CN101660118A - Nanometer composite phase-change material, preparation and application thereof - Google Patents
Nanometer composite phase-change material, preparation and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 24
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- 239000010703 silicon Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- -1 chalcogenide compound Chemical class 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
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Abstract
The invention belongs to the microelectronics technical field, particularly relates to a nanometer composite phase-change thin film and preparation and an application thereof. In the invention, the nanometer composite phase-change material is formed by compounding 12-36% of HfO2 with 64-88% of the phase-change material according to the weight percent. The nanometer composite phase-change thin filmcan be applied to a memory, thus being beneficial to realizing high-density storage, improving heating efficiency of a phase-change memory during a programming process, reducing power consumption, and enhancing data retention capability, fatigue property and irradiation resistance capability.
Description
Technical field
The invention belongs to microelectronics technology, relate in particular to a kind of nano combined phase-change thin film and preparation thereof and application.
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 RAM (SRAM), dynamic RAM (DRAM) etc., and non-volatile technology, as ferroelectric random storer (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 media 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 non-crystalline state (high resistant), and the variation of reading by measuring resistance of information realizes.In C-RAM research and development, be to improve one of gordian technique of C-RAM device performance as the research and development of the phase change material of memory media and the lifting of performance.In phase change material crystalline process, the crystal grain of phase change material constantly increases, and growing up of phase change material crystal grain is the resistance main reasons for decrease, so the restriction of grain size is had important meaning to the lifting of memory data confining force.In addition, the trend that size is constantly dwindled in bigger crystal grain and the research and development of current phase transition storage is contradiction, and the appearance of big crystal grain has negative influence for the reliability of C-RAM device.So in highdensity C-RAM, should avoid the appearance of big crystal grain as far as possible, it is the problem that must face in the middle of the present C-RAM research and development that the size that effectively reduces phase change material crystal grain makes it be fit to the following semiconductor process techniques of 90nm more.On the other hand, in order to reduce the power consumption of phase transition storage, people have taked several different methods: the contact area that reduces electrode and phase change material in the C-RAM research and development; Improve the resistance of phase change material, promote heating efficiency; Between electrode and phase change material or the inner thermoresistance layer that adds of phase change material; Further improve the device architecture design, explore novel texture 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 " by between each component of matrix 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, Si and Sb
2Te
3Phase change material compound.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of novel nano composite phase-change material and preparation and application, by with phase change material and HfO
2Compound, improve the thermostability of material, reduce the power consumption in the device phase transition process, under the situation that does not change device architecture, can boost device stability, performances such as data holding ability and power consumption.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme: a kind of nano-composite phase-changing material, this nano-composite phase-changing material is to use HfO
2Be composited with phase change material, wherein, HfO
2Weight percent be 12-36%, the weight percent of phase change material is 64-88%.
Preferable, phase change material and HfO
2In composite phase-change material, be uniformly dispersed and phase change material is limited in by HfO
2In the zone of the nanometer scale of surrounding.
The particle of described phase change material can be spherule or other three-dimensional shapes, and preferred spherule, particle diameter are less than 100nm, and preferred particle diameter is 5-30nm.
Phase change material can be chalcogenide compound.In C-RAM, be germanium antimony tellurium alloy (Ge-Sb-Te) at present, and phase change material in the present invention can be germanium antimony tellurium alloy (Ge-Sb-Te), also can be antimony tellurium alloy (Sb-Te) or germanium antimony alloy a series of materials such as (Ge-Sb) with more phase change material.
Described HfO
2Chemical reaction does not take place with phase change material.
Phase change material in the nano-composite phase-changing material has the reversible phase-change characteristic, and the material before and after the reversible transformation has different resistivity, or different optical reflectivities is arranged.Nano-composite phase-changing material of the present invention is being introduced HfO
2After, the matrix material that obtains keeps original reversible transformation characteristic, and the laminated film before and after the phase transformation has different resistivity, or different optical reflectivities is arranged.And HfO
2Adding can further optimize the phase change material performance, as improved the heating efficiency in the memory program process, reduced programming power consumption, the thermostability of laminated film and reliability are significantly improved etc.
Nano-composite phase-changing material of the present invention can adopt semiconductor deposition process preparation, as in sputtering method, chemical Vapor deposition process, pulsed laser deposition method, sol-gel method or the ion implantation any.Phase change composite material of the present invention is in the preparation phase change material and HfO
2Uniform mixing makes HfO
2The phase change material homodisperse is become size and the uniform nano-scale of shape zone, thereby the reversible transformation of phase change material is limited in tiny area.
