CN1604210A - Phase change material capable of being used for phase transformation memory multi-stage storage - Google Patents
Phase change material capable of being used for phase transformation memory multi-stage storage Download PDFInfo
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- CN1604210A CN1604210A CNA2004100679875A CN200410067987A CN1604210A CN 1604210 A CN1604210 A CN 1604210A CN A2004100679875 A CNA2004100679875 A CN A2004100679875A CN 200410067987 A CN200410067987 A CN 200410067987A CN 1604210 A CN1604210 A CN 1604210A
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- 239000012782 phase change material Substances 0.000 title claims abstract description 80
- 238000003860 storage Methods 0.000 title claims description 71
- 230000009466 transformation Effects 0.000 title claims description 19
- 230000015654 memory Effects 0.000 title abstract description 11
- 230000008859 change Effects 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 230000007704 transition Effects 0.000 claims description 25
- 230000002441 reversible effect Effects 0.000 claims description 13
- 230000014759 maintenance of location Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 230000002427 irreversible effect Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- -1 Chalcogenide compound Chemical class 0.000 description 2
- 230000035479 physiological effects, processes and functions Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Abstract
This invention relates to phase-change material used in phase-change memory, which is characterized by the following: the said phase-change material is the memory material mixed with nitrogen or boric Ge#-[2]Sb#-[2]Te#-[5]; the material structure change accompanies the resistance change with multiple scale degrees of change range; impulse voltage can make the material converse between different structures; it realizes the multiple memory by use of resistance property change of different states to breakthrough the traditional memory mode of zero and one.
Description
Technical field
The present invention relates to can be used for the phase-change material of the multistage storage of phase transition storage.Or rather, the preparation method who relates to phase-change material with a plurality of store statuss, can adopt pulse voltage or pulse laser to drive phase-change material but inverse conversion takes place between the different structure state, make the performance of phase-change material that reversible variation takes place simultaneously, thereby realize the multistage storage of phase transition storage.The invention belongs to the photoelectron technology field.
Background technology
Phase-change random access memory (PC-RAM, Phase Change-Random Access Memory) technology is based on S.R.Ovshinsky at late 1960s (Phys.Rev.Lett., 21,1450～1453,1968) beginning of the seventies (Appl.Phys.Lett., 18,254～257,1971) phase-change thin film of Ti Chuing can be applied to that the conception of phase change memory medium sets up, and is the memory device of a kind of low price, stable performance.The PC-RAM storer can be made on the silicon wafer substrate, and its critical material is recordable phase-change thin film.The key features of phase-change alloy material is can make material between amorphous state and polycrystalline attitude reversible transition take place when giving its electric pulse.Present high resistant when being in amorphous state, present low-resistance during the polycrystalline attitude, amplitude of variation can reach several magnitude, so just can be used as a multi-level store.Though utilize the PC-RAM memory technology of phase-change thin film resistive performance to propose more in early days, because the restriction of technology of preparing and technology, phase-change material at that time can only just undergo phase transition than under the highfield, and this has just limited the process of its practicability development.Development along with nanometer technology of preparing and technology, the size of material in the device (comprising the two-dimension sizes in film thickness direction and the plane) can narrow down to nanometer scale, make material undergo phase transition that required voltage reduces greatly, power consumption reduces, great variety has also taken place in the performance of material simultaneously.1999, (Energy Conversion Devices Inc) realized the phase transition process of phase-change thin film under low-voltage very, and good electrical characteristics are arranged after the phase transformation, is specially adapted to make storer (SPIE, 3891,2～9,1999) in ECD company.From then on, the PC-RAM storer has obtained development faster.
Companies such as Ovonyx, Intel, Samsung, Hitachi, STMicroelectronics and British Aerospace are arranged in the world in the research of carrying out the PC-RAM storer, carrying out at present that technology is improved and the R﹠D work of manufacturability aspect.PC-RAM storer owing to have reads at a high speed, high erasable number of times, non-volatile, advantages such as component size is little, strong motion low in energy consumption, anti-and radioresistance, is thought flash memories that most possible replacement is present by international semiconductor TIA and becomes following storer main product and become the device of commercial product at first.
The research of storer develops towards high speed, highdensity direction always, and the PC-RAM storer can reach a plurality of orders of magnitude just because of the resistance variations of its phase-change material, therefore be expected to utilize a plurality of intermediate state resistance of phase-change material to realize the multistage storage of storer, thereby break through the memory module of traditional " 0 " Yu " 1 ", improve storage density greatly.Thereby draw purpose of the present invention.
