CN106098934B - One kind mixing oxygen GeSb nano phase change film and its preparation method and application - Google Patents
One kind mixing oxygen GeSb nano phase change film and its preparation method and application Download PDFInfo
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- 230000008859 change Effects 0.000 title claims abstract description 89
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000001301 oxygen Substances 0.000 title claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 59
- 229910005872 GeSb Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000002156 mixing Methods 0.000 title claims description 27
- 239000010408 film Substances 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 74
- 239000010409 thin film Substances 0.000 claims abstract description 49
- 238000004544 sputter deposition Methods 0.000 claims abstract description 33
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000003860 storage Methods 0.000 claims abstract description 20
- 230000007704 transition Effects 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 10
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 10
- 239000013077 target material Substances 0.000 claims description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005477 sputtering target Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 239000000428 dust Substances 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 101100337994 Arabidopsis thaliana GSO2 gene Proteins 0.000 description 24
- 238000002425 crystallisation Methods 0.000 description 16
- 230000008025 crystallization Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 12
- 101100337993 Arabidopsis thaliana GSO1 gene Proteins 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012782 phase change material Substances 0.000 description 8
- 230000009466 transformation Effects 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 241001269238 Data Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000001552 radio frequency sputter deposition Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 102100023696 Histone-lysine N-methyltransferase SETDB1 Human genes 0.000 description 1
- 101710168120 Histone-lysine N-methyltransferase SETDB1 Proteins 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- -1 chalcogenide compound Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
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- 238000004080 punching Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8828—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
- H10N70/011—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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- Physical Vapour Deposition (AREA)
- Semiconductor Memories (AREA)
Abstract
The present invention relates to one kind to mix oxygen GeSb nano phase change film and its preparation method and application, and the chemical composition of the phase-change thin film meets chemical general formula GSOx, and wherein GS is Ge8Sb92, x represents oxygen stream magnitude, and unit sccm, wherein x=1,2 or 3, pass through cleaning SiO2Prepare before/Si (100) substrate, radio-frequency sputtering, prepare three steps of nano phase change thin-film material using magnetically controlled sputter method and be prepared and mix oxygen GeSb nano phase change film, it can be in the application in phase transition storage.Compared with prior art, the present invention has many advantages, such as.
Description
Technical field
The present invention relates to the phase-change storage material of microelectronics technology and its preparations and application, mix more particularly, to one kind
Oxygen GeSb nano phase change film and its preparation method and application.
Background technique
The working principle of phase transition storage (Phase Change Random Access Memory, abbreviation PCRAM) is
Utilize reversible transformation of the chalcogenide compound between crystalline state (low resistance, high reflectance) and amorphous state (high resistance, antiradar reflectivity)
A kind of nonvolatile semiconductor memory of information " 0 " and " 1 " storage is realized as phase change layer.The record of phase transition storage is
Using electric pulse generate heat make storage medium material between crystalline and amorphous mutually conversion realize information write-in and
The reading of erasing, information is realized by measuring the difference of resistance.Process of the PCRAM from high resistant to low-resistance is defined as SET process,
And it is known as RESET process from the process that low-resistance changes to high resistant.PCRAM is with read or write speed is fast, power consumption is lower, storage is close
The advantages that degree is high, compatible with traditional CMOS technology, manufacturing process is simple is known as being possible to replace DRAM in future by industry
And flash storage.
The phase-change material of GeSb phase-change storage material, especially richness Sb has the advantages that the phase transformation of high speed, crystallization mechanism category
It is dominant type in grain growth, crystallization velocity is up to 5ns.Even if GeSb film thickness is reduced to 3nm, excellent deposit still remain
Performance is stored up, the application potential stored with good device dimensions shrink and high density.Nevertheless, GeSb film there is also
Some disadvantages: thermal stability is not high enough, and data holding ability sharply declines at higher temperatures；Lower crystalline resistance makes
RESET electric current is excessive, and high current density is that current large scale integrated circuit (LSI) cannot bear (< 8MA/cm2), because
This simple GeSb phase-change thin film not can be used directly in civilian and industrial circle.
