CN106229409A - A kind of Er Se Sb nano phase change thin-film material and its preparation method and application - Google Patents
A kind of Er Se Sb nano phase change thin-film material and its preparation method and application Download PDFInfo
- Publication number
- CN106229409A CN106229409A CN201610852807.7A CN201610852807A CN106229409A CN 106229409 A CN106229409 A CN 106229409A CN 201610852807 A CN201610852807 A CN 201610852807A CN 106229409 A CN106229409 A CN 106229409A
- Authority
- CN
- China
- Prior art keywords
- phase change
- film material
- nano
- sputtering
- thin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 70
- 230000008859 change Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011669 selenium Substances 0.000 claims abstract description 64
- 238000000034 method Methods 0.000 claims abstract description 39
- 230000007704 transition Effects 0.000 claims abstract description 12
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003860 storage Methods 0.000 claims abstract description 9
- 230000009466 transformation Effects 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 238000004544 sputter deposition Methods 0.000 claims description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 16
- 239000013077 target material Substances 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 14
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 238000001552 radio frequency sputter deposition Methods 0.000 claims description 6
- 238000005477 sputtering target Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000231 atomic layer deposition Methods 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 238000004549 pulsed laser deposition Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims 1
- 239000012782 phase change material Substances 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 5
- 230000008025 crystallization Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000002441 reversible effect Effects 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000011232 storage material Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 58
- 239000010408 film Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 230000033228 biological regulation Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- -1 thickness is 50nm Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 229910005936 Ge—Sb Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000003068 static effect Effects 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
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- H10N70/023—Formation of switching materials, e.g. deposition of layers by chemical vapor deposition, e.g. MOCVD, ALD
-
- 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
- H10N70/8825—Selenides, e.g. GeSe
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention belongs to technical field of nano material, relate to a kind of Er Se Sb nano phase change thin-film material and its preparation method and application.The thin-film material of the present invention is elementary composition by erbium, selenium, three kinds of antimony, and its chemical general formula is Erx(SeySb100‑y)1‑x, wherein 0 < x≤0.05,0 < y≤50.The nano phase change material of the present invention can realize reversible phase transition process, and the low-resistance difference of height before and after phase transformation is bigger, it is easy to accomplish needs " 0 " or " 1 " differentiated in storage, is ideal phase-change storage material；The preparation method of the present invention is the most ripe, it is easy to accomplish with the compatibility of existing semiconductor technology；The nano phase change material of the present invention inherits the advantage that rich antimony phase phase velocity is fast, is provided simultaneously with higher crystallization temperature and data retention, is also equipped with higher crystalline state and amorphous state resistance, advantageously reduces the power consumption of phase change memory device.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of Er-Se-Sb nano phase change thin-film material and system thereof
Preparation Method and application.
Background technology
At 21 century global age, information plays increasing effect in daily life and work.Meanwhile, with person
It is day by day frequent that people exchange, and the data volume that human society is obtained is skyrocketed through year by year.In order to not restrict sending out of human civilization
Exhibition, it is achieved the efficient utilization of information, is necessary for realizing long-time stable storage (the storage i.e. record of information of super amount information
And preserve).
At present, the major product in semiconductor memory market be dynamic memory (DRAM), static memory (SRAM) and
Flash memory (FLASH) etc..Wherein, flash memory occupies the share of more than 90% in non-volatility memorizer market, becomes quasiconductor and deposits
The main product in reservoir market.But, along with improving constantly of flush memory device memory density, industrial quarters and scientific circles find flash memory
Technology has faced huge challenge, essentially consists in that flush memory device size is difficult to reduce, writing speed is slow, erasable number of times is limited etc. and asks
Topic.
In recent years, in order to solve a difficult problem for conventional flash memory, industrial quarters (as international in Samsung, Micron Technology, Intel etc. well-known is partly led
Body company) and scientific circles all active development a new generation storage material and technology, wherein phase transition storage (Phase-Change
Random Access Memory, is abbreviated as PCRAM) owing to having (> 10 that have extended cycle life13Secondary), component size is little, it is close to store
Degree is high, reading speed is fast, stability is strong, high-low temperature resistant (-55～125 DEG C), anti-vibration and with existing integrated circuit technology phase
The advantage such as compatible, is paid close attention to by scientific circles and industrial quarters and (sees Yifeng Hu, et al., Applied Physics
Letter,2015,107:263105).PCRAM utilizes the reversible transition between phase-change material crystalline state and amorphous state to store letter
Breath: there is during amorphous state high electrical resistance, may be configured as logical zero state；There is during crystalline state relatively low resistance, may be configured as logical one
State.