Summary of the invention
The object of the present invention is to provide the phase-change material that can be used for the multistage storage of phase transition storage.
The objective of the invention is based on following principle: the electric property of phase-change material can in very large range change, the change of phase change material structure state will be accompanied by the variation of electric property, its amplitude of variation may reach a plurality of orders of magnitude, but potential pulse can make phase-change material inverse conversion between different configuration states, utilize the change of electric property between different conditions can realize the multistage storage of phase transition storage, thereby under the situation that does not change storage device structure, increase substantially the capacity of storer.
Chalcogenide compound is a kind of common phase-change material, and its electric property can great changes will take place under different conditions, and Fig. 1 is the electric property of phase-change material issues the stepped change that physiology thinks in different condition a synoptic diagram.Yet the crystallinity of the phase-change material that different treatment conditions obtain is different with structure, and its electric property is also inequality, can utilize the reversible transition between the different electric properties to realize multistage storage like this.Phase-change material is applied pulse voltage or pulse current, and electric energy changes heat energy into, and phase-change material rises temperature because of absorbing heat energy, by crystallization takes place after the structural adjustment, thereby brings the variation of its electric property.
If the existing state of phase-change material under the different condition be designated as respectively attitude " 0 ", attitude " 1 ", attitude " 2 " ..., attitude " n ", and can take on phase-change material, to apply pulse voltage, or a kind of in the pulse current, make phase-change material between the two states reversible transition take place arbitrarily, can break through traditional only memory module of " 0 " of reversible variation and " 1 " between two kinds of store statuss like this, storage density increases substantially.
As being stored as example with the simplest three-state, for convenience's sake, resistive performance with phase-change material changes as the approach that realizes storage, if there are three stable Resistance states in certain storage medium, be respectively high-impedance state, middle resistance state and low resistance state, can be easy to realize three grades of storages as shown in Figure 2, be that high-impedance state is designated as " 0 " attitude, middle resistance state is designated as one state, low resistance state is designated as " 2 " attitude, phase co-conversion between three kinds of states can be realized three grades of storages, that is: the one-level storage is corresponding to the reversible transition between high-impedance state and the middle resistance state; Secondary storage is corresponding to the phase transformation between high-impedance state and the low resistance state; Three grades of storages are corresponding to the phase transformation between middle resistance state and the low resistance state.For three grades of storages of institute's mark among Fig. 2, can be by realizing phase-change material reversible variation between three kinds of different conditions applying different pulse voltage on the phase-change material, the waveform synoptic diagram of pulse voltage as shown in Figure 3, pulse voltage V
1For data write voltage, pulse voltage V
2Be data read-out voltage, pulse voltage V
3Be data erase voltage, pulse voltage V
1, V
2And V
3Should satisfy following condition: V
2Can not cause a devastating effect to the storage data; V
1, V
2And V
3Voltage strength be 0.001-20V, corresponding pulse width is 0.001-1000ns.The determining and can obtain of pulse voltage parameter: 1) by following steps. the width of determining pulse voltage according to the crystallization time of phase-change material and decrystallized time; 2). determine the pulse voltage intensity that realizes different resistance states according to the resistance-temperature profile curve of phase-change material; 3) but. according to the inverse conversion between the different structure state, design at other characteristic pulse voltage waveform of different storage levels.Like this, the realization of the multistage storage of phase transition storage is exactly to rely on the different characteristic pulse voltage waveform of utilization to act on phase-change material, make it to take place between different conditions reversible transition, the resistance value of measuring phase-change material simultaneously changes the purpose that writes, reads and wipe of the information that reaches.
The phase-change material that can be used for the multistage storage of phase transition storage provided by the invention is the Ge of doping N or B
2Sb
2Te
5Phase-change material, its doping are the nitrogen of 0.01-10 (atomic percent) and the boron of 0.01-5 (atomic percent), and preferential doping of recommending is that N is 0.5-3 (atomic percent), and the doping of B is 0.3-1 (atomic percent).
