CN102268738A - Sb-Te-Ti phase-change storage material - Google Patents

Sb-Te-Ti phase-change storage material Download PDF

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Publication number
CN102268738A
CN102268738A CN201110196219XA CN201110196219A CN102268738A CN 102268738 A CN102268738 A CN 102268738A CN 201110196219X A CN201110196219X A CN 201110196219XA CN 201110196219 A CN201110196219 A CN 201110196219A CN 102268738 A CN102268738 A CN 102268738A
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phase
change
storage material
change storage
target
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吴良才
朱敏
宋志棠
饶峰
宋三年
彭程
刘波
封松林
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Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Institute of Microsystem and Information Technology of CAS
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Priority to CN 201210076528 priority patent/CN102569652B/en
Priority to CN2012100764919A priority patent/CN102593355B/en
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Abstract

The invention relates to a phase-change material and a preparation method thereof, in particular an Sb-Te-Ti phase-change thin film material, which can be used in a phase-change storage. The novel Sb-Te-Ti phase-change storage material disclosed by the invention is formed by doping Ti on the basis of a Sb-Te phase-change material; the doped Ti is bonded with both the Sb and the Te to form a chemical general formula of SbxTeyTi100-x-y, where x is more than 0 and less than 80, and y is more than 0 and less than 100-x. The crystallization process of the conventional Sb-Te phase-change material is dominated by grain growth, so that the phase-change speed is high, however, the retention force cannot meet the industrial requirement. The crystallization temperature of the novel Sb-Te-Ti phase-change storage material disclosed by the invention is greatly increased, the retention force is improved, and the heat stability is strengthened; meanwhile, amorphous resistance is reduced, and the crystalline-state resistance is increased; and the material can be widely applied to the phase-change storages.

Description

A kind of Sb-Te-Ti phase-change storage material
Technical field
The present invention relates to phase change material and preparation method thereof, be particularly useful for the Sb-Te-Ti phase change film material of phase transition storage.
Background technology
Phase transition storage (PCRAM) principle is to be storage media with the chalcogenide compound, utilize electric energy (heat) to make material between crystalline state (low-resistance) and non-crystalline state (high resistant), change writing and wiping of realization information mutually, information read size by measuring resistance, relatively its high resistant " 1 " still low-resistance " 0 " realize.
Sb-Te series phase change material crystallisation process accounts for leading with grain growing, so transformation rate is fast, and fusing point is than GST (Ge 2Sb 2Te 5) low, therefore required low in energy consumption.Yet Sb-Te series phase change material also exists Tc low simultaneously, poor heat stability, shortcomings such as data confining force difference.
Summary of the invention
Purpose of the present invention mainly is to provide a kind of Sb-Te-Ti phase change material that is used for phase transition storage, to improve thermostability, the non-crystalline state resistance of phase change material, the Reset electric current of reduction material and temperature of fusion etc.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme to realize:
A kind of Sb-Te-Ti phase-change storage material that is used for phase transition storage is to mix Ti to form on the basis of Sb-Te phase change material, and its chemical general formula is Sb xTe yTi 100-x-y, 0＜x＜80,0＜y＜100-x wherein.The lower right corner part of element is represented mol ratio in the chemical general formula of the present invention.
Preferable, the span of described x is 45≤x≤72, the span of y is 5≤y≤45.
In the described Sb-Te-Ti phase-change storage material, the Ti that mixes all becomes chemical bond with Sb, Te.
Preferable, described Sb-Te-Ti phase-change storage material is the Sb-Te-Ti phase change film material.Preferably, the thickness of described Sb-Te-Ti phase change film material is 100-250nm.
Preferable, described Sb-Te-Ti phase-change storage material adopts the electricimpulse effect to realize the reversible transition of resistivity.
Preferable, described Sb-Te-Ti phase-change storage material adopts the laser pulse effect to realize the reversible transition of optical reflectivity.
The Tc of described Sb-Te-Ti phase-change storage material is improved significantly, and thermostability strengthens, and the data confining force strengthens.