Chinese patent CN 102800807A, which is disclosed, a kind of mixes oxygen Sb for low power consumption and high reliability4The nanometer phase of Te
Thinning membrane material, chemical component indicate that ST represents Sb using STOx4Te, x=1,2 or 3；By in radio frequency sputtering deposition
Sb4It is passed through argon gas and oxygen simultaneously during Te film, and is prepared in nanometer scale.Patent phase-change thin film preparation choosing
Use Sb4Te binary parent phase-change material, element containing Te in the material.One side Te is readily volatilized at high temperature to lead to phase-change thin film
Ingredient non-stoichiometric, chemical constituent are not sufficiently stable, for being easy to cause component failure when phase transition storage.On the other hand,
Te element has toxicity, is easy pollution semiconductor technology and to environment and human body nocuousness.Oxygen is mixed by prepared by magnetron sputtering method
Nano phase change film STO3Crystallization temperature be 202 DEG C, crystallization activation energy be 2.99eV, ten annual datas keep temperature be 119 DEG C,
Amorphous state thermal stability is still not high enough, is not directly applicable high temperature applicationss, as ten annual data of vehicle electric field keeps temperature
Reach 120 DEG C.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind can be improved phase transformation
Material thermal stability, while reduce its RESET power consumption mixes oxygen GeSb nano phase change film and its preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions:
One kind mixing oxygen GeSb nano phase change film, and chemical composition meets chemical general formula GSOx, and wherein GS is Ge8Sb92, x
Represent oxygen stream magnitude, unit sccm, wherein x=1,2 or 3.Oxygen GeSb nano phase change film is mixed using magnetron sputtering side
Method is grown on SiO2On/Si (100) substrate, with a thickness of 30-100nm.
The preparation method for mixing oxygen GeSb nano phase change film, using following steps:
(1) SiO is cleaned2/ Si (100) substrate: clean the surface, the back side remove dust granule, organic and inorganic impurity；
(2) prepare before radio-frequency sputtering: installing Ge8Sb92Sputtering target material utilizes high-purity Ar and high-purity O2As sputter gas；
(3) nano phase change thin-film material is prepared using magnetically controlled sputter method: cleaning Ge8Sb92Target material surface, then will be wait splash
It penetrates substrate and rotates to Ge8Sb92Target position opens Ge8Sb92Oxygen Ge is mixed in the sputtering of target position radio-frequency power supply8Sb92Film.
Step (1) specifically uses following steps:
(1-a) is by SiO2/ Si (100) substrate is cleaned by ultrasonic by force 5-10 minutes in acetone soln, and deionized water is rinsed；
(1-b) substrate is cleaned by ultrasonic by force 5-10 minutes in ethanol solution by treated, and deionized water is rinsed, high-purity N2
Dry up surface and the back side；
The substrate handled well in 100-150 DEG C of drying in oven steam, is obtained substrate to be sputtered by (1-c).
Step (2) specifically uses following steps:
(2-a) installs Ge8Sb92Sputtering target material, the purity of target reach atomic percent 99.999%, and background is true
Empty pump is to 2 × 10-4Pa；
(2-b) sets exchange radio-frequency sputtering power as 15-30W；
(2-c) reached using percent by volume 99.999% high-purity Ar and high-purity O2, control Ar throughput and O2Flow
Than for 49-47:1-3, sputtering pressure is adjusted to 2 × 10-1Pa。
Ar throughput and O are controlled as a preferred technical solution,2Flow-rate ratio is 49:1,48:2 or 47:3.
