CN105428531A - Gd-Ge-Sb-Te and Gd-Sb-Te phase change memory material - Google Patents
Gd-Ge-Sb-Te and Gd-Sb-Te phase change memory material Download PDFInfo
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- CN105428531A CN105428531A CN201510959334.6A CN201510959334A CN105428531A CN 105428531 A CN105428531 A CN 105428531A CN 201510959334 A CN201510959334 A CN 201510959334A CN 105428531 A CN105428531 A CN 105428531A
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- 239000000463 material Substances 0.000 title claims abstract description 27
- 230000008859 change Effects 0.000 title claims abstract description 7
- 239000010409 thin film Substances 0.000 claims abstract description 24
- 230000014759 maintenance of location Effects 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000011232 storage material Substances 0.000 claims description 26
- 238000002425 crystallisation Methods 0.000 claims description 20
- 230000007704 transition Effects 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 17
- 239000000956 alloy Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 6
- 239000012782 phase change material Substances 0.000 claims description 6
- 239000010408 film Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 238000002310 reflectometry Methods 0.000 claims description 2
- 230000002441 reversible effect Effects 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 230000004913 activation Effects 0.000 description 8
- 241001269238 Data Species 0.000 description 4
- 239000000523 sample Substances 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 chalcogenide compound Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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 Gd-Ge-Sb-Te and Gd-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 Gd element to the Ge-Sb-Te or Sb-Te; the chemical structural formula is Gd100-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 Gd-Ge-Sb-Te and Gd-Sb-Te phase change memory thin film material has the advantages that an excellent property can be obtained by doping very little Gd; the 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 performance is achieved.
Description
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 Gd-Ge-Sb-Te and the Gd-Sb-Te phase transiting storing thin-film material for phase transition storage, belong to microelectronic.
Background technology
Phase transition storage (PCRAM) principle is storage medium with chalcogenide compound, utilizes electric pulse, laser pulse etc. to provide energy that material is mutually changed with the write realizing information and erasing between crystalline state (low resistance) and amorphous state (high resistance).Data read process is then distinguished logical data " 1 " and " 0 " of storage by the state (high or low) of measuring element resistance.
The crystallization of Ge-Sb-Te phase-change storage material is taken as the leading factor with forming core, the crystallization temperature lower due to it and the poor heat stability caused, be its main cause further developed of restriction, for this reason a large amount of research work is attempted to improve its thermal stability by doping, and achieves good effect always.Another kind of phase-change storage material Sb-Te, its crystallization behavior shows as grows up leading, and its feature is that phase velocity is fast, right poor heat stability, and data retention is poor, not only can keep its rapid phase transition, can also improve its thermal stability by adulterating.
Summary of the invention
Object of the present invention is mainly to provide a kind of Gd-Ge-Sb-Te and Gd-Sb-Te phase transiting storing thin-film material for phase transition storage, to improve thermal stability, the amorphous state resistance of phase-change storage material and device, 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 Gd-Ge-Sb-Te and Gd-Sb-Te phase-change storage material for phase transition storage, mix Gd element and form in Ge-Sb-Te (or Sb-Te) phase-change storage material, its chemical general formula is Gd
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 Gd-Ge-Sb-Te and the Gd-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 Gd-Ge-Sb-Te and the Gd-Sb-Te phase-change storage material for phase transition storage is a kind of thin-film material.
Preferably, its film thickness of Gd-Ge-Sb-Te and Gd-Sb-Te phase-change storage material obtained is 10-300nm.
Described Gd-Ge-Sb-Te and the Gd-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 Gd-Ge-Sb-Te and the Gd-Sb-Te phase-change storage material amorphous state resistance for phase transition storage raises, and crystalline resistance raises.
The preparation method of Gd-Ge-Sb-Te and the Gd-Sb-Te phase-change storage material for phase transition storage of the present invention, comprises the steps:
According to chemical general formula Gd
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 Gd target co-sputtering obtain described Gd-Ge-Sb-Te (or Gd-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, Gd 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 Gd 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 Gd target power supply.But be not limited to this, also can open Ge again after Gd 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 5-50 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, and between amorphous state and crystalline state, obvious resistance difference, can have better data retention characteristics.
Accompanying drawing explanation
Fig. 1 is that the Gd-Ge-Sb-Te phase transiting storing thin-film material square resistance of different Gd content in embodiment varies with temperature relation curve.