The non-crystalline state resistance of described Sb-Te-Ti phase-change storage material reduces, and crystalline resistance raises.
The preparation method of Sb-Te-Ti phase-change storage material of the present invention comprises the steps:
According to chemical general formula Sb xTe yTi 100-x-yThe proportioning of middle Sb and Te adopts Sb xTe yAlloys target and Ti target co-sputtering obtain described Sb-Te-Ti phase-change storage material.
Preferable, the sputtering condition of described cosputtering is: feed purity simultaneously and be the Ar gas more than 99.999% in the cosputtering process, Sb xTe yAlloys target adopts radio-frequency power supply, and the Ti target adopts direct supply.Preferably, described radio-frequency power supply power is 25W, and described direct supply power is 15W.
Preferable, during cosputtering, described Sb xTe yBehind the alloys target build-up of luminance, open the Ti target power supply again.
Preferable, the time of described cosputtering is 15 minutes-50 minutes.
The Sb-Te-Ti phase-change storage material that is obtained is a phase change film material, and the thickness of its film is 100nm-250nm.
Sputter instrument used in the present invention is a sputter equipment conventional in the state of the art.
Useful result of the present invention is:
The present invention mixes Ti on the basis of Sb-Te phase-change storage material, Ti and Sb, the equal Cheng Jian of Te, and the Tc of mixing the Sb-Te-Ti phase-change storage material of gained behind the Ti raises, and the data confining force promotes, and thermostability strengthens.Crystalline resistance raises, and the Reset power consumption reduces.
Description of drawings
Fig. 1 is the Sb of different temperature rise rates among the embodiment 1 60Te 30Ti 10The square resistance of film and the relation curve of temperature.
Fig. 2 is Sb among the embodiment 1 60Te 30Ti 10The time that film keeps under differing temps.
Fig. 3 is Sb among the embodiment 1 60Te 30Ti 10The crystallization intensity of activation of film and 10 years maintenance temperature.
Fig. 4 is based on Sb among the embodiment 1 60Te 30Ti 10Unitary voltage-the resistance curve of the phase-change devices of film.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
Embodiment 1
Preparation Sb 60Te 30Ti 10Nano-composite phase-changing material:
Nano-composite phase-changing material in the present embodiment adopts Sb 60Te 30Alloys target and Ti target co-sputtering obtain.Its concrete preparation condition is: feed purity simultaneously and be 99.999% Ar gas, Sb in the cosputtering process 60Te 30Target adopts radio-frequency power supply, and the Ti target adopts direct supply, and the radio-frequency power supply power that is adopted is 25W, and the direct supply power that is adopted is 15W.Sb 2Behind the Te target build-up of luminance, open the Ti target power supply again.The cosputtering time is 20 minutes, and film thickness is greatly about 170nm.
With the Sb that present embodiment obtained 60Te 30Ti 10Nano-composite phase-changing material obtains Fig. 1-3 after testing:
Fig. 1 is the Sb of different temperature rise rates 60Te 30Ti 10The graph of relation of square resistance and temperature.Used temperature rise rate is respectively from 10 ℃/min-50 ℃/min.At 10 ℃/min of temperature rise rate is pure Sb 60Te 30Tc be approximately 130 ℃, mix Ti after, Tc is approximately 212 ℃, than original high more than 80 degree.Temperature rise rate is high more, and Tc is high more, and this is that atom has little time diffusion because temperature rise rate is fast, so required time of crystallization is elongated.