Step (3) specifically uses following steps:
Space base support is rotated to Ge by (3-a)8Sb92Target position opens Ge8Sb92The radio-frequency power supply applied on target, to Ge8Sb92
Target as sputter 120-300s cleans Ge8Sb92Target material surface；
(3-b)Ge8Sb92After the completion of target material surface cleaning, Ge is closed8Sb92The radio-frequency power supply applied on target, will be to be sputtered
Substrate rotates to Ge8Sb92Target position opens Ge8Sb92Target position radio-frequency power supply starts sputtering and mixes oxygen Ge8Sb92Film 150-300s,
It obtains mixing oxygen GeSb nano phase change film.
Be prepared mix oxygen GeSb nano phase change film can be in the application in phase transition storage.
Doping is the effective means of a kind of improvement and optimization material property, former by mixing a small amount of O in phase-change material
Son can reduce average grain size, make the crystal grain refinement of film, and small crystallite dimension can generate more crystal boundaries and carrier
Scattering improves crystalline resistance rate to inhibit the transformation of crystal phase.High crystallization temperature is conducive to improve the data of PCRAM device
Holding capacity, high SET state resistance advantageously reduce PCRAM device R ESET power consumption.
With pure Ge8Sb92Alloy is compared, the Ge for mixing oxygen of the invention8Sb92Alloy preferably resolves Ge8Sb92Material
Shortcoming and defect.By mixing different oxygen atoms, make Ge8Sb92The crystallization temperature of phase-change material significantly improves, crystallization activation
It can significantly increase, data holding ability is significantly promoted, so that its thermal stability is improved, data when it being made to be applied to PCRAM
It is more permanent to keep, and information storage is more reliable.Meanwhile mixing different oxygen atoms and making the raising of crystalline resistance, to reduce
RESET power consumption.Therefore, by adulterating oxygen element, make Ge8Sb92Alloy becomes a kind of high speed, high stability and the phase transformation of low-power consumption
Material, to have preferable market application prospect.
Oxygen GSOx nano film material of mixing of the invention can be applied to phase transition storage, with traditional phase change film material
Compared to having the advantages that
(1) GSOx nano phase change thin-film material has faster crystallization rate, can greatly improve the storage speed of PCRAM
Degree；
(2) GSOx nano phase change thin-film material crystallization temperature with higher, crystallization activation energy and ten annual data retentivities,
So as to greatly improve the stability of PCRAM；
(3) compared to the Ge for not mixing oxygen8Sb92Thin-film material, GSOx nano phase change thin-film material have higher amorphous state and
Crystalline resistance, so as to which PCRAM operation power consumption is effectively reduced.
Detailed description of the invention
Fig. 1 is GSOx (x=1,2,3) nano phase change thin-film material of the invention and the Ge for comparative example 18Sb92Film
The In-situ resistance of phase-change material and the relation curve of temperature.
Fig. 2 is GSOx (x=1,2,3) nano phase change thin-film material of the invention and the Ge for comparative example 18Sb92Film
The Kissinger matched curve of phase-change material.
Fig. 3 is GSOx (x=1,2,3) nano phase change thin-film material of the invention and the Ge for comparative example 18Sb92Film
The out-of-service time of phase-change material and the corresponding relationship curve of inverse temperature.
Fig. 4 is the diffraction pattern of GSO2 nano phase change thin-film material X ray reflection rate of the invention with incidence angle.
Fig. 5 is SET and RESET operation characteristic curve based on GSO2 nano phase change thin-film material PCRAM of the invention.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1
What is prepared in the present embodiment mixes oxygen Ge8Sb92Nano phase change Thin Films are specially GSO1.
Preparation step are as follows:
1. cleaning SiO2/ Si (100) substrate, clean the surface, the back side remove dust granule, organic and inorganic impurity；
A) it is cleaned by ultrasonic by force in acetone soln 5-10 minutes, deionized water is rinsed；
B) it is cleaned by ultrasonic by force in ethanol solution 5-10 minutes, deionized water is rinsed, high-purity N2Dry up surface and the back side；
C) in 120 DEG C of drying in oven steam, about 20 minutes.
