CN101783391B - Nano-composite phase change material, preparation method thereof and application thereof as phase change memory - Google Patents
Nano-composite phase change material, preparation method thereof and application thereof as phase change memory Download PDFInfo
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- CN101783391B CN101783391B CN2010101057028A CN201010105702A CN101783391B CN 101783391 B CN101783391 B CN 101783391B CN 2010101057028 A CN2010101057028 A CN 2010101057028A CN 201010105702 A CN201010105702 A CN 201010105702A CN 101783391 B CN101783391 B CN 101783391B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 46
- 239000012782 phase change material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000015654 memory Effects 0.000 title abstract description 9
- 230000008859 change Effects 0.000 title abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 60
- 238000003860 storage Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 21
- 230000007704 transition Effects 0.000 claims description 29
- 239000000758 substrate Substances 0.000 claims description 16
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- -1 chalcogenide compound Chemical class 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000004065 semiconductor Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 9
- 229910000618 GeSbTe Inorganic materials 0.000 claims description 6
- 229910001245 Sb alloy Inorganic materials 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001215 Te alloy Inorganic materials 0.000 claims description 6
- 239000002140 antimony alloy Substances 0.000 claims description 6
- CBJZJSBVCUZYMQ-UHFFFAOYSA-N antimony germanium Chemical compound [Ge].[Sb] CBJZJSBVCUZYMQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- DDJAGKOCVFYQOV-UHFFFAOYSA-N tellanylideneantimony Chemical compound [Te]=[Sb] DDJAGKOCVFYQOV-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 3
- 238000001020 plasma etching Methods 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 claims description 2
- 239000012774 insulation material Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000002349 favourable effect Effects 0.000 abstract description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract 4
- 239000000203 mixture Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 9
- 239000010409 thin film Substances 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 7
- 239000002131 composite material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000000151 deposition Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
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- 238000005566 electron beam evaporation Methods 0.000 description 1
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Abstract
The invention provides a nano-composite phase change material, a preparation method thereof and application thereof as a phase change memory. The nano-composite phase change material comprises the following components in percentage by weight: 8 to 36 percent of Ta2O5 and 64 to 92 percent of phase change material. Due to the uniform composition of the phase change material and the Ta2O5 in nanometer scales, on one hand, the growth of the phase change material crystalline grains is inhibited in the existence of Ta2O5 so that the resistivity is improved and the crystallizing temperature of the material is increased and the heat stability of the material is improved; and on the other hand, the heat conductivity of the material is reduced due to the increment of crystal boundary density, and the dielectric constant of the material is increased due to the introduce of Ta2O5, which is favorable for reducing the threshold voltage of appliances. A novel nano-composite phase change film is applied to the memory so as to reduce the RESET voltage of the phase change memory device, contribute to realizing high-density storage, improve the heating efficiency of the phase change memory in the programming process, reduce the power consumption, improve data maintaining property, fatigue property and anti-irradiation capacity and the like.
Description
Technical field
The present invention relates to a kind of nano-composite phase-changing material, and preparation method thereof, with and as the purposes of phase transition storage.
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, like static random access memory (SRAM), dynamic random access memory (DRAM) etc., and non-volatile technology; Like 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 between crystalline state (low-resistance) and amorphous state (high resistant), transform writing and wiping of realization information each other, and the variation of leaning on measuring resistance of reading of information realizes.In the C-RAM research and development, the power consumption that how to reduce device always is the emphasis of research, and for this reason, people have taked several different methods, as: the contact area that reduces electrode and phase-change material; Improve the resistance of phase-change material, promote the efficiency of heating surface; Between electrode and phase-change material or the inner thermoresistance layer that adds of phase-change material; Further improve the device architecture design, explore new structure and research and development novel phase-change material etc.
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 " through 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 a kind of nano-composite phase-changing material, with thermal stability, the thermal conductivity that reduces material that improves material, the dielectric constant that reaches the increase material etc.
Another object of the present invention is to provide a kind of preparation method of nano-composite phase-changing material.
A purpose more 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.
In order to achieve the above object, nano-composite phase-changing material provided by the invention comprises: percentage by weight is the Ta of 8-36%
2O
5, and percentage by weight be the phase-change material of 64-92%.
Wherein, said phase-change material can be chalcogenide compound, for example can be selected from germanium antimony tellurium alloy, antimony tellurium alloy and germanium antimony alloy etc.