Fig. 2 is Sb 60Te 30Ti 10The time diagram that film keeps under differing temps.Confining force is that phase change material causes and closes an important characteristic, be weigh this phase change material one of can direct applied important parameter.By top discussion as can be known, Sb 60Te 30Ti 10Tc be 212 ℃, the probe temperature point of therefore getting confining force is respectively 195 ℃, 200 ℃, 205 ℃, 210 ℃, referring to Fig. 2.This is because the probe temperature point of confining force must be below Tc, confining force is to be used for characterizing amorphous thermostability, therefore phase change material crystallization in the process that heats up when the probe temperature point is higher than Tc can not test out this amorphous hold-time.Here the out-of-service time is defined as when sheet resistance and drops to half the pairing time that probe temperature is put pairing initial resistance that just is raised to.Can get after tested, be respectively 1560s, 610s, 275s, 70s 195 ℃, 200 ℃, 205 ℃, 210 ℃ pairing out-of-service times, promptly temperature is low more, and the out-of-service time is long more.
Among Fig. 3, can extrapolate pairing temperature of hold-time according to the Arrhenius formula is 137 ℃, higher 52 ℃ than GST (85 ℃).10 years confining forces of automotive electronics are 120 degree, therefore based on Sb 60Te 30Ti 10The phase transition storage of phase change material can satisfy this demand.When obtaining keeping temperature in 10 years, we also can obtain Sb 60Te 30Ti 10The crystallization intensity of activation.Sb 60Te 30Ti 10The crystallization intensity of activation be 3.5ev, than the high 1.2ev of GST (2.3ev).The increase of crystallization intensity of activation helps amorphous thermostability.
Fig. 4 is based on Sb among the embodiment 1 60Te 30Ti 10Unitary voltage-the resistance curve of the phase-change devices of film.The pulse of test applied voltage is 300ns, and the pulse negative edge is 30ns.As can be seen from Figure 4, voltage required from the amorphous to the polycrystalline is 1.1V, and required voltage is 3.5V from the crystalline state to the amorphous.So Sb of present embodiment 60Te 30Ti 10Nano-composite phase-changing material can be realized reversible transformation in the voltage pulse effect.
The Sb of present embodiment 60Te 30Ti 10Nano-composite phase-changing material under the pulse laser heating condition, its structure can be between amorphous and polycrystalline reversible transition, thereby realize the reversible transition of optical reflectivity.
Embodiment 2
Preparation Sb 72Te 18Ti 10Nano-composite phase-changing material:
Nano-composite phase-changing material in the present embodiment adopts Sb 72Te 18Alloys target and Ti target co-sputtering obtain.Its concrete preparation condition is: feed purity simultaneously and be 99.999% Ar gas, Sb in the cosputtering process 72Te 18Target adopts radio-frequency power supply, and the Ti target adopts direct supply, and the radio-frequency power supply power that is adopted is 25W, and the direct supply power that is adopted is 15W.Sb 72Te 18Behind the target build-up of luminance, open the Ti target power supply again.The cosputtering time is 30 minutes, and film thickness is greatly about 200nm.
With the Sb that present embodiment obtained 72Te 18Ti 10Nano-composite phase-changing material is after testing as can be known:
From the Sb that is obtained 72Te 18Ti 10The Sb of the different temperature rise rates of nano-composite phase-changing material 80Te 10Ti 10The graph of relation of square resistance and temperature is as can be known: temperature rise rate is high more, and Tc is high more.
The Sb that is obtained 72Te 18Ti 10The probe temperature of nano-composite phase-changing material is low more, and the out-of-service time is long more.
The Sb that is obtained 72Te 18Ti 10Nano-composite phase-changing material has the maintenance temperature in 10 years, when obtaining keeping temperature in 10 years, and Sb 72Te 18Ti 10The crystallization intensity of activation far above GST (2.3ev).The increase of crystallization intensity of activation helps amorphous thermostability.
The Sb that is obtained 72Te 18Ti 10Nano-composite phase-changing material can be realized reversible transformation in the voltage pulse effect; Under the pulse laser heating condition, its structure can be between amorphous and polycrystalline reversible transition, thereby realize the reversible transition of optical reflectivity.
