metal oxide (TMO) is because technology is simple, stable performance and become the first-selection of resistive material film, the TMO-RRAM structure as shown in Figure 1,1-top electrode wherein, 2-resistive material film, 3-hearth electrode.Voltage is V between two-plate, and under the initial condition, the TMO material generally is initial high-impedance state (IRS), and when V was increased to certain value, the resistive material became low-resistance (LRS), and this process is called as forming, and corresponding V is V
FormDevice is when low-resistance, and after applying V and reaching a certain value, the resistive material becomes high-impedance state (HRS), and this process is reset, and corresponding V is V
Reset; The resistance of high-impedance state is lower than initial high-impedance state resistance slightly behind the general reset.Like this, device applies V again and reaches a certain less than V when high resistant
FormMagnitude of voltage after, the resistive material can become low-resistance again, this process is set, corresponding V is V
SetSo cycling is the read-write process of corresponding stored device.The main flow viewpoint think resistive material low-resistance and high resistant respectively corresponding conductive filament (CF) formation and interrupt process, promptly work as V=V
SetThe time, electric field action moves metal ion or oxygen room (or being equivalent to oxonium ion) orientation, thereby has formed the conductive channel that connects upper/lower electrode, the low resistance state of corresponding resistive material in regional area; When voltage is V
ResetThe time, because the comprehensive function of electric field and heat makes passage fusing, the resistive material becomes high resistant.So moving with acting in the behavior of control resistive of heat of ion plays an important role under the electric field action.
Because the break-make at random of conductive channel among the RRAM, can produce the consistency problem of device, promptly the parameters of corresponding resistive can be in fluctuation to some extent in different components and the different switching processes; In addition, form because conductive channel (CF) is moved by metal ion or oxygen room (or being equivalent to oxonium ion), the ion translational speed has restricted the switching speed of device in a way.The present invention promptly is primarily aimed at above two aspect problems and proposes solution.
Summary of the invention
Based on foregoing, the present invention's employing is carried out metal-doped method and can effectively be improved device consistency and devices switch speed in the resistive material.Its dopant material should satisfy lower thermal conductivity, two conditions of high Gibbs free energy.
Technical scheme of the present invention is as follows: a kind of high conforming high speed resistance-variable storing device, comprise: hearth electrode, resistive material film and top electrode, hearth electrode is on substrate, and described resistive material film has metal-doped, and the metal of doping satisfies low heat conductivity and high Gibbs free energy simultaneously.
Further, described doping metals satisfies low heat conductivity: the thermal conductivity of described doping metals and corresponding oxide thereof is lower than the thermal conductivity of resistive material.
Further, described doping metals satisfies high Gibbs free energy: described doping metals generates the corresponding Gibbs free energy of oxide with the oxygen reaction and is higher than the metal and the corresponding Gibbs free energy of oxygen reaction generation oxide that metal oxide is corresponding in the resistive material film.
Further, described hearth electrode and top electrode form cross type crossbar structure.
Alternatively, described substrate adopts the Si substrate; Described upper/lower electrode material is high conductivity material: Pt, W, Ir or TiN, described resistive material selection transition metal oxide material: HfOx, TaOx, WOx.
The present invention also proposes a kind of high conforming high speed resistance-variable storing device preparation method, and its step comprises:
1) graphical hearth electrode behind the substrate splash-proofing sputtering metal;
2) the PVD sputter is carried out in the hearth electrode graphics field and form the resistive material film of forming by the transition metal oxide;
3) in described resistive material film, inject corresponding doping metals by ion injection method; Described doping metals satisfies: the metal of metal oxide correspondence is lower than the corresponding Gibbs free energy of doping metals with the Gibbs free energy that the oxygen reaction generates oxide; Described doping metals satisfies simultaneously: the thermal conductivity of doping metals and corresponding oxide is lower than the thermal conductivity of resistive material film;
4) sputter and graphical top electrode on the resistive material film are finished preparation.
Further, described substrate adopts the Si substrate; Described upper/lower electrode material is high conductivity material: Pt, W, Ir or TiN, described resistive material selection transition metal oxide material: HfOx, TaOx, WOx.
Further, at described substrate preparation insulating barrier SIO
2
Further, adopt cross type crossbar structure to prepare described hearth electrode and top electrode.
Further, corresponding doping metals all adopts Zr.
Described doping metals satisfies two conditions:
1, the thermal conductivity of doping metals and corresponding oxide thereof is lower than the thermal conductivity of resistive material; Guarantee that it is the requirement of selecting on the material that thermal conductivity is hanged down, by consulting material parameter, can just select material, and then determine corresponding doping metals according to the thermal conductivity between different oxides;
2, doping metals and the oxygen reaction Gibbs free energy that generates oxide is higher than the Gibbs free energy of metal oxide is corresponding in the resistive material film metal and oxygen reaction generation oxide.Gibbs free energy is to pass judgment on the thermodynamics standard of a chemical reaction generation complexity.
Such as metal M
1+ oxygen O generates oxide M
1The O correspondence value X of a Gibbs free energy
1, same M
2The reaction of O is the value X of a corresponding Gibbs free energy also
2, relatively these two values are supposed X
1＜X
2, M then is described
10 compares M
20 is more stable.
So guaranteeing the relation of Gibbs free energy also is to select the foundation of material.
A kind of resistance-variable storing device, its structure such as Fig. 2 show, comprise resistive material film, the top electrode of substrate, insulating barrier, hearth electrode, doping from top to bottom successively.
The specific descriptions of schematic structure are as follows:
(1) substrate adopts the Si substrate;
(2) the upper/lower electrode material is the high conductivity material, as Pt, W, Ir or TiN etc.;
(3) the resistive material can preferentially be selected the transition metal oxide material (as HfOx, TaOx, WOx etc.) of present main flow for use;
(4) doping metals in the resistive material should satisfy following two basic demands simultaneously (metal of metal oxide correspondence is M in the definition resistive material
1, doping metals is M
2): a) M
1Gibbs free energy Δ M with oxygen reaction generation oxide
1Be lower than M
2Corresponding Δ M
2, b) M
2And the thermal conductivity of corresponding oxide is lower than the thermal conductivity of resistive material.
Resistance-variable storing device prepared flow process of the present invention is as follows:
(1) PVD method splash-proofing sputtering metal Ti on the Si substrate is adopted in preparation hearth electrode BE(Bottom Electrode), and wherein Ti is as adhesion layer, and BE is the hearth electrode material, by the graphical hearth electrode of stripping technology;
(2) resistive film preparation adopts the PVD reactive sputtering method to prepare the resistive material film;
(3) resistive is material doped, injects corresponding metal impurity by the method that ion injects;
(4) preparation top electrode TE(TOP Electrode), PVD top electrode TE and graphical top electrode.
Beneficial effect of the present invention:
The present invention adopts doping to satisfy the method for low heat conductivity and higher Gibbs free energy metal material simultaneously, by selecting qualified resistive material, dopant material, can prepare high conforming high speed resistance-variable storing device with the RRAM conventional process, better improve the performance of resistance-variable storing device.
Description of drawings
TMO-RRAM resistance-variable storing device schematic diagram in Fig. 1 prior art;
Fig. 2 is the high conforming high speed resistance variation memory structure schematic diagram of the present invention;
Fig. 3 is that the high conforming high speed resistance-variable storing device of the present invention prepares the insulating barrier schematic diagram;
Fig. 4 is that the high conforming high speed resistance-variable storing device of the present invention prepares the hearth electrode schematic diagram;
Fig. 5 is that the high conforming high speed resistance-variable storing device of the present invention prepares resistive film schematic diagram;
Fig. 6 is that the high conforming high speed resistance-variable storing device of the present invention carries out metal-doped schematic diagram to the resistive film;
Fig. 7 is that the high conforming high speed resistance-variable storing device of the present invention prepares the top electrode schematic diagram;
Fig. 8 is the vertical view of unit component crossbar structure;
Wherein, 1-top electrode, 2-resistive material film, 2 '-metal impurities, 3-hearth electrode, 4-insulating barrier, 5-substrate.
Specific embodiments
Below in conjunction with the accompanying drawing in the embodiment of the invention, the technical scheme in the embodiment of the invention is clearly and completely described, be understandable that described embodiment only is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those skilled in the art belong to the scope of protection of the invention not making the every other embodiment that is obtained under the creative work prerequisite.
The RRAM design that the present invention proposes mainly contains following 3 advantages:
(1) manufacture craft is simple, and with the CMOS process compatible.
(2) the satisfy condition doping of a can effectively improve the consistency of device: condition a; The metal M of metal oxide correspondence in the resistive material
1Gibbs free energy Δ M with oxygen reaction generation oxide
1Be lower than doping metals M
2Corresponding Δ M
2, i.e. the metal M of resistive material correspondence
1Easier and oxygen reacts, and promptly has higher oxygen uptake; Otherwise, M
2Then can stay a large amount of oxygen vacancy defects on every side.To sum up, after device mixed, the most intensive doped pathway ambient oxygen vacancy defect concentration of doping metals atom was apparently higher than other zones of device, so when making alive is operated, oxygen room conductive channel (CF) is easier to be formed along this doped pathway, thereby effectively improves consistency.
(3) the satisfy condition doping of b can effectively improve devices switch speed, further improves consistency: condition b simultaneously: doping metals M
2And the thermal conductivity of corresponding oxide is low, and promptly the thermal insulation of dopant material is better, then assembles easily in its ambient heat, helps the raising of ionic mobility.Particularly, after the forming process, around doped pathway, form the conductive channel in oxygen room, because aisle resistance is low, electric current is big, thus on conductive channel, can produce more heat, because the thermal insulation of doped pathway, the heat that produces can accumulate in around the conductive channel, effectively improve the mobility of oxonium ion, thereby ensuing set and reset process can both be finished faster, promptly effectively raise the switching speed of device.
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail:
The technology that the present invention prepares high conforming high speed resistance-variable storing device is described below in conjunction with the accompanying drawings:
1) preparation insulating barrier.SiO grows on substrate 5 silicon chips
2As insulating barrier 4, as shown in Figure 3;
2) preparation hearth electrode.Splash-proofing sputtering metal Ti/Pt(thickness is about 100～200nm) on insulating barrier 4, and wherein Ti is as adhesion layer, and Pt is a hearth electrode, by the graphical hearth electrode 3 of stripping technology, as shown in Figure 4;
3) preparation resistive film.Prepare TaOx resistive material film 2 by the PVD sputtering method, (thickness about 20～50nm) as shown in Figure 5;
4) resistive is material doped.Inject metal impurities Zr2 ' by the method that ion injects at the TaOx film, as shown in Figure 6;
5) preparation top electrode, PVD sputter preparation and graphical top electrode 1, Pt is a top electrode, definition device size scope (2 μ m * 2 μ m～100 μ m * 100 μ m) as shown in Figure 7, makes high conforming high speed resistance-variable storing device.
The vertical view of unit component crossbar structure as shown in Figure 8, Fig. 1-7 performance be the sectional view of resistance-variable storing device device area, complete device architecture adopts the crossbar structure.
Claims (10)
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Cited By (3)
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| CN106229407A (en) * | 2016-09-08 | 2016-12-14 | 北京大学 | A kind of high concordance resistance-variable storing device and preparation method thereof |
| CN110931634A (en) * | 2018-08-31 | 2020-03-27 | 清华大学 | Resistive device and preparation method and design method thereof |
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| CN103594622B (en) * | 2013-11-28 | 2016-10-05 | 北京大学 | High conforming resistance variation memory structure and preparation method thereof |
| CN106229407A (en) * | 2016-09-08 | 2016-12-14 | 北京大学 | A kind of high concordance resistance-variable storing device and preparation method thereof |
| CN110931634A (en) * | 2018-08-31 | 2020-03-27 | 清华大学 | Resistive device and preparation method and design method thereof |
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