CN101299454B - Method for preparing nano composite phase-changing material - Google Patents
Method for preparing nano composite phase-changing material Download PDFInfo
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- CN101299454B CN101299454B CN2008100389071A CN200810038907A CN101299454B CN 101299454 B CN101299454 B CN 101299454B CN 2008100389071 A CN2008100389071 A CN 2008100389071A CN 200810038907 A CN200810038907 A CN 200810038907A CN 101299454 B CN101299454 B CN 101299454B
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Abstract
The invention relates to a preparation method of the nm compound phase-change material, characterized in that, through the different chemical properties between each element in the phase-change material, the reacting gas of right amount is provided in the preparation of the phase-change material, to cause one or a plurality element(s) in the phase-change material preferentially react(s) with the reaction atmosphere in the growing process of the material to form the solid compound and form the composite material with the remnant phase-change material, wherein the compound separates the phase-change material into the even and minute areas with controlled shape and size, thereby restricting the phase-change behavior of the phase-change material in the small area, to reduce the grain of the phase-change material, meanwhile the solid compound and the phase-change material learn from others' strong points to offset self weakness, which fully makes up the drawback of the single materials, generates the superior property that the single material does not have. The nm compound phase-change material is applied in the phase-change storage, which not only advances the heating efficiency of the phase-change storage, reduces the power waste of the device, but also increases the storage speed and the data retention ability and the like.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the nano-composite phase-changing material of phase transition storage, belong to semiconductor memory and make the field.
Background technology
The research of phase transition storage (PCRAM) is the focus of present memory research, core content as the PCRAM device, the research and development of phase-change material have been played crucial effects in the PCRAM research and development, the research and development of phase-change material and the lifting of performance are to promote one of key technology of PCRAM device performance.
Nano-composite phase-changing material has played crucial effects in research and development low-power consumption, power PC RAM device, in the nano composite material, the material (functional material) that zone with phase transformation ability is not possessed the phase transformation ability scatter, form separate granule, thereby formed composite material.This dispersion phenomenon in the nano-composite phase-changing material has not only dwindled the zone of phase transformation in the phase-change material, has also promoted the thermal stability of phase-change material; Not only promoted phase-change material in programming process from the efficiency of heating surface, also promoted the heat utilization ratio of phase-change material; Not only promoted the data holding ability of storage medium, made the application of the following CMOS technology of the more suitable 90nm of material simultaneously again by the control of grain size.So nano-composite phase-changing material can significantly reduce the power consumption of device, the performance of boost device in the application of PCRAM.
In the nano combined phase transformation, functional material need possess certain thermal stability, and phase-change material effectively can be disperseed.Compound by functional material and phase-change material makes between functional material and phase-change material and " learns from other's strong points to offset one's weaknesses ", fully remedied the shortcoming of single phase-change material, produced the not available superior performance of single phase-change material.The difficult point of nano-composite phase-changing material preparation is how evenly to use function dispersion of materials phase-change material effectively, thereby forms reliable composite construction.
The preparation of phase change composite material can be taked the method that is mixed with of functional material and phase-change material, phase-change material and functional material are evenly mixed, and handle by subsequent anneal and to make functional material that phase-change material evenly is dispersed into size and shape is regional uniformly, thereby the transformation behavior of phase-change material is limited in tiny area; Also can prepare functional material and phase-change material by layering, formation has the material layer of some cycles, thereby more effectively makes functional material that phase-change material is disperseed (separate case application).And the present invention's elaboration is another method for preparing the nano phase change composite material.
Summary of the invention
The object of the present invention is to provide a kind of cheapness and the preparation method of nano-composite phase-changing material easily.
The preparation method of preparation nano composite material of the present invention is: introduce reacting gas in the phase-change material preparation process, auxiliary with the substrate process conditions of heating, make one or more element preferential reaction in reacting gas and the phase-change material, form compound with certain heat-insulating property and thermal stability; By optimization of preparation, the material that makes this compound will have the phase transformation ability evenly is divided into the zone of size and controllable shapes, thereby the grain size of dwindling phase-change material is limited in tiny area to the transformation behavior of phase-change material.Memory device with the preparation of this kind phase change composite material has lower power consumption, because crystal grain is difficult for growing up, the data holding ability of memory will be significantly improved simultaneously.
