CN107732009A - A kind of samarium doping tin antimony phase change film material for phase transition storage and preparation method thereof - Google Patents
A kind of samarium doping tin antimony phase change film material for phase transition storage and preparation method thereof Download PDFInfo
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- CN107732009A CN107732009A CN201710767367.XA CN201710767367A CN107732009A CN 107732009 A CN107732009 A CN 107732009A CN 201710767367 A CN201710767367 A CN 201710767367A CN 107732009 A CN107732009 A CN 107732009A
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 230000008859 change Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000003860 storage Methods 0.000 title claims abstract description 14
- 230000007704 transition Effects 0.000 title claims abstract description 14
- 229910052772 Samarium Inorganic materials 0.000 title claims abstract description 12
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 title claims abstract description 12
- GVFOJDIFWSDNOY-UHFFFAOYSA-N antimony tin Chemical compound [Sn].[Sb] GVFOJDIFWSDNOY-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 3
- 238000004544 sputter deposition Methods 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 229910052681 coesite Inorganic materials 0.000 claims description 7
- 229910052906 cristobalite Inorganic materials 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229910052682 stishovite Inorganic materials 0.000 claims description 7
- 229910052905 tridymite Inorganic materials 0.000 claims description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 22
- 239000013077 target material Substances 0.000 description 15
- 239000010409 thin film Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000001552 radio frequency sputter deposition Methods 0.000 description 5
- 238000005477 sputtering target Methods 0.000 description 5
- 239000012782 phase change material Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
Classifications
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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
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8825—Selenides, e.g. GeSe
-
- 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
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention belongs to microelectronics technology, and in particular to a kind of samarium doping tin antimony phase change film material for phase transition storage and preparation method thereof.A kind of samarium doping tin antimony phase change film material for phase transition storage, its chemical molecular formula is (Sn15Sb85)xSmy；Wherein 0<X≤0.92,0<Y≤0.58, x+y=1.00.The heat endurance of samarium doping tin antimony phase change film material provided by the invention is good, and data retention is good, low-power consumption.
Description
Technical field
The invention belongs to microelectronics technology, and in particular to a kind of samarium doping tin antimony for phase transition storage is mutually thinning
Membrane material and preparation method thereof.
Background technology
At present, in order to realize the sustainable development of mobile device and Internet technology, human needs more at a high speed, higher storage
Density and more inexpensive nonvolatile memory.In nonvolatile memory family, phase transition storage (PCRAM) has very
Excellent performance：Storage speed is fast, energy expenditure, stability is good and is got well etc. with existing semiconductor device technology compatibility
(Yifeng Hu etc., Scripta MatSmialia, 2014,92：4-7).Phase change memory technology is Ovshinsky et al. in 20
The end of the sixties in century (Phys.Rev.Lett., 21,1450~1453,1968) and the beginning of the seventies (Appl.Phys.Lett., 18,
254~257,1971) propose.PCRAM data storages are to utilize crystalline state and the amorphous reversible transition state in phase-change material
Carry out storage information：There is high electrical resistance may be configured as logical zero state in amorphous state, having in crystalline state can set compared with low resistance
It is set to logical one state.
As the core of phase transition storage and phase transformation display, the phase-change characteristic of phase-change thin film determines each of resulting devices
Item performance.In order to improve the performance of phase-change thin film it may first have to know that those factors are most important and most critical.Phase speed change
Degree, power consumption and temperature stability are most important three factors of phase change memory device.But phase velocity and its heat endurance are
It is conflicting, such as faster crystallization rate generally means that relatively low crystallization temperature, and relatively low crystallization temperature would generally
Cause data retention undesirable.In order to improve combination property, most important is exactly to select suitable phase transition temperature and temperature stabilization
The material (T.C.Chong etc., Applied Physics LettSms, 88,122114,2006) of property.In order to meet such a need
Will, mainly phase-change material is modified using two kinds of means at present：One is superlattices (multilayer) phase-change material is prepared, secondly
It is to be modified using metal or semi-conducting material, the Sb adulterated such as Cr3T1Phase-change thin film (Yangyang Xia etc., Journal
Of Non-Crystalline Solids, 2015,422:46-50).