2. using preparing before RF sputtering method preparation GSO1 film:
A) Ge is installed8Sb92Sputtering target material, the purity of target reach 99.999% (atomic percent), and background is true
Empty pump is to 2 × 10-4Pa；
B) exchange radio-frequency sputtering power is set as 20W；
C) high-purity Ar and high-purity O are used2As sputter gas (percent by volume reaches 99.999%), Ar gas is set
Flow is 49sccm, O2Flow is 1sccm, and sputtering pressure is adjusted to 2 × 10-1Pa。
3. preparing GSO1 nano phase change thin-film material using magnetically controlled sputter method:
A) space base support is rotated into Ge8Sb92Target position opens Ge8Sb92The radio-frequency power supply applied on target, according to setting
Sputtering time (180s), starts to Ge8Sb92Target is sputtered, and Ge is cleaned8Sb92Target material surface；
b)Ge8Sb92After the completion of target material surface cleaning, Ge is closed8Sb92The radio-frequency power supply applied on target, by base to be sputtered
Piece rotates to Ge8Sb92Target position opens Ge8Sb92Target position radio-frequency power supply starts sputtering and mixes oxygen according to the sputtering time of setting
Ge8Sb92Film.
The GSO1 film thickness being prepared is 50nm, and film thickness is controlled by sputtering time, the sputtering speed of GSO1
Rate is 5.13s/nm.
Embodiment 2
The GSOx nano phase change thin-film material of the present embodiment is prepared, specific structure is respectively GSO2 and GSO3, and described
The thickness of GSO2 and GSO3 nano phase change thin-film material is 50nm.
The preparation method of above-mentioned GSO2 and GSO3 nano phase change thin-film material is identical as example 1, only prepares GSO2 nanometers
The Ar throughput that phase change film material is set is 48sccm, O2Flow is 2sccm；Only prepare GSO3 nano phase change film material
The Ar throughput that material is set is 47sccm, O2Flow is 3sccm.
Comparative example 1
Single layer GS phase change film material, thickness 50nm are prepared in this comparative example.
Preparation step are as follows:
1. cleaning SiO2/ Si (100) substrate, clean the surface, the back side remove dust granule, organic and inorganic impurity；
A) it is cleaned by ultrasonic by force in acetone soln 5-10 minutes, deionized water is rinsed；
B) it is cleaned by ultrasonic by force in ethanol solution 5-10 minutes, deionized water is rinsed, high-purity N2Dry up surface and the back side；
C) in 120 DEG C of drying in oven steam, about 20 minutes.
2. using preparing before RF sputtering method preparation GS film:
A) Ge is installed8Sb92Sputtering target material, the purity of target reach 99.999% (atomic percent), and background is true
Empty pump is to 2 × 10-4Pa；
B) exchange radio-frequency sputtering power is set as 20W；
C) use high-purity Ar gas as sputter gas (percent by volume reaches 99.999%), set Ar throughput as
50sccm, and sputtering pressure is adjusted to 2 × 10-1Pa。
3. preparing GS nano phase change thin-film material using magnetically controlled sputter method:
A) space base support is rotated into Ge8Sb92Target position opens Ge8Sb92The radio-frequency power supply applied on target, according to setting
Sputtering time (180s), starts to Ge8Sb92Target is sputtered, and Ge is cleaned8Sb92Target material surface；
b)Ge8Sb92After the completion of target material surface cleaning, Ge is closed8Sb92The radio-frequency power supply applied on target, by base to be sputtered
Piece rotates to Ge8Sb92Target position opens Ge8Sb92Target position radio-frequency power supply starts to sputter Ge according to the sputtering time of setting8Sb92It is thin
Film.
