CN1996633A - Phase-varying storage layer, its making method and phase-varying storage unit - Google Patents
Phase-varying storage layer, its making method and phase-varying storage unit Download PDFInfo
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- CN1996633A CN1996633A CN 200510137671 CN200510137671A CN1996633A CN 1996633 A CN1996633 A CN 1996633A CN 200510137671 CN200510137671 CN 200510137671 CN 200510137671 A CN200510137671 A CN 200510137671A CN 1996633 A CN1996633 A CN 1996633A
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Abstract
This invention discloses one phase change memory layer and its process method and relative memory unit, which adds one or more heterogenic particles non reacting to the materials as crystal nuclear as phase change memory layer to reduce the needed time to convert non-crystal status into crystal status.
Description
Technical field
The present invention relates to the phase change accumulation layer, one or more do not react with phase-transition material particularly to relate to interpolation, and not with the heterogeneous tiny crystal grains of temperature change material character, as phase change accumulation layer and the manufacture method and the phase change memory cell of the nucleus of phase change layer crystalline growth.
Background technology
Phase-change memory element is realized the purpose that writes and reset by the transition between phase change accumulation layer generation crystalline state and the noncrystalline attitude.When the phase change accumulation layer is in non-crystalline state (having chaotic atomic structure of arranging), will presents high resistance, and when the phase change accumulation layer is in crystalline state (atomic structure with proper alignment), then present low-resistance value.Therefore, the phase change accumulation layer can produce reversible alternate as a kind of nonvolatile programmable resistance between high resistance and low-resistance value.
The phase change accumulation layer is formed by the sulfur family material (Chalcogenide) with amorphous/crystallization two-phase translation function.S.R.Ovsinsky once proposed Tc in U.S. Patent number is 3,530,441 patent
85Ge
15With Te
81Ge
15S
2Sb
2These the two kinds storage mediums that can carry out reversible transitionization under the high energy laser irradiation, the sulfur family material promptly becomes the focus of everybody research afterwards.The phase change storage medium of development all belonged to the sulfur family material successively afterwards, for example GeTe, InSe, InSeT1, GeTeSb and GeTeSnAu or the like.Wherein the GeSbTe system of being developed with Japanese Matsushita company is attracted attention by everybody most.
Japan Matsushita company once delivered the many pieces of United States Patent (USP)s about the GeSbTe system, as on August 3rd, 1993 U.S.'s patent No. be to disclose a kind of GeSbTe GeSb in ternary phase diagrams in 5,233,599 the patent
2Te
4With Ge on the Sb on line
12Sb
39Te
49A certain G point form, (44～54at.%Te) have best storage characteristics (lower jitter (shake) value) for 7～17 atomic percents (at.%) Ge, 34～44at.%Sb near the compositing range the G point.
In addition, on January 11st, 1994, U.S.'s patent No. was then to be set forth in GeTe-Sb in 5,278,011 the patent
2Te
3With GeTe-BiTe
3Intend replacing the Te of part with Se, or adding an amount of Bi element near the compositing range of bianry alloy line, its objective is when improving the storage susceptibility, can keep crystallization rate fast again.
At present, the service speed of phase-change memory element depends on the rate of transformation of phase change accumulation layer.But the phase change accumulation layer adopts Ag-In-Te-Sb to form more, it is for being used for the material of phase change layer now, yet crystallization temperature is higher relatively, therefore, the phase change accumulation layer is longer relatively by the time that amorphous structure is converted to the crystalline state structure, when resetting, also need the long time, fully the amorphous structure of phase change layer is converted to the crystalline state structure, this is because be subject to phase-change material crystallization time, the just required pregnant nuclear and the time of crystal grain-growth.
Summary of the invention
The technical problem that the present invention mainly solves is to provide a kind of phase change accumulation layer and manufacture method and phase change memory cell, main by in phase-change material layer, manufacturing the nucleus of heterogeneous tiny crystal grains as phase change accumulation layer crystalline growth, be converted to the required time of crystalline state to reduce amorphous state, and then improve the service speed of phase-change memory element.
The manufacture method of phase change accumulation layer disclosed in this invention, described phase change accumulation layer provides by transition between noncrystalline attitude and the crystalline state, this manufacture method comprises the following steps: at first, by a plurality of heterogeneous passivating material thin layers and a plurality of phase-change material layer interlaced form laminated; And be a plurality of crystal grain with the transition of a plurality of heterogeneous passivating material thin layer, wherein crystal grain is as the nucleus position during transition between noncrystalline attitude and the crystalline state.