Fig. 2 is activation energy and the data retention result of calculation figure of the Gd-Ge-Sb-Te phase transiting storing thin-film material of different Gd 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 Gd-Ge-Sb-Te phase transiting storing thin-film material of different Gd content:
Phase-change material in the present embodiment adopts Ge
2sb
2te
5alloys target and Gd 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 Gd 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 Gd target power supply.The described cosputtering time is 30 minutes, and film thickness is approximately 150-200nm.
The Gd-Ge-Sb-Te phase transiting storing thin-film material of the different Gd content obtained by the present embodiment obtains Fig. 1 and Fig. 2 after testing:
Fig. 1 is that the Gd-Ge-Sb-Te phase transiting storing thin-film material square resistance for different Gd content in embodiment varies with temperature relation curve.As shown in Figure 1, resistivity measurement is carried out to serial Gd-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, Gd
0.3(Ge
2sb
2te
5)
99.7, Gd
3.14(Ge
2sb
2te
5)
96.86, Gd
4(Ge
2sb
2te
5)
96, Gd
6.14(Ge
2sb
2te
5)
93.8and Gd
8.52(Ge
2sb
2te
5)
91.48the Gd-Ge-Sb-Te phase transiting storing thin-film material of different Gd content, the crystallization temperature of its correspondence is respectively 166 DEG C, 177.1 DEG C, 181.7 DEG C, 190 DEG C, 223 DEG C and 242 DEG C.Can find out, below crystallization temperature, Gd-Ge-Sb-Te series phase transiting storing thin-film material is in the amorphous state of high-resistance state, and on the contrary, more than crystallization temperature, Gd-Ge-Sb-Te series phase transiting storing thin-film material is in the crystalline state of low resistance state.Here, after Gd doping, Gd-Ge-Sb-Te series phase transiting storing thin-film material crystallization temperature comparatively Ge
2sb
2te
5all increase, thus, be conducive to the raising of data retention.For the present invention, the crystallization temperature of described Gd-Ge-Sb-Te series phase transiting storing thin-film material increases along with Gd content and raises, and therefore can change crystallization temperature by adjustment Gd content.
Fig. 2 is activation energy and the data retention result of calculation figure of the Gd-Ge-Sb-Te phase transiting storing thin-film material of different Gd content in embodiment.Confining force is phase-change material vital characteristic, is one of important parameter weighing this phase-change material performance.First, confining force is mainly used for characterizing amorphous thermal stability, when probe temperature point is higher than phase-change material crystallization in the process heated up during crystallization temperature, and cannot test out this amorphous retention time, therefore the probe temperature point of confining force must lower than crystallization temperature.Moreover 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 Gd content of Fig. 1 corresponding Gd-Ge-Sb-Te series phase transiting storing thin-film material crystallization temperature, we choose Gd
0.3(Ge
2sb
2te
5)
99.7, Gd
3.14(Ge
2sb
2te
5)
96.86and Gd
6.14(Ge
2sb
2te
5)
93.86three compositions are used for out-of-service time mensuration, and extrapolate the temperature corresponding to crystallization activation energy and retention time.As shown in Figure 2, Gd
0.3(Ge
2sb
2te
5)
99.7crystallization activation energy (E
a) be 2.45eV, 10 annual datas keep temperature to be 87 DEG C; Gd
3.14(Ge
2sb
2te
5)
96.86crystallization activation energy (E
a) be 2.88eV, 10 annual datas keep temperature to be 94 DEG C; Gd
6.14(Ge
2sb
2te
5)
93.86crystallization activation energy (E
a) be 3.98eV, 10 annual datas keep temperature to be 115 DEG C.As can be drawn from Figure 2, the activation energy of Gd-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 improving amorphous thermal stability.
Compared with prior art, usefulness of the present invention is: this thin-film material, excellent performance can be obtained by the Gd element adulterating considerably less, show as and have stronger thermal stability, higher crystalline resistance, obvious resistance difference between amorphous state and crystalline state, and better data retention characteristics etc.
The description of the embodiment of the present invention and application are illustrative, and can not by scope restriction of the present invention in the above-described embodiments.
Claims (10)
1., for a Gd-Ge-Sb-Te or Gd-Sb-Te phase-change storage material for phase transition storage, be in Ge-Sb-Te or Sb-Te phase-change storage material, mix Gd form, its chemical general formula is Gd
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 Gd-Ge-Sb-Te or the Gd-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, and the atomic ratio of Sb-Te is 4:1,2:1 or 2:3.
3. as claimed in claim 1 for Gd-Ge-Sb-Te or the Gd-Sb-Te phase-change storage material of phase transition storage, it is characterized in that, compared with pure Ge-Sb-Te or Sb-Te, this phase-change material has higher crystallization temperature or better data retention, and its thermal stability improves simultaneously.