As the core of phase transition storage, the performance of nano phase change thin film is (such as heat stability, phase velocity, phase transformation
Power consumption etc.) it is the key factor affecting device performance.In order to make memory device realize higher stability, longer circulation simultaneously
Life-span and ultrafast reading speed, it is desirable to corresponding phase-change material must simultaneously have bigger amorphous state/crystalline resistance ratio, non-
Chemical stability the most stability, preferable under crystalline state and relatively low fusing point and thermal conductivity.But, crystallization rate faster
Generally mean that relatively low crystallization temperature, and relatively low crystallization temperature to normally result in data retention undesirable.
(Sb accounts for leading phase-change alloy thin film to rich antimony (Sb) Nanoalloy thin film in the structure, such as Ga-Sb, Ge-Sb, Sn-
Sb etc.) due to the existence of Sb, there is high phase velocity (generally less than 10ns), by the extensive concern of researcher, but this
Class material there is also the shortcoming that heat stability is poor, and the phase transition performance therefore improving rich antimony Nanoalloy thin film will become in the future
The Hot Contents of research.
Summary of the invention
For above-mentioned situation, it is an object of the invention to utilization and be widely used in the fields such as agricultural, industry, space flight, especially
It is that the rare earth played a significant role at information technology and illumination field is doped modification to rich antimony Nanoalloy thin film, obtains one
Plant the nano phase change thin-film material that phase velocity is fast, Heat stability is good, data retention are good, low in energy consumption.
To achieve these goals, the present invention adopts the following technical scheme that
A kind of Er-Se-Sb nano phase change thin-film material, it is elementary composition by erbium (Er), selenium (Se), three kinds of antimony (Sb).Logical
Cross the content controlling erbium, change selenium and the ratio of antimony simultaneously, different crystallization temperature, different activation energy and different melting points can be obtained
Phase-change material, these phase-change materials can occur reversible transition under the effect of outside electric pulse or laser pulse.
Preferably, the chemical general formula of described Er-Se-Sb nano phase change thin-film material is Erx(SeySb100-y)1-x, wherein 0 <
X≤0.05,0 < y≤50, preferably 0.006≤x≤0.015,5≤y≤50.
It should be noted that although described Er-Se-Sb nano phase change thin-film material belongs to nano-level thin-membrane material, but its
It is not limited to the final forms such as nano thin-film, different thickness can be made according to specific needs.
The preparation method of above-mentioned Er-Se-Sb nano phase change thin-film material, it is selected from magnetron sputtering method, chemical gaseous phase deposition
Any one in method, atomic layer deposition method, electron-beam vapor deposition method, pulsed laser deposition, galvanoplastic, preferably magnetron sputtering
Method, its reason is that the preparation process of the method is the most flexible, the method that both can use Er, Se, Sb target co-sputtering, it is also possible to
Use Er and SeySb100-yThe method of alloys target cosputtering, it is also possible to use and Er block is directly placed at SeySb100-yAlloy target material
The method of upper sputtering.Said method can prepare the Er-Se-Sb nano phase change of the present invention according to the proportioning in chemical general formula
Thin-film material.
Preferably, the substrate that described magnetron sputtering method uses is SiO2/ Si (100) substrate.
Preferably, the target that described magnetron sputtering method uses is Erx(Se30Sb70)1-xComposition target, wherein 0.006≤x≤
0.05, i.e. at Se30Sb70Pinwheel stacks Er sheet, Se30Sb70The atomic percent purity of target reaches 99.999%, Er sheet former
Sub-percent purity reaches 99.999%.
Preferably, the sputter gas that described magnetron sputtering method uses is high-purity argon gas, and percent by volume purity reaches
99.999%.
Preferably, the background vacuum of described magnetron sputtering method is not more than 1 × 10-4Pa。
Preferably, the sputtering power of described magnetron sputtering method is 20～40W, preferably 30W.