Preferably, nano-composite phase-changing material of the present invention adopts Ge
2Sb
2Te
5Alloys target and HfO
2The preparation of target two target co-sputtering methods.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; Sputtering power: be added in Ge
2Sb
2Te
5Be 30~60 watts of direct currents on the alloys target, be added in HfO
2Be 15~45 watts of radio frequencies on the target, sputtering time is 10~20 minutes, and deposit thickness is roughly 120~240nm.
As one of disclosed preferred version of the embodiment of the invention, be added in Ge in the process of preparation nano-composite phase-changing material
2Sb
2Te
5On the alloys target is 50 watts of direct currents, is added in HfO
2On the target is 45 watts of radio frequencies, and sputtering time is 14 minutes, and deposit thickness is 180nm.
Nano-composite phase-changing material of the present invention can be used for preparing the phase transition storage of chalcogenide compound.Nano-composite phase-changing material of the present invention can effectively reduce the programming power consumption of device, prolongs working life, promotes memory data hold facility and anti-irradiation ability etc.
The present invention further provides a kind of phase transition storage, its storage media is aforementioned nano-composite phase-changing material.
Described phase transition storage can be various employing Transformation Principle and carries out the functional device of data storage, as chalcogenide compound random access memory for adopting electricimpulse to programme, or for adopting the stored CD of laser pulse programming, or storer, or for adopting the storer of other energy particle programming for adopting electron beam to programme.
The invention still further relates to a kind of preparation method of phase transition storage, this method may further comprise the steps,
1) cleans substrate, prepare tungsten electrode on the substrate therein;
2) depositing silicon oxide layer deposited on the substrate of tungsten electrode;
3) utilize exposure-etching technics on the silicon oxide layer of substrate, to carve aperture and obtain the aperture substrate;
4) the aforementioned nano combined phase-change thin film of preparation on the aperture substrate;
5) depositing deposition of aluminum electrode on the aperture substrate of nano combined phase-change thin film;
6) utilize exposure-etching technics that part aluminium electrode and the nano combined phase-change thin film of part are carved together again, prepare top electrode, thereby form C-RAM device (chalcogenide compound random access memory).
Preferable, the silicon substrate of described substrate preferred (100) orientation.
Preferable, the exposure method that described exposure-etching technics adopts is an electron beam exposure, lithographic method is a reactive ion etching.
In the described step 3, the diameter of aperture is less than 300nm.
In the described step 6, part aluminium electrode and the nano combined phase-change thin film of part are carved together, made remaining aluminium electrode and nano combined phase-change thin film can cover aperture, and can expose the partial oxidation silicon layer on the substrate.
In nano-composite phase-changing material of the present invention, HfO
2With phase change material be separated into shape and controlled amount, uniformly, the zone of nano-scale, thereby the phase change limitation of phase change material in the zonule, owing to small-size effect and HfO
2The adiabatic heat-insulation effect that parcel produces, phase change material is with the just energy phase transformation of lower power consumption, simultaneously because HfO
2Buffer 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), has reduced resistivity lowering speed in time, has promptly promoted data holding ability.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 HfO
2Adding also can effectively promote the mean heat capacity of laminated film, and the power that the lifting of thermal capacitance will effectively reduce in the phase transition process to be consumed has big meaning for the application of low power consumption memories part.In a word, nano combined phase-change thin film of the present invention has stronger thermostability, higher resistivity, and higher mean heat capacity, and certain dielectric characteristics and resistance wear performance capability, is a kind of storage media that is fit to phase transition storage more.This novel nano composite phase-change material is applied in the storer, helps realizing the high-density storage, and the heating efficiency in the programming process of raising phase transition storage reduces its power consumption, promotes data holding ability, fatigue characteristic and anti-irradiation ability etc.
Description of drawings
Fig. 1-the 5th, C-RAM device preparation technology schema in the embodiment of the invention 2;
Fig. 1: be the tungsten electrode of preparation 100nm on silicon substrate
Fig. 2: for continuing the silicon oxide of deposition 100nm again
Fig. 3: for etch the hole of 260nm diameter with exposure, etching way
Fig. 4: be deposition laminated film and aluminium electrode
Fig. 5: for using exposure, etching way again unnecessary matrix material and electrode are partly carved, formed top electrode, lead-in wire test at last
The transmission electron microscope picture of Fig. 6 laminated film
The resistivity of Fig. 7 matrix material and temperature relation figure
Fig. 8: be the XRD figure of laminated film
Fig. 9: be the electric property figure of device
Embodiment
Further specify concrete implementation step of the present invention below in conjunction with accompanying drawing.