But Sn15Sb85Series storage material occupies critical role in phase-change material, but its data retention is paid no attention to
Think, it is impossible to meet the needs of many industries, govern Sn always15Sb85The development of series storage material.Therefore, a kind of number is sought
According to the good Sn of confining force15Sb85Series storage material turns into the road of the certainty of information technology advancement.
The content of the invention
It is an object of the invention to overcome prior art Sn15Sb85The data retention of series storage material is undesirable to be lacked
Fall into, there is provided a kind of samarium doping tin antimony phase change film material for phase transition storage and preparation method thereof.
The invention provides a kind of samarium doping tin antimony phase change film material for phase transition storage, its chemical molecular formula
For (Sn15Sb85)x Smy；Wherein 0<X≤0.92,0<Y≤0.58, x+y=1.00.
Present invention also offers a kind of preparation method of phase change film material, preparation process are as follows：
(a) Sn is prepared15Sb85Target；
(b) Sm targets are prepared, and Sn is adhered on after Sm targets are cut15Sb85Target surface；
(c) to posting Sm Sn15Sb85Target carries out magnetron sputtering, and the film of needs is prepared；Wherein, the film
Middle Sm doping passes through Sn15Sb85The quantity of the Sm targets that target surface posts regulates and controls.
Further, in described step (b), Sm targets cut into the sector structure of rule, and it is fan-shaped to circle
The number of degrees at heart angle are 30 °.
Further, in described step (c), substrate during magnetron sputtering is SiO2/ Si (100) substrate；And/or magnetic control
Power supply during sputtering uses radio-frequency power supply, and sputtering power is 25-35W；And/or the sputter gas that magnetron sputtering uses is Ar
Gas.
Further, the sputtering power is 30W.
Further, the purity of the Ar gas is percent by volume more than 99.999%, and gas flow is 15~45SCCM, is splashed
Pressure of emanating is 0.10~0.35Pa.
Further, the gas flow is 30SCCM, sputtering pressure 0.3Pa.
Further, the gross thickness for the film being prepared is 50nm.
Further, the purity of described Sm targets and Sb targets is in atomic percent more than 99.999%, background vacuum
No more than 1 × 10-4Pa。
Further, the thickness of the film is regulated and controled by the sputtering time of magnetron sputtering.
Beneficial effects of the present invention：(1) heat endurance of samarium doping tin antimony phase change film material provided by the invention is good, number
Good, the low-power consumption according to confining force；(2) thickness of samarium doping tin antimony phase change film material provided by the invention can pass through sputtering time
Control, crystalline resistance, phase transition temperature, heat endurance and the power consumption of film can be regulated and controled by the amount of samarium doping, therefore this
Class film can apply to phase transition storage and phase transformation display etc..
Embodiment
With reference to specific embodiment, the present invention is further illustrated.
Embodiment 1
This example prepares undoped Sn15Sb85Phase change film material, thickness 50nm.
Preparation process is：
1. clean SiO2/ Si (100) substrate, cleaning surface, the back side, removes dust granule, organic and inorganic impurity；
A) it is cleaned by ultrasonic 3-5 minutes, deionized water rinsing by force in acetone soln；
B) it is cleaned by ultrasonic 3-5 minutes, deionized water rinsing, high-purity N by force in ethanol solution2Dry up surface and the back side；
C) in 120 DEG C of drying in oven steam, about 20 minutes.
2. Sn is prepared using RF sputtering method15Sb85Prepare before film：
A) Sn is installed15Sb85Sputtering target material, the purity of target reach 99.999% (atomic percent), and background is true
Sky is evacuated to 1 × 10-4Pa；
B) sputtering power 30W is set；
C) use high-purity Ar gas as sputter gas (percent by volume reaches 99.999%), set Ar throughputs as
30SCCM, and sputtering pressure is adjusted to 0.3Pa.