Specifically the invention provides a kind of preparation method of nano-composite phase-changing material, it is characterized in that in the preparation process of nano-composite phase-changing material, feed an amount of specific reacting gas, make reacting gas one or more element reactions in preferential and the phase-change material in the material growth course, the generation solid chemical compound; Form composite material with the remaining phase-change material of reaction.This compound will have the dispersion of materials forming shape of phase transformation ability and the tiny area of controlled amount.This peptizaiton is limited in the tiny area transformation behavior of material; The phase-change material that is adopted has reversible phase-change characteristic;
A certain element generation chemical reaction in reaction gas physical efficiency that in described nano composite material preparation process, feeds and the phase-change material;
The reacting gas that feeds in described nano composite material preparation process is oxygen, nitrogen, ammonia, chlorine or nitric oxide, other have the gas of oxidizability, or be the mixture of above gas;
The reaction gas physical efficiency that in described nano composite material preparation process, feeds preferential with phase-change material in one or more element reactions, and formation compound;
The compound that generates in described nano composite material preparation process is direct reactant, the indirect reaction thing of reacting gas and phase-change material or is the mixture of reactant and phase-change material;
The compound that generates in described nano composite material preparation process is compared with this kind phase-change material has lower conductivity and thermal conductivity, and has thermal stability preferably;
The compound that is generated behind the described chemical reaction is separated into the material zonule, that have phase-change characteristic, for initial phase-change material or be the mixture of the compound of initial phase transformation material and generation;
The preparation method of described composite material also should comprise the subsequent heat treatment to composite material;
Described composite material is characterized in that this composite material is used for phase transition storage, can reduce device programming power consumption, can improve device read or write speed, can promote the memory data hold facility or can boost device anti-irradiation ability; Described phase transition storage adopts Transformation Principle and carries out the function element of storage, the phase-change random access memory that electricity causes heating, the multi-medium data CD of LASER HEATING, the memory that electron beam causes phase transformation or the memory that causes phase transformation for other energy particle;
In described phase-change material, have different chemical properties between each atom of composition, some atom in the material can be preferentially and specific reacting gas generation chemical reaction, and form solid compounds;
Described nano-composite phase-changing material preparation method is sputtering method, chemical vapour deposition technique or is pulsed laser deposition;
Described nano-composite phase-changing material preparation method is characterized in that being grown to continuous growth method, or is alternating growth multi-layer thin embrane method;
The feature of described nano composite material is that phase-change material (the perhaps mixture of itself and reaction product) is disperseed by reaction product, thereby phase change region is limited in the small scope, and the diameter of tiny area is below 100nm; And the nano composite material of preparation is characterized in that the size and the controllable shapes of composite material, and is uniformly dispersed; Nano composite material is characterized in that composite material has two above different conditions, between each state or have different resistivity, or has different reflectivity.
In a word, the preparation method of nano-composite phase-changing material provided by the invention is because the solid chemical compound that forms and the preparation method of phase-change material, because " learning from other's strong points to offset one's weaknesses " fully remedied the shortcoming of homogenous material between the solid chemical compound of formation and the phase-change material.The nano-composite phase-changing material of preparation is applied in the phase transition storage, has not only promoted the efficiency of heating surface of phase transition storage, reduced power consumption, and improved device stores speed, data holding ability (seeing embodiment for details) simultaneously again.
Description of drawings
The oxygen-doped Si of Fig. 1 (a)
2Sb
2Te
5The high-resolution-ration transmission electric-lens schematic diagram of composite material.(b) oxygen-doped Si
2Sb
2Te
5The I-V curve of composite material film.
Si under Fig. 2 equal conditions
2Sb
2Te
5The high-resolution-ration transmission electric-lens schematic diagram of material.
Fig. 3 is based on oxygen-doped Si
2Sb
2Te
5The resistance of the PCRAM device of composite material-voltage tester curve.