Embodiment 3
Preparation Sb 50Te 30Ti 20Nano-composite phase-changing material:
Nano-composite phase-changing material in the present embodiment adopts Sb 50Te 30Alloys target and Ti target co-sputtering obtain.Its concrete preparation condition is: feed purity simultaneously and be 99.999% Ar gas, Sb in the cosputtering process 50Te 30Target adopts radio-frequency power supply, and the Ti target adopts direct supply, and the radio-frequency power supply power that is adopted is 25W, and the direct supply power that is adopted is 15W.Sb 2Behind the Te target build-up of luminance, open the Ti target power supply again.The cosputtering time is 50 minutes, and film thickness is greatly about 250nm.
With the Sb that present embodiment obtained 50Te 30Ti 20Nano-composite phase-changing material is after testing as can be known:
From the Sb that is obtained 50Te 30Ti 20The Sb of the different temperature rise rates of nano-composite phase-changing material 50Te 30Ti 20The graph of relation of square resistance and temperature is as can be known: temperature rise rate is high more, and Tc is high more.
The Sb that is obtained 50Te 30Ti 20The probe temperature of nano-composite phase-changing material is low more, and the out-of-service time is long more.
The Sb that is obtained 50Te 30Ti 20Nano-composite phase-changing material has the maintenance temperature in 10 years, when obtaining keeping temperature in 10 years, and Sb 50Te 30Ti 20The crystallization intensity of activation far above GST (2.3ev).The increase of crystallization intensity of activation helps amorphous thermostability.
The Sb that is obtained 50Te 30Ti 20Nano-composite phase-changing material can be realized reversible transformation in the voltage pulse effect; Under the pulse laser heating condition, its structure can be between amorphous and polycrystalline reversible transition, thereby realize the reversible transition of optical reflectivity.
Embodiment 4
Preparation Sb 45Te 45Ti 10Nano-composite phase-changing material:
Nano-composite phase-changing material in the present embodiment adopts Sb 45Te 45Alloys target and Ti target co-sputtering obtain.Its concrete preparation condition is: feed purity simultaneously and be 99.999% Ar gas, Sb in the cosputtering process 45Te 45Target adopts radio-frequency power supply, and the Ti target adopts direct supply, and the radio-frequency power supply power that is adopted is 25W, and the direct supply power that is adopted is 15W.Sb 45Te 45Behind the target build-up of luminance, open the Ti target power supply again.The cosputtering time is 15 minutes, and film thickness is greatly about 100nm.
With the Sb that present embodiment obtained 45Te 45Ti 10Nano-composite phase-changing material is after testing as can be known:
From the Sb that is obtained 45Te 45Ti 10The Sb of the different temperature rise rates of nano-composite phase-changing material 45Te 45Ti 10The graph of relation of square resistance and temperature is as can be known: temperature rise rate is high more, and Tc is high more.
The Sb that is obtained 45Te 45Ti 10The probe temperature of nano-composite phase-changing material is low more, and the out-of-service time is long more.
The Sb that is obtained 45Te 45Ti 10Nano-composite phase-changing material has the maintenance temperature in 10 years, when obtaining keeping temperature in 10 years, and Sb 45Te 45Ti 10The crystallization intensity of activation far above GST (2.3ev).The increase of crystallization intensity of activation helps amorphous thermostability.
The Sb that is obtained 45Te 45Ti 10Nano-composite phase-changing material can be realized reversible transformation in the voltage pulse effect; Under the pulse laser heating condition, its structure can be between amorphous and polycrystalline reversible transition, thereby realize the reversible transition of optical reflectivity.
Embodiment 5
Preparation Sb 69Te 23Ti 8Nano-composite phase-changing material:
Nano-composite phase-changing material in the present embodiment adopts Sb 69Te 23Alloys target and Ti target co-sputtering obtain.Its concrete preparation condition is: feed purity simultaneously and be 99.999% Ar gas, Sb in the cosputtering process 69Te 23Target adopts radio-frequency power supply, and the Ti target adopts direct supply, and the radio-frequency power supply power that is adopted is 25W, and the direct supply power that is adopted is 15W.Sb 69Te 23Behind the target build-up of luminance, open the Ti target power supply again.The cosputtering time is 20 minutes, and film thickness is greatly about 160nm.
