CN105428532A - Dy-Ge-Sb-Te and Dy-Sb-Te phase change memory material - Google Patents

Dy-Ge-Sb-Te and Dy-Sb-Te phase change memory material Download PDF

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Publication number
CN105428532A
CN105428532A CN201510962145.4A CN201510962145A CN105428532A CN 105428532 A CN105428532 A CN 105428532A CN 201510962145 A CN201510962145 A CN 201510962145A CN 105428532 A CN105428532 A CN 105428532A
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phase
target
storage material
change
change storage
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韩晓东
陈永金
张斌
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Beijing University of Technology
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Beijing University of Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors
    • H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/011—Manufacture or treatment of multistable switching devices
    • H10N70/021—Formation of switching materials, e.g. deposition of layers
    • H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/881—Switching materials
    • H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
    • H10N70/8828—Tellurides, e.g. GeSbTe

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a Dy-Ge-Sb-Te and Dy-Sb-Te phase change memory material, and belongs to the field of microelectronics. The invention provides a technology for improving the phase change property of Ge-Sb-Te and Sb-Te and a thin film preparation method by doping a Dy element to the Ge-Sb-Te or Sb-Te; the chemical structural formula is Dy100-x-y-z(GexSbyTez), wherein x is greater than or equal to 0, and x+y+z is greater than 80 and less than 100. The Dy-Ge-Sb-Te and Dy-Sb-Te phase change memory thin film material has the advantages that an excellent property can be obtained by doping very little Dy; the y-Ge-Sb-Te and Dy-Sb-Te phase change memory thin film material is higher in thermal stability and crystalline state resistance; and the resistance difference between a non-crystalline state and the crystalline state is obvious, and a better data retention property is achieved.