The method for preparing nano-composite phase-changing material of the present invention mainly comprises: adopt chalcogenide compound alloys target and Ta
2O
5The sputter simultaneously of target two targets forms the step of nano-composite phase-changing material.Wherein, said chalcogenide compound can be Ge
2Sb
2Te
5
In particular, when 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 Ge
2Sb
2Te
5Be 30～60 watts of direct currents on the alloys target, be added in Ta
2O
5Be 12～30 watts of radio frequencies on the target, sputtering time is 10～20 minutes, and deposit thickness is 120～240nm.
Phase transition storage of the present invention comprises the nano-composite phase-changing material layer as storage medium, and wherein, it is the Ta of 8-36% that the material of said nano-composite phase-changing material layer adopts percentage by weight
2O
5, and percentage by weight be the formed composite material of phase-change material of 64-92%.
Preferable, said phase-change material and Ta
2O
5Can be evenly distributed, said phase-change material can be three-dimensional graininess, and particle diameter is less than 100nm.
Preferably, said three-dimensional graininess is the orbicule particle; Particle diameter is 5-30nm.
The method for preparing phase transition storage of the present invention 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) have employing chalcogenide compound alloys target and Ta on the poroid Semiconductor substrate
2O
5The sputter simultaneously of target two targets forms the nano-composite phase-changing material film, so that said hole body is filled and covered to said 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; And 4) utilize exposure-etching technics that part second metal electrode layer and nano-composite phase-changing material film are carved together once more, exposing first metal electrode layer as electrode, and then the formation phase transition storage.
Wherein, said Semiconductor substrate can be the silicon substrate of (100) orientation; The adoptable exposure method of said exposure-etching technics is an electron beam exposure, and lithographic method can be reactive ion etching etc.
In sum, nano-composite phase-changing material of the present invention passes through phase-change material and Ta
2O
5Compound, 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 all are able to promote.
Description of drawings
Fig. 1 is the transmission electron microscope sketch map of nano-composite phase-changing material of the present invention.
Fig. 2 is the resistivity and the temperature relation sketch map of nano-composite phase-changing material of the present invention.
Fig. 3 be nano-composite phase-changing material of the present invention thermal conductivity change sketch map.
Fig. 4 to Fig. 8 is a phase transition storage preparation flow sketch map of the present invention.
Fig. 9 is the electric property sketch map of phase transition storage of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention is elaborated.
One, nano-composite phase-changing material of the present invention is the Ta of 8-36% by percentage by weight
2O
5, and percentage by weight be that the phase-change material of 64-92% is formed, wherein, said phase-change material can be chalcogenide compound, as is selected from germanium antimony tellurium alloy, antimony tellurium alloy and germanium antimony alloy etc.The preparation method of said nano-composite phase-changing material can adopt chalcogenide compound alloys target and Ta
2O
5Target two targets simultaneously sputter form, below to utilize magnetron sputtering to be equipped with nano combined phase-change thin film-Ge
2Sb
2Te
5With Ta
2O
5Composite material is that example is explained.
Nano-composite phase-changing material as claimed in claim 2 is characterized in that:
At first, clean the silicon substrate of (100) orientation; Then, adopt Ge
2Sb
2Te
5Alloys target and Ta
2O
5Target two target co-sputtering thin films, wherein, Ge
2Sb
2Te
5And Ta
2O
5But weight ratio reference table 1.In the preparation process, base vacuum can be 10
-5Pa, the ar pressure during sputter can be 0.2Pa, sputtering power: be added in Ge
2Sb
2Te
5On the alloys target is 50 watts of direct currents, is added in Ta
2O
5On the target is 15 watts of radio frequencies, and sputtering time is 12 minutes, and deposit thickness is roughly 150nm.
Table 1:
| |
1 | 2 | 4 | Comparative Examples |
| ?Ge 2Sb 2Te 5(wt％) | 80 | 74 | 68 | 100 |
| ?Ta 2O 5(wt％) | 20 | 26 | 32 | 0 |
Phase-change characteristic to the nano combined phase-change thin film of above-mentioned formation; Comprise that structure and the distribution of dopant material in material etc. before and after the phase transition temperature, phase transformation have carried out multinomial test; Comprise: the relation (as shown in Figure 2) of transmission electron microscope (as shown in Figure 1), resistivity of material and temperature, thermal conductivity test (as shown in Figure 3) etc.As shown in Figure 1, through the observation of transmission electron microscope, Ge in the nano combined phase-change thin film
2Sb
2Te
5With Ta
2O
5Disperse all to compare evenly; Through resistivity and temperature relation test to nano-composite phase-changing material, as shown in Figure 2, find Ta in nano-composite phase-changing material
2O
5When content increased, its phase transition temperature moved to the high temperature direction, and the crystalline resistance rate of nano-composite phase-changing material increases gradually, and this helps the reduction of device power consumption; The crystallization temperature of nano combined phase-change thin film is higher than pure Ge
2Sb
2Te
5The crystallization temperature of film, this helps the stability and the data holding ability of material.