Description of drawings
The resistance of Fig. 1 phase-change material issues the synoptic diagram of the stepped change that physiology thinks in different condition
Three grades of storage synoptic diagram of Fig. 2 phase-change material
Fig. 3 realizes the pulse voltage waveform synoptic diagram of the multistage storage of phase-change material
Fig. 4 Ge
2Sb
2Te
5The resistance of phase-change material-temperature profile curve
Fig. 5 Ge
2Sb
2Te
5The resistance of-N phase-change material-temperature profile curve, wherein the atom percentage content of N is 1%
The pulse voltage waveform synoptic diagram of three grades of storages among Fig. 6 Fig. 2
Fig. 7 Ge
2Sb
2Te
5The resistance of-B phase-change material-temperature profile curve, wherein the atom percentage content of B is 0.5%
Embodiment
Chalcogenide compound is a kind of common phase-change material, wherein Ge
2Sb
2Te
5Phase-change material is the phase-change memory phase-change material that generally adopts in the world at present, and its resistance-the temperature profile curve as shown in Figure 4.Because the Ge that different heat treatment temperatures obtains
2Sb
2Te
5The crystallinity of phase-change material is different with structure, and its resistance value is also inequality, can utilize the reversible transition between the different resistance to realize multistage storage like this.Phase-change material is applied voltage, and electric energy changes heat energy into, and phase-change material rises temperature because of absorbing heat energy, by crystallization takes place after the structural adjustment, thereby brings the variation of its resistive performance.The interaction of synthetic study voltage and phase-change material can be summed up the waveform that draws pulse voltage, and pulse voltage intensity is in the 0.001-20V scope, and the pulse voltage width is 0.001-1000ns.
As shown in Figure 4, because Ge
2Sb
2Te
5The resistance of phase-change material is a continuous process with variation of temperature, temperature range corresponding to certain specific electrical resistance is very narrow, just the thermal adaptability of resistance is very poor, this is unfavorable for multistage storage, because the deviation owing to voltage in operating process can make the temperature of phase-change material change within the specific limits, thereby can change the resistance of material, cause influencing each other between the different storage states, this is crosstalks.
But, the Ge that N mixes
2Sb
2Te
5Very big change has taken place in the resistance-temperature characterisitic of phase-change material, when the doping of N hour (atomic percent is 0.01-10%), two steps have clearly appearred in its resistance-temperature profile curve, that is to say, resistance can remain unchanged in bigger temperature range substantially, as shown in Figure 5, this just is easy to realize multistage storage.For the situation among Fig. 5, if utilize Ge
2Sb
2Te
5-1%N (atomic percent) is as storage medium, can be easy to realize three grades of storages as shown in Figure 2, and amorphous state is a high-impedance state, is designated as " 0 " attitude; Face-centred cubic structure (FCC) crystalline state is middle resistance state, is designated as one state; Hexagonal structure (HCP) crystalline state is a low resistance state, is designated as " 2 " attitude, and the phase co-conversion between three kinds of states can be realized three grades of storages, that is: the one-level storage is corresponding to the reversible transition between amorphous state and the FCC structure crystalline state; Secondary storage is corresponding to the phase transformation between amorphous state and the HCP structure crystalline state; Three grades of storages are corresponding to the phase transformation between FCC structure crystalline state and the HCP structure crystalline state.For the one-level storage and the secondary storage of institute's mark among Fig. 2, its pulse voltage waveform is identical with Fig. 3's.But for three grades of some differences of storage condition among Fig. 2, because Ge
2Sb
2Te
5The FCC structure of-1%N (atomic percent) and the conversion between the HCP structure are irreversible, be that the FCC structure can directly change the HCP structure into, and the HCP structure can not directly change the FCC structure into, then can realize of the transformation of HCP structure by the pulse voltage waveform that changes erase process to the FCC structure, as shown in Figure 6, by this transformation of realization of two steps, promptly at first making phase-change material is amorphous state from the HCP structural transformation, and then changing the FCC structure into, this method also is a crucial part of the present invention.
For realizing phase-change material Ge
2Sb
2Te
5The condition that each pulse voltage of three grades of storages of-1%N (atomic percent) should satisfy is as follows:
1) one-level storage.Voltage V
1Be phase-change material from crystalline state to amorphous phase time variant voltage, voltage V
1Should guarantee to make the phase-change material fusing and remove V
1After can make material form amorphous state, the voltage strength exemplary value is 3V, V
1Pairing pulse width exemplary value is 20ns; Voltage V
2Be the read-out voltage of recorded information, voltage V
2Should guarantee to make the temperature of phase-change material to be lower than its Tc, the voltage strength exemplary value is 0.1V, and pairing pulse width exemplary value is 200ns; Voltage V
3Be the phase time variant voltage of phase-change material from amorphous state to FCC structure crystalline state, voltage V
3Should guarantee to make the satisfied transformation that only takes place amorphous state to FCC structure crystalline state of temperature of phase-change material, and the transformation of FCC structure crystalline state to HCP structure crystalline state do not take place, the voltage strength exemplary value is 1V, V
3Pairing pulse width exemplary value is 50ns.