Preferably, the gas flow of described magnetron sputtering method is 25～35sccm, preferably 30sccm
Preferably, the sputtering pressure of described magnetron sputtering method is 0.2～0.4Pa, preferably 0.3Pa.
The Er-Se-Sb nano phase change thin-film material of the present invention, uses the method deposition of magnetron sputtering to form.By stacking
The number of plies of Er sheet control Erx(Se30Sb70)1-xThe composition ratio of middle Er.
Preferably, the concrete preparation method of described Er-Se-Sb nano phase change thin-film material comprises the following steps:
1) SiO is cleaned2/ Si (100) substrate；
2) install composite sputtering target material, set sputtering power, Sputtering Ar gas flow and sputtering pressure；
3) RF sputtering method is used to prepare Er-Se-Sb nano phase change thin-film material.
The application in preparing phase transition storage and phase transformation display of the above-mentioned Er-Se-Sb nano phase change thin-film material.
Compared with prior art, present invention have the advantage that of technique scheme is used
(1) nano phase change material provided by the present invention can realize reversible phase transition process, and the height before and after phase transformation
Low-resistance difference is bigger, it is easy to accomplish needs " 0 " or " 1 " differentiated in storage, is ideal phase-change storage material；
(2) preparation method of the present invention is the most ripe, it is easy to accomplish with the compatibility of existing semiconductor technology；
(3) the nano phase change material of the present invention inherits the advantage that rich antimony phase phase velocity is fast, is provided simultaneously with higher crystalline substance
Change temperature and data retention；
(4) the nano phase change material of the present invention is also equipped with higher crystalline state and amorphous state resistance, advantageously reduces phase transformation and deposits
The power consumption of memory device.
Accompanying drawing explanation
Fig. 1 is by being carried in 3 kinds of Er-Se-Sb nano phase change thin-film materials provided in embodiment 2 to 4 and embodiment 1
The In-situ resistance of the Se-Sb nano film material of undoped p Er of confession and the relation curve of temperature.
Fig. 2 is the Arrhenius curve of the thin-film material provided in embodiment 1 to 3.
Fig. 3 is the level analysis figure of the thin-film material provided in embodiment 1 to 4.
Detailed description of the invention
Technical scheme is expanded on further below in conjunction with the drawings and specific embodiments.It should be appreciated that
These embodiments are merely to illustrate the present invention, and are not limiting as protection scope of the present invention.It addition, unless specifically indicated, following
In embodiment, the instrument of use, reagent, material etc. all can be obtained by routine business means.
Embodiment 1: prepare the Se without Er doping30Sb70Nano phase change thin-film material.
1, SiO is cleaned2The surface of/Si (100) substrate and the back side, remove dust granule, organic and inorganic impurity；
A) strong ultrasonic cleaning 3～5 minutes in acetone soln, deionized water rinsing；
B) strong ultrasonic cleaning 3～5 minutes in ethanol solution, deionized water rinsing, high-purity N2Dry up surface and the back side；
C) at 120 DEG C of drying in oven steam, about 20 minutes.
2, RF sputtering method is used to prepare Se30Sb70Prepare before thin film:
A) Se is installed30Sb70Sputtering target material (atomic percent purity reaches 99.999%), and background vacuum is evacuated to 1
×10-4Pa；
B) sputtering power 30W is set；
C) use high-purity argon gas (percent by volume purity reaches 99.999%) as sputter gas, set argon flow amount as
30sccm, and by sputtering pressure regulation to 0.3Pa.
3, magnetically controlled sputter method is used to prepare Se30Sb70Nano phase change thin-film material:
A) space base torr is rotated to target position, open the radio-frequency power supply applied on target, according to the sputtering time set
(300s), start target surface is sputtered, clean target material surface；
B), after target material surface has cleaned, close the radio-frequency power supply applied on target, substrate to be sputtered rotated to target position,
Open target position radio-frequency power supply, according to the sputtering time (145s) set, start sputtered film.
Measuring through EDS, gained thin film is Se30Sb70Thin film, thickness is 50nm, and film thickness can be come by sputtering time
Control.
Embodiment 2: preparation Er0.006(Se30Sb70)0.994Nano phase change thin-film material.
