CN110120453A - A kind of C-Ti-Sb-Te phase-change material - Google Patents
A kind of C-Ti-Sb-Te phase-change material Download PDFInfo
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- CN110120453A CN110120453A CN201810112299.8A CN201810112299A CN110120453A CN 110120453 A CN110120453 A CN 110120453A CN 201810112299 A CN201810112299 A CN 201810112299A CN 110120453 A CN110120453 A CN 110120453A
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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
- H10N70/011—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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- 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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- 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
- H10N70/884—Switching materials based on at least one element of group IIIA, IVA or VA, e.g. elemental or compound semiconductors
- H10N70/8845—Carbon or carbides
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Abstract
The present invention provides a kind of C-Ti-Sb-Te phase-change material, and the C-Ti-Sb-Te phase-change material is the compound for including four kinds of carbon, titanium, antimony and tellurium elements, and the chemical formula of the C-Ti-Sb-Te phase-change material is Cz[Tix(SbyTe100‑y)100‑x]100‑z；Wherein, 0 < x < 50,0 < y < 100 and 0 < z < 50, x indicate that the atomic percent of titanium elements, y indicate that the atomic percent of antimony element, z indicate the atomic percent of carbon；C-Ti-Sb-Te phase-change material of the invention can be used as phase change film material；C-Ti-Sb-Te phase-change material crystallization temperature is higher, data holding ability is strong；Applied to the stability that phase-changing memory unit is helped to improve in phase transition storage and facilitate reduce phase-changing memory unit RESET power consumption.
Description
Technical field
The invention belongs to technical field of semiconductor material preparation, more particularly to a kind of C-Ti-Sb-Te phase-change material.
Background technique
Memory is the important component of current semi-conductor market, is the foundation stone of information technology, no matter is gone back in life
It is to play an important role in national economy.Currently, the storage product of memory mainly has: flash memory, disk, dynamic memory
Device, static memory etc..Other non-volatile technologies: ferroelectric RAM, magnetic ram, carbon nanotube RAM, resistance-type RAM, copper
RAM (CopperBridge), Hologram Storage, single electron storage, molecular recording, polymer storage, racing track storage
(RacetrackMemory) and detection stores (ProbeMemory) etc. and also receives extensively as the candidate of next-generation memory
General research, each have their own characteristic of these technologies, but mostly also in theoretical research or orientation test stage, distance is a wide range of
It is practical also very remote.
Currently, phase transition storage (PCM) has walked out laboratory, market has been moved towards.The phase transition storage of Numonyx uses
A kind of synthetic material Ge of germanic, antimony, tellurium2Sb2Te5, mostly referred to as GST, most of companies deposit in research and development phase transformation now
All using the related synthetic material of GST or approximate when reservoir.Shipment Omneo series phase change memory chip is announced after Numonyx
Afterwards, Samsung is also announced to be proposed first multi-chip package 512Mbit phase change memory grain products, is contemplated to be to phase transition storage
Replace the NOR type flash memory in consumer electronics field.
The basic principle of phase transition storage is using storage material in phase transition storage between high resistance and low resistance
Reversible transition realizes the storage of high resistant " 1 " and low-resistance " 0 ", passes through and realizes the high-resistance company of storage material using electric signal control
Multistage storage may be implemented in continuous variation, to greatly improve the information storage capability of memory.In phase transition storage, it is utilized
Reversible transition of the phase-change material between amorphous and polycrystalline realizes above-mentioned resistance variations.
In phase-change material research and development, there are commonly Ge2Sb2Te5And Tix(SbyTe100-y)100-xPhase-change material.Existing research
Show Tix(SbyTe100-y)100-xMaterial has many advantages, such as that phase velocity is fast, low in energy consumption, but the crystallization temperature of this material compared with
Low, data holding ability is poor.
In conclusion developing a kind of solution Ti in the prior artx(SbyTe100-y)100-xPhase-change material crystallization temperature is low, counts
It is necessary according to the problem of holding capacity difference.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of C-Ti-Sb-Te phase transformation materials
Material, for solving Ti in the prior artx(SbyTe100-y)100-xCrystallization temperature existing for phase-change material is low, data holding ability is poor
The problem of.The C-Ti-Sb-Te phase-change material is the compound for including four kinds of carbon, titanium, antimony and tellurium elements, the C-Ti-Sb-
The chemical formula of Te phase-change material is Cz[Tix(SbyTe100-y)100-x]100-z, wherein 0 < x < 50,0 < y < 100 and 0 < z < 50, x is indicated
The atomic percent of titanium elements, y indicate that the atomic percent of antimony element, z indicate the atomic percent of carbon.
Preferably, in the C-Ti-Sb-Te phase-change material, the value range of y is 40≤y≤80.
Preferably, in the C-Ti-Sb-Te phase-change material, the value range of x is 0 < x≤20.
Preferably, the C-Ti-Sb-Te phase-change material is C-Ti-Sb-Te phase change film material.
Preferably, the C-Ti-Sb-Te phase-change material realizes the conversion repeatedly of high low resistance under electric signal operation, and
Maintain resistance value constant in the operation of no electric signal.
A method of the C-Ti-Sb-Te phase-change material being prepared, according to the carbon, titanium, antimony and tellurium in the chemical formula
Cz[Tix(SbyTe100-y)100-x]100-zIn component ratio, using magnetron sputtering method, pulsed laser deposition and electron beam evaporation method
One of prepare the C-Ti-Sb-Te phase-change material.
Preferably, the magnetron sputtering method includes in two target co-sputtering methods, three target co-sputtering methods and four target co-sputtering methods
It is a kind of.
Preferably, the two target co-sputterings method includes using Ti0.43Sb2Te3Alloys target and C simple substance target co-sputtering.