3. nano phase change thin-film material is prepared using magnetically controlled sputter method：
A) space base support is rotated into target position, opens the radio-frequency power supply applied on target, the sputtering time according to setting
(200s), start to sputter target, clean target material surface；
B) after the completion of the cleaning of Sb target material surfaces, the dc source applied is closed on target, target will be rotated to for sputtering substrate
Position, target position radio-frequency power supply is opened, according to the sputtering time (130s) of setting, start to sputter single thin film.
Embodiment 2
This example prepares the Sn of Sm doping (x=0.08, one block of fan-shaped material)15Sb85Phase change film material, thickness 50nm.
Preparation process is：
1. clean SiO2/ Si (100) substrate, cleaning surface, the back side, removes dust granule, organic and inorganic impurity；
A) it is cleaned by ultrasonic 3-5 minutes, then deionized water rinsing by force in acetone soln；
B) it is cleaned by ultrasonic 3-5 minutes, then deionized water rinsing, high-purity N by force in ethanol solution2Dry up surface and the back side；
C) in 120 DEG C of drying in oven steam, about 20 minutes.
2. prepare before preparing film using RF sputtering method：
A) Sn is installed15Sb85Sputtering target material, it is being 2mm by thickness, a diameter of 40mm, the number of degrees of central angle are 30 degree of fan
Shape Sm pieces are a piece of to be positioned over Sn15Sb85Target surface, and overlap its center of circle.The purity of target reaches 99.999% (atom hundred
Divide ratio), and base vacuum is evacuated to 1 × 10-4Pa；
B) sputtering power 30W is set；
C) use high-purity Ar gas as sputter gas (percent by volume reaches 99.999%), set Ar throughputs as
30SCCM, and sputtering pressure is adjusted to 0.3Pa.
3. nano phase change thin-film material is prepared using magnetically controlled sputter method：
A) space base support is rotated into target position, opens the radio-frequency power supply applied on target, the sputtering time according to setting
(200s), start to sputter target, clean target material surface；
B) after the completion of target material surface cleaning, the radio-frequency power supply applied is closed on target, target position will be rotated to for sputtering substrate,
Target position radio-frequency power supply is opened, according to the sputtering time (130s) of setting, starts to sputter single thin film.
Embodiment 3
This example prepares the Sn of rare-earth Sm doping (x=0.16, two blocks of fan-shaped materials)15Sb85Phase change film material, thickness
50nm。
Preparation process is：
1. clean SiO2/ Si (100) substrate, cleaning surface, the back side, removes dust granule, organic and inorganic impurity；
A) it is cleaned by ultrasonic 3-5 minutes, then deionized water rinsing by force in acetone soln；
B) it is cleaned by ultrasonic 3-5 minutes, then deionized water rinsing, high-purity N by force in ethanol solution2Dry up surface and the back side；
C) in 120 DEG C of drying in oven steam, about 20 minutes.
2. prepare before preparing film using RF sputtering method：
A) Sn is installed15Sb85Sputtering target material, it is being 2mm by thickness, a diameter of 40mm, the number of degrees of central angle are the two of 30 degree
Piece sector Sm pieces are positioned over Sb targets surface, and overlap its center of circle.The purity of target reaches 99.999% (atomic percent),
And base vacuum is evacuated to 1 × 10-4Pa；
B) sputtering power 30W is set；
C) use high-purity Ar gas as sputter gas (percent by volume reaches 99.999%), set Ar throughputs as
30SCCM, and sputtering pressure is adjusted to 0.3Pa.