The GS phase change film material of GSO1, GSO2, GSO3 of above-described embodiment 1 and 2 and comparative example 1 is tested, is obtained
To the In-situ resistance of each phase change film material and relation curve Fig. 1 of temperature；By the GSO1, GSO2 of above-described embodiment 1 and 2,
GSO3 and the GS phase change film material of comparative example 1 are tested, and the Kissinger matched curve figure of each phase change film material is obtained
2；The GS phase change film material of GSO1, GSO2, GSO3 of above-described embodiment 1 and 2 and comparative example 1 is tested, each phase is obtained
The out-of-service time of thinning membrane material and the corresponding relationship curve graph 3 of inverse temperature；By the GSO2 phase change film material of above-mentioned implementation 2
It is tested, obtains X ray reflection rate with diffraction curve Fig. 4 of incidence angle；By GSO2 nano phase change film in above-described embodiment 2
Material, which is prepared into PCRAM as phase change layer and carries out device detection, obtains its SET and RESET operation process characteristic curve graph 5.Figure
The testing result of 1- Fig. 5 is as follows:
GS thin-film material of the Fig. 1 for GSOx (x=1,2,3) nano phase change film of the invention and for comparison is in heating speed
Rate is the relation curve of the resistance and temperature under 10 DEG C/min test condition.When being less than crystallization temperature, all films are height
Resistance state (104-106Ω), show the amorphous structure of thin-film material.As temperature gradually rises, film resistor is slowly reduced, when
When reaching its phase transition temperature, film resistor dramatic decrease is held essentially constant after reaching a certain resistance value, shows thin-film material
Transformation of the phase structure from amorphous state to crystalline state.As shown in Figure 1: first, with the increase for mixing oxygen content, the crystallization of thin-film material
168 DEG C of GS are increased to 208 DEG C of GSO3 when temperature is not by mixing oxygen, show that the thermal stability of phase change film material GSOx obtains
It significantly improves.Second, with the increase for mixing oxygen content, the crystalline resistance of phase change film material is not by mixing 10 when oxygen2Ω is improved
To the 10 of GSO34Ω, crystalline resistance improves about 100 times, so that RESET power consumption be effectively reduced.Third, with mixing oxygen content
Increase, the ratio between phase change film material GSOx amorphous state high resistant and crystalline state low-resistance keep two orders of magnitude, be conducive to improve PCRAM
Signal-to-noise ratio, enhance anti-interference ability.
Fig. 2 be GSOx (x=1,2,3) nano phase change thin-film material of the invention and for comparison GS thin-film material according to
Resistance and temperature under Kissinger equation and different heating rates (10 DEG C/min, 20 DEG C/min, 30 DEG C/min and 40 DEG C/min)
The Kissinger matched curve that degree relationship is made.From the crystallization activation energy of the available thin-film material of slope of a curve.With mixing
The increase of oxygen content, the crystallization activation energy of phase change film material are increased to the 2.96eV of GSO3 by 2.43eV when not mixing oxygen.Knot
It is bigger that brilliant activation energy shows that more greatly material to be made undergoes phase transition required energy, it is meant that GSOx (x=1,2,3) nano phase change is thin
The thermal stability of film is high.
Fig. 3 be GSOx (x=1,2,3) nano phase change thin-film material of the invention and for comparison GS thin-film material according to
The relationship of isothermal method measures under Arrhenius formula and different temperatures resistance and temperature extrapolates ten annual datas and keeps temperature.
With the increase for mixing oxygen content, 87 DEG C when ten annual data holding capacities of phase change film material are not by mixing oxygen are increased to GSO3's
132℃.Ten annual data retentivities are higher, and the information storage for implying GSOx (x=1,2,3) nano phase change film is more permanent.
Fig. 4 is that the X ray of GSO2 nano phase change thin-film material of the invention after deposited and 250 DEG C of annealing 5min is anti-
Rate is penetrated with the diffraction curve of incidence angle.After Fig. 4 discovery GSO2 phase-change thin film crystallization, critical angle and maximum intensity or minimum strong
The corresponding angle of degree is whole to be deviated to wide-angle direction, it is meant that the density of film becomes larger, volume becomes smaller.By modified
The volume change that Bragg formula calculates GSO2 phase change film material is 4.39%, and conventional phase change material Ge2Sb2Te5?