Preferably, the Ti0.43Sb2Te3Alloys target and C simple substance target use radio-frequency power supply, are obtained by changing radio-frequency power
The adjustable C of component Cz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material.
Preferably, the Ti0.43Sb2Te3The radio frequency power range that alloys target and C simple substance target use between 10W~100W it
Between.
Preferably, the three target co-sputterings method includes using Sb2Te alloys target, Ti simple substance target and C simple substance target and use
Sb2Te3One of alloys target, Ti simple substance target and C simple substance target co-sputtering.
Preferably, when using Sb2The method of three target co-sputtering of Te alloys target, Ti simple substance target and C simple substance target prepares the C-
When Ti-Sb-Te phase-change material, the Sb2Te alloys target uses DC power supply, and the Ti simple substance target and C simple substance target use radio frequency
Power supply obtains the Ti and adjustable C of component C by changing radio-frequency powerz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material.
Preferably, the Sb2The dc power range that Te alloys target uses is between 10W~30W, the Ti simple substance target
And the radio frequency power range that C simple substance target uses is between 10W~100W.
Preferably, when using Sb2Te3The method of three target co-sputtering of alloys target, Ti simple substance target and C simple substance target prepares the C-
When Ti-Sb-Te phase-change material, the Sb2Te3Alloys target uses DC power supply, and the Ti simple substance target and C simple substance target use radio frequency
Power supply obtains the Ti and adjustable C of component C by changing radio-frequency powerz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material.
Preferably, the Sb2Te3The dc power range that alloys target uses is between 10W~30W, the Ti simple substance target
And the radio frequency power range that C simple substance target uses is between 10W~100W.
Preferably, the four target co-sputterings method includes using Sb2Te3Alloys target, Te simple substance target, Ti simple substance target and C simple substance target
With using one of Sb simple substance target, Te simple substance target, Ti simple substance target and C simple substance target co-sputtering.
Preferably, when using Sb2Te3The method system of alloys target, four target co-sputtering of Te simple substance target, Ti simple substance target and C simple substance target
When the standby C-Ti-Sb-Te phase-change material, the Sb2Te3Alloys target and Te simple substance target use DC power supply, the Ti simple substance target
And C simple substance target uses radio-frequency power supply；The component ratio of Sb and Te are adjusted by changing the dc power of the Te simple substance target, is passed through
Change radio-frequency power to adjust the component ratio of Ti and C, obtains the Ti and adjustable C of component Cz[Tix(SbyTe100-y)100-x]100-zSystem
Column phase-change material.
Preferably, the Sb2Te3The dc power range that alloys target and Te simple substance target use is between 10W~30W, institute
Radio frequency power range that Ti simple substance target and C simple substance target use is stated between 10W~100W.
Preferably, when the method preparation using Sb simple substance target, four target co-sputtering of Te simple substance target, Ti simple substance target and C simple substance target
When the C-Ti-Sb-Te phase-change material, the Sb simple substance target and Te simple substance target use DC power supply, and the Ti simple substance target and C are mono-
Matter target uses radio-frequency power supply；The component of Sb and Te are adjusted by changing the dc power of the Sb simple substance target and Te simple substance target
Than adjusting the component ratio of Ti and C by changing radio-frequency power, obtaining the Ti and adjustable C of component Cz[Tix
(SbyTe100-y)100-x]100-zSerial phase-change material.
Preferably, the dc power range that the Sb simple substance target and Te simple substance target use is described between 10W~30W
The radio frequency power range that Ti simple substance target and C simple substance target use is between 10W~100W.
Preferably, the C-Ti-Sb-Te phase-change material of acquisition is phase change film material, the phase change film material
Thickness range is between 1nm~500nm.
A kind of phase-changing memory unit, the phase-changing memory unit include the C-Ti-Sb-Te phase-change material.
Preferably, the C-Ti-Sb-Te phase-change material is the phase-change storage material of C doping, described in the C doping raising
The thermal stability of phase-changing memory unit and the RESET power consumption for reducing the phase-changing memory unit.
As described above, C-Ti-Sb-Te phase-change material of the invention, has the advantages that C-Ti-Sb-Te phase transformation material
The preparation of a variety of methods can be used in material, by the way that magnetron sputtering method can more convenient, flexible preparation component be adjustable, the higher C- of quality
Ti-Sb-Te phase-change material and C-Ti-Sb-Te phase change film material；C-Ti-Sb-Te phase-change material has faster crystallization rate
And higher deposited stability, reversible transition can be achieved under electric pulse effect, there is apparent resistance height afterwards before phase change
Point of difference, distinguishable high resistant " 1 " and low-resistance " 0 " out, is a kind of ideal phase-change material, can be used for preparing phase transition storage list
Member improves the thermal stability of the phase-changing memory unit and reduces the RESET power consumption of the phase-changing memory unit.
Detailed description of the invention
Fig. 1 is shown as pure Sb2Te3、Ti8(Sb2Te3)92And the C prepared in embodiment onez[Tix
(SbyTe100-y)100-x]100-zThe resistance variation with temperature relation curve schematic diagram of (x=8, y=40, z=10) phase-change material.
Fig. 2 is shown as the C prepared in embodiment onez[Tix(SbyTe100-y)100-x]100-z(x=8, y=40, z=10) phase
Become material and Ti8(Sb2Te3)92Ten annual data retentivity correlation curve schematic diagrames.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
Please refer to Fig. 1-Fig. 2.It should be noted that diagram provided in the present embodiment only illustrates this hair in a schematic way
Bright basic conception, only shown in schema then with related component in the present invention rather than component count when according to actual implementation,
Shape and size are drawn, when actual implementation kenel, quantity and the ratio of each component can arbitrarily change for one kind, and its component
Being laid out kenel may also be increasingly complex.