The material of heterogeneous passivating material thin layer need select not the phase-transition material with phase-change material layer to react and not with the material of temperature change character, and material selects to comprise oxide, nitride or carbide preferably.
Moreover, can carry out annealing process (process annealing), plate in film process, plasma method for implantation and the ion implantation method any one or more altogether heterogeneous passivating material thin layer, making the transition of heterogeneous passivating material thin layer is a plurality of crystal grain.
In addition, the invention also discloses the phase change accumulation layer of using preceding method to form, comprising: phase-change material layer.Comprise a plurality of crystal grain in this phase-change material layer, crystal grain by a plurality of phase-change material layer and a plurality of heterogeneous passivating material thin layer interlaced form laminated after, again by the transition and forming in laminated of heterogeneous passivating material thin layer, wherein crystal grain is as the nucleus position during transition between noncrystalline attitude and the crystalline state.
The material of heterogeneous passivating material thin layer comprises silica (SiO
X), silicon nitride (SiN
X), titanium oxide (TiO
X), tantalum oxide (TaO
X), aluminium oxide (Al
2O
3) or carbonitride (CN
X) or the like, and the phase-transition material of phase-change material layer can be selected the sulfur family material.
Phase change memory cell disclosed in this invention comprises: first dielectric layer, first electrode (or being called heating electrode), phase-change material layer, second dielectric layer and second electrode.First electrode then is positioned at first dielectric layer, phase-change material layer then is positioned on first electrode, and have a plurality of crystal grain, each crystal grain by a plurality of phase-change material layer and a plurality of heterogeneous passivating material thin layer interlaced form laminated after, the transition and forming in laminated of the heterogeneous passivating material thin layer of each layer, wherein crystal grain is as the nucleus position during transition between noncrystalline attitude and the crystalline state.
Second dielectric layer is positioned on the phase-change material layer, and second electrode then is positioned at second dielectric layer.
Wherein, the phase-change material layer in phase change memory cell is aforementioned phase-change material layer disclosed in this invention.
To in embodiment, be described in detail detailed features of the present invention and advantage below, it can make those of ordinary skills understand technology contents of the present invention and implement with this, and according to the disclosed content of this specification, claim and accompanying drawing, those of ordinary skill in the art all can understand purpose and the advantage that the present invention is correlated with easily.
Description of drawings
Figure 1A and Figure 1B are phase change accumulation layer of the present invention and manufacture method thereof;
Fig. 2 provides the nucleus position of phase change reaction for heterogeneous crystal grain;
Tension force and stress that Fig. 3 provides for heterogeneous crystal grain; And
Fig. 4 is the phase change memory cell with phase change accumulation layer of the present invention.
Wherein, Reference numeral:
10: phase-change material layer 20: heterogeneous passivating material thin layer
21: crystal grain 30: laminated
40: 50: the first dielectric layers of nucleus
70: the second dielectric layers of 60: the first electrodes
80: the second electrodes
Embodiment
Usually, utilize the properties of materials that changes phase-change material layer 10 to improve the service speed of phase-change memory element, for example doped tin (Sn), antimony (Sb), arsenic (As), selenium (Se), sulphur (S), oxygen (O) and bismuth elements such as (Bi), and then change the growth mechanism (just transition amorphous state and crystalline state between) of phase-change material layer 10 when phase change is reacted; But this method is in the process of carrying out repeatedly the phase change reaction, and doped chemical can produce phenomenon pockety, thereby causes repeating the uncertain of erasable number of times, easily causes phase-change memory element to need bigger power operation; Yet, the present invention does not change the material of phase-change material layer 10, but make the heterogeneous tiny crystal grains 21 that one or more do not react with phase-change material layer 10, the nucleus 40 of growing up during as the phase-transition material crystallization in noncrystalline zone is converted to the required time of crystalline state to reduce noncrystalline attitude.