1) cleans the silicon substrate that (100) are orientated.
2) the nano combined phase-change thin film 4 of preparation on silicon substrate.Adopt Ge
2Sb
2Te
5Alloys target and HfO
2Target two target co-sputtering thin films.Ge
2Sb
2Te
5And HfO
2Weight ratio reference table 1.In the preparation process, base vacuum is 10-5Pa, and the ar pressure during sputter is 0.2Pa, sputtering power: be added in Ge
2Sb
2Te
5On the alloys target is 50 watts of direct currents, is added in HfO
2On the target is 45 watts of radio frequencies, and sputtering time is 14 minutes, and deposit thickness is roughly 180nm.
Table 1
Prescription | ??1 | ??2 | ??4 | Comparative Examples |
??Ge 2Sb 2Te 5Alloy (wt%) | ??64 | ??76 | ??88 | ??100 |
??HfO 2(wt%) | ??36 | ??24 | ??12 | ??0 |
3) material is tested, the content measurement of material is had: the relation of resistivity of material and annealing temperature (Fig. 7), X-ray diffraction (Fig. 8), transmission electron microscope (Fig. 6) etc.Above-mentioned means of testing is used for weighing the phase-change characteristic of material, comprises the structure and the distribution of dopant material in material of transformation temperature, phase transformation front and back.
Conclusion: by the observation of projection Electronic Speculum, as shown in Figure 6, Ge in the laminated film
2Sb
2Te
5With HfO
2Disperse all to compare evenly; By resistivity and temperature relation test, as shown in Figure 7, find HfO in matrix material to matrix material
2When content increased, the transformation temperature of material moved to the high temperature direction, and the crystalline resistance rate of matrix material increases gradually, and this helps the reduction of device power consumption; The crystallization temperature of laminated film is higher than pure Ge
2Sb
2Te
5The crystallization temperature of film, this helps the stability and the data holding ability of material.
The preparation of embodiment 2 phase transition storages.
1) cleans the silicon substrate that two (100) are orientated, prepare the thick tungsten electrode of 100nm 2 with the CVD method on a silicon substrate 1 therein, as shown in Figure 1.
2) depositing usefulness sputtering method silicon oxide layer deposited 3 on the 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, 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) prepare nano combined phase-change thin film 4 at silicon substrate on the silicon substrate that tungsten electrode is arranged with growing.Utilize Ge
2Sb
2Te
5Alloys target and HfO
2Target two target co-sputtering thin films.Preparation process is with embodiment 1, and the prescription of nano combined phase-change thin film adopts in the table 11 and 2 prescription.
5) depositing Ge
2Sb
2Te
5With HfO
2Deposited by electron beam evaporation method deposition 300nm aluminium electrode 5 on the aperture substrate of laminated film, as shown in Figure 4.
6) utilize exposure-etching technics with part aluminium electrode and part Ge again
2Sb
2Te
5With HfO
2Laminated film is carved together, prepares top electrode, thereby forms the C-RAM device, as shown in Figure 5.
7) the C-RAM device is carried out electrical performance testing with impulse source.As shown in Figure 9, adopt the device R ESET loss of voltage of Composite Preparation, device power consumption reduces.
In sum, by to phase change material and HfO
2Compound, improve the thermostability of material, reduce the power consumption in the device phase transition process, the boost device fatigue characteristic, under the situation that does not change device architecture, can boost device stability, performances such as data holding ability and power consumption.
The foregoing description is the unrestricted technical scheme of the present invention in order to explanation only.Any technical scheme that does not break away from spirit and scope of the invention all should be encompassed in the middle of the patent claim of the present invention.
Claims (13)
1. nano-composite phase-changing material, this nano-composite phase-changing material is to use HfO
2Be composited with phase change material, wherein, HfO
2Weight percent be 12-36%, the weight percent of phase change material is 64-88%.
2. nano-composite phase-changing material according to claim 1 is characterized in that described phase change material and HfO
2In composite phase-change material, be uniformly dispersed and phase change material is limited in by HfO
2In the zone of the nanometer scale of surrounding.
3. as nano-composite phase-changing material as described in the claim 2, it is characterized in that the phase change material in the described nano-composite phase-changing material is the spherule particle, particle diameter is less than 100nm.
4. nano-composite phase-changing material according to claim 1 is characterized in that described phase change material is a chalcogenide compound.
5. as nano-composite phase-changing material as described in the claim 4, it is characterized in that described chalcogenide compound is selected from germanium antimony tellurium alloy, antimony tellurium alloy and germanium antimony alloy.
