CN102157681A - Sb2Te3-HfO2 nano compound phase change material and application of Sb2Te3-HfO2 nano compound phase change material in phase change memory - Google Patents

Sb2Te3-HfO2 nano compound phase change material and application of Sb2Te3-HfO2 nano compound phase change material in phase change memory Download PDF

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CN102157681A
CN102157681A CN2010102639789A CN201010263978A CN102157681A CN 102157681 A CN102157681 A CN 102157681A CN 2010102639789 A CN2010102639789 A CN 2010102639789A CN 201010263978 A CN201010263978 A CN 201010263978A CN 102157681 A CN102157681 A CN 102157681A
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phase change
phase
nano
hfo
composite
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宋三年
宋志棠
吕业刚
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Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Institute of Microsystem and Information Technology of CAS
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Abstract

The invention provides a Sb2Te3-HfO2 nano compound phase change material and application of the Sb2Te3-HfO2 nano compound phase change material in a phase change memory. The Sb2Te3-HfO2 nano compound phase change material comprises the following components in percentage by weight: 2 to 30 percent of medium material HfO2 and 70 to 98 percent of Sb2Te3 phase change material; due to uniform mixing of the Sb2Te3 phase change material and the HfO2 in nanoscale, the phase change material is distributed in a nano framework structure formed by the medium material HfO2; on the one hand, the crystallization of the phase change material is restrained and the crystallizing temperature of the material is raised; on the other hand, the volatilization of the phase change material can be restrained effectively, the component segregation is improved and the stability of the material is enhanced. The novel nano compound phase change thin film is applied to the memory so that the RESET voltage of the phase change memory is reduced, and the high-density storage is realized conveniently; moreover, the heating efficiency of the phase change memory during programming is improved, the power consumption of the phase change memory is reduced, and the data retention capability, the fatigue resistant characteristic, the radiation resistance and the like are improved.