Description

Dy-Ge-Sb-Te and Dy-Sb-Te phase-change storage material
Technical field
The present invention relates to a kind of technology and the method for manufacturing thin film thereof that improve Ge-Sb-Te and Sb-Te phase-change material performance, particularly relate to Dy-Ge-Sb-Te and the Dy-Sb-Te phase transiting storing thin-film material for phase transition storage, belong to microelectronic.
Background technology
Phase transition storage (PCRAM) principle take chalcogenide compound as storage medium, electric pulse, laser pulse etc. is utilized to provide energy to make material between crystalline state (low resistance) and amorphous state (high resistance), mutually change write and the erasing of the information that realizes, the reading of information, by the size of measuring resistance, compares that its high resistance " 1 " or low resistance " 0 " realize.
Ge-Sb-Te is the phase-change storage material that forming core is dominated, and its crystallization temperature is low and cause poor heat stability, restricts it always and further develops, and improves its thermal stability just seem particularly important by doping.Sb-Te is leading type phase-change storage material of growing up, and phase velocity is fast, but its poor heat stability, and data retention is poor, not only can keep rapid phase transition, can also improve its thermal stability by doping.
Summary of the invention
Object of the present invention is mainly to provide a kind of Dy-Ge-Sb-Te and Dy-Sb-Te phase transiting storing thin-film material for phase transition storage, to improve thermal stability, the amorphous state resistance of phase-change material, and the RESET electric current of reduction material and fusion temperature etc.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme to realize:
For a Dy-Ge-Sb-Te and Dy-Sb-Te phase-change storage material for phase transition storage, mix Dy and form in Ge-Sb-Te (or Sb-Te) phase-change storage material, its chemical general formula is Dy 100-x-y-z(Ge xsb yte z), wherein 0≤x<40,0<y<40,40<z<80,80<x+y+z<100.In the present invention, in chemical general formula, the lower right corner part of element represents mol ratio.
Component for Ge-Sb-Te and Sb-Te of phase-change storage material is unrestricted, and preferably, the atomic ratio of such as Ge-Sb-Te is 1:2:4,2:3:6,3:2:6 or 2:2:5 etc., and the atomic ratio of Sb-Te can be 4:1,2:1 or 2:3 etc.
Preferably, described Dy-Ge-Sb-Te and the Dy-Sb-Te phase-change storage material for phase transition storage, realizing the external drive energy of the reversible transition of resistivity and light refractive index reflectivity, can be electric pulse, laser pulse, electron beam and thermal drivers effect.
Preferably, described Dy-Ge-Sb-Te and the Dy-Sb-Te phase-change storage material for phase transition storage is a kind of thin-film material.
Preferably, its film thickness of Dy-Ge-Sb-Te and Dy-Sb-Te phase-change storage material obtained is 100-250nm.
Described Dy-Ge-Sb-Te and the Dy-Sb-Te phase-change storage material for phase transition storage has higher crystallization temperature and better data retention, and its thermal stability is greatly improved.
Described Dy-Ge-Sb-Te and the Dy-Sb-Te phase-change storage material amorphous state resistance for phase transition storage raises, and crystalline resistance raises.
The preparation method of Dy-Ge-Sb-Te and the Dy-Sb-Te phase-change storage material for phase transition storage of the present invention, comprises the steps:
According to chemical general formula Dy 100-x-y-z(Ge xsb yte z) in Ge, Sb and Te proportioning adopt Ge xsb yte z(or Sb yte z) alloys target and Dy target co-sputtering obtain described Dy-Ge-Sb-Te (or Dy-Sb-Te) phase-change storage material.
Preferably, described cosputtering condition is: in cosputtering process, pass into the Ar gas that purity is more than 99.999%, Ge xsb yte z(or Sb yte z) alloys target employing radio-frequency power supply, Dy target adopts DC power supply or radio-frequency power supply.Preferably, described Ge xsb yte z(or Sb yte z) alloys target radio-frequency power supply power is 25W, described Dy target DC power supply power is 15W.
Preferably, during cosputtering, described Ge xsb yte z(or Sb yte z) after alloys target build-up of luminance, then open Dy target power supply.But be not limited to this, also can open Ge again after Dy target build-up of luminance xsb yte z(or Sb yte z) alloys target, or both power supplys are opened simultaneously.
Preferably, the described cosputtering time is 10-30 minute.
Preferably, sputtering instrument used in the present invention is sputter equipment conventional in state of the art.
Compared with prior art, usefulness of the present invention is: this thin-film material, has stronger high high-temp stability and crystalline resistance, obvious resistance difference between amorphous state and crystalline state, better data retention characteristics.
Accompanying drawing explanation
Fig. 1 is that the Dy-Ge-Sb-Te phase transiting storing thin-film material square resistance of different Dy content in embodiment varies with temperature relation curve.
Fig. 2 is activation energy and the data retention result of calculation figure of the Dy-Ge-Sb-Te phase transiting storing thin-film material of different Dy content in embodiment.