Crystallization front and back volume change is 6.8%, it is seen that GSO2 nano phase change film has lesser density and volume change, facilitates
Guarantee phase change medium layer and upper/lower electrode reliable contacts in PCRAM, is conducive to the fatigue properties for promoting PCRAM.
Fig. 5 is SET and RESET operation characteristic curve based on GSO2 nano phase change thin-film material PCRAM of the invention.It inserts
Figure is shown as the SET process that PCRAM is realized under dc sweeps mode, and threshold value conversion phenomena occurs in curve, shows GSO2 nanometers
For phase change film material from high resistant amorphous state to low resistive crystalline state, threshold voltage and threshold current are respectively 3.51V and 8 μ A,
It is below traditional Ge2Sb2Te5The threshold transition voltage and current of thin-film material SET process, it is meant that GSO2 nanometer of the invention
Phase change film material has lower SET power consumption.Fig. 5 is based on GSO2 nano phase change thin-film material PCRAM of the present invention in difference
RESET process under pulse width effect.Electric arteries and veins is applied to the PCRAM for the GSO2 nano phase change thin-film material for being in low-resistance
Punching can make GSO2 nano phase change thin-film material be converted to amorphous from crystalline state in the case where pulse width is 2000ns and 200ns effect
State realizes RESET process, and RESET threshold transition voltage is respectively 2.7V and 3.1V, is below traditional Ge2Sb2Te5Film material
Expect RESET process threshold transition voltage 3.5V, it is meant that GSO2 nano phase change thin-film material of the invention has than tradition
Ge2Sb2Te5The lower RESET power consumption of thin-film material.Meanwhile the PCRAM of GSO2 nano phase change thin-film material of the invention can be
The lower realization RESET process of 200ns pulse width effect, and traditional Ge2Sb2Te5Thin-film material is difficult in 500ns pulse width
Lower realization RESET process shows the PCRAM ratio Ge based on GSO2 nano phase change thin-film material2Sb2Te5Thin-film material has more
Fast service speed.
The present invention, which discloses the oxygen GeSb nano phase change film of mixing being prepared, can be used as phase change medium layer applied to high number
According in retentivity, the low phase transition storage for operating power consumption.Currently invention addresses the doping vario-property of material and optimizations, are not that phase transformation is deposited
The preparation of memory device.Material property optimization is carried out by the method for oxygen doping, and the material is used for phase transition storage and is carried out in fact
Card, Fig. 5 show that mix oxygen GeSb nano phase change film is able to achieve SET and RESET operation, the height of device in phase transition storage
Resistance value can be applied to storage information data " 0 " and " 1 ".
Embodiment 3
One kind mixing oxygen GeSb nano phase change film, and chemical composition meets chemical general formula GSOx, and wherein GS is Ge8Sb92, x
Represent oxygen stream magnitude, unit sccm, wherein x=1.Oxygen GeSb nano phase change film is mixed to grow using magnetically controlled sputter method
In SiO2On/Si (100) substrate, with a thickness of 30nm.