The present invention provides a kind of C-Ti-Sb-Te phase-change material, the C-Ti-Sb-Te phase-change material be include carbon, titanium, antimony
And the compound of four kinds of elements of tellurium, the chemical formula of the C-Ti-Sb-Te phase-change material are Cz[Tix(SbyTe100-y)100-x]100-z,
Wherein 0 < x < 50,0 < y < 100 and 0 < z < 50, x indicate that the atomic percent of titanium elements, y indicate the atomic percent of antimony element, z
Indicate the atomic percent of carbon.Since C element is easily enriched in grain boundaries, suitable C element will be helpful to limitation crystal grain
It grows up, reach refinement crystal grain and improves material thermal stability, therefore, the present invention passes through in Tix(SbyTe100-y)100-xPhase-change material
Middle doping C element, to have the function that improve material thermal stability.
As an example, the value range of y is 40≤y≤80 in the C-Ti-Sb-Te phase-change material.
As an example, the value range of x is 0 < x≤20 in the C-Ti-Sb-Te phase-change material.
As an example, the C-Ti-Sb-Te phase-change material is C-Ti-Sb-Te phase change film material.
As an example, the C-Ti-Sb-Te phase-change material realizes the conversion repeatedly of high low resistance under electric signal operation,
And maintain resistance value constant in the operation of no electric signal.
The present invention also provides a kind of methods for preparing the C-Ti-Sb-Te phase-change material.
As an example, according to the carbon, titanium, antimony and tellurium in the chemical formula Cz[Tix(SbyTe100-y)100-x]100-zIn
Component ratio prepares the C-Ti-Sb-Te using one of magnetron sputtering method, pulsed laser deposition and electron beam evaporation method
Phase-change material.
Specifically, the magnetron sputtering method is that one kind is filled with suitable argon gas (Ar) under high vacuum state, in cathode (target
Material) and anode (plated film locular wall) between apply the DC voltage of several hundred K, magnet controlled abnormal glow discharge is generated in coating chamber,
Make argon gas that ionization occur and generate argon ion, argon ion accelerates simultaneously bombarding cathode target material surface by cathode, target material surface atom is splashed
Shoot out the method that deposition forms film on the surface of a substrate.Since this method by the target of replacement unlike material and controls not
Same sputtering time, can obtain the film of unlike material and different-thickness, and the binding force with film plating layer and substrate is strong, plates
The advantages that film layer is fine and close, uniform.Therefore magnetron sputtering method application is more flexible, can be convenient that obtained component is adjustable, quality is higher
Thin-film material.The preferably described magnetron sputtering method, which is used as, in the present embodiment prepares the C-Ti-Sb-Te phase-change material and C-Ti-
The method of Sb-Te phase change film material.
As an example, the magnetron sputtering method includes in two target co-sputtering methods, three target co-sputtering methods and four target co-sputtering methods
One kind.
As an example, the two target co-sputterings method includes using Ti0.43Sb2Te3Alloys target and C simple substance target co-sputtering；It is described
Ti0.43Sb2Te3Alloys target and C simple substance target use radio-frequency power supply, obtain the adjustable C of component C by changing radio-frequency powerz[Tix
(SbyTe100-y)100-x]100-zSerial phase-change material；The Ti0.43Sb2Te3The radio-frequency power model that alloys target and C simple substance target use
It encloses between 10W~100W.
As an example, the three target co-sputterings method includes using Sb2Te alloys target, Ti simple substance target and C simple substance target and use
Sb2Te3One of alloys target, Ti simple substance target and C simple substance target co-sputtering.When using Sb2Te alloys target, Ti simple substance target and C simple substance
When the method for three target co-sputtering of target prepares the C-Ti-Sb-Te phase-change material, the Sb2Te alloys target uses DC power supply, institute
Ti simple substance target and C simple substance target are stated using radio-frequency power supply, obtains the Ti and adjustable C of component C by changing radio-frequency powerz[Tix
(SbyTe100-y)100-x]100-zSerial phase-change material；The Sb2Te alloys target use dc power range between 10W~30W it
Between, the radio frequency power range that the Ti simple substance target and C simple substance target use is between 10W~100W.When using Sb2Te3Alloy
When the method for three target co-sputtering of target, Ti simple substance target and C simple substance target prepares the C-Ti-Sb-Te phase-change material, the Sb2Te3It closes
Gold target uses DC power supply, and the Ti simple substance target and C simple substance target use radio-frequency power supply, obtains Ti and C by changing radio-frequency power
The adjustable C of componentz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material；The Sb2Te3The dc power model that alloys target uses
It encloses between 10W~30W, the radio frequency power range that the Ti simple substance target and C simple substance target use is between 10W~100W.
As an example, the four target co-sputterings method includes using Sb2Te3Alloys target, Te simple substance target, Ti simple substance target and C simple substance
One of target and use Sb simple substance target, Te simple substance target, Ti simple substance target and C simple substance target co-sputtering, when using Sb2Te3Alloys target,
It is described when the method for four target co-sputtering of Te simple substance target, Ti simple substance target and C simple substance target prepares the C-Ti-Sb-Te phase-change material
Sb2Te3Alloys target and Te simple substance target use DC power supply, and the Ti simple substance target and C simple substance target use radio-frequency power supply；Pass through change
The dc power of the Te simple substance target adjusts the component ratio of Sb and Te, by changing radio-frequency power adjusts the component of Ti and C
Than obtaining the Ti and adjustable C of component Cz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material；The Sb2Te3Alloys target and institute
The dc power range of Te simple substance target use is stated between 10W~30W, the radio frequency that the Ti simple substance target and C simple substance target use
Power bracket is between 10W~100W.When using Sb simple substance target, four target co-sputtering of Te simple substance target, Ti simple substance target and C simple substance target
Method when preparing the C-Ti-Sb-Te phase-change material, the Sb simple substance target and Te simple substance target use DC power supply, the Ti
Simple substance target and C simple substance target use radio-frequency power supply；Sb is adjusted by changing the dc power of the Sb simple substance target and Te simple substance target
And the component ratio of Te, the component ratio of Ti and C are adjusted by changing radio-frequency power, obtains the Ti and adjustable C of component Cz[Tix
(SbyTe100-y)100-x]100-zSerial phase-change material.The dc power range that the Sb simple substance target and Te simple substance target use between
Between 10W~30W, the radio frequency power range that the Ti simple substance target and C simple substance target use is between 10W~100W.