1, SiO is cleaned2The surface of/Si (100) substrate and the back side, remove dust granule, organic and inorganic impurity；
A) strong ultrasonic cleaning 3～5 minutes in acetone soln, deionized water rinsing；
B) strong ultrasonic cleaning 3～5 minutes in ethanol solution, deionized water rinsing, high-purity N2Dry up surface and the back side；
C) at 120 DEG C of drying in oven steam, about 20 minutes.
2, RF sputtering method is used to prepare Er0.006(Se30Sb70)0.994Prepare before thin film:
A) Se is installed30Sb70Sputtering target material, is 2mm by 1 thickness, a diameter of 40mm, and radian is that the fan-shaped Er sheet of 15 ° is put
In Se30Sb70Target material surface, makes the two center of circle overlap, and background vacuum is evacuated to 1 × 10-4Pa, wherein Se30Sb70Target and
The atomic percent purity of Er sheet all reaches 99.999%；
B) sputtering power 30W is set；
C) use high-purity argon gas (percent by volume purity reaches 99.999%) as sputter gas, set argon flow amount as
30sccm, and by sputtering pressure regulation to 0.3Pa.
3, magnetically controlled sputter method is used to prepare Er0.006(Se30Sb70)0.994Nano phase change thin-film material:
A) space base torr is rotated to Erx(Se30Sb70)1-xTarget position, opens Erx(Se30Sb70)1-xThe radio frequency applied on target
Power supply, according to the sputtering time (300s) set, starts Erx(Se30Sb70)1-xTarget surface sputters, and cleans Erx
(Se30Sb70)1-xTarget target material surface；
b)Erx(Se30Sb70)1-xAfter target surface cleaning completes, close Erx(Se30Sb70)1-xThe radio frequency electrical applied on target
Source, rotates to Er by substrate to be sputteredx(Se30Sb70)1-xTarget target position, opens Erx(Se30Sb70)1-xTarget target position radio-frequency power supply, depends on
According to the sputtering time (145s) set, start to sputter single thin film.
Measuring through EDS, gained thin film is Er0.006(Se30Sb70)0.994Thin film, thickness is 50nm, and film thickness can pass through
Sputtering time controls.
Embodiment 3: preparation Er0.012(Se30Sb70)0.988Nano phase change thin-film material.
1, SiO is cleaned2The surface of/Si (100) substrate and the back side, remove dust granule, organic and inorganic impurity；
A) strong ultrasonic cleaning 3～5 minutes in acetone soln, deionized water rinsing；
B) strong ultrasonic cleaning 3～5 minutes in ethanol solution, deionized water rinsing, high-purity N2Dry up surface and the back side；
C) at 120 DEG C of drying in oven steam, about 20 minutes.
2, RF sputtering method is used to prepare Er0.012(Se30Sb70)0.988Prepare before thin film:
A) Se is installed30Sb702 thickness are 2mm by sputtering target material, a diameter of 40mm, and radian is that the fan-shaped Er sheet of 15 ° is put
In Se30Sb70Target material surface, makes the two center of circle overlap, and background vacuum is evacuated to 1 × 10-4Pa, wherein Se30Sb70Target and
The atomic percent purity of Er sheet all reaches 99.999%；
B) sputtering power 30W is set；
C) use high-purity argon gas (percent by volume purity reaches 99.999%) as sputter gas, set argon flow amount as
30sccm, and by sputtering pressure regulation to 0.3Pa.
3, magnetically controlled sputter method is used to prepare Er0.012(Se30Sb70)0.988Nano phase change thin-film material:
A) space base torr is rotated to Erx(Se30Sb70)1-xTarget position, opens Erx(Se30Sb70)1-xThe radio frequency applied on target
Power supply, according to the sputtering time (300s) set, starts Erx(Se30Sb70)1-xTarget surface sputters, and cleans Erx
(Se30Sb70)1-xTarget target material surface；
b)Erx(Se30Sb70)1-xAfter target surface cleaning completes, close Erx(Se30Sb70)1-xThe radio frequency electrical applied on target
Source, rotates to Er by substrate to be sputteredx(Se30Sb70)1-xTarget target position, opens Erx(Se30Sb70)1-xTarget target position radio-frequency power supply, depends on
According to the sputtering time (145s) set, start to sputter single thin film.
Measuring through EDS, gained thin film is Er0.012(Se30Sb70)0.988Thin film, thickness is 50nm, and film thickness can pass through
Sputtering time controls.