6. nano-composite phase-changing material according to claim 1 is characterized in that described nano-composite phase-changing material has the reversible phase-change characteristic, and the laminated film before and after the phase transformation has different resistivity, or different optical reflectivities is arranged.
7. as the preparation method of nano-composite phase-changing material as described in arbitrary among the claim 1-6, be to adopt Ge
2Sb
2Te
5Alloys target and HfO
2The sputtering method preparation simultaneously of target two targets.
8. as the preparation method of nano-composite phase-changing material as described in the claim 7, it is characterized in that, adopting Ge
2Sb
2Te
5Alloys target and HfO
2When target two target co-sputterings prepared film, the base vacuum degree was less than 10
-4Pa, sputtering pressure are 0.18-0.25Pa, and temperature is a room temperature, is added in Ge
2Sb
2Te
5Be direct current 30-60 watt on the alloys target, be added in HfO
2Be radio frequency 15-45 watt on the target, sputtering time is 10-20 minute, and deposit thickness is 120-240nm.
9. be used to prepare the phase transition storage of chalcogenide compound as nano-composite phase-changing material as described in arbitrary among the claim 1-6.
10. phase transition storage, its storage media is arbitrary described nano-composite phase-changing material among the claim 1-6.
11. the preparation method of a phase transition storage, this method may further comprise the steps,
1) cleans substrate, prepare tungsten electrode on the substrate therein;
2) depositing silicon oxide layer deposited on the substrate of tungsten electrode;
3) utilize exposure-etching technics on the silicon oxide layer of substrate, to carve aperture and obtain the aperture substrate;
4) on the aperture substrate, prepare the described nano combined phase-change thin film of arbitrary claim among the claim 1-6;
5) depositing deposition of aluminum electrode on the aperture substrate of nano combined phase-change thin film;
6) utilize exposure-etching technics that part aluminium electrode and the nano combined phase-change thin film of part are carved together again, prepare top electrode, thereby form the C-RAM device.
12. the preparation method as phase transition storage as described in the claim 11 is characterized in that, the substrate in the step 1 is the silicon substrate of (100) orientation.
13. the preparation method as phase transition storage as described in the claim 11 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.
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CN101976725A (en) * | 2010-08-17 | 2011-02-16 | 同济大学 | SiO2/Sb80Te20 nano composite multi-layered phase-change film material with adjustable crystallization temperature and preparation method thereof |
CN102082228A (en) * | 2010-10-14 | 2011-06-01 | 中国科学院上海微***与信息技术研究所 | Nano compound phase-change material and application thereof to phase-change storage |
CN102157681A (en) * | 2010-08-24 | 2011-08-17 | 中国科学院上海微***与信息技术研究所 | Sb2Te3-HfO2 nano compound phase change material and application of Sb2Te3-HfO2 nano compound phase change material in phase change memory |
CN102169958A (en) * | 2011-04-29 | 2011-08-31 | 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 |
CN102453823A (en) * | 2010-10-21 | 2012-05-16 | 中国科学院上海微***与信息技术研究所 | Carbide composite phase change storage material and preparation method thereof |
CN102487119A (en) * | 2010-12-02 | 2012-06-06 | 中国科学院上海微***与信息技术研究所 | Sb2Tex-SiO2 nano composite phase change material used on phase change memory and preparation method of Sb2Tex-SiO2 nano composite phase change material |
CN102569644A (en) * | 2010-12-15 | 2012-07-11 | 中国科学院上海微***与信息技术研究所 | Sb2Tey-Si3N4 composite phase change material for phase change memory and preparation method thereof |
CN106191773A (en) * | 2016-08-26 | 2016-12-07 | 北京工业大学 | A kind of method of the doping Ge2Sb2Te5 phase-change thin film determining atomic ratio based on analytic method preparation |
CN108598256A (en) * | 2015-04-27 | 2018-09-28 | 江苏理工学院 | Preparation method of Ge/Sb superlattice phase-change thin film material for phase-change memory |
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2009
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101976725A (en) * | 2010-08-17 | 2011-02-16 | 同济大学 | SiO2/Sb80Te20 nano composite multi-layered phase-change film material with adjustable crystallization temperature and preparation method thereof |
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CN102082228A (en) * | 2010-10-14 | 2011-06-01 | 中国科学院上海微***与信息技术研究所 | Nano compound phase-change material and application thereof to phase-change storage |
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CN106191773A (en) * | 2016-08-26 | 2016-12-07 | 北京工业大学 | A kind of method of the doping Ge2Sb2Te5 phase-change thin film determining atomic ratio based on analytic method preparation |
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