As an example, the C-Ti-Sb-Te phase-change material obtained is phase change film material, the phase change film material
Thickness range between 1nm~500nm.
The present invention also provides a kind of phase-changing memory unit, the phase-changing memory unit includes the C-Ti-Sb-Te
Phase-change material.
As an example, the C-Ti-Sb-Te phase-change material is the phase-change storage material of C doping, the C doping improves institute
It states the thermal stability of phase-changing memory unit and reduces the RESET power consumption of the phase-changing memory unit.
In the following, in conjunction with specific embodiments to the C-Ti-Sb-Te phase-change material, phase-changing memory unit and its preparation side
Method is specifically addressed.
Embodiment one
For the present embodiment by preparing a kind of C-Ti-Sb-Te phase-change material, the C-Ti-Sb-Te phase-change material is to include
Carbon, titanium, four kinds of elements of antimony and tellurium compound, the chemical formula of the C-Ti-Sb-Te phase-change material is Cz[Tix
(SbyTe100-y)100-x]100-z, wherein x=8, y=40 and 0 < z < 50, x indicate that the atomic percent of titanium elements, y indicate antimony element
Atomic percent, z indicate carbon atomic percent.And it is tested to further illustrate a kind of skill of the invention
Art scheme, specific solution are as follows:
Using two target co-sputtering methods in magnetron sputtering method, the C-Ti-Sb-Te phase-change material phase-change material is prepared.
As an example, the C-Ti-Sb-Te phase-change material is phase change film material, when by adjusting long film on substrate
Between can be by the thickness control of the phase change film material between 1nm~500nm.Wherein the substrate includes silicon substrate, oxidation
One of silicon substrate.In the present embodiment, using silica as substrate, in another embodiment, silicon can also be used as lining
Bottom, herein with no restriction.
Specifically, comprising the following steps:
S1-1: the silicon oxide substrate is passed through into acetone, alcohol and deionized water ultrasonic cleaning respectively and is placed on coating chamber
It is interior.
S1-2: the C-Ti-Sb-Te phase-change material is prepared.
The step S1-2 includes: under an argon atmosphere, using Ti0.43Sb2Te3Alloys target and two target of C simple substance target splash altogether
It penetrates, wherein the Ti0.43Sb2Te3Alloys target and the C simple substance target use radio-frequency power supply；By changing the radio-frequency power supply
Radio-frequency power adjusts the atomic percent of C, obtains the adjustable C of component Cz[Tix(SbyTe100-y)100-x]100-z(x=8, y
=40) serial phase-change material, due to using the Ti0.43Sb2Te3Alloys target, therefore in the Cz[Tix
(SbyTe100-y)100-x]100-zThe component ratio of Sb and Te is 2:3 in the phase-change material of series.
Further, the Ti0.43Sb2Te3Alloys target use the radio frequency power range between 10W~30W,
Argon gas gas of the radio frequency power range that the C simple substance target uses between 20W~100W, when background vacuum and sputtering
Pressure can be adjusted according to actual needs.
Specifically, the C simple substance target uses high-purity C and Ti0.43Sb2Te3Alloy target co-sputtering.In sputtering process, background is true
Reciprocal of duty cycle is selected as 2 × 10-4Pa；The flow set of high-purity argon gas (purity 99.999%) as aura source is 20sccm (standard
Ml/min)；Sputtering pressure is 0.4Pa；Sample stage temperature is room temperature；By recirculated cooling water to high-purity C and
Ti0.43Sb2Te3Alloys target is cooled down；High-purity C and Ti0.43Sb2Te3The radio-frequency power of alloys target is preferably 20W,
A length of 20min when sputtering.Wherein, the resistance height difference that phase-change material can be reduced since the component of C is excessively high, so that high resistant " 1 "
And low-resistance " 0 " is not easily distinguishable；The too low deposited stability that can reduce phase-change material of the component of C, thus in the present embodiment C group
Dividing range is 5 < z < 20, and preferably z=10, that is, it is C that chemical formula, which is prepared,z[Tix(SbyTe100-y)100-x]100-z(x=8, y=
40, z=10) phase-change material.Due to the phase change material deposition for selecting, using silica as substrate, to generate through sputtering
On the substrate surface, the phase change film material is formed.It can be by the phase-change thin film thickness control by adjusting the long film time
System is in 100nm~250nm.
Further, the fresh section thickness of the phase-change thin film obtained by field emission microscopy observation.This reality
In example, the section for measuring the phase-change thin film deposited in the silicon oxide substrate by field emission scanning electron microscope is average thick
Degree is 100nm.