Embodiment 4: preparation Er0.018(Se30Sb70)0.982Nano phase change thin-film material.
1, SiO is cleaned2The surface of/Si (100) substrate and the back side, remove dust granule, organic and inorganic impurity；
A) strong ultrasonic cleaning 3～5 minutes in acetone soln, deionized water rinsing；
B) strong ultrasonic cleaning 3～5 minutes in ethanol solution, deionized water rinsing, high-purity N2Dry up surface and the back side；
C) at 120 DEG C of drying in oven steam, about 20 minutes.
2, RF sputtering method is used to prepare Er0.018(Se30Sb70)0.982Prepare before thin film:
A) Se is installed30Sb703 thickness are 2mm by sputtering target material, a diameter of 40mm, and radian is that the fan-shaped Er sheet of 15 ° is put
In Se30Sb70Target material surface, makes the two center of circle overlap, and background vacuum is evacuated to 1 × 10-4Pa, wherein Se30Sb70Target and
The atomic percent purity of Er sheet all reaches 99.999%；
B) sputtering power 30W is set；
C) use high-purity argon gas (percent by volume purity reaches 99.999%) as sputter gas, set argon flow amount as
30sccm, and by sputtering pressure regulation to 0.3Pa.
3, magnetically controlled sputter method is used to prepare Er0.018(Se30Sb70)0.982Nano phase change thin-film material:
A) space base torr is rotated to Erx(Se30Sb70)1-xTarget position, opens Erx(Se30Sb70)1-xThe radio frequency applied on target
Power supply, according to the sputtering time (300s) set, starts Erx(Se30Sb70)1-xTarget surface sputters, and cleans Erx
(Se30Sb70)1-xTarget target material surface；
b)Erx(Se30Sb70)1-xAfter target surface cleaning completes, close Erx(Se30Sb70)1-xThe radio frequency electrical applied on target
Source, rotates to Er by substrate to be sputteredx(Se30Sb70)1-xTarget target position, opens Erx(Se30Sb70)1-xTarget target position radio-frequency power supply, depends on
According to the sputtering time (145s) set, start to sputter single thin film.
Measuring through EDS, gained thin film is Er0.018(Se30Sb70)0.982Thin film, thickness is 50nm, and film thickness can pass through
Sputtering time controls.
Embodiment 5: the performance test of nano phase change thin-film material.
In order to investigate the performance of the Er-Se-Sb nano phase change thin-film material of the present invention, described in embodiment 2 to 4
Preparation method, prepares respectively and has the Er-Se-Sb nano phase change thin-film material of different Er doping (film thickness is
50nm), and with embodiment 1 in prepare non-impurity-doped thin-film material compare test, obtain each nano phase change thin-film material
The relation curve (as shown in Figure 1) of In-situ resistance and temperature and the out-of-service time of each nano phase change thin-film material and temperature
Corresponding relation curve (as shown in Figure 2) reciprocal.
The In-situ resistance of each nano phase change thin-film material is as follows with the relation test method of temperature: outside by heating platform
Connect 6517B type megameter (Keithley instrument company, the U.S.) and build in site measurement resistance v. temperature and resistivity-time pass
The test system of system.The temperature of heating platform is by TP94 type temperature control system (Linkam scientific instrument Co., Ltd, English
State) regulation, temperature rate reaches as high as 90 DEG C/min, and temperature control is the most accurate.Heating rate employed in this test process
It is 10 DEG C/min.In heating and cooling process, the fixing voltage being added on film probe is 2.5V, utilizes megameter to measure with temperature
The electric current of change, then it is converted into corresponding resistance.
As it is shown in figure 1, at low temperatures, all thin-film materials are in high-resistance amorphous state.Continuous liter along with temperature
Height, the resistance of thin-film material slowly reduces, when reaching its phase transition temperature, except Er0.018(Se30Sb70)0.982Nano phase change is thin
The resistance of other thin-film materials beyond membrane material reduces rapidly, and after arriving a certain value, basic this resistance of holding is constant.Above-mentioned survey
Test result shows, 3 kinds of thin-film materials of resistance generation rapid drawdown there occurs by the transformation of amorphous state to crystalline state.