3. nano phase change thin-film material is prepared using magnetically controlled sputter method：
A) space base support is rotated into target position, opens the radio-frequency power supply applied on target, the sputtering time according to setting
(200s), start to sputter target, clean target material surface；
B) after the completion of target material surface cleaning, the radio-frequency power supply applied is closed on target, target position will be rotated to for sputtering substrate,
Target position radio-frequency power supply is opened, according to the sputtering time (130s) of setting, starts to sputter single thin film.
Embodiment 4
This example prepares the Sn of rare-earth Sm doping (x=0.24, three blocks of fan-shaped materials)15Sb85Phase change film material, thickness
50nm。
Preparation process is：
1. clean SiO2/ Si (100) substrate, cleaning surface, the back side, removes dust granule, organic and inorganic impurity；
A) it is cleaned by ultrasonic 3-5 minutes, then deionized water rinsing by force in acetone soln；
B) it is cleaned by ultrasonic 3-5 minutes, then deionized water rinsing, high-purity N by force in ethanol solution2Dry up surface and the back side；
C) in 120 DEG C of drying in oven steam, about 20 minutes.
2. prepare before preparing film using RF sputtering method：
A) Sn is installed15Sb85Sputtering target material, it is being 2mm by thickness, a diameter of 40mm, radian is 30 degree of three fan-shaped Sm
Piece is positioned over Sn15Sb85Target surface, and overlap its center of circle.The purity of target reaches 99.999% (atomic percent), and
Base vacuum is evacuated to 1 × 10-4Pa；
B) sputtering power 30W is set；
C) use high-purity Ar gas as sputter gas (percent by volume reaches 99.999%), set Ar throughputs as
30SCCM, and sputtering pressure is adjusted to 0.3Pa.
3. nano phase change thin-film material is prepared using magnetically controlled sputter method：
A) space base support is rotated into target position, opens the radio-frequency power supply applied on target, the sputtering time according to setting
(200s), start to sputter target, clean target material surface；
B) after the completion of target material surface cleaning, the dc source applied is closed on target, target position will be rotated to for sputtering substrate,
Target position radio-frequency power supply is opened, according to the sputtering time (120s) of setting, starts to sputter single thin film.
Embodiment 5
This example prepares the Sn of rare-earth Sm doping (x=0.32, four blocks of fan-shaped materials)15Sb85Phase change film material, thickness
50nm。
Preparation process is：
1. clean SiO2/ Si (100) substrate, cleaning surface, the back side, removes dust granule, organic and inorganic impurity；
A) it is cleaned by ultrasonic 3-5 minutes, then deionized water rinsing by force in acetone soln；
B) it is cleaned by ultrasonic 3-5 minutes, then deionized water rinsing, high-purity N by force in ethanol solution2Dry up surface and the back side；
C) in 120 DEG C of drying in oven steam, about 20 minutes.
2. prepare before preparing film using RF sputtering method：
A) Sn is installed15Sb85Sputtering target material, it is being 2mm by thickness, a diameter of 40mm, radian is 30 degree of four fan-shaped Sm
Piece is positioned over Sb targets surface, and overlaps its center of circle.The purity of target reaches 99.999% (atomic percent), and by background
Vacuum is evacuated to 1 × 10-4Pa；
B) sputtering power 30W is set；
C) use high-purity Ar gas as sputter gas (percent by volume reaches 99.999%), set Ar throughputs as
30SCCM, and sputtering pressure is adjusted to 0.3Pa.
3. nano phase change thin-film material is prepared using magnetically controlled sputter method：
A) space base support is rotated into target position, opens the radio-frequency power supply applied on target, the sputtering time according to setting
(200s), start to sputter target, clean target material surface；
B) after the completion of target material surface cleaning, the radio-frequency power supply applied is closed on target, target position will be rotated to for sputtering substrate,
Target position radio-frequency power supply is opened, according to the sputtering time (130s) of setting, starts to sputter single thin film.
The above is only the section Example of the present invention, any formal limitation not done to the present invention, it is every according to
Any simple modification made according to the technical spirit of the present invention to above-described embodiment, equivalent variations and modification, belong to the present invention
In the range of technical scheme.