2) secondary storage.Voltage V
1Be phase-change material from crystalline state to amorphous phase time variant voltage, voltage V
1Should guarantee to make the phase-change material fusing and remove V
1After can make material form amorphous state, the voltage strength exemplary value is 3V, V
1Pairing pulse width exemplary value is 20ns; Voltage V
2Be the read-out voltage of recorded information, voltage V
2Should guarantee to make the temperature of phase-change material to be lower than its Tc, the voltage strength exemplary value is 0.1V, and pairing pulse width exemplary value is 200ns; Voltage V
3Be the phase time variant voltage of phase-change material from amorphous state to HCP structure crystalline state, voltage V
3Should guarantee to make the satisfied transformation that only takes place amorphous state to HCP structure crystalline state of temperature of phase-change material, and the transformation of amorphous state to FCC structure crystalline state do not take place, the voltage strength exemplary value is 2V, V
3Pairing pulse width exemplary value is 60ns.
3) three grades of storages.As shown in Figure 6, voltage V
1Be phase-change material from crystalline state to amorphous phase time variant voltage, voltage V
1Should guarantee to make the phase-change material fusing and remove V
1After can make material form amorphous state, the voltage strength exemplary value is 3V, V
1Pairing pulse width exemplary value is 20ns; Voltage V
2Be the read-out voltage of recorded information, voltage V
2Should guarantee to make the temperature of phase-change material to be lower than its Tc, the voltage strength exemplary value is 0.1V, and pairing pulse width exemplary value is 200ns; Voltage V
3Be the phase time variant voltage of phase-change material from amorphous state to FCC structure crystalline state, voltage V
3Should guarantee to make the satisfied transformation that only takes place amorphous state to FCC structure crystalline state of temperature of phase-change material, and the transformation of FCC structure crystalline state to HCP structure crystalline state do not take place, the voltage strength exemplary value is 1V, V
3Pairing pulse width exemplary value is 50ns; Voltage V
4Be the phase time variant voltage of phase-change material from FCC to HCP structure crystalline state, voltage V
4Should guarantee to make the temperature of phase-change material to satisfy the transformation of FCC to HCP structure crystalline state only takes place, arrive amorphous transformation and FCC structure crystalline state does not take place, the voltage strength exemplary value is 2V, V
4Pairing pulse width exemplary value is 60ns.
The doping of nitrogen changes similar three grades of storage change, just V
1, V
2, V
3, V
4Concrete numerical value is different.
Embodiment 3
Phase-change material among the embodiment 2 is become the Ge that B mixes
2Sb
2Te
5Phase-change material, the doping of B (boron) is 0.01-5% (atomic percent), Fig. 7 is Ge
2Sb
2Te
5Two steps have clearly appearred in the resistance-temperature profile curve of-0.5%B (atomic percent) phase-change material in the curve, also can realize three grades of storages.All the other and embodiment 1 duplicate.
Embodiment 4
The different Ge that mix
2Sb
2Te
5Phase-change material, but realize inverse conversion between the phase-change material different conditions with pulse current, substantially to different conditions that embodiment 2,3 pulse voltages cause between reversible variation similar.
Claims (7)
1, a kind of phase-change material that can be used for the multistage storage of phase transition storage is characterized in that described phase-change material is the Ge of doping nitrogen or boron
2Sb
2Te
5Storage medium, its doping are the nitrogen of 0.01-10 atomic percent or the boron of 0.01-5 atomic percent.
By the described phase-change material that can be used for the multistage storage of phase transition storage of claim 1, it is characterized in that in the described storage medium that 2, the doping of N is the 0.5-3 atomic percent, the doping of B is the 0.3-1 atomic percent.
3,, but it is characterized in that the inverse conversion between the described phase-change material different conditions is to realize by the pulse voltage or the pulse current that impose on phase-change material by the described phase-change material that can be used for the multistage storage of phase transition storage of claim 1.
4,, but it is characterized in that the phase-change material inverse conversion is the reversible variation between high-impedance state, middle resistance state and three kinds of different conditions of low resistance state by the described phase-change material that can be used for the multistage storage of phase transition storage of claim 3.
5, by claim 3 or the 4 described phase-change materials that can be used for the multistage storage of phase transition storage, it is characterized in that the data that applied write voltage V
1, data read-out voltage V
2, data erase voltage V
3Intensity be 0.001-20V, the respective pulses width is 0.001-1000ns.