Further, the in-situ resistance measurements system pair by independently being built by Shanghai micro-system and information technology research institute
The square resistance of the phase-change thin film is tested, wherein heating rate is set as 10 DEG C/min, passes through resistance v. temperature (R-T)
Test, the crystallization temperature (T of the available phase-change materialc), as shown in Figure 1, being shown as pure Sb2Te3、Ti8(Sb2Te3)92And
The C prepared in the present embodimentz[Tix(SbyTe100-y)100-x]100-zThe resistance of (x=8, y=40, z=10) phase-change material with
The variation relation curve synoptic diagram of temperature, wherein Pure Sb in figure2Te3Represent pure Sb2Te3, TST represent Ti8(Sb2Te3)92、
CTST represents Cz[Tix(SbyTe100-y)100-x]100-z(x=8, y=40, z=10) phase-change material.As shown in Figure 1, identical
Under conditions of 10 DEG C/min of heating rate, the pure Sb2Te3、Ti8(Sb2Te3)92And Cz[Tix(SbyTe100-y)100-x]100-z(x
=8, y=40, z=10) phase-change material crystallization temperature TcRelationship are as follows: Tc(Pure Sb2Te3) < Tc(TST) < Tc
(CTST), wherein the Cz[Tix(SbyTe100-y)100-x]100-z(x=8, y=40, z=10) phase-change material knot with higher
Brilliant temperature Tc=175 DEG C.
Specifically, the temperature of holdings in 10 years of material can be extrapolated by the out-of-service time of the material under measurement different temperatures
Degree, retentivity is a phase-change material characteristic of crucial importance, is to measure phase-change material for characterizing amorphous thermal stability
It can one of direct applied important parameter.Wherein, when measuring the material failure time under different temperatures, the test of retentivity
Temperature must be in material crystalline temperature TcHereinafter, when test temperature is higher than material crystalline temperature TcWhen, material during heating
It is crystallized, therefore material amorphous retention time cannot be tested out；Wherein, the definition of out-of-service time is when thin-film material electricity
Resistance, which drops to, is just raised to the time corresponding when the half of initial resistance corresponding when test temperature.
Specifically, temperature is first risen to corresponding holding temperature using the heating rate of 40 DEG C/min, at this time when test
The rule of the resistance decline of thin-film material and resistance v. temperature (R-T) curve one in the square resistance test of the phase-change thin film
Sample only corresponds to abscissa and becomes time, i.e., the out-of-service time longest of the described C-Ti-Sb-Te phase-change material.Then by warm table
Temperature is maintained at test temperature, and measurement thin-film material resistance is then intended according to Arrhenius formula with the relation curve of time
It closes, ten annual datas for extrapolating thin-film material keep temperature.As shown in Fig. 2, being shown as the C prepared in the present embodimentz[Tix
(SbyTe100-y)100-x]100-zThe ten annual data retentivities and Ti of (x=8, y=40, z=10) phase-change material8(Sb2Te3)92Pair
Compare curve synoptic diagram, wherein TST represents Ti8(Sb2Te3)92, CTST represent Cz[Tix(SbyTe100-y)100-x]100-z(x=8, y=
40, z=10) phase-change material.The Cz[Tix(SbyTe100-y)100-x]100-zThe number of (x=8, y=40, z=10) phase-change material
Test temperature according to retentivity is 118 DEG C, compared with Ti8(Sb2Te3)9289 DEG C of test temperature of retentivity are obviously improved, and therefore, are had
Conducive to the raising amorphous thermal stability of material.
Specifically, the C-Ti-Sb-Te phase-change material is the phase-change storage material of C doping, the C-Ti-Sb-Te phase transformation
Material has faster crystallization rate and higher sedimentation Stability, reversible transition can be achieved under electric pulse effect, before phase change
Point with apparent resistance height difference afterwards, distinguishable high resistant " 1 " and low-resistance " 0 " out, are a kind of ideal phase-change materials, can
It is used to prepare phase-changing memory unit.In the C-Ti-Sb-Te phase-change material, since C is easily enriched in grain boundaries, suitable C
It will be helpful to growing up for limitation crystal grain, to achieve the purpose that refine crystal grain and improve material thermal stability, help to improve phase
The stability of transition storage unit；And the crystalline resistance of material significantly improves after C incorporation, this will be helpful to reduce phase change memory
The RESET power consumption of device unit.
In the present embodiment, using Ti0.43Sb2Te3Sb, Te component has been prepared in alloys target and two target co-sputtering of C simple substance target
Than the C for 2:3z[Tix(SbyTe100-y)100-x]100-zThe phase-change material of (x=8, y=40) series, the Cz[Tix
(SbyTe100-y)100-x]100-zThe phase-change material crystallization temperature with higher and data holding ability of (x=8, y=40) series,
Reversible transition is realized under electric pulse effect, is a kind of ideal phase-change material, applied to facilitating in phase transition storage
Improve the stability of phase-changing memory unit.
Embodiment two
For the present embodiment by preparing a kind of C-Ti-Sb-Te phase-change material, the C-Ti-Sb-Te phase-change material is to include
Carbon, titanium, four kinds of elements of antimony and tellurium compound, the chemical formula of the C-Ti-Sb-Te phase-change material is Cz[Tix
(SbyTe100-y)100-x]100-z, wherein 0 < x < 50, y=66 and 0 < z < 50, x indicates that the atomic percent of titanium elements, y indicate antimony member
The atomic percent of element, z indicates the atomic percent of carbon, to further illustrate a kind of technical solution of the invention.Specifically
Preparation method is as follows:
Using three target co-sputtering methods in magnetron sputtering, the C-Ti-Sb-Te phase-change material is prepared.
As an example, the C-Ti-Sb-Te phase-change material is phase change film material, when by adjusting long film on substrate
Between can be by the thickness control of the phase change film material between range 1nm~500nm.Wherein the substrate include silicon substrate,
One of silicon oxide substrate.In the present embodiment, using silica as substrate, thickness is prepared on the silicon oxide surface
For the phase change film material of 100nm~250nm.