4. as claimed in claim 1 for Gd-Ge-Sb-Te or the Gd-Sb-Te phase-change storage material of phase transition storage, it is characterized in that, described Gd-Ge-Sb-Te or Gd-Sb-Te phase-change storage material realizes the external drive energy of the reversible transition of resistivity or light refractive index reflectivity, is electric pulse, laser pulse, electron beam or thermal drivers.
5., as claimed in claim 1 for Gd-Ge-Sb-Te or the Gd-Sb-Te phase-change storage material of phase transition storage, it is characterized in that, described Gd-Ge-Sb-Te or Gd-Sb-Te phase-change storage material is a kind of thin-film material.
6. the preparation method of Gd-Ge-Sb-Te or the Gd-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 Gd
100-x-y-z(Ge
xsb
yte
z) in Ge, Sb or Te proportioning adopt Ge
xsb
yte
zalloys target and Gd target co-sputtering, and obtain described Gd-Ge-Sb-Te phase-change storage material;
Or according to chemical general formula Gd
100-x-y-z(Ge
xsb
yte
z) in Sb or Te proportioning adopt Sb
yte
zalloys target and Gd target co-sputtering, and obtain described Gd-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 Gd target adopts DC power supply or radio-frequency power supply.
8. preparation method as claimed in claim 6, is characterized in that, during cosputtering, treat Ge
xsb
yte
zafter alloys target build-up of luminance, then open Gd target power supply, or open Ge again after Gd target build-up of luminance
xsb
yte
zalloys target, or both power supplys are opened simultaneously;
Or treat or Sb
yte
zafter alloys target build-up of luminance, then open Gd target power supply, or open Sb again after Gd 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 15-100W, and the described cosputtering time is 5-50 minute.
10. preparation method as claimed in claim 6, it is characterized in that, Gd-Ge-Sb-Te or the Gd-Sb-Te phase-change storage material obtained is phase change film material, and film thickness is 10-300nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510959334.6A CN105428531A (en) | 2015-12-20 | 2015-12-20 | Gd-Ge-Sb-Te and Gd-Sb-Te phase change memory material |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510959334.6A CN105428531A (en) | 2015-12-20 | 2015-12-20 | Gd-Ge-Sb-Te and Gd-Sb-Te phase change memory material |
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| Publication Number | Publication Date |
|---|---|
| CN105428531A true CN105428531A (en) | 2016-03-23 |
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ID=55506581
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|---|---|---|---|
| CN201510959334.6A Pending CN105428531A (en) | 2015-12-20 | 2015-12-20 | Gd-Ge-Sb-Te and Gd-Sb-Te phase change memory material |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002240432A (en) * | 2001-02-20 | 2002-08-28 | Ricoh Co Ltd | Optical recording medium, manufacturing method therefor, and optical recording reproducing apparatus |
| US20030031823A1 (en) * | 1999-05-12 | 2003-02-13 | Kazunori Ito | Phase-change optical recording medium and recording method and apparatus for the same |
| 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 |
| CN1874898A (en) * | 2003-11-05 | 2006-12-06 | 株式会社理光 | Dual-layer phase-change information recording medium and recording method thereof |
| CN101630559A (en) * | 2009-07-03 | 2010-01-20 | 北京工业大学 | (GeTe)*(SbTe*)*base dilute magnetic semiconductor material for storing information |
-
2015
- 2015-12-20 CN CN201510959334.6A patent/CN105428531A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030031823A1 (en) * | 1999-05-12 | 2003-02-13 | Kazunori Ito | Phase-change optical recording medium and recording method and apparatus for the same |
| JP2002240432A (en) * | 2001-02-20 | 2002-08-28 | Ricoh Co Ltd | Optical recording medium, manufacturing method therefor, and optical recording reproducing apparatus |
| 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 |
| CN1874898A (en) * | 2003-11-05 | 2006-12-06 | 株式会社理光 | Dual-layer phase-change information recording medium and recording method thereof |
| CN101630559A (en) * | 2009-07-03 | 2010-01-20 | 北京工业大学 | (GeTe)*(SbTe*)*base dilute magnetic semiconductor material for storing information |
Non-Patent Citations (1)
| Title |
|---|
| YU-JEN HUANG, ET AL.: "Characterizations and thermal stability improvement of phase-change memory device containing Ce-doped GeSbTe films", 《THIN SOLID FILMS》 * |
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