Description

Sb＜sub〉2＜/sub〉Te＜sub〉3＜/sub 〉-HfO＜sub〉2＜/sub〉nano-composite phase-changing material and the purposes in phase transition storage thereof
Technical field
The present invention relates to a kind of nano-composite phase-changing material, preparation method, reach purposes, relate in particular to a kind of Sb as phase transition storage 2Te 3-HfO 2Nano-composite phase-changing material and the purposes in phase transition storage thereof.
Background technology
Phase transition storage (C-RAM) is a kind of emerging semiconductor memory, compare with present existing multiple semiconductor memory technologies, comprise conventional volatibility technology, as static random access memory (SRAM), dynamic random access memory (DRAM) etc., and non-volatile technology, as dielectric random asccess memory (FeRAM), Electrically Erasable Read Only Memory (EEPROM), flash memory (FLASH) etc., have non-volatile, have extended cycle life (＞10 13Inferior), component size is little, low in energy consumption, can multistagely store, read at a high speed, anti-irradiation, high-low temperature resistant (55-125 ℃), anti-vibration, anti-electronic jamming and manufacturing process advantages such as simple (can and prior integrated circuit process be complementary).
Phase transition storage (C-RAM) is a storage medium with the chalcogenide compound, utilizes electric energy (heat) to make material transform writing and wiping of realization information mutually between crystalline state (low-resistance) and amorphous state (high resistant), and the variation of reading by measuring resistance of information realizes.In the C-RAM research and development, material commonly used mainly contains Ge 2Sb 2Te 5, Sb 2Te 3, GeTe etc., wherein Sb 2Te 3It is fast to have phase velocity, characteristics low in energy consumption.But the crystallization temperature of this material is lower, data confining force and thermal stability are bad, in addition, in the phase-change material that contains Sb and Te element, repetitious high temperature is write and is wiped the component segregation that operation can cause material internal itself, and Sb or Te be to segregation at the interface, and also be proved to be very big threat to device reliability with the phenomenon of active electrode material reaction.Therefore, how to improve its thermal stability with the data confining force and prevent that Elements Diffusion from just having become urgent problem.In order to reach this purpose, common way is that it is carried out doping vario-property.About the existing a large amount of bibliographical information of the work of this respect.
Nano-composite phase-changing material is a kind of novel phase-change material, it is meant that a phase-change material and dissimilar materials are compound, " learning from other's strong points to offset one's weaknesses " by between each component of composite material remedies the defective of single phase-change material, thereby reaches the purpose of optimizing phase-change material phase transformation performance.At present in phase-change material research, that has reported has a SiO 2With Ge 2Sb 2Te 5Phase-change material compound, but because SiO 2The carrier mobility that less dielectric constant and composite material are lower, SiO 2With Ge 2Sb 2Te 5The threshold voltage of composite phase-change material is higher.For the further performance of boost device, seek a kind of dielectric material that can reduce threshold voltage and RESET voltage simultaneously and seem particularly important.
Summary of the invention
The object of the present invention is to provide little, and the big Sb of dielectric constant of a kind of thermal stability height, thermal conductivity 2Te 3-HfO 2Nano-composite phase-changing material.
Another object of the present invention is to provide a kind of Sb 2Te 3-HfO 2The preparation method of nano-composite phase-changing material.
A further object of the present invention is to provide a kind of high and strong phase transition storage of data holding ability low in energy consumption, stable of phase transition process.
The preparation method who also has a purpose to be to provide a kind of phase transition storage of superior performance of the present invention.
Reach other purposes in order to achieve the above object, Sb provided by the invention 2Te 3Nano-composite phase-changing material comprises: percentage by weight is the dielectric material HfO of 2-30% 2With percentage by weight be the Sb of 70-98% 2Te 3Phase-change material.
Preferable, in the composite material that forms, described phase-change material Sb 2Te 3With dielectric material HfO 2Be uniformly dispersed.
Preferable, described phase-change material Sb 2Te 3Be the orbicule particle in composite material, its particle diameter is less than 100nm.
Comprise among the preparation method of above-mentioned nano composite material and adopt Sb 2Te 3Alloys target and HfO 2The step of target two targets sputter simultaneously.
Preferable, during sputter, the base vacuum degree is less than 10 -4Pa, sputtering pressure are 0.18-0.25Pa, and temperature is a room temperature, is added in Sb 2Te 3Be direct current 10-30 watt on the alloys target, be added in HfO 2Be radio frequency 10-50 watt on the target, sputtering time is 10-20 minute, and deposit thickness is 50-240nm.
In addition, phase transition storage provided by the invention comprises the nano-composite phase-changing material layer of the above-mentioned nano-composite phase-changing material of employing as storage medium.
The preparation method of above-mentioned phase transition storage comprises step: 1) preparation first metal electrode layer and insulating barrier on Semiconductor substrate, utilize exposure-etching technics to remove the SI semi-insulation material to form hole body; 2) adopt Sb having on the poroid Semiconductor substrate 2Te 3Alloys target and HfO 2The sputter simultaneously of target two targets forms the nano-composite phase-changing material film, so that described hole body is filled and covered to described nano-composite phase-changing material film; 3) preparation second metal electrode layer on the Semiconductor substrate that is formed with the nano-composite phase-changing material film; 4) utilize exposure-etching technics that part second metal electrode layer and nano-composite phase-changing material film are carved together once more, to form phase transition storage.
Wherein, described Semiconductor substrate can be the silicon substrate of (100) orientation; The exposure method that described exposure-etching technics adopts is an electron beam exposure, and lithographic method is a reactive ion etching.
In sum, Sb of the present invention 2Te 3-HfO 2Nano-composite phase-changing material passes through Sb 2Te 3Phase-change material and HfO 2Compound, can improve the thermal stability of material, little by its phase transition storage that constitutes power consumption in phase transition process, performances such as the fatigue properties of device, stability, data holding ability and power consumption are all promoted.
Description of drawings
Fig. 1 to Fig. 5 is Sb of the present invention 2Te 3-HfO 2Preparation method's flow chart of phase transition storage.