Claims (10)
- A kind of 1. samarium doping tin antimony phase change film material for phase transition storage, it is characterised in that：Its chemical molecular formula is (Sn15Sb85)x Smy；Wherein 0<X≤0.92,0<Y≤0.58, x+y=1.00.
- A kind of 2. preparation method of phase change film material as claimed in claim 1, it is characterised in that：Preparation process is as follows：(a) Sn is prepared15Sb85Target；(b) Sm targets are prepared, and Sn is adhered on after Sm targets are cut15Sb85Target surface；(c) to posting Sm Sn15Sb85Target carries out magnetron sputtering, and the film of needs is prepared；Wherein, the middle Sm of the film Doping pass through Sn15Sb85The quantity of the Sm targets that target surface posts regulates and controls.
- 3. the preparation method of phase change film material according to claim 2, it is characterised in that：In described step (b), Sm targets cut into the sector structure of rule, and it is fan-shaped to the number of degrees of central angle be 30 °.
- 4. the preparation method of phase change film material according to claim 2, it is characterised in that：In described step (c), Substrate during magnetron sputtering is SiO2/ Si (100) substrate；And/or power supply during magnetron sputtering uses radio-frequency power supply, and sputter work( Rate is 25-35W；And/or the sputter gas that magnetron sputtering uses is Ar gas.
- 5. the preparation method of phase change film material according to claim 4, it is characterised in that：The sputtering power is 30W.
- 6. the preparation method of phase change film material according to claim 2, it is characterised in that：The purity of the Ar gas is body Product percentage more than 99.999%, gas flow is 15~45SCCM, and sputtering pressure is 0.10~0.35Pa.
- 7. the preparation method of phase change film material according to claim 6, it is characterised in that：The gas flow is 30SCCM, sputtering pressure 0.3Pa.
- 8. the preparation method of phase change film material according to claim 2, it is characterised in that：The film being prepared it is total Thickness is 50nm.
- 9. the preparation method of phase change film material according to claim 2, it is characterised in that：Described Sm targets and Sb targets The purity of material is not more than 1 × 10 in atomic percent more than 99.999%, background vacuum-4Pa。
- 10. the preparation method of phase change film material according to claim 2, it is characterised in that：The thickness of the film leads to The sputtering time of magnetron sputtering is crossed to regulate and control.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108615811A (en) * | 2018-04-27 | 2018-10-02 | 江苏理工学院 | A kind of lanthanide-doped ZnSb nano phase change materials and preparation method thereof |
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| CN1756667A (en) * | 2003-03-24 | 2006-04-05 | 三菱化学株式会社 | Phase variation recording material and information recording medium |
| CN105514266A (en) * | 2015-12-03 | 2016-04-20 | 江苏理工学院 | Rare earth doped Sb-based phase thinned film material and film preparation method |
| CN106229409A (en) * | 2016-09-26 | 2016-12-14 | 江苏理工学院 | A kind of Er Se Sb nano phase change thin-film material and its preparation method and application |
-
2017
- 2017-08-31 CN CN201710767367.XA patent/CN107732009A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1442853A (en) * | 2002-03-05 | 2003-09-17 | 三菱化学株式会社 | Phase change recording material for information recording medium and information recording medium using said material |
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| CN105514266A (en) * | 2015-12-03 | 2016-04-20 | 江苏理工学院 | Rare earth doped Sb-based phase thinned film material and film preparation method |
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Non-Patent Citations (1)
| Title |
|---|
| HUA ZOU等: "Simultaneous thermal stability and phase change speed improvement of Sn15Sb85 thin film through erbium doping", 《JOURNAL OF APPLIED PHYSICS》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108615811A (en) * | 2018-04-27 | 2018-10-02 | 江苏理工学院 | A kind of lanthanide-doped ZnSb nano phase change materials and preparation method thereof |
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