Specifically, comprising the following steps:
S2-1: the silicon oxide substrate is passed through into acetone, alcohol and deionized water ultrasonic cleaning respectively and is placed on coating chamber
It is interior.
S2-2: the C-Ti-Sb-Te phase-change material is prepared.
The step S2-2 includes: under an argon atmosphere, using Sb2Te alloys target, Ti simple substance target and three target of C simple substance target are total
Sputtering, wherein the Sb2Te alloys target uses DC power supply, and the C simple substance target and Ti simple substance target use radio-frequency power supply；Pass through
Change the radio-frequency power of the radio-frequency power supply to adjust the atomic percent of C and Ti, obtains the adjustable C of C and Ti componentz
[Tix(SbyTe100-y)100-x]100-z(y=66) serial phase-change material.Due to using the Sb2Te alloys target, therefore in institute
State Cz[Tix(SbyTe100-y)100-x]100-z(y=66) component ratio of Sb and Te is 2:1 in serial phase-change material.
Further, the Sb2The dc power range that Te alloys target uses is between 10W~30W, the C
The radio frequency power range that simple substance target and Ti simple substance target use is between 20W~100W, when background vacuum and sputtering
Ar pressure can be adjusted according to actual needs, and the resistance height difference that can reduce phase-change material since the component of C is excessively high makes
It obtains high resistant " 1 " and low-resistance " 0 " is not easily distinguishable；The too low deposited stability that can reduce phase-change material of the component of C, therefore this implementation
The compositional range of C is 5 < z < 20 in example, and the compositional range of preferably z=10, the Ti are 0 < x < 50.
Further, the in-situ resistance measurements system pair by independently being built by Shanghai micro-system and information technology research institute
The square resistance of the phase-change thin film is tested, wherein heating rate is set as 10 DEG C/min, passes through resistance v. temperature (R-T)
Test, the crystallization temperature (T of the available phase-change materialc)。
Specifically, measured resistance v. temperature (R-T) relationship is further processed, logarithm is taken to obtain log resistance R
(R), then make log (R) to the once differentiation curve of temperature T, obtain the crystallization temperature (T of the phase-change materialc)。
Specifically, the C-Ti-Sb-Te phase-change material is the phase-change storage material of C doping, the C-Ti-Sb-Te phase transformation
Material has faster crystallization rate and higher sedimentation Stability, reversible transition can be achieved under electric pulse effect, before phase change
Point with apparent resistance height difference afterwards, distinguishable high resistant " 1 " and low-resistance " 0 " out, are a kind of ideal phase-change materials, can
It is used to prepare phase-changing memory unit.In the C-Ti-Sb-Te phase-change material, since C is easily enriched in grain boundaries, suitable C
It will be helpful to growing up for limitation crystal grain, to achieve the purpose that refine crystal grain and improve material thermal stability, help to improve phase
The stability of transition storage unit；And the crystalline resistance of material significantly improves after C incorporation, this will be helpful to reduce phase change memory
The RESET power consumption of device unit.In the present embodiment, using Sb2Te alloys target, C simple substance target and the preparation of three target co-sputtering of Ti simple substance target
The C that Sb and Te component ratio is 2:1 is obtainedz[Tix(SbyTe100-y)100-x]100-z(y=66) serial phase-change material, institute
State Cz[Tix(SbyTe100-y)100-x]100-z(y=66) serial phase-change material crystallization temperature with higher and data keep energy
Power realizes reversible transition under electric pulse effect, is a kind of ideal phase-change material, applied to helping in phase transition storage
In the stability for improving phase-changing memory unit.
Embodiment three
For the present embodiment by preparing a kind of C-Ti-Sb-Te phase-change material, the C-Ti-Sb-Te phase-change material is to include
Carbon, titanium, four kinds of elements of antimony and tellurium compound, the chemical formula of the C-Ti-Sb-Te phase-change material is Cz[Tix
(SbyTe100-y)100-x]100-zWherein 0 < x < 50, y=33 and 0 < z < 50, x indicate that the atomic percent of titanium elements, y indicate antimony member
The atomic percent of element, z indicates the atomic percent of carbon, to further illustrate a kind of technical solution of the invention.Specifically
Preparation method is as follows:
Using four target co-sputtering methods in magnetron sputtering, the C-Ti-Sb-Te phase-change material is prepared.
As an example, the C-Ti-Sb-Te phase-change material is phase change film material, when by adjusting long film on substrate
Between can be by the thickness control of the phase change film material between range 1nm~500nm.Wherein the substrate include silicon substrate,
One of silicon oxide substrate.In the present embodiment, using silica as substrate, prepared on the silica with a thickness of
The phase change film material of 100nm~250nm.
Specifically, comprising the following steps:
S3-1: the silicon oxide substrate is passed through into acetone, alcohol and deionized water ultrasonic cleaning respectively and is placed on coating chamber
It is interior.
S3-2: the C-Ti-Sb-Te phase-change material is prepared.
The step S3-2 includes: under an argon atmosphere, using Sb2Te3Alloys target, Te simple substance target, C simple substance target and Ti are mono-
Four target co-sputtering of matter target, wherein the Sb2Te3Alloys target and Te simple substance target use DC power supply, the C simple substance target and Ti simple substance
Target uses radio-frequency power supply；The component ratio of Sb and Te are adjusted by changing the dc power of the Te simple substance target, by changing institute
The radio-frequency power of radio-frequency power supply is stated to adjust the atomic percent of C and Ti, obtains the adjustable C of C and Ti componentz[Tix
(SbyTe100-y)100-x]100-z(y=33) serial phase-change material.Due to using the Sb2Te3Alloys target, therefore described
Cz[Tix(SbyTe100-y)100-x]100-z(y=33) in serial phase-change material, the component ratio of Sb and Te are 2:3.