The out-of-service time of each nano phase change thin-film material is as follows from the corresponding relation method of testing of inverse temperature: different
Constant annealing temperature under measure the curve that changes with annealing time of resistance of nano phase change thin-film material.Electricity when thin-film material
When resistance is reduced to the 50% of original numerical value, i.e. think that resistance had lost efficacy.By the out-of-service time under different temperatures and corresponding temperature
Mapping reciprocal, and by curve extending to 10 year (about 315360000s), obtain the temperature of correspondence.Utilize phase-change material by data
Temperature corresponding when keeping 10 years can be used to pass judgment on the data holding ability of material, this be also the judgment criteria generally acknowledged in the industry it
One.
As in figure 2 it is shown, data are only kept the temperature of 10 years by the nano phase change thin-film material of undoped p rare earth in embodiment 1
There are 126 DEG C, and the temperature that data keep 10 years is all improved, wherein by the Er-Se-Sb nano phase change thin film of the present invention
Er0.012(Se30Sb70)0.988The temperature that data keep 10 years can be improved to 150 DEG C by nano film material, and traditional
Ge2Sb2Te5The temperature that data keep 10 years is only 85 DEG C by thin-film material.It follows that the Er-Se-Sb nanometer phase of the present invention
Variation film material has than traditional Ge2Sb2Te5The data holding ability that thin-film material is more excellent.
The Kunbelka-Munk function relation curve of each phase change film material is as it is shown on figure 3, this curve can be used for characterizing
The optical absorption characteristic of material, concrete method of testing is as follows: use 7100CRT type near infrared spectrometer (Shanghai precision instrument
Instruments and meters company limited) in the range of the test wavelength of 400～2500nm, test the optical reflectivity (R) of material, the suction of material
Yield (A) is by (1-R)2/ 2R determines, the optical band gap of material is determined by the character in high-absorbility region, the wherein optics of thin film
Absorption characteristic changes closely related with interband.
As it is shown on figure 3, the linear fit part of curve is in energy axes when the optical band gap correspondence absorbance of material is 0
Values of intercept.In embodiment 1, the optical band gap of the nano phase change thin-film material of undoped p rare earth only has 1.41eV, and the present invention
The optical band gap of Er-Se-Sb nano phase change thin film is all improved, wherein Er0.018(Se30Sb70)0.082Nano phase change thin film material
The optical band gap of material can improve to 1.68eV.The optical band gap increased will cause bigger Eg/kBT ratio, the basis of thin-film material
Levying carrier concentration and electrical conductivity then can decline accordingly, this will assist in the RESET operation power consumption reducing device.
From the result of above-described embodiment, the thickness of the Er-Se-Sb nano phase change thin-film material that the present invention provides is permissible
By sputtering time control, its crystalline resistance, phase transition temperature, heat stability and power consumption can be carried out by the doping of rare earth Er
Regulation and control, the most this kind of thin-film material can apply to prepare the device such as phase transition storage and phase transformation display.
Claims (7)
1. an Er-Se-Sb nano phase change thin-film material, it is elementary composition by erbium, selenium, three kinds of antimony.
Er-Se-Sb nano phase change thin-film material the most according to claim 1, it is characterised in that:
The chemical general formula of described Er-Se-Sb nano phase change thin-film material is Erx(SeySb100-y)1-x, wherein 0 < x≤0.05,0 < y
≤50。
Er-Se-Sb nano phase change thin-film material the most according to claim 2, it is characterised in that:
0.006≤x≤0.015,5≤y≤50.
4. a preparation method for Er-Se-Sb nano phase change thin-film material according to any one of claim 1 to 3, its
Selected from magnetron sputtering method, chemical vapour deposition technique, atomic layer deposition method, electron-beam vapor deposition method, pulsed laser deposition, galvanoplastic
In any one.
Preparation method the most according to claim 4, it is characterised in that:
The design parameter of described magnetron sputtering method is as follows:
Substrate is SiO2/ Si (100) substrate；
Target is Erx(Se30Sb70)1-xComposition target, wherein Se30Sb70The atomic percent purity of target reaches 99.999%, Er sheet
Atomic percent purity reach 99.999%；
Sputter gas is high-purity argon gas, and percent by volume purity reaches 99.999%；
Background vacuum is not more than 1 × 10-4Pa；
Sputtering power is 20～40W；
Gas flow is 25～35sccm；
Sputtering pressure is 0.2～0.4Pa.