With the Sb that present embodiment obtained 69Te 23Ti 8Nano-composite phase-changing material is after testing as can be known:
From the Sb that is obtained 69Te 23Ti 85The Sb of the different temperature rise rates of nano-composite phase-changing material 69Te 23Ti 8The graph of relation of square resistance and temperature is as can be known: temperature rise rate is high more, and Tc is high more.
The Sb that is obtained 69Te 23Ti 8The probe temperature of nano-composite phase-changing material is low more, and the out-of-service time is long more.
The Sb that is obtained 69Te 23Ti 8Nano-composite phase-changing material has the maintenance temperature in 10 years, when obtaining keeping temperature in 10 years, and Sb 69Te 23Ti 8The crystallization intensity of activation far above GST (2.3ev).The increase of crystallization intensity of activation helps amorphous thermostability.
The Sb that is obtained 69Te 23Ti 8Nano-composite phase-changing material can be realized reversible transformation in the voltage pulse effect; Under the pulse laser heating condition, its structure can be between amorphous and polycrystalline reversible transition, thereby realize the reversible transition of optical reflectivity.
The description of the embodiment of the invention and application are illustrative, are not to want with scope restriction of the present invention in the above-described embodiments.Here the distortion of disclosed embodiment and change are possible, and the various parts of the replacement of embodiment and equivalence are known for those those of ordinary skill in the art.Those skilled in the art are noted that under the situation that does not break away from spirit of the present invention or essential characteristic, and the present invention can be with other forms, structure, layout, ratio, and realize with other substrates, material and parts.Under the situation that does not break away from the scope of the invention and spirit, can carry out other distortion and change here to disclosed embodiment.

Claims (10)

1. a Sb-Te-Ti phase-change storage material that is used for phase transition storage forms for mix Ti in the Sb-Te phase-change storage material, and its chemical general formula is Sb xTe yTi 100-x-y, 0＜x＜80,0＜y＜100-x wherein.
2. the Sb-Te-Ti phase-change storage material that is used for phase transition storage as claimed in claim 1 is characterized in that the span of x is 45≤x≤72, and the span of y is 5≤y≤45.
3. the Sb-Te-Ti phase-change storage material that is used for phase transition storage as claimed in claim 1 is characterized in that, described Sb-Te-Ti phase-change storage material adopts the electricimpulse effect to realize the reversible transition of resistivity.
4. the Sb-Te-Ti phase-change storage material that is used for phase transition storage as claimed in claim 1 is characterized in that, described Sb-Te-Ti phase-change storage material adopts the laser pulse effect to realize the reversible transition of optical reflectivity.
5. the Sb-Te-Ti phase-change storage material that is used for phase transition storage as claimed in claim 1 is characterized in that described Sb-Te-Ti phase-change storage material is the Sb-Te-Ti phase change film material.
6. as the arbitrary described preparation method who is used for the Sb-Te-Ti phase-change storage material of phase transition storage of claim 1-5, comprise the steps: according to chemical general formula Sb xTe yTi 100-x-yThe proportioning of middle Sb and Te adopts Sb xTe yAlloys target and Ti target co-sputtering obtain described Sb-Te-Ti phase-change storage material.
7. preparation method as claimed in claim 6 is characterized in that, the sputtering condition of described cosputtering is: feed purity simultaneously and be the Ar gas more than 99.999% in the cosputtering process, Sb xTe yAlloys target adopts radio-frequency power supply, and the Ti target adopts direct supply.
8. preparation method as claimed in claim 7 is characterized in that, during cosputtering, and described Sb xTe yBehind the alloys target build-up of luminance, open the Ti target power supply again.
9. preparation method as claimed in claim 7 is characterized in that, described radio-frequency power supply power is 25W, and described direct supply power is 15W; The time of described cosputtering is 15-50 minute.
10. preparation method as claimed in claim 6 is characterized in that the Sb-Te-Ti phase-change storage material that is obtained is a phase change film material, and the thickness of its film is 100nm-250nm.
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