Further, the Sb2Te3The dc power range that alloys target and Te simple substance target use is between 10W~30W
Between, the radio frequency power range that the C simple substance target and Ti simple substance target use is between 20W~100W, background vacuum
And ar pressure when sputtering can be adjusted according to actual needs, due to the excessively high resistance that can reduce phase-change material of the component of C
Height difference, so that high resistant " 1 " and low-resistance " 0 " are not easily distinguishable；The too low deposited that can reduce phase-change material of the component of C is stablized
Property, therefore the compositional range of C is 5 < z < 20 in the present embodiment, the compositional range of preferably z=10, the Ti are 0 < x < 50, this
Place is with no restriction.
Further, the in-situ resistance measurements system pair by independently being built by Shanghai micro-system and information technology research institute
The square resistance of the phase-change thin film is tested, wherein heating rate is set as 10 DEG C/min, passes through resistance v. temperature (R-T)
Test, the crystallization temperature (T of the available phase-change materialc)。
Specifically, measured resistance v. temperature (R-T) relationship is further processed, logarithm is taken to obtain log resistance R
(R), then make log (R) to the once differentiation curve of temperature T, obtain the crystallization temperature (T of the phase-change materialc)。
Specifically, the C-Ti-Sb-Te phase-change material is the phase-change storage material of C doping, the C-Ti-Sb-Te phase transformation
Material has faster crystallization rate and higher sedimentation Stability, reversible transition can be achieved under electric pulse effect, before phase change
Point with apparent resistance height difference afterwards, distinguishable high resistant " 1 " and low-resistance " 0 " out, are a kind of ideal phase-change materials, can
It is used to prepare phase-changing memory unit.In the C-Ti-Sb-Te phase-change material, since C is easily enriched in grain boundaries, suitable C
It will be helpful to growing up for limitation crystal grain, to achieve the purpose that refine crystal grain and improve material thermal stability, help to improve phase
The stability of transition storage unit；And the crystalline resistance of material significantly improves after C incorporation, this will be helpful to reduce phase change memory
The RESET power consumption of device unit.
In the present embodiment, using Sb2Te3Alloys target, Te simple substance target, Ti simple substance target and four target co-sputtering of C simple substance target are prepared into
The C that Sb and Te component ratio is 2:3 is arrivedz[Tix(SbyTe100-y)100-x]100-z(y=33) serial phase-change material, it is described
Cz[Tix(SbyTe100-y)100-x]100-z(y=33) serial phase-change material crystallization temperature with higher and data holding ability,
Reversible transition is realized under electric pulse effect, is a kind of ideal phase-change material, applied to facilitating in phase transition storage
Improve the stability of phase-changing memory unit.
In conclusion a variety of method preparations can be used in C-Ti-Sb-Te phase-change material of the invention, phase-change thin film can be used as
Material；C-Ti-Sb-Te phase-change material has faster crystallization rate and higher deposited stability, under electric pulse effect
Reversible transition can be achieved, point with apparent resistance height difference, distinguishable high resistant " 1 " and low-resistance " 0 " out are afterwards before phase change
A kind of ideal phase-change material, can be used for preparing phase-changing memory unit；C-Ti-Sb-Te phase-change material crystallization temperature is higher, counts
It is strong according to holding capacity；Applied to the stability for helping to improve phase-changing memory unit in phase transition storage and reduce phase change memory
The RESET power consumption of device unit；The present invention effectively overcomes various shortcoming in the prior art and has high industrial utilization value.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (23)
1. a kind of C-Ti-Sb-Te phase-change material, it is characterised in that: the C-Ti-Sb-Te phase-change material be include carbon, titanium, antimony
And the compound of four kinds of elements of tellurium, the chemical formula of the C-Ti-Sb-Te phase-change material are Cz[Tix(SbyTe100-y)100-x]100-z；
Wherein, 0 < x < 50,0 < y < 100 and 0 < z < 50, x indicate that the atomic percent of titanium elements, y indicate the atomic percent of antimony element, z
Indicate the atomic percent of carbon.
2. C-Ti-Sb-Te phase-change material described according to claim 1, it is characterised in that: the value range of y be 40≤y≤
80。
3. the C-Ti-Sb-Te phase-change material according to claim 2, it is characterised in that: the value range of x is 0 < x≤20.
4. C-Ti-Sb-Te phase-change material described according to claim 1, it is characterised in that: the C-Ti-Sb-Te phase-change material
For C-Ti-Sb-Te phase change film material.
5. C-Ti-Sb-Te phase-change material described according to claim 1, it is characterised in that: the C-Ti-Sb-Te phase-change material
Under electric signal operation, the conversion repeatedly of high low resistance is realized, and maintain resistance value constant in the operation of no electric signal.
6. a kind of preparation method of the C-Ti-Sb-Te phase-change material as described in any one of Claims 1 to 5, it is characterised in that:
According to the carbon, titanium, antimony and tellurium in the chemical formula Cz[Tix(SbyTe100-y)100-x]100-zIn component ratio, splashed using magnetic control
It penetrates one of method, pulsed laser deposition and electron beam evaporation method and prepares the C-Ti-Sb-Te phase-change material.
7. the preparation method of C-Ti-Sb-Te phase-change material according to claim 6, it is characterised in that: the magnetron sputtering
Method includes one of two target co-sputtering methods, three target co-sputtering methods and four target co-sputtering methods.
8. the preparation method of C-Ti-Sb-Te phase-change material according to claim 7, it is characterised in that: two target splashes altogether
Penetrating method includes using Ti0.43Sb2Te3Alloys target and C simple substance target co-sputtering.