Preparation method the most according to claim 5, it is characterised in that:
Specifically comprising the following steps that of described magnetron sputtering method
1) SiO is cleaned2/ Si (100) substrate；
2) install composite sputtering target material, set sputtering power, Sputtering Ar gas flow and sputtering pressure；
3) RF sputtering method is used to prepare Er-Se-Sb nano phase change thin-film material.
Phase transition storage prepared by Er-Se-Sb nano phase change thin-film material the most according to any one of claim 1 to 3
With the application in phase transformation display.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610852807.7A CN106229409B (en) | 2016-09-26 | 2016-09-26 | A kind of Er-Se-Sb nano phase change thin-film material and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610852807.7A CN106229409B (en) | 2016-09-26 | 2016-09-26 | A kind of Er-Se-Sb nano phase change thin-film material and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106229409A true CN106229409A (en) | 2016-12-14 |
| CN106229409B CN106229409B (en) | 2019-01-22 |
Family
ID=58076321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610852807.7A Active CN106229409B (en) | 2016-09-26 | 2016-09-26 | A kind of Er-Se-Sb nano phase change thin-film material and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106229409B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106960907A (en) * | 2017-02-28 | 2017-07-18 | 宁波大学 | A kind of rare earth Er doping Ge2Sb2Te5Phase transiting storing thin-film material and preparation method thereof |
| CN107732009A (en) * | 2017-08-31 | 2018-02-23 | 江苏理工学院 | A kind of samarium doping tin antimony phase change film material for phase transition storage and preparation method thereof |
| CN108922960A (en) * | 2018-06-27 | 2018-11-30 | 中国科学院上海微系统与信息技术研究所 | Ge-Se-Sb composite material, 1S1R phase-changing memory unit and preparation method |
| CN109817806A (en) * | 2018-12-26 | 2019-05-28 | 江苏理工学院 | A kind of ZnSb/SiO2Composite phase-change film and its preparation method and application |
| US10889887B2 (en) | 2016-08-22 | 2021-01-12 | Honeywell International Inc. | Chalcogenide sputtering target and method of making the same |
| CN112397644A (en) * | 2019-08-15 | 2021-02-23 | 中国科学院上海微系统与信息技术研究所 | Phase change material, phase change storage unit and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101488558A (en) * | 2009-02-25 | 2009-07-22 | 中国科学院上海微系统与信息技术研究所 | M-Sb-Se phase changing thin-film material used for phase changing memory |
| CN103378289A (en) * | 2012-12-20 | 2013-10-30 | 同济大学 | Multi-layer nanometer composite thin film material for high-speed high-density phase transition storage and method for preparing material |
| CN103855302A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院上海微系统与信息技术研究所 | Al-Sb-Se material used for phase change memory and preparation method |
-
2016
- 2016-09-26 CN CN201610852807.7A patent/CN106229409B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101488558A (en) * | 2009-02-25 | 2009-07-22 | 中国科学院上海微系统与信息技术研究所 | M-Sb-Se phase changing thin-film material used for phase changing memory |
| CN103855302A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院上海微系统与信息技术研究所 | Al-Sb-Se material used for phase change memory and preparation method |
| CN103378289A (en) * | 2012-12-20 | 2013-10-30 | 同济大学 | Multi-layer nanometer composite thin film material for high-speed high-density phase transition storage and method for preparing material |
Non-Patent Citations (1)
| Title |
|---|
| HUA ZOU等: ""Improvement of the thermal stability of Sb thin films through erbium doping"", 《ROYAL SOCIETY OF CHENISTRY》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10889887B2 (en) | 2016-08-22 | 2021-01-12 | Honeywell International Inc. | Chalcogenide sputtering target and method of making the same |
| US11946132B2 (en) | 2016-08-22 | 2024-04-02 | Honeywell International Inc. | Chalcogenide sputtering target and method of making the same |
| CN106960907A (en) * | 2017-02-28 | 2017-07-18 | 宁波大学 | A kind of rare earth Er doping Ge2Sb2Te5Phase transiting storing thin-film material and preparation method thereof |
| CN106960907B (en) * | 2017-02-28 | 2019-03-15 | 宁波大学 | A kind of rare earth Er doping Ge2Sb2Te5Phase transiting storing thin-film material and preparation method thereof |