Two: phase transition storage of the present invention comprises at least: semiconductor substrate layer, the metal level as bottom electrode, nano-composite phase-changing material layer and as the metal level of top electrode; Wherein, the material of nano-composite phase-changing material layer employing is that above-mentioned percentage by weight is the Ta of 8-36%
2O
5, and percentage by weight be the formed composite material of phase-change material of 64-92%.In said nano-composite phase-changing material layer, phase-change material and Ta
2O
5Be evenly distributed, phase-change material is three-dimensional graininess, and particle diameter is less than 100nm, and said particle can be spherical or other three-dimensional shapes, and usually, particle diameter is preferable in the 5-30nm scope.
The preparation method of said phase transition storage is following:
1) clean the silicon substrate that two (100) are orientated, prepare the thick metal level 2 (like tungsten) of 100nm as bottom electrode with chemical vapour deposition technique (CVD) on a silicon substrate 1 therein, as shown in Figure 4.
2) depositing on the Semiconductor substrate of tungsten electrode with sputtering method depositing insulating layer 3 (like silicon oxide layer), thickness is 100nm, and is as shown in Figure 5.
3) utilize exposure-etching technics on silicon oxide layer 3, to carve the aperture of diameter 260nm: the exposure method of employing is an electron beam exposure, and lithographic method is a reactive ion etching, and structure is as shown in Figure 6.
4) etching the nano combined phase-change thin film 4 of preparation on the silicon substrate of aperture: utilize Ge
2Sb
2Te
5Alloys target and Ta
2O
5Target two target co-sputtering methods prepare nano combined phase-change thin film 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 Ge
2Sb
2Te
5With Ta
2O
5Deposited by electron beam evaporation method deposition 300nm metal electrode 5 (like the aluminium electrodes) are as shown in Figure 7 on the structure of laminated film.
6) utilize exposure-etching technics with part aluminium electrode 5 and part Ge again
2Sb
2Te
5With Ta
2O
5Laminated film 4 is carved together and gone, and prepares top electrode, thereby forms phase change memory device (C-RAM), and is as shown in Figure 8.
7) the C-RAM device that forms is carried out electrical performance testing with clock, as shown in Figure 9, the RESET voltage of the device of preparing that comprises nano composite material reduces, and device power consumption reduces.
Comprehensive above-mentioned each item test result can be known: the various performance parameters of laminated film and device performance parameter such as table 2:
Table 2:
In sum, in the nano-composite phase-changing material provided by the invention, Ta
2O
5Evenly compound with phase-change material at nano-scale, because Ta
2O
5Buffer action, phase-change material crystal grain is not easy to grow up, and has suppressed further crystallization (less crystal grain is favourable to the lifting of material and device performance); Reduced resistivity decrease speed in time; Promptly promoted data holding ability, owing to the increase of crystal boundary density, the thermal conductivity of material reduces simultaneously; (RESET) voltage that resets reduces, and phase-change material just can phase transformation with lower power consumption.In addition, little crystal grain phase-change material can solve the contradiction between phase-change material particle bigger under the high density and the less heating electrode, and it is mated more, help boost device wiping, write number of times.At last, discover Ta
2O
5Adding also can effectively promote the dielectric constant of laminated film, and the lifting of dielectric constant will make the threshold voltage of device be reduced, and for the application of low power consumption memories part big meaning arranged.In a word, nano combined phase-change thin film of the present invention has stronger thermal stability, higher resistivity, and lower thermal conductivity, higher dielectric constant, and certain breakdown characteristics are a kind of storage mediums that is fit to phase transition storage more.This novel nano composite phase-change material is applied in the memory, helps realizing the high density storage, and the efficiency of heating surface in the programming process of raising phase transition storage reduces its power consumption, promotes data holding ability, fatigue properties and anti-irradiation ability etc.
The foregoing description is just listed 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, rights protection scope of the present invention should be listed like claims.
Claims (11)
1. nano-composite phase-changing material is characterized in that comprising:
Percentage by weight is the Ta of 8-36%
2O
5, and percentage by weight be the phase-change material of 64-92%, said phase-change material is a chalcogenide compound, is selected from germanium antimony tellurium alloy, antimony tellurium alloy and germanium antimony alloy.
2. a method for preparing nano-composite phase-changing material is characterized in that comprising: adopt chalcogenide compound alloys target and Ta
2O
5The sputter simultaneously of target two targets forms the step of nano-composite phase-changing material; Nano-composite phase-changing material is the Ta of 8-36% by percentage by weight
2O
5, and percentage by weight be that the phase-change material of 64-92% is formed, wherein, said phase-change material is a chalcogenide compound, is selected from germanium antimony tellurium alloy, antimony tellurium alloy and germanium antimony alloy.
3. the method for preparing nano-composite phase-changing material as claimed in claim 2 is characterized in that: said chalcogenide compound is Ge
2Sb
2Te
5
4. phase transition storage is characterized in that: comprise the nano-composite phase-changing material layer as storage medium, the material of said nano-composite phase-changing material layer comprises that percentage by weight is the Ta of 8-36%
2O
5, and percentage by weight be the phase-change material of 64-92%, said phase-change material is a chalcogenide compound, is selected from germanium antimony tellurium alloy, antimony tellurium alloy and germanium antimony alloy.
5. phase transition storage as claimed in claim 4 is characterized in that: said phase-change material and Ta
2O
5Be evenly distributed.
6. phase transition storage as claimed in claim 4 is characterized in that: said phase-change material is three-dimensional graininess, and particle diameter is less than 100nm.
7. phase transition storage as claimed in claim 6 is characterized in that: said three-dimensional graininess is the orbicule particle.
8. phase transition storage as claimed in claim 7 is characterized in that: said particle diameter is 5-30nm.
9. method for preparing phase transition storage is characterized in that comprising 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) have employing chalcogenide compound alloys target and Ta on the Semiconductor substrate of hole body
2O
5The sputter simultaneously of target two targets forms the nano-composite phase-changing material film, so that said hole body is filled and covered to said nano-composite phase-changing material film; Nano-composite phase-changing material is the Ta of 8-36% by percentage by weight
2O
5, and percentage by weight be that the phase-change material of 64-92% is formed, wherein, said phase-change material is a chalcogenide compound, is selected from germanium antimony tellurium alloy, antimony tellurium alloy and germanium antimony alloy;
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, exposing first metal electrode layer as electrode, and then the formation phase transition storage.
10. the method for preparing phase transition storage as claimed in claim 9 is characterized in that: said Semiconductor substrate is the silicon substrate of (100) orientation.
11. the method for preparing phase transition storage as claimed in claim 9 is characterized in that: the exposure method that said exposure-etching technics adopts is an electron beam exposure, and lithographic method is a reactive ion etching.
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| CN102169958B (en) * | 2011-04-29 | 2013-07-10 | 中国科学院上海微***与信息技术研究所 | Nanocomposite phase-change material, preparation method and application thereof in phase-change memory |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020074658A1 (en) * | 2000-12-20 | 2002-06-20 | Chien Chiang | High-resistivity metal in a phase-change memory cell |
| CN101110464A (en) * | 2007-08-01 | 2008-01-23 | 中国科学院上海微***与信息技术研究所 | Heating layer for reducing phase-change memory device unit power consumption and its manufacturing method |
| US20090201716A1 (en) * | 2008-02-12 | 2009-08-13 | Klaus-Dieter Ufert | Memory Element with Positive Temperature Coefficient Layer |
| CN101521260A (en) * | 2009-03-25 | 2009-09-02 | 中国科学院上海微***与信息技术研究所 | Nano composite phase-change material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020074658A1 (en) * | 2000-12-20 | 2002-06-20 | Chien Chiang | High-resistivity metal in a phase-change memory cell |
| CN101110464A (en) * | 2007-08-01 | 2008-01-23 | 中国科学院上海微***与信息技术研究所 | Heating layer for reducing phase-change memory device unit power consumption and its manufacturing method |
| US20090201716A1 (en) * | 2008-02-12 | 2009-08-13 | Klaus-Dieter Ufert | Memory Element with Positive Temperature Coefficient Layer |
| CN101521260A (en) * | 2009-03-25 | 2009-09-02 | 中国科学院上海微***与信息技术研究所 | Nano composite phase-change material and preparation method thereof |
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