The preparation method for mixing oxygen GeSb nano phase change film, using following steps:
(1) SiO is cleaned2/ Si (100) substrate: clean the surface, the back side remove dust granule, organic and inorganic impurity, tool
Body uses following steps:
(1-a) is by SiO2/ Si (100) substrate is cleaned by ultrasonic by force 5 minutes in acetone soln, and deionized water is rinsed；
(1-b) substrate is cleaned by ultrasonic by force 5 minutes in ethanol solution by treated, and deionized water is rinsed, high-purity N2It blows
Dry surface and the back side；
The substrate handled well in 100 DEG C of drying in oven steam, is obtained substrate to be sputtered by (1-c)；
(2) prepare before radio-frequency sputtering: installing Ge8Sb92Sputtering target material utilizes high-purity Ar and high-purity O2As sputter gas,
Specifically use following steps:
(2-a) installs Ge8Sb92Sputtering target material, the purity of target reach atomic percent 99.999%, and background is true
Empty pump is to 2 × 10-4Pa；
(2-b) sets exchange radio-frequency sputtering power as 15W；
(2-c) reached using percent by volume 99.999% high-purity Ar and high-purity O2, control Ar throughput and O2Flow
Than for 49:1, sputtering pressure is adjusted to 2 × 10-1Pa；
(3) nano phase change thin-film material is prepared using magnetically controlled sputter method: cleaning Ge8Sb92Target material surface, then will be wait splash
It penetrates substrate and rotates to Ge8Sb92Target position opens Ge8Sb92Oxygen Ge is mixed in the sputtering of target position radio-frequency power supply8Sb92Film, specifically using following
Step:
Space base support is rotated to Ge by (3-a)8Sb92Target position opens Ge8Sb92The radio-frequency power supply applied on target, to Ge8Sb92
Target as sputter 120s cleans Ge8Sb92Target material surface；
(3-b)Ge8Sb92After the completion of target material surface cleaning, Ge is closed8Sb92The radio-frequency power supply applied on target, will be to be sputtered
Substrate rotates to Ge8Sb92Target position opens Ge8Sb92Target position radio-frequency power supply starts sputtering and mixes oxygen Ge8Sb92Film 150s to get
It, can be in the application in phase transition storage to oxygen GeSb nano phase change film is mixed.
Embodiment 4
One kind mixing oxygen GeSb nano phase change film, and chemical composition meets chemical general formula GSOx, and wherein GS is Ge8Sb92, x
Represent oxygen stream magnitude, unit sccm, wherein x=3.Oxygen GeSb nano phase change film is mixed to grow using magnetically controlled sputter method
In SiO2On/Si (100) substrate, with a thickness of 100nm.
The preparation method for mixing oxygen GeSb nano phase change film, using following steps:
(1) SiO is cleaned2/ Si (100) substrate: clean the surface, the back side remove dust granule, organic and inorganic impurity, tool
Body uses following steps:
(1-a) is by SiO2/ Si (100) substrate is cleaned by ultrasonic by force 10 minutes in acetone soln, and deionized water is rinsed；
(1-b) substrate is cleaned by ultrasonic by force 10 minutes in ethanol solution by treated, and deionized water is rinsed, high-purity N2It blows
Dry surface and the back side；
The substrate handled well in 100-150 DEG C of drying in oven steam, is obtained substrate to be sputtered by (1-c)；
(2) prepare before radio-frequency sputtering: installing Ge8Sb92Sputtering target material utilizes high-purity Ar and high-purity O2As sputter gas,
Specifically use following steps:
(2-a) installs Ge8Sb92Sputtering target material, the purity of target reach atomic percent 99.999%, and background is true
Empty pump is to 2 × 10-4Pa；
(2-b) sets exchange radio-frequency sputtering power as 30W；
(2-c) reached using percent by volume 99.999% high-purity Ar and high-purity O2, control Ar throughput and O2Flow
Than for 47:3, sputtering pressure is adjusted to 2 × 10-1Pa；
(3) nano phase change thin-film material is prepared using magnetically controlled sputter method: cleaning Ge8Sb92Target material surface, then will be wait splash
It penetrates substrate and rotates to Ge8Sb92Target position opens Ge8Sb92Oxygen Ge is mixed in the sputtering of target position radio-frequency power supply8Sb92Film, specifically using following
Step:
Space base support is rotated to Ge by (3-a)8Sb92Target position opens Ge8Sb92The radio-frequency power supply applied on target, to Ge8Sb92
Target as sputter 300s cleans Ge8Sb92Target material surface；
(3-b)Ge8Sb92After the completion of target material surface cleaning, Ge is closed8Sb92The radio-frequency power supply applied on target, will be to be sputtered
Substrate rotates to Ge8Sb92Target position opens Ge8Sb92Target position radio-frequency power supply starts sputtering and mixes oxygen Ge8Sb92Film 300s to get
It, can be in the application in phase transition storage to oxygen GeSb nano phase change film is mixed.