| CN107732009A (en) * | 2017-08-31 | 2018-02-23 | 江苏理工学院 | A kind of samarium doping tin antimony phase change film material for phase transition storage and preparation method thereof |
| CN108922960A (en) * | 2018-06-27 | 2018-11-30 | 中国科学院上海微系统与信息技术研究所 | Ge-Se-Sb composite material, 1S1R phase-changing memory unit and preparation method |
| CN109817806A (en) * | 2018-12-26 | 2019-05-28 | 江苏理工学院 | A kind of ZnSb/SiO2Composite phase-change film and its preparation method and application |
| CN109817806B (en) * | 2018-12-26 | 2023-04-07 | 江苏理工学院 | ZnSb/SiO2 composite phase change film and preparation method and application thereof |
| CN112397644A (en) * | 2019-08-15 | 2021-02-23 | 中国科学院上海微系统与信息技术研究所 | Phase change material, phase change storage unit and preparation method thereof |
| CN112397644B (en) * | 2019-08-15 | 2023-07-14 | 中国科学院上海微系统与信息技术研究所 | Phase change material, phase change memory unit and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106229409B (en) | 2019-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106229409B (en) | A kind of Er-Se-Sb nano phase change thin-film material and its preparation method and application | |
| CN106374041B (en) | A kind of Sb70Se30/SiO2Multi-layer nano composite phase-change thin-film material and its preparation method and application | |
| CN105514266B (en) | Rear-earth-doped Sb bases phase change film material and method for manufacturing thin film | |
| CN107359238B (en) | The nano combined phase-change thin film of high-speed low-power-consumption Ti-Ge-Sb and its preparation and application | |
| CN106449972B (en) | A kind of Ti-Sb nano phase change thin-film material and its preparation method and application | |
| CN102227015B (en) | Phase transition storage material and preparation method thereof | |
| CN105006519B (en) | The tin antimony of high-speed low-power-consumption-tin selenium nano composite multiple layer film and preparation and application | |
| CN105355783A (en) | Multilayer nano-composite film material used for high-density phase-transition memory and preparation method thereof | |
| CN106953006A (en) | A kind of SiO2Doping Sb nano phase change thin-film materials and preparation method thereof and purposes | |
| CN109585649A (en) | Class superlattices germanium antimony/zinc antimony nano phase change film and its preparation and application | |
| CN106816528B (en) | A kind of multilayer nanocomposite phase transition film and its preparation method and application | |
| CN108493337A (en) | A kind of lanthanide series cerium dopping star antimony nano phase change material and preparation method thereof | |
| CN104328326A (en) | Zn-Sb-Se phase-change memory thin-film material for phase change memory | |
| CN106206942B (en) | GeSb nano thin-films of rare earth Er doping vario-property and preparation method thereof | |
| CN107342362A (en) | A kind of Mg Sb Se nano phase change films and preparation method thereof | |
| CN106098934A (en) | One mixes oxygen GeSb nano phase change thin film and its preparation method and application | |
| CN105957962A (en) | TiO<x>/Al<2>O<3>/TiO<x> sandwich laminated layer resistive random access memory thin film and preparation method therefor | |
| Sun et al. | Phase-change behaviors of Sb80Te20/SbSe nanocomposite multilayer films | |
| CN101527349B (en) | Amorphous indium and tin oxide film and application thereof in manufacturing resistive memory element | |
| Zhang et al. | Superlattice‐like Zn15Sb85/Ga30Sb70 thin films for low power and ultrafast phase change memory application | |
| CN106340585A (en) | Oxygen-doped SbSe nano phase-change thin film material, preparation method and application of oxygen-doped SbSe nano phase-change thin film material | |
| CN110158043A (en) | A kind of Pr doping Sn-Sb nano phase change thin-film material and preparation method thereof | |
| CN105514271B (en) | For the Er ions Sn of phase transition storage15Sb85Base phase change film material and method for manufacturing thin film | |
| CN102169958B (en) | Nanocomposite phase-change material, preparation method and application thereof in phase-change memory | |
| CN109166965A (en) | A kind of Sb70Se30/ Si MULTILAYER COMPOSITE phase-change thin film and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |