CN103887430B - Nitrogen-doped modified phase-change film material and preparation method thereof - Google Patents
Nitrogen-doped modified phase-change film material and preparation method thereof Download PDFInfo
- Publication number
- CN103887430B CN103887430B CN201410123117.9A CN201410123117A CN103887430B CN 103887430 B CN103887430 B CN 103887430B CN 201410123117 A CN201410123117 A CN 201410123117A CN 103887430 B CN103887430 B CN 103887430B
- Authority
- CN
- China
- Prior art keywords
- film material
- phase
- sputtering
- preparation
- modified
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000010408 film Substances 0.000 claims abstract description 56
- 230000008859 change Effects 0.000 claims abstract description 47
- 238000004544 sputter deposition Methods 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010409 thin film Substances 0.000 claims abstract description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- 229910052786 argon Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 230000000802 nitrating effect Effects 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 16
- 239000013077 target material Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 238000001552 radio frequency sputter deposition Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 11
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 description 50
- 239000012782 phase change material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 230000033228 biological regulation Effects 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910052714 tellurium Inorganic materials 0.000 description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 5
- 229910001245 Sb alloy Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000000137 annealing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910017629 Sb2Te3 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000009527 percussion Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
- H10N70/021—Formation of switching materials, e.g. deposition of layers
- H10N70/026—Formation of switching materials, e.g. deposition of layers by physical vapor deposition, e.g. sputtering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/20—Multistable switching devices, e.g. memristors
- H10N70/231—Multistable switching devices, e.g. memristors based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N70/00—Solid-state devices having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses a nitrogen-doped modified phase-change thin film material and a preparation method thereof, wherein the phase-change thin film material consists of three elements of Zn, Sb and N, and the chemical composition general formula of the phase-change thin film material is Nx（Zn15Sb85）1‑xWherein x is more than or equal to 0.29 and less than or equal to 0.49. Prepared by depositing Zn by radio frequency sputtering15Sb85In the process of filmAnd introducing argon and nitrogen to obtain the phase-change film material doped with nitrogen. The nitrogen-doped modified phase-change film material and pure Zn15Sb85Compared with the film, the modified film has higher crystallization speed, and the storage speed of the phase change memory is greatly improved; the crystallization temperature and the activation energy of the modified film are higher, and the data retention capability is enhanced; the crystalline resistance and the amorphous resistance of the nitrogen-doped modified phase-change film material are higher, so that the RESET power consumption is reduced, and the operation power consumption of the phase-change memory manufactured by using the nitrogen-doped modified phase-change film material is limited to be reduced.
Description
Technical field
Phase-change storage material that the present invention relates to microelectronics technology and preparation method thereof, is specifically related to a kind of for phase
Phase change film material that the nitrating of transition storage is modified and preparation method thereof.
Background technology
Phase transition storage (PCRAM) is to utilize sulfur based material reversible transformation between crystalline and amorphous thus realizes letter
The novel non-volatility memorizer of one of breath storage.There is when phase-change material is in amorphous state high resistance, have low during crystalline state
Resistance, the Joule heat utilizing electric pulse to produce realizes repeating between high-impedance state and low resistance state and changes, reaches the mesh of information storage
's.It has the advantages such as CMOS technology low in energy consumption, that reading speed is fast, stability is strong, memory density is high and traditional is compatible, because of
And paid close attention to (Zhou Xilin etc., Applied Physics Letter, 103(7) by increasing researcher,
072114,2013).
With traditional Ge2Sb2Te5Phase-change material is compared, and it is more than needed that Zn-Sb alloy has faster phase velocity, especially Sb
Zn-Sb alloy there is the phase velocity of superelevation so that it is there is the great potential becoming ultrahigh speed PCRAM phase-change material
(the Japanese Journal Of Applied Physics, 46(23 such as Park, Tae Jin), L543,2007).But
Zn-Sb alloy there is also some shortcomings of self, that is, stability is the highest.The purest Zn15Sb85The crystallization temperature of alloy
It is about 160 DEG C, utilizes its phase transition storage manufactured data can only be kept 10 years at 91 DEG C, data at higher temperatures
Holding capacity can drastically decline, thus cannot meet the needs of actual application.
Improve relatively conventional the having of method of the data retention of phase-change storage material: 1, change each element group in material
Point；2, other elements that adulterate are modified；3, research and development new material.