Embodiment
Set forth the present invention further below in conjunction with specific embodiment, should be understood that this embodiment is only not used in for illustration of the present invention and limit the scope of the invention.
Prepare the Dy-Ge-Sb-Te phase transiting storing thin-film material of different Dy content:
Phase-change material in the present embodiment adopts Ge 2sb 2te 5alloys target and Dy target co-sputtering obtain.Described cosputtering condition is: in cosputtering process, pass into the Ar gas that purity is more than 99.999%, Ge 2sb 2te 5alloys target adopts radio-frequency power supply, and Dy target adopts DC power supply.Described radio-frequency power supply power is 25W, and described DC power supply power is 10-30W.Ge 2sb 2te 5after alloys target build-up of luminance, then open Dy target power supply.The described cosputtering time is 30 minutes, and film thickness is approximately 150-200nm.
The Dy-Ge-Sb-Te phase transiting storing thin-film material of the different Dy content obtained by the present embodiment obtains Fig. 1 and Fig. 2 after testing:
Fig. 1 is that the Dy-Ge-Sb-Te phase transiting storing thin-film material square resistance for different Dy content in embodiment varies with temperature relation curve.As shown in Figure 1, resistivity measurement is carried out to serial Dy-Ge-Sb-Te phase transiting storing thin-film material of the present invention, obtains temperature-resistance rate relation curve.In FIG, Ge is respectively for component 2sb 2te 5, Dy 0.3(Ge 2sb 2te 5) 99.7, Dy 1.1(Ge 2sb 2te 5) 98.9, Dy 2.5(Ge 2sb 2te 5) 97.5, Dy 4.14(Ge 2sb 2te 5) 95.86and Dy 5.2(Ge 2sb 2te 5) 94.8the Dy-Ge-Sb-Te phase transiting storing thin-film material of different Dy content, the crystallization temperature of its correspondence is respectively 166 DEG C, 172.2 DEG C, 176.4 DEG C, 180.1 DEG C, 194.7 DEG C and 202.5 DEG C.Can find out, below crystallization temperature, Dy-Ge-Sb-Te series phase transiting storing thin-film material is in the amorphous state that resistance is high-impedance state, and more than crystallization temperature, Dy-Ge-Sb-Te series phase transiting storing thin-film material is in the crystalline state that resistance is low resistance state.Here, after Dy doping, Dy-Ge-Sb-Te series phase transiting storing thin-film material crystallization temperature comparatively Ge 2sb 2te 5all increase, be conducive to the raising of data retention.For the present invention, the crystallization temperature of described Dy-Ge-Sb-Te series phase transiting storing thin-film material increases along with Dy content and raises, and therefore can change crystallization temperature by adjustment Dy content.
Fig. 2 is activation energy and the data retention result of calculation figure of the Dy-Ge-Sb-Te phase transiting storing thin-film material of different Dy content in embodiment.Confining force is the vital characteristic of phase-change material, is one of important parameter weighing this phase-change material performance.Confining force is used to characterize amorphous thermal stability, when probe temperature point is higher than phase-change material crystallization in the process heated up during crystallization temperature, therefore can not test out this amorphous retention time, therefore the probe temperature point of confining force must below crystallization temperature.Here the out-of-service time is defined as film resistor and drops to the time corresponding to half being just raised to initial resistance corresponding to probe temperature point.By the different Dy content of Fig. 1 corresponding Dy-Ge-Sb-Te series phase transiting storing thin-film material crystallization temperature, we choose Dy 0.3(Ge 2sb 2te 5) 99.7, Dy 1.1(Ge 2sb 2te 5) 98.9, Dy 2.5(Ge 2sb 2te 5) 97.5three compositions are used for the test failure time, and extrapolate the temperature corresponding to crystallization activation energy and retention time.As shown in Figure 2, Dy 0.3(Ge 2sb 2te 5) 99.7crystallization activation energy (E a) be 2.37eV, 10 annual datas keep temperature to be 86 DEG C; Dy 1.1(Ge 2sb 2te 5) 98.9crystallization activation energy (E a) be 2.74eV, 10 annual datas keep temperature to be 88 DEG C; Dy 2.5(Ge 2sb 2te 5) 97.5crystallization activation energy (E a) be 2.95eV, 10 annual datas keep temperature to be 99 DEG C.As can be drawn from Figure 2, the activation energy of Dy-Ge-Sb-Te phase transiting storing thin-film material comparatively Ge 2sb 2te 5(2.24eV) large, 10 annual datas keep temperature comparatively Ge 2sb 2te 5(85 DEG C) are higher.The increase of crystallization activation energy is conducive to amorphous thermal stability.
Compared with prior art, usefulness of the present invention is: this thin-film material, just can obtain excellent performance, have stronger high high-temp stability and crystalline resistance by the considerably less Dy that adulterates, obvious resistance difference between amorphous state and crystalline state, better data retention characteristics.
The description of the embodiment of the present invention and application are illustrative, and not picture by scope restriction of the present invention in the above-described embodiments.

Claims (10)

1. for a Dy-Ge-Sb-Te or Dy-Sb-Te phase-change storage material for phase transition storage, mix Dy and form in Ge-Sb-Te or Sb-Te phase-change storage material, its chemical general formula is Dy 100-x-y-z(Ge xsb yte z), wherein 0≤x<40,0<y<40,40<z<80,80<x+y+z<100; In chemical general formula, the lower right corner part of element represents mol ratio.
2., as claimed in claim 1 for Dy-Ge-Sb-Te or the Dy-Sb-Te phase-change storage material of phase transition storage, it is characterized in that, the atomic ratio of Ge-Sb-Te is 1:2:4,2:3:6,3:2:6 or 2:2:5; The atomic ratio of Sb-Te is 4:1,2:1 or 2:3.
3. as claimed in claim 1 for Dy-Ge-Sb-Te and the Dy-Sb-Te phase-change storage material of phase transition storage, it is characterized in that, as compared to pure Ge-Sb-Te with Sb-Te, this phase-change material has higher crystallization temperature and better data retention, and its thermal stability improves.
4. as claimed in claim 1 for Dy-Ge-Sb-Te or the Dy-Sb-Te phase-change storage material of phase transition storage, it is characterized in that, described Dy-Ge-Sb-Te or Dy-Sb-Te phase-change storage material realizes the external drive energy of the reversible transition of resistivity and light refractive index reflectivity, is electric pulse, laser pulse, electron beam or thermal drivers effect.
5., as claimed in claim 1 for Dy-Ge-Sb-Te or the Dy-Sb-Te phase-change storage material of phase transition storage, it is characterized in that, described Dy-Ge-Sb-Te or Dy-Sb-Te phase-change storage material is a kind of thin-film material.
6. the preparation method of Dy-Ge-Sb-Te or the Dy-Sb-Te phase-change storage material for phase transition storage as described in as arbitrary in claim 1-5, comprises the steps: according to chemical general formula Dy 100-x-y-z(Ge xsb yte z) in Ge, Sb and Te proportioning adopt Ge xsb yte zalloys target and Dy target co-sputtering obtain described Dy-Ge-Sb-Te phase-change storage material;
Or according to chemical general formula Dy 100-x-y-z(Ge xsb yte z) in Sb and Te proportioning adopt Sb yte zalloys target and Dy target co-sputtering obtain Dy-Sb-Te phase-change storage material.
7. preparation method as claimed in claim 6, it is characterized in that, described cosputtering condition is: in cosputtering process, pass into the Ar gas that purity is more than 99.999%, Ge xsb yte zor Sb yte zalloys target adopts radio-frequency power supply, and Dy target adopts DC power supply or radio-frequency power supply.
8. preparation method as claimed in claim 6, is characterized in that, during cosputtering, and described Ge xsb yte zafter alloys target build-up of luminance, then open Dy target power supply; Or open Ge again after Dy target build-up of luminance xsb yte zalloys target, or both power supplys are opened simultaneously;
During cosputtering, Sb yte zafter alloys target build-up of luminance, then open Dy target power supply; Or open Sb again after Dy target build-up of luminance yte zalloys target, or both power supplys are opened simultaneously.
9. preparation method as claimed in claim 6, it is characterized in that, described radio-frequency power supply power is 15-100W, and described DC power supply power is 15-80W, and the described cosputtering time is 5-50 minute.
10. preparation method as claimed in claim 6, it is characterized in that, Dy-Ge-Sb-Te or the Dy-Sb-Te phase-change storage material obtained is phase change film material, and its film thickness is 10-300nm.
CN201510962145.4A 2015-12-20 2015-12-20 Dy-Ge-Sb-Te and Dy-Sb-Te phase change memory material Pending CN105428532A (en)

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Cited By (1)

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CN107768516A (en) * 2016-08-22 2018-03-06 中国科学院上海微系统与信息技术研究所 Y Sb Te phase-change materials, phase-changing memory unit and preparation method thereof

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EP1494230A2 (en) * 2003-07-03 2005-01-05 Mitsubishi Materials Corporation Phase change recording film having high electrical resistance and sputtering target for forming phase change recording film
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EP1494230A2 (en) * 2003-07-03 2005-01-05 Mitsubishi Materials Corporation Phase change recording film having high electrical resistance and sputtering target for forming phase change recording film
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Publication number Priority date Publication date Assignee Title
CN107768516A (en) * 2016-08-22 2018-03-06 中国科学院上海微系统与信息技术研究所 Y Sb Te phase-change materials, phase-changing memory unit and preparation method thereof

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Application publication date: 20160323