9. the preparation method of C-Ti-Sb-Te phase-change material according to claim 8, it is characterised in that: described
Ti0.43Sb2Te3Alloys target and C simple substance target use radio-frequency power supply, obtain the adjustable C of component C by changing radio-frequency powerz[Tix
(SbyTe100-y)100-x]100-zSerial phase-change material.
10. the preparation method of C-Ti-Sb-Te phase-change material according to claim 9, it is characterised in that: described
Ti0.43Sb2Te3The radio frequency power range that alloys target and C simple substance target use is between 10W~100W.
11. the preparation method of C-Ti-Sb-Te phase-change material according to claim 7, it is characterised in that: three target is total
Sputtering method includes using Sb2Te alloys target, Ti simple substance target and C simple substance target with use Sb2Te3Alloys target, Ti simple substance target and C simple substance
One of target co-sputtering.
12. the preparation method of C-Ti-Sb-Te phase-change material described in 1 according to claim 1, it is characterised in that: when using Sb2Te
It is described when the method for three target co-sputtering of alloys target, Ti simple substance target and C simple substance target prepares the C-Ti-Sb-Te phase-change material
Sb2Te alloys target uses DC power supply, and the Ti simple substance target and C simple substance target use radio-frequency power supply, is obtained by changing radio-frequency power
To the Ti and adjustable C of component Cz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material.
13. the preparation method of C-Ti-Sb-Te phase-change material described in 2 according to claim 1, it is characterised in that: the Sb2Te is closed
The dc power range that gold target uses is between 10W~30W, the radio-frequency power model of the Ti simple substance target and the use of C simple substance target
It encloses between 10W~100W.
14. the preparation method of C-Ti-Sb-Te phase-change material described in 1 according to claim 1, it is characterised in that: work as use
Sb2Te3When the method for three target co-sputtering of alloys target, Ti simple substance target and C simple substance target prepares the C-Ti-Sb-Te phase-change material, institute
State Sb2Te3Alloys target uses DC power supply, and the Ti simple substance target and C simple substance target use radio-frequency power supply, by changing radio-frequency power
Obtain the Ti and adjustable C of component Cz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material.
15. the preparation method of C-Ti-Sb-Te phase-change material described in 4 according to claim 1, it is characterised in that: the Sb2Te3
The dc power range that alloys target uses is between 10W~30W, the radio-frequency power of the Ti simple substance target and the use of C simple substance target
Range is between 10W~100W.
16. the preparation method of C-Ti-Sb-Te phase-change material according to claim 7, it is characterised in that: four target is total
Sputtering method includes using Sb2Te3Alloys target, Te simple substance target, Ti simple substance target and C simple substance target and using Sb simple substance target, Te simple substance target,
One of Ti simple substance target and C simple substance target co-sputtering.
17. the preparation method of C-Ti-Sb-Te phase-change material described in 6 according to claim 1, it is characterised in that: work as use
Sb2Te3Alloys target, the method for four target co-sputtering of Te simple substance target, Ti simple substance target and C simple substance target prepare the C-Ti-Sb-Te phase transformation
When material, the Sb2Te3Alloys target and Te simple substance target use DC power supply, and the Ti simple substance target and C simple substance target use radio frequency electrical
Source；The component ratio of Sb and Te are adjusted by changing the dc power of the Te simple substance target, is adjusted by changing radio-frequency power
The component ratio of Ti and C obtains the Ti and adjustable C of component Cz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material.
18. the preparation method of C-Ti-Sb-Te phase-change material described in 7 according to claim 1, it is characterised in that: the Sb2Te3
Between 10W~30W, the Ti simple substance target and C simple substance target use the dc power range that alloys target and Te simple substance target use
Radio frequency power range between 10W~100W.
19. the preparation method of C-Ti-Sb-Te phase-change material described in 6 according to claim 1, it is characterised in that: when mono- using Sb
Method when preparing the C-Ti-Sb-Te phase-change material of matter target, four target co-sputtering of Te simple substance target, Ti simple substance target and C simple substance target,
The Sb simple substance target and Te simple substance target use DC power supply, and the Ti simple substance target and C simple substance target use radio-frequency power supply；Pass through change
The dc power of the Sb simple substance target and Te simple substance target adjusts the component ratio of Sb and Te, by changing radio-frequency power adjusts Ti
And the component ratio of C, obtain the Ti and adjustable C of component Cz[Tix(SbyTe100-y)100-x]100-zSerial phase-change material.
20. the preparation method of C-Ti-Sb-Te phase-change material described in 9 according to claim 1, it is characterised in that: the Sb simple substance
Between 10W~30W, what the Ti simple substance target and C simple substance target used penetrates the dc power range that target and Te simple substance target use
Frequency power bracket is between 10W~100W.
21. the preparation method of C-Ti-Sb-Te phase-change material according to any one of claim 6~20, it is characterised in that:
The C-Ti-Sb-Te phase-change material obtained is phase change film material, and the thickness range of the phase change film material is between 1nm
Between~500nm.
22. a kind of phase-changing memory unit, it is characterised in that: the phase-changing memory unit includes as appointed in Claims 1 to 5
C-Ti-Sb-Te phase-change material described in one.
23. the phase-changing memory unit according to claim 22, it is characterised in that: the C-Ti-Sb-Te phase-change material is
The phase-change storage material of C doping, the C doping improve the thermal stability of the phase-changing memory unit and reduce the phase transformation and deposit
The RESET power consumption of storage unit.
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|---|---|---|---|---|
| WO2023184667A1 (en) * | 2022-03-30 | 2023-10-05 | 华中科技大学 | Tetrahedral structure compound doped sb-te phase change material and phase change memory |
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