Such as Chinese patent literature CN 103247757 A discloses a kind of Zn-Sb-Te phase transformation for phase transition storage
Storing thin-film material and preparation method thereof, this material is a kind of by zinc, antimony, three kinds of elementary composition mixture of tellurium.Described Zn-
Sb-Te phase transiting storing thin-film material uses Sb2Te3Alloys target and Zn simple substance target co-sputtering are formed.Compared to Zn-Sb alloy, this article
Offering and add tellurium element in disclosed storing thin-film material, storage performance gets a promotion.But it is unfriendly that tellurium element belongs to environment
Chemical element, easily cause certain environmental pollution.And, tellurium element is susceptible to volatilization in semiconductor processing, thus
Pollute whole semiconductor production equipment.It addition, be susceptible to split-phase after repeatedly circulating containing the phase-change material of tellurium, thus shadow
The fatigue properties of Chinese percussion instrument part.
Summary of the invention
The technical problem to be solved is to provide modified phase change film material of a kind of nitrating and preparation method thereof.
The technical scheme realizing the object of the invention is the phase change film material of a kind of nitrating modification, by tri-kinds of units of Zn, Sb, N
Element composition, its chemical composition formula is Nx(Zn15Sb85)1-x, wherein 0.29≤x≤0.49.
Preferably, 0.32≤x≤0.41 in chemical composition formula.
The preparation method of the phase change film material that a kind of nitrating as above is modified, comprises the following steps:
1. the preparation of substrate, cleans drying by substrate stand-by.
2. the preparation of magnetron sputtering, in magnetron sputtering coating system, the substrate to be sputtered step 1. prepared is placed
On base, by Zn15Sb85Alloy target material is arranged in magnetron RF sputtering system target, and by the sputtering chamber of magnetron sputtering coating system
Room carries out evacuation；Then to sputtering chamber be passed through high-purity argon gas and high pure nitrogen to sputtering chamber internal gas pressure reach 0.15Pa～
0.25Pa。
③Nx(Zn15Sb85)1-xThe preparation of thin film, regulation is 24 sccm to the flow of the high-purity argon gas that sputtering chamber is passed through
～27sccm, high pure nitrogen flow is 3sccm～6sccm, and sputtering pressure is 0.15 Pa～0.25 Pa；Set sputtering power
15W～25W；First Zn is cleaned15Sb85Target material surface, treats Zn15Sb85After target material surface has cleaned, close Zn15Sb85Institute on target
The radio-frequency power supply applied, rotates to Zn by substrate to be sputtered15Sb85Target position, opens Zn15Sb85Target position radio-frequency power supply, at room temperature
Obtain, after sputtering 20s～40s, the phase change film material that nitrating is modified.
Above-mentioned steps 1. in when carrying out the operation of substrate cleaning, drying, first in supersonic cleaning machine, substrate is the most ultrasonic
Clean 3～5 minutes, wash complete taking-up deionized water rinsing；Then by substrate ultrasonic cleaning 3 in ethanol in supersonic cleaning machine
～5 minutes, wash complete taking-up deionized water rinsing, after rinsing well, use high-purity N2Dry up surface and the back side；Substrate after drying up
Send into and baking oven is dried steam, complete the preparation of substrate.
Above-mentioned steps 3. middle cleaning Zn15Sb85During target material surface, space base torr is rotated to Zn15Sb85Target position, opens
Zn15Sb85The radio-frequency power supply applied on target, starts Zn15Sb85Target carries out sputtering to clean Zn15Sb85Target material surface, spatters
The time of penetrating is 80s～120s.
The present invention has positive effect: (1) present invention is by radio frequency sputtering deposition Zn15Sb85During thin film together
Time be passed through argon and nitrogen, nitrogen doped in the phase change film material obtained, it is non-that N with Zn forms the higher nitride of stability
Brilliant granule, is distributed in around phase-change material, on the one hand stops the crystallization of phase-change material, improves the thermally-stabilised of phase-change material entirety
Property；On the other hand, Zn can reduce crystallite dimension, increases number of grain boundaries, thus increases crystalline resistance, reduces device in RESET mistake
Power consumption in journey.(2) the nitrating modification phase change film material of the present invention and pure Zn15Sb85Thin film is compared, and mixes nitrogen former
After son, modified thin film has crystallization rate faster, it is possible to be greatly improved the storage speed of phase transition storage；And it is modified
After the crystallization temperature of thin film and activation energy higher, data holding ability is strengthened, and improves the phase change memory made of it
The stability of device；Zn compared to non-nitrating15Sb85Thin-film material, the crystalline resistance of nitrating modification phase change film material and amorphous
State resistance is higher so that RESET lower power consumption, the finite reduction operation power consumption of its phase transition storage made.
Nitrating modification Zn15Sb85The phase change film material obtained is the phase transformation material of a kind of high speed, high stability, low-power consumption
Material, preparation method low cost, process controllability is strong, it is easy to industrialization large-scale production, has preferable market application foreground.
Accompanying drawing explanation
Fig. 1 be embodiments of the invention 1 to embodiment 4 preparation phase change film material and the Zn of comparative example 115Sb85Thin
The In-situ resistance of film phase-change material and the relation curve of temperature.
Fig. 2 be embodiments of the invention 1 to embodiment 4 preparation phase change film material and the Zn of comparative example 115Sb85Thin
Film phase-change material out-of-service time and the corresponding relation curve of inverse temperature.
Detailed description of the invention
(embodiment 1)
The phase change film material of the present embodiment is by N doping vario-property Zn15Sb85The phase change film material obtained, its chemical group
One-tenth formula is Nx(Zn15Sb85)1-x, wherein 0.29≤x≤0.49(the present embodiment is 0.2913).
The preparation method of the phase change film material that the nitrating of the present embodiment is modified comprises the following steps:
1. the preparation of substrate.Choose the SiO of a size of 5mm × 5mm2/ Si (100) substrate, first will in supersonic cleaning machine
Substrate ultrasonic cleaning 3～5 minutes in acetone (purity is more than 99%), wash complete taking-up deionized water rinsing；Then ultrasonic
By substrate ultrasonic cleaning 3～5 minutes in ethanol (purity is more than 99%) in cleaning machine, wash complete taking-up deionized water rinsing,
High-purity N is used after rinsing well2Dry up surface and the back side；Substrate after drying up is sent into and is dried steam, the substrate after drying in baking oven
Stand-by, wherein oven temperature is set to 120 DEG C, drying time 20 minutes.
2. the preparation of magnetron sputtering.In magnetron sputtering coating system (JGP-450 type), step 1. prepared is to be sputtered
Substrate be placed on base, by Zn15Sb85Alloy (purity all reaches 99.999%) target is arranged on magnetic control radio frequency (RF) sputtering
In target, and the sputtering chamber of magnetron sputtering coating system is carried out evacuation until vacuum reaches 1 × 10 in chamber-4 Pa；So
Backward sputtering chamber is passed through high-purity argon gas and high pure nitrogen and reaches 0.2Pa to sputtering chamber internal gas pressure.
In high-purity argon gas, argon percent by volume all reaches 99.999%；In high pure nitrogen, nitrogen percent by volume all reaches
99.999%。
③Nx(Zn15Sb85)1-xThe preparation of thin film.
Regulation is 27sccm to the flow of the high-purity argon gas that sputtering chamber is passed through, and high pure nitrogen flow is 3sccm, sputters gas
Pressure is 0.15 Pa～in 0.25 Pa(the present embodiment for 0.2Pa)；Set in sputtering power 15W～25W(the present embodiment and be
20W).
Space base torr is rotated to Zn15Sb85Target position, opens Zn15Sb85The radio-frequency power supply applied on target, it is right to start
Zn15Sb85Target carries out sputtering to clean Zn15Sb85Target material surface, sputtering time is 100s.
Treat Zn15Sb85After target material surface has cleaned, close Zn15Sb85The radio-frequency power supply applied on target, by base to be sputtered
Sheet rotates to Zn15Sb85Target position, opens Zn15Sb85Target position radio-frequency power supply, obtains N doping Zn at room temperature after sputtering 20s15Sb85
Phase change film material, sputter rate is 2.5s/nm, Nx(Zn15Sb85)1-xThe thickness of thin film is 50nm.If thin film to be increased
Thickness, increase sputtering time, such as sputtering time is extended to 40s, the thickness of obtained thin film is 100nm.
Through power spectrum (EDS) quantitative analysis, the chemical constitution formula N of the thin-film material of the present embodimentx(Zn15Sb85)1-xMiddle x=
0.2913。
(embodiment 2)
Remaining is same as in Example 1 for the preparation method of the phase change film material that the nitrating of the present embodiment is modified, difference
It is:
The flow of the step 3. high-purity argon gas that middle regulation is passed through to sputtering chamber is 26sccm, and high pure nitrogen flow is
4sccm.The chemical constitution formula N of the phase change film material that obtained nitrating is modifiedx(Zn15Sb85)1-xMiddle x=0.3252.