6, by claim 1,2, the 3 or 4 described phase-change materials that can be used for the multistage storage of phase transition storage, it is characterized in that for the Ge that mixes 1% atomic percent nitrogen
2Sb
2Te
5Material, the one-level storage is corresponding to the reversible transition between amorphous state and the face-centred cubic structure crystalline state, secondary storage is corresponding to the phase transformation between face-centred cubic structure crystalline state and the hexagonal structure crystalline state, and three grades of storages are corresponding to the phase transformation between face-centred cubic structure crystalline state and the hexagonal structure crystalline state.
7, by the described phase-change material that can be used for the multistage storage of phase transition storage of claim 6, it is irreversible it is characterized in that changing between centroid structure and the hexagonal structure, hexagonal structure at first changes amorphous state into, change face-centred cubic structure into by amorphous state again, thereby realize that hexagonal structure changes face-centred cubic structure into.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1909239B (en) * | 2005-08-04 | 2010-04-21 | 三星电子株式会社 | Phase change material, phase change random access memory including the same, and methods of manufacturing and operating the same |
| CN101818294A (en) * | 2010-04-28 | 2010-09-01 | 中国科学院上海微系统与信息技术研究所 | Nanometer composite phase-change material, preparation method and optimization method |
| US7943918B2 (en) | 2003-02-24 | 2011-05-17 | Samsung Electronics Co., Ltd. | Multi-layer phase-changeable memory devices |
| US7960224B2 (en) | 2007-04-03 | 2011-06-14 | Macronix International Co., Ltd. | Operation method for multi-level switching of metal-oxide based RRAM |
| CN106374042A (en) * | 2016-09-26 | 2017-02-01 | 江苏理工学院 | Nitrogen-doped Sb nano phase change thin film material and preparation method and application thereof |
| CN107425118A (en) * | 2017-07-21 | 2017-12-01 | 吉林大学 | A kind of high-performance Ge-Sb-Te phase change film material and preparation method thereof |
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0261833A (en) * | 1988-08-26 | 1990-03-01 | Matsushita Electric Ind Co Ltd | Optical information recording medium |
| JPH04223191A (en) * | 1990-12-26 | 1992-08-13 | Fuji Electric Co Ltd | Phase change type optical recording medium |
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|---|---|---|---|---|
| US7943918B2 (en) | 2003-02-24 | 2011-05-17 | Samsung Electronics Co., Ltd. | Multi-layer phase-changeable memory devices |
| CN1909239B (en) * | 2005-08-04 | 2010-04-21 | 三星电子株式会社 | Phase change material, phase change random access memory including the same, and methods of manufacturing and operating the same |
| US7960224B2 (en) | 2007-04-03 | 2011-06-14 | Macronix International Co., Ltd. | Operation method for multi-level switching of metal-oxide based RRAM |
| CN101818294A (en) * | 2010-04-28 | 2010-09-01 | 中国科学院上海微系统与信息技术研究所 | Nanometer composite phase-change material, preparation method and optimization method |
| CN106374042A (en) * | 2016-09-26 | 2017-02-01 | 江苏理工学院 | Nitrogen-doped Sb nano phase change thin film material and preparation method and application thereof |
| CN107425118A (en) * | 2017-07-21 | 2017-12-01 | 吉林大学 | A kind of high-performance Ge-Sb-Te phase change film material and preparation method thereof |
| CN108899416A (en) * | 2018-06-21 | 2018-11-27 | 华中科技大学 | A kind of erasing-writing method of phase transition storage |
| WO2019242079A1 (en) * | 2018-06-21 | 2019-12-26 | 华中科技大学 | Erasing and writing method of phase-change memory |
| CN108899416B (en) * | 2018-06-21 | 2021-07-27 | 华中科技大学 | Erasing and writing method of phase change memory |
| CN113724757A (en) * | 2021-09-01 | 2021-11-30 | 哈尔滨工程大学 | Optical fiber memristor unit |
| CN113724758A (en) * | 2021-09-01 | 2021-11-30 | 哈尔滨工程大学 | Multi-core optical fiber memristor and erasing, writing and reading scheme |
| CN113724757B (en) * | 2021-09-01 | 2023-07-14 | 哈尔滨工程大学 | Optical fiber memristor unit |
| CN113724758B (en) * | 2021-09-01 | 2023-07-14 | 哈尔滨工程大学 | Multicore fiber memristor device and scheme of erasing, writing and reading |
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| CN1326137C (en) | 2007-07-11 |
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