Consult Figure 1A and Figure 1B explanation according to phase change accumulation layer provided by the invention and manufacture method thereof, the phase change accumulation layer is used to carry out the phase change reaction, also is to change crystalline state into by noncrystalline attitude.At first, consult Figure 1A with chemical vapour deposition (CVD) (Chemical Vapor Deposition, CVD) method, or physical vapour deposition (PVD) (Physical Vapor Deposition, PVD) method is with one or more heterogeneous passivating material (silica (SiO for example
X), silicon nitride (SiN
X), titanium oxide (TiO
X), tantalum oxide (TaO
X), aluminium oxide (Al
2O
3) and carbonitride (CN
X) or the like) and with phase-transition material (for example sulfur family material) form by a plurality of heterogeneous passivating material films 20 and a plurality of phase-change material layer 10 interlaced laminated 30.
Here, in the interlaced film laminated 30, the thickness of heterogeneous passivating material thin layer 20 is preferably 1nm～3nm, and laminated 30 1/2～1/3 places that are formed on the phase change accumulation layer, and needs the position near the heating electrode of phase-change memory element.
Then, annealing process (process annealing) is carried out in laminated 30 of interlaced formation, make that laminated 30 interior heterogeneous passivating material thin layer 20 transitions are crystal grain 21, just utilize the thermal expansion coefficient difference between heterogeneous passivating material and the phase-transition material, making the transition in interlaced laminated 30 of heterogeneous passivating material thin layer 20 is a plurality of spherical, thread or crystal grain of irregularly shaped existence 21, and these crystal grain 21 must be evenly distributed in the phase-change material layer 10, shown in Figure 1B.
Wherein, can also use in common plating film process, plasma method for implantation and the ion implantation method any one or more to make the transition in laminated 30 of heterogeneous passivating material thin layer 20 is a plurality of crystal grain 21.
Moreover Figure 1B also is according to phase change accumulation layer provided by the invention, and this phase change accumulation layer comprises: phase-change material layer 10.This phase-change material layer 10 is after forming interlaced laminated 30 earlier by a plurality of phase-change material layer 10 and a plurality of heterogeneous passivating material thin layer 20, again with the transition in laminated 30 of a plurality of heterogeneous passivating material thin layer 20, forming a plurality of crystal grain 21, and crystal grain 21 is as nucleus 40 positions during transition between noncrystalline attitude and the crystalline state.
In addition, the material of foregoing heterogeneous passivating material thin layer 20 need select not the material with phase-change material layer 10 to react and not with the material of temperature change character, and material selects to comprise oxide, carbide or nitride preferably.Therefore, carry out phase change when reaction when the phase change accumulation layer, any chemical reaction does not take place with phase-transition material in small heterogeneous crystal grain 21, can prevent known technology owing to doped chemical produces phenomenon pockety.
In other words, equally distributed small heterogeneous crystal grain 21 carries out phase change seasonable (just changing crystalline state into by noncrystalline attitude) in the phase change accumulation layer, the position of growth nucleus 40 when small heterogeneous crystal grain 21 provides the phase-transition material crystallization in noncrystalline zone, as shown in Figure 2, to reduce the phase change required time of breeding nucleus 40 of course of reaction, realize changing mutually fast, and then reduce the required power consumption of phase change reaction.
Moreover, phase-change memory element has the ability of rewritable, when reducing the phase change accumulation layer by foregoing doped chemical technology and carry out the time of phase change reaction, after repeatedly phase change is reacted, institute's doping elements can produce phenomenon pockety in the phase change accumulation layer, so that the phase change accumulation layer can't return back to noncrystalline attitude from crystalline state accurately, can repeat the uncertain of erasable number of times and produce.
Yet,, make the phase change accumulation layer return back to noncrystalline attitude from crystalline state more accurately, as shown in Figure 3 though foundation phase change accumulation layer provided by the invention still can provide tension force and stress by small heterogeneous crystal grain 21 through repeatedly phase change reaction.
According to phase change accumulation layer provided by the invention and manufacture method thereof, heterogeneous passivating material thin layer 20 transitions are formed a plurality of crystal grain 21, crystal grain 21 is nucleus 40 positions during transition between this noncrystalline attitude of conduct and this crystalline state then, make the phase change accumulation layer provide tension force and stress by small heterogeneous crystal grain 21, during with the crystallization of minimizing phase-change material, the time that required pregnant nuclear and nucleus 40 are grown up, and then the service speed of raising phase-change memory element.
In addition, seeing also Fig. 4 will be applied in the phase change memory cell according to phase change accumulation layer provided by the present invention, and phase change memory cell comprises: first dielectric layer 50, first electrode 60 (also can be described as heating electrode), phase-change material layer 10, second dielectric layer 70 and second electrode 80.
Wherein, also can utilize in common plating film process, plasma method for implantation and the ion implantation method any one or more to realize that the transition in laminated 30 of heterogeneous passivating material thin layer 20 is a plurality of crystal grain 21.The material of heterogeneous passivating material thin layer 20 can be selected from nitride, oxide or carbide, and nitride, oxide or carbide further comprise silica (SiO
X), silicon nitride (SiN
X), titanium oxide (TiO
X), tantalum oxide (TaO
X), aluminium oxide (Al
2O
3) or carbonitride (CN
X) or the like.
In addition, second dielectric layer is positioned on the phase-change material layer 10, and second electrode 80 then is positioned at second dielectric layer 70.
Wherein, the material of first electrode (or being called heating electrode) 60 can be the electric conducting material of titanium (Ti), tantalum (Ta), titanium nitride (TiN), tantalum nitride (TaN), nitrogen titanium aluminide (TiAlNx), titanium carbonitride (TiCNx), tungsten tantalum (TaW), tungsten titanium (TiW), tantalum oxide (TaOx), polysilicon (poly-Si), tantalum silicon oxide (TaSiO), carbon (C), carbon silicide (SiC), germanium nitride high value such as (GeN).And the material of first dielectric layer 50 and second dielectric layer 70 can be silicon dioxide (SiO
2), silicon nitride (Si
3N
4) wait dielectric material.The material of second electrode 80 can be conduction favorable conductive materials such as aluminium (Al), tungsten (W), molybdenum (Mo), titanium (Ti), copper (Cu).
In addition, this phase change memory cell also can utilize known CMOS (Complementary Metal Oxide Semiconductor) (Complementary Metal-Oxide Semiconductor; CMOS) technology is finished.
Though disclose preferred implementation of the present invention as mentioned above; yet it is not to be used to limit the present invention, for those of ordinary skill in the art, under the premise without departing from the spirit and scope of the present invention; for various distortion and the improvement that the present invention did, all belong to protection scope of the present invention.Protection scope of the present invention is limited by the present invention appended claim and equivalent thereof.
Claims (15)
1, a kind of manufacture method of phase change accumulation layer, described phase change accumulation layer is provided at transition between a noncrystalline attitude and the crystalline state, it is characterized in that, and described manufacture method comprises the following steps:
By a plurality of heterogeneous passivating material thin layers and a plurality of phase-change material layer interlaced form one laminated; And
With described these heterogeneous passivating material thin layer transitions is a plurality of crystal grain, and wherein said these crystal grain are as the nucleus position during transition between described noncrystalline attitude and the described crystalline state.
2, the manufacture method of phase change accumulation layer according to claim 1, it is characterized in that, described these heterogeneous passivating material thin layer transitions are in the step of a plurality of crystal grain, the material of described heterogeneous passivating material thin layer is selected from mononitride, monoxide or monocarbide, and wherein said nitride, described oxide or described carbide comprise silica (SiO
X), silicon nitride (SiN
X), titanium oxide (TiO
X), tantalum oxide (TaO
X), aluminium oxide (Al
2O
3) or carbonitride (CN
X).
3, the manufacture method of phase change accumulation layer according to claim 1 is characterized in that, in forming a laminated step, adopts a chemical vapor deposition (CVD) method.
4, the manufacture method of phase change accumulation layer according to claim 1 is characterized in that, in forming a laminated step, adopts a physical vapor deposition (PVD) method.
5, the manufacture method of phase change accumulation layer according to claim 1, it is characterized in that, the transition of described heterogeneous passivating material thin layer is the step of a plurality of crystal grain, can select an annealing process for use, plate film process, a plasma method for implantation one ion implantation method (group of composition altogether.
6, a kind of phase change accumulation layer, the transition between a noncrystalline attitude and a crystalline state of described phase change accumulation layer is characterized in that, comprising:
One phase-change material layer, comprise a plurality of crystal grain in the described phase-change material layer, described these crystal grain by a plurality of phase-change material layer and a plurality of heterogeneous passivating material thin layer interlaced form one laminated after, described these heterogeneous passivating material thin layers described laminated in transition and forming, wherein said these crystal grain are as the nucleus position during transition between described noncrystalline attitude and the described crystalline state.