(embodiment 3)
Remaining is same as in Example 1 for the preparation method of the phase change film material that the nitrating of the present embodiment is modified, difference
It is:
The flow of the step 3. high-purity argon gas that middle regulation is passed through to sputtering chamber is 25sccm, and high pure nitrogen flow is
5sccm.The chemical constitution formula N of the phase change film material that obtained nitrating is modifiedx(Zn15Sb85)1-xMiddle x=0.4086.
(embodiment 4)
Remaining is same as in Example 1 for the preparation method of the phase change film material that the nitrating of the present embodiment is modified, difference
It is:
The flow of the step 3. high-purity argon gas that middle regulation is passed through to sputtering chamber is 24sccm, and high pure nitrogen flow is
6sccm.The chemical constitution formula N of the phase change film material that obtained nitrating is modifiedx(Zn15Sb85)1-xMiddle x=0.4812.
(comparative example 1)
That prepared by this comparative example is the Zn of non-nitrating15Sb85Phase change film material, its preparation method remaining with embodiment 1 phase
With, difference is:
During the preparation of step 2. magnetron sputtering, after sputtering chamber evacuation, it is passed through high-purity argon gas to sputtering chamber to sputtering chamber
Room pressure reaches 0.2Pa.
Step 3. in, the flow regulating the high-purity argon gas being passed through to sputtering chamber is 30sccm, and sputtering pressure is 0.2Pa.
Zn15Sb85After target material surface cleaning, close Zn15Sb85The radio-frequency power supply applied on target, by substrate to be sputtered
Rotate to Zn15Sb85Target position, opens Zn15Sb85Target position radio-frequency power supply, obtains Zn after sputtering 20s at room temperature15Sb85Phase-change thin film
Material, film thickness is 50nm.
(experimental example 1)
In order to understand the performance of the modified phase change film material of the nitrating prepared by embodiment 1 to embodiment 4, to embodiment
Phase change film material prepared by 1 to embodiment 4 and comparative example 1 carries out In-situ resistance performance test, obtains each phase-change thin film
The In-situ resistance of material is corresponding with inverse temperature with the out-of-service time of the graph of relation of temperature and each phase change film material to close
It it is curve chart.
The In-situ resistance of each phase change film material and the graph of relation of temperature are shown in Fig. 1, the inefficacy of each phase change film material
The corresponding relation curve chart of time and inverse temperature is shown in Fig. 2；In Fig. 1 and Fig. 2, ZS represents the non-nitrating prepared by comparative example 1
Zn15Sb85Phase change film material, ZSN1 represents the phase change film material that the nitrating prepared by embodiment 1 is modified, and ZSN2 represents real
Executing the phase change film material that the nitrating prepared by example 2 is modified, ZSN3 represents the phase-change thin film that the nitrating prepared by embodiment 3 is modified
Material, ZSN4 represents the phase change film material that the nitrating prepared by embodiment 4 is modified.
The In-situ resistance of each phase change film material is as follows with the relation test method of temperature: external by a heating platform
The test system of an in site measurement resistance v. temperature and resistivity-time relation built by one Keithley 6517 megameter
System.The temperature of heating platform is regulated by Linkam scientific instrument Co., Ltd of Britain TP 94 type temperature control system,
Cooling utilizes liquid nitrogen to be controlled by LNP94/2 type cooling system, and temperature rate ranges up to 90
DEG C/min, temperature control is the most accurate.Heating rate employed in this test process is 10 DEG C/min.In heating and cooling
Cheng Zhong, the fixing voltage being added on film probe is 2.5V, utilizes megameter to measure the electric current varied with temperature, then is converted into phase
The resistance answered.
As shown in Figure 1, at low temperatures, all thin film are in high-resistance amorphous state.Along with the continuous rising of temperature, thin film
Resistance slowly reduces, and when reaching its phase transition temperature, film resistor reduces rapidly, and after arriving a certain value, basic this resistance of holding is not
Become, show that thin film there occurs by the transformation of amorphous state to crystalline state.Test result shows, along with the increase of itrogen content of getter with nitrogen doped in thin film, thin
The crystallization temperature of film is increased 230 DEG C of ZSN4 by 160 DEG C during non-nitrating, shows that the heat stability of phase change film material has
Bigger raising.Meanwhile, the crystalline resistance of phase change film material by 205 Ω during non-nitrating increase ZSN4 2.1 ×
103Ω, expands original 10 times to, thus effectively reduces the power consumption of RESET process.