The oxygen-doped Si of Fig. 4
2Sb
2Te
5Composite material, Si
2Sb
2Te
5And Ge
2Sb
2Te
5150 ℃ of data confining force test results.Drop to the failure criteria of phase-change material at the resistance of this definition 50%.Oxygen-doped Si
2Sb
2Te
5The composite material out-of-service time is 5900 seconds, and Si
2Sb
2Te
5The out-of-service time of material is 250 seconds, Ge
2Sb
2Te
5The out-of-service time of material is 70 seconds.
Embodiment
Embodiment 1
In three kinds of elements of SiSbTe, Si has minimum electronegativity, and Sb takes second place, and the Te maximum, thus in three kinds of elements Si the easiest with the oxygen formation silica that reacts, and Sb and Te only just can form oxide with the oxygen reaction when oxygen content is higher.Silica is compared Si
2Sb
2Te
5Phase-change material has lower thermal conductivity and lower conductivity, and has good thermal stability, is a kind of good dispersion.At this a kind of novel preparation oxygen doping Si is proposed
2Sb
2Te
5The embodiment of composite material, specific as follows:
1. the W electrode that will be deposited on the silicon substrate is put into magnetron sputtering apparatus, is evacuated down to 1 * 10
-4Below the Pa.
2. after reaching vacuum requirements, underlayer temperature is raised to 300 ℃, and keeps temperature stabilization.
3. in magnetron sputtering, feed sputter gas Ar and reacting gas O
2, both flows are respectively 68 ml/min and 6 ml/min.
4. power-on, the beginning sputter, employing be respectively Si, three simple substance targets of Sb and Te, purity is better than 99.99%, sputter rate is 10nm/min.
5. sputtering time is 20 minutes, and deposition finishes and takes out sample after waiting for the substrate cool to room temperature.In this process, form silica because oxygen is the easiest with the Si reaction, so the material that obtains is the mixture of SiSbTe phase-change material and silica.
6. obtain the micro-structural of thin-film material by tem analysis, the TEM figure shown in Fig. 1 (a) has demonstrated the micro-structural of composite material, and promptly darker regions is disperseed by light areas.This be because, in the preparation process of material, oxygen preferential with phase-change material in pasc reaction generate silica, after Overheating Treatment, the zone that Si-Sb-Te is more than needed, the zone of silica more than needed disperses the formation composite construction.And by contrast, do not have Si through overdoping
2Sb
2Te
5The TEM of film as shown in Figure 2, its crystal grain is very big, the formation of silica is apparent for the peptizaiton of phase-change material.
7. thin-film material has been carried out the test of electric property.Fig. 1 (b) is depicted as the I-V curve of composite material film, measures for the first time to show that the transformation that material exists high resistant to arrive low-resistance is the I-V curve of typical amorphous state phase-change material when measuring voltage surpasses threshold voltage; And when carrying out scanning for the second time on the primary basis, the material basic display has gone out ohm property.More than test shows that the composite material for preparing has good phase-change characteristic.
Oxygen doping Si
2Sb
2Te
5The preparation method of nano phase change material composite material memory device.
1. clean the silicon substrate of two (100) orientation, prepare the thick tungsten electrode of 100nm on a silicon substrate therein.
2. growing mixed material on silicon chip and the long silicon chip that tungsten electrode arranged.Utilizing purity is 99.999% Si, Sb and Te target three target co-sputtering thin films.In the preparation process, the base vacuum degree is better than 1 * 10
-4Pa, Ar and O during sputter
2Ratio be 68: 6, sputtering pressure is 0.21Pa; Sputtering power: be added in and be 155 watts of radio frequencies on the Si target, be added in power on Sb and the Te target and be direct current 15 and 20 watts, sputtering time is 15 minutes, and deposit thickness is roughly 320nm.
3. at Si (100)/W/ oxygen doping Si
2Sb
2Te
5The insulating layer of silicon oxide of preparation 100nm on the film, utilize the exposure-etching technics of semiconductor routine on silica, to carve the aperture of diameter 500nm, deposit 300nm aluminium electrode again, utilize exposure-etching technics to prepare top electrode again, thereby form memory device.