7, phase change accumulation layer according to claim 6, it is characterized in that, the material of described heterogeneous passivating material thin layer is selected from mononitride, monoxide or monocarbide, and wherein said nitride, described oxide or described carbide comprise silica (SiO
X), silicon nitride (SiN
X), titanium oxide (TiO
X), tantalum oxide (TaO
X), aluminium oxide (Al
2O
3) or carbonitride (CN
X).
8, phase change accumulation layer according to claim 6, it is characterized in that described these heterogeneous passivating material thin layers select an annealing process for use, plate group's transition that film process, a plasma method for implantation and an ion implantation method form altogether forms described these crystal grain.
9, phase change accumulation layer according to claim 6 is characterized in that, described laminated employing one chemical vapor deposition (CVD) method forms.
10, phase change accumulation layer according to claim 6 is characterized in that, described laminated employing one physical vapor deposition (PVD) method forms.
11, a kind of phase change memory cell is characterized in that, includes:
One first dielectric layer;
One first electrode is positioned at described first dielectric layer;
One phase-change material layer, be positioned on described first electrode, have a plurality of crystal grain, wherein, described these crystal grain by a plurality of phase-change material layer and a plurality of heterogeneous passivating material thin layer interlaced form one laminated after, described these heterogeneous passivating material thin layers described laminated in transition and forming, wherein said these crystal grain are as the nucleus position during transition between described noncrystalline attitude and the described crystalline state;
One second dielectric layer is positioned on the described phase-transition material; And
One second electrode is positioned at described second dielectric layer.
12, phase change memory cell according to claim 11, it is characterized in that, the material of described heterogeneous passivating material thin layer is selected from mononitride, monoxide or monocarbide, and wherein said nitride, described oxide or described carbide comprise silica (SiO
X), silicon nitride (SiN
X), titanium oxide (TiO
X), tantalum oxide (TaO
X), aluminium oxide (Al
2O
3) or carbonitride (CN
X).
13, phase change memory cell according to claim 11, it is characterized in that described these heterogeneous passivating material thin layers select an annealing process for use, plate group's transition that film process, a plasma method for implantation and an ion implantation method form altogether forms described these crystal grain.
14, phase change memory cell according to claim 11 is characterized in that, described laminated employing one chemical vapor deposition (CVD) method forms.
15, phase change memory cell according to claim 11 is characterized in that, described laminated employing one physical vapor deposition (PVD) method forms.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393964B (en) * | 2007-09-20 | 2010-07-21 | 台湾积体电路制造股份有限公司 | Phase change memory with various grain sizes and forming method thereof |
| CN102237390A (en) * | 2010-04-29 | 2011-11-09 | 台湾积体电路制造股份有限公司 | Semiconductor device and method of manufacturing same |
| CN110335941A (en) * | 2019-07-03 | 2019-10-15 | 芯盟科技有限公司 | Structure of phase transition storage and forming method thereof |
| WO2020001510A1 (en) * | 2018-06-29 | 2020-01-02 | 中车石家庄车辆有限公司 | Energy storage device |
| CN113571635A (en) * | 2020-09-16 | 2021-10-29 | 中国科学院上海微系统与信息技术研究所 | Gating tube material, gating tube unit, preparation method and memory structure |
-
2005
- 2005-12-31 CN CN 200510137671 patent/CN1996633A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393964B (en) * | 2007-09-20 | 2010-07-21 | 台湾积体电路制造股份有限公司 | Phase change memory with various grain sizes and forming method thereof |
| CN102237390A (en) * | 2010-04-29 | 2011-11-09 | 台湾积体电路制造股份有限公司 | Semiconductor device and method of manufacturing same |
| CN102237390B (en) * | 2010-04-29 | 2013-08-21 | 台湾积体电路制造股份有限公司 | Semiconductor device and method of manufacturing same |
| WO2020001510A1 (en) * | 2018-06-29 | 2020-01-02 | 中车石家庄车辆有限公司 | Energy storage device |
| CN110335941A (en) * | 2019-07-03 | 2019-10-15 | 芯盟科技有限公司 | Structure of phase transition storage and forming method thereof |
| CN110335941B (en) * | 2019-07-03 | 2023-08-18 | 芯盟科技有限公司 | Phase change memory structure and forming method thereof |
| CN113571635A (en) * | 2020-09-16 | 2021-10-29 | 中国科学院上海微系统与信息技术研究所 | Gating tube material, gating tube unit, preparation method and memory structure |
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