Claims (4)
1. one kind mixes oxygen GeSb nano phase change film, which is characterized in that the chemical composition of the phase-change thin film meets chemical general formula
GSOx, wherein GS is Ge8Sb92, x represents oxygen stream magnitude, unit sccm, wherein x=1,2 or 3, and described mixes oxygen GeSb
Nano phase change film is grown on SiO using magnetically controlled sputter method2On/Si (100) substrate, described to mix oxygen GeSb nano phase change thin
Film with a thickness of 30-100nm, be prepared using following methods:
(1) SiO is cleaned2/ Si (100) substrate: clean the surface, the back side remove dust granule, organic and inorganic impurity；
(2) prepare before radio-frequency sputtering: installing Ge8Sb92Sputtering target material utilizes high-purity Ar and high-purity O2As sputter gas, specifically adopt
With following steps:
(2-a) installs Ge8Sb92Sputtering target material, the purity of target reaches atomic percent 99.999%, and base vacuum is taken out
To 2 × 10-4Pa；
(2-b) sets exchange radio-frequency sputtering power as 15-30W；
(2-c) reached using percent by volume 99.999% high-purity Ar and high-purity O2, control Ar throughput and O2Flow-rate ratio is
49-47:1-3, sputtering pressure are adjusted to 2 × 10-1Pa；
(3) nano phase change thin-film material is prepared using magnetically controlled sputter method: cleaning Ge8Sb92Target material surface, then by base to be sputtered
Piece rotates to Ge8Sb92Target position opens Ge8Sb92Oxygen Ge is mixed in the sputtering of target position radio-frequency power supply8Sb92Film specifically uses following steps:
Space base support is rotated to Ge by (3-a)8Sb92Target position opens Ge8Sb92The radio-frequency power supply applied on target, to Ge8Sb92Target
120-300s is sputtered, Ge is cleaned8Sb92Target material surface；
(3-b)Ge8Sb92After the completion of target material surface cleaning, Ge is closed8Sb92The radio-frequency power supply applied on target, by substrate to be sputtered
Rotate to Ge8Sb92Target position opens Ge8Sb92Target position radio-frequency power supply starts sputtering and mixes oxygen Ge8Sb92Film 150-300s is to get arriving
Mix oxygen GeSb nano phase change film.
2. according to claim 1 mix oxygen GeSb nano phase change film, which is characterized in that step (1) is specifically using following
Step:
(1-a) is by SiO2/ Si (100) substrate is cleaned by ultrasonic by force 5-10 minutes in acetone soln, and deionized water is rinsed；
(1-b) substrate is cleaned by ultrasonic by force 5-10 minutes in ethanol solution by treated, and deionized water is rinsed, high-purity N2Drying
Surface and the back side.
3. the preparation method according to claim 1 for mixing oxygen GeSb nano phase change film, which is characterized in that control Ar air-flow
Amount and O2Flow-rate ratio is 49:1,48:2 or 47:3.
4. mixing application of the oxygen GeSb nano phase change film in phase transition storage as described in claim 1.
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| CN110911557A (en) * | 2019-10-30 | 2020-03-24 | 华中科技大学 | Doped Ge-Sb phase change material, phase change memory and preparation method thereof |
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| CN101461071A (en) * | 2005-12-20 | 2009-06-17 | Nxp股份有限公司 | A vertical phase change memory cell and methods for manufacturing thereof |
| CN101546728A (en) * | 2009-04-30 | 2009-09-30 | 中国科学院上海微系统与信息技术研究所 | Preparation method for nano level columnar phase change memory cell array |
| WO2012138615A2 (en) * | 2011-04-03 | 2012-10-11 | Advanced Technology Materials, Inc. | Oxic germanium-antimony-tellurium material and phase change memory comprising same |
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