4. to the test of this phase-change memory device, as shown in Figure 3, based on oxygen doping Si
2Sb
2Te
5The PCRAM device have the Ge of ratio
2Sb
2Te
5The program voltage that device is littler, and wideer height resistance difference is arranged.
5. for oxygen doping Si
2Sb
2Te
5The data holding ability test shows, oxygen doping Si
2Sb
2Te
5The data holding ability of material is much better than Si
2Sb
2Te
5And Ge
2Sb
2Te
5, as shown in Figure 4.
Claims (5)
1. the preparation method of a nano-composite phase-changing material is characterized in that Si
2Sb
2Te
5Aerating oxygen reacting gas in the preparation process of phase-change material makes oxygen preferential and Si in the material growth course
2Sb
2Te
5Element silicon reaction in the phase-change material, generate solid chemical compound, form composite material with the remaining phase-change material of reaction, the solid chemical compound that generates will have the dispersion of materials forming shape of phase transformation ability and the tiny area of controlled amount, and this peptizaiton is limited in the tiny area transformation behavior of material;
Concrete process conditions are:
The W electrode that 1. will be deposited on the silicon substrate is put into magnetron sputtering apparatus, is evacuated down to 1 * 10
-4Below the Pa;
2. after reaching vacuum requirements, underlayer temperature is raised to 300 ℃, and keeps temperature stabilization;
3. in magnetron sputtering, feed sputter gas Ar and reacting gas O
2, both flows are respectively 68 ml/min and 6 ml/min;
4. power-on, the beginning sputter, employing be respectively Si, three simple substance targets of Sb and Te, purity is better than 99.99%, sputtering rate is 10nm/min;
5. sputtering time is 20 minutes, and deposition finishes and takes out sample after waiting for cool to room temperature, in this process, forms silica because oxygen is the easiest with the Si reaction, so the material that obtains is the mixture of SiSbTe phase-change material and silica.
2. according to the preparation method of the described nano-composite phase-changing material of claim 1, it is characterized in that the solid chemical compound of comparing generation with phase-change material has lower conductivity and thermal conductivity, and have thermal stability preferably.
3. according to the preparation method of the described nano-composite phase-changing material of claim 1, it is characterized in that material that the solid chemical compound that generates will have a phase transformation ability is separated into the tiny area of shape and controlled amount, the diameter of tiny area is below 100nm; And be uniformly dispersed.
4. according to the preparation method of the described nano-composite phase-changing material of claim 1, it is characterized in that described preparation method is sputtering method, is grown to continuous growth method, or be alternating growth multi-layer thin embrane method; And subsequent heat treatment.
5. according to the preparation method of the described nano-composite phase-changing material of claim 4, it is characterized in that the nano-composite phase-changing material for preparing has two above different conditions, have different resistivity between each state, or have different reflectivity.
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| CN101924180A (en) * | 2010-05-13 | 2010-12-22 | 中国科学院上海微系统与信息技术研究所 | Antimony-rich Si-Sb-Te sulfur group compound phase-change material for phase change memory |
| CN102082228A (en) * | 2010-10-14 | 2011-06-01 | 中国科学院上海微系统与信息技术研究所 | Nano compound phase-change material and application thereof to phase-change storage |
| CN104241527B (en) * | 2014-09-30 | 2017-10-27 | 中国科学院上海微系统与信息技术研究所 | V Sb Te phase-change material systems for phase transition storage and preparation method thereof |
| US10889887B2 (en) | 2016-08-22 | 2021-01-12 | Honeywell International Inc. | Chalcogenide sputtering target and method of making the same |
| CN110335941B (en) * | 2019-07-03 | 2023-08-18 | 芯盟科技有限公司 | Phase change memory structure and forming method thereof |
| CN113201944A (en) * | 2021-03-26 | 2021-08-03 | 苏州经贸职业技术学院 | Intelligent material and preparation method thereof |
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