Fig. 6 is Sb of the present invention 2Te 3-HfO 2The XRD figure of nano-composite phase-changing material.
Fig. 7 is Sb of the present invention 2Te 3-HfO 2The resistivity of nano-composite phase-changing material and temperature relation figure.
Fig. 8 is the resistance and the voltage relationship figure of phase transition storage of the present invention.
Fig. 9 is the fatigue behaviour figure of phase transition storage of the present invention.
Embodiment
The present invention is described in detail below in conjunction with accompanying drawing.
One, Sb of the present invention 2Te 3-HfO 2Nano-composite phase-changing material is the dielectric material HfO of 2-30% by percentage by weight 2, percentage by weight is that the sulfur series compound phase-change material of 70-98% is formed, wherein, described sulfur series compound phase-change material can be Sb 2Te 3In described nano-composite phase-changing material, described phase-change material Sb 2Te 3With dielectric material HfO 2In composite material, be uniformly dispersed, and described phase-change material Sb 2Te 3Be the orbicule particle, its particle diameter is less than 100nm.The preparation method of described nano-composite phase-changing material can adopt chalcogenide compound alloys target and HfO 2Target two targets simultaneously sputter form, below to utilize magnetron sputtering to be equipped with nano combined phase-change thin film one Sb 2Te 3With HfO 2Composite material is that example illustrates.
At first, clean the silicon substrate of (100) orientation; Then, adopt Sb 2Te 3Alloys target and HfO 2Target two target co-sputtering thin films, wherein, Sb 2Te 3And HfO 2But weight ratio reference table 1.In the preparation process, the base vacuum degree is less than 10 -4Pa, sputtering pressure are 0.18-0.25Pa, and temperature is a room temperature, is added in Sb 2Te 3Be direct current 10-30 watt on the alloys target, be added in HfO 2Be radio frequency 10-50 watt on the target, sputtering time is 10-20 minute, and deposit thickness is 50-240nm.
Table 1:
Prescription 1 2 3 Comparative Examples
Sb 2Te 3(wt％) 97.8 95.2 70 100
HfO 2(wt％) 2.2 4.8 30 0
Two: phase transition storage of the present invention comprises at least: semiconductor substrate layer, the metal level as bottom electrode, insulating barrier, nano-composite phase-changing material layer and as the metal level of top electrode, wherein, the material that adopts of nano-composite phase-changing material layer is the dielectric material HfO of above-mentioned 2-30% 2With percentage by weight be the formed composite material of sulfur series compound phase-change material of 70-98%.In described nano-composite phase-changing material layer, phase-change material and HfO 2Be evenly distributed, phase-change material is three-dimensional graininess, and particle diameter is less than 100nm, and described particle can be spherical or other three-dimensional shapes.
The preparation method of described phase transition storage is as follows:
1) cleans the silicon substrate that (100) are orientated, prepare the thick metal level 2 (as tungsten) of 100nm as bottom electrode, as shown in Figure 1 with chemical vapour deposition technique (CVD) on the silicon substrate 1.
2) depositing usefulness sputtering method depositing insulating layer 3 (as silicon oxide layers) on the Semiconductor substrate of tungsten electrode, thickness is 100nm, as shown in Figure 2.
3) utilize exposure-etching technics to carve the aperture of diameter 260nm on silicon oxide layer 3: the exposure method of employing is an electron beam exposure, and lithographic method is a reactive ion etching, and structure as shown in Figure 3.
4) etching the nano combined phase-change thin film 4 of preparation on the silicon substrate of aperture: utilize Sb 2Te 3Alloys target and HfO 2Target two target co-sputtering methods prepare nano combined phase-change thin film 4, as shown in Figure 4.Preparation process as mentioned above, the prescription of nano combined phase-change thin film 4 can adopt in the table 1 prescription of 1 and 2 etc.
5) depositing Sb 2Te 3With HfO 2Deposited by electron beam evaporation method deposition 300nm metal electrode 5 (as the aluminium electrodes) on the structure of laminated film, as shown in Figure 4.
6) utilize exposure-etching technics with part aluminium electrode 5 and part Sb again 2Te 3With HfO 2Laminated film 4 is carved together and is gone, and prepares top electrode, thereby forms phase change memory device (C-RAM), as shown in Figure 5.
The nano combined phase-change thin film that forms on the aforesaid semiconductor substrate and the C-RAM device of formation have been carried out every test, content measurement has: the relation (Fig. 7) of the XRD figure of material (Fig. 6), resistivity of material and temperature, the relation of device resistance and voltage (Fig. 8), device fatigue behaviour (Fig. 9) etc.Above-mentioned means of testing is used for weighing the phase-change characteristic of material, comprises the structure and the device performance of phase transition temperature, phase transformation front and back.
Conclusion: by the observation of XRD, as shown in Figure 7, the crystallization temperature of laminated film improves, and thermal stability strengthens; By resistivity and temperature relation test, as shown in Figure 6, find HfO in composite material to composite material 2When content increased, the crystalline resistance rate of composite material increased gradually, and this helps the reduction of device power consumption.
In sum, Sb of the present invention 2Te 3-HfO 2Nano-composite phase-changing material is at Sb 2Te 3In the material, by introducing dielectric material HfO 2Form the composite material of phase-change material and dielectric material, phase-change material Sb 2Te 3Be distributed in dielectric material HfO 2In the nanometer frame structure that forms, suppressed phase-change material Sb on the one hand 2Te 3Crystallization, improved the crystallization temperature of material, on the other hand phase-change material Sb 2Te 3Volatilization obtained effective inhibition, the solute segregation situation be improved significantly, increased the stability of material.In addition, because the introducing of a large amount of crystal boundaries, the thermal conductivity of composite material reduces, and thermal loss reduces in the device operation process, helps the reduction of device power consumption.While HfO 2Introducing promoted the dielectric constant of material, help reducing of device threshold voltage.This novel nano composite phase-change film is applied in the memory, the RESET voltage of phase change memory device is reduced, help realizing the high density storage, improved the efficiency of heating surface in the programming process of phase transition storage, reduce its power consumption, promoted data holding ability, fatigue properties and anti-irradiation ability etc.
The foregoing description just lists expressivity principle of the present invention and effect is described, but not is used to limit the present invention.Any personnel that are familiar with this technology all can make amendment to the foregoing description under spirit of the present invention and scope.Therefore, the scope of the present invention should be listed as claims.

Claims (9)

1. Sb 2Te 3-HfO 2Nano-composite phase-changing material is characterized in that comprising:
Percentage by weight is the dielectric material HfO of 2-30% 2With percentage by weight be the Sb of 70-98% 2Te 3Phase-change material.
2. Sb as claimed in claim 1 2Te 3-HfO 2Nano-composite phase-changing material is characterized in that: described phase-change material Sb 2Te 3With dielectric material HfO 2In composite material, be uniformly dispersed.
3. Sb as claimed in claim 1 or 2 2Te 3-HfO 2Nano-composite phase-changing material is characterized in that: described phase-change material Sb 2Te 3Be the orbicule particle in composite material, its particle diameter is less than 100nm.
4. Sb 2Te 3-HfO 2The preparation method of nano composite material is characterized in that comprising: adopt Sb 2Te 3Alloys target and HfO 2The step of target two targets sputter simultaneously.
5. Sb as claimed in claim 4 2Te 3-HfO 2The preparation method of nano composite material is characterized in that: during sputter, the base vacuum degree is less than 10 -4Pa, sputtering pressure are 0.18-0.25Pa, and temperature is a room temperature, is added in Sb 2Te 3Be direct current 10-30 watt on the alloys target, be added in HfO 2Be radio frequency 10-50 watt on the target, sputtering time is 10-20 minute, and deposit thickness is 50-240nm.
6. phase transition storage is characterized in that: comprise the nano-composite phase-changing material layer as storage medium, the material of described nano-composite phase-changing material layer is any in the claim 1～3.
7. method for preparing phase transition storage is characterized in that comprising step:
A) preparation first metal electrode layer and insulating barrier on Semiconductor substrate utilize exposure-etching technics to remove the SI semi-insulation material to form hole body;
B) adopt Sb having on the poroid Semiconductor substrate 2Te 3Alloys target and HfO 2The sputter simultaneously of target two targets forms the nano-composite phase-changing material film, so that described hole body is filled and covered to described nano-composite phase-changing material film;
C) preparation second metal electrode layer on the Semiconductor substrate that is formed with the nano-composite phase-changing material film;
D) utilize exposure-etching technics that part second metal electrode layer and nano-composite phase-changing material film are carved together once more, to form phase transition storage.
8. the method for preparing phase transition storage as claimed in claim 7 is characterized in that: described Semiconductor substrate is the silicon substrate of (100) orientation.
9. the method for preparing phase transition storage as claimed in claim 7 is characterized in that: the exposure method that described exposure-etching technics adopts is an electron beam exposure, and lithographic method is a reactive ion etching.
CN2010102639789A 2010-08-24 2010-08-24 Sb2Te3-HfO2 nano compound phase change material and application of Sb2Te3-HfO2 nano compound phase change material in phase change memory Pending CN102157681A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104040746A (en) * 2011-11-07 2014-09-10 桑迪士克3D有限责任公司 Composition of memory cell with resistance-switching layers
CN110752292A (en) * 2019-09-24 2020-02-04 华中科技大学 Method for regulating and controlling crystallization threshold of phase-change material by using interface effect of covering layer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101660118A (en) * 2009-09-10 2010-03-03 中国科学院上海微系统与信息技术研究所 Nanometer composite phase-change material, preparation and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101660118A (en) * 2009-09-10 2010-03-03 中国科学院上海微系统与信息技术研究所 Nanometer composite phase-change material, preparation and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104040746A (en) * 2011-11-07 2014-09-10 桑迪士克3D有限责任公司 Composition of memory cell with resistance-switching layers
CN110752292A (en) * 2019-09-24 2020-02-04 华中科技大学 Method for regulating and controlling crystallization threshold of phase-change material by using interface effect of covering layer

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Application publication date: 20110817