The out-of-service time of each phase change film material is as follows from the corresponding relation method of testing of inverse temperature: different constant
The phase-change thin film resistance change curve with annealing time is measured under annealing temperature, when film resistor is reduced to originally be worth 50%,
We i.e. think that resistance had lost efficacy.By the out-of-service time under different temperatures and the mapping reciprocal of corresponding temperature, and curve is prolonged
Long to 10 years (about 315360000s), obtain the temperature of correspondence.
According to one of unified judgment criteria in the industry, come utilizing the temperature that phase-change material is corresponding when data being kept 10 years
Pass judgment on the data holding ability of material.
By Fig. 2 it will be seen that data are only kept the temperature of 10 years by the ZS phase change film material of the comparative example 1 of non-nitrating
91 oC, and the ZSN of the present inventionx ( x=1,2,3) temperature that data keep 10 years is all improved by phase-change thin film, its
The temperature that data keep 10 years has been brought up to 134 by middle ZSN3 nano film material oC.Traditional Ge2Sb2Te5Thin-film material will
The temperature that data keep 10 years is 85 oC.The ZSN of the visible present inventionx ( x=1,2,3) tradition Ge is compared2Sb2Te5Thin film
Material data holding capacity significantly improves.
Claims (5)
1. the phase change film material that a nitrating is modified, it is characterised in that: elementary composition by Zn, Sb, N tri-kinds, its chemical composition
Formula is Nx(Zn15Sb85)1-x, wherein 0.29≤x≤0.49.
The phase change film material that nitrating the most according to claim 1 is modified, it is characterised in that: in chemical composition formula 0.32
≤x≤0.41。
3. the preparation method of the phase change film material that a nitrating as claimed in claim 1 is modified, it is characterised in that include with
Lower step:
1. the preparation of substrate, cleans drying by substrate stand-by；
2. the preparation of magnetron sputtering, in magnetron sputtering coating system, the substrate to be sputtered step 1. prepared is placed on base
In torr, by Zn15Sb85Alloy target material is arranged in magnetron RF sputtering system target, and is entered by the sputtering chamber of magnetron sputtering coating system
Row evacuation；Then to sputtering chamber be passed through high-purity argon gas and high pure nitrogen to sputtering chamber internal gas pressure reach 0.15Pa～
0.25Pa；
③Nx(Zn15Sb85)1-xThe preparation of thin film, regulate the flow of the high-purity argon gas being passed through to sputtering chamber be 24 sccm～
27sccm, high pure nitrogen flow is 3sccm～6sccm, and sputtering pressure is 0.15 Pa～0.25 Pa；Set sputtering power 15W
～25W；First Zn is cleaned15Sb85Target material surface, treats Zn15Sb85After target material surface has cleaned, close Zn15Sb85Executed on target
The radio-frequency power supply added, rotates to Zn by substrate to be sputtered15Sb85Target position, opens Zn15Sb85Target position radio-frequency power supply, spatters at room temperature
The phase change film material that nitrating is modified is obtained after penetrating 20s～40s.
The preparation method of the phase change film material that nitrating the most according to claim 3 is modified, it is characterised in that: step 1. in
When carrying out the operation of substrate cleaning, drying, first by substrate ultrasonic cleaning 3 in acetone～5 minutes in supersonic cleaning machine, wash to finish and take
Go out to use deionized water rinsing；Then by substrate ultrasonic cleaning 3 in ethanol～5 minutes in supersonic cleaning machine, wash to finish to take out and use
Deionized water rinsing, uses high-purity N after rinsing well2Dry up surface and the back side；Substrate after drying up is sent into and is dried steam in baking oven,
Complete the preparation of substrate.
The preparation method of the phase change film material that nitrating the most according to claim 3 is modified, it is characterised in that: step 3. in
Cleaning Zn15Sb85During target material surface, space base torr is rotated to Zn15Sb85Target position, opens Zn15Sb85The radio frequency electrical applied on target
Source, starts Zn15Sb85Target carries out sputtering to clean Zn15Sb85Target material surface, sputtering time is 80s～120s.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410123117.9A CN103887430B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase-change film material and preparation method thereof |
| CN201610788846.5A CN106206943B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase change film material and preparation method thereof |
| CN201610794092.4A CN106252508B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase-change thin film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410123117.9A CN103887430B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase-change film material and preparation method thereof |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610794092.4A Division CN106252508B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase-change thin film material and preparation method thereof |
| CN201610788846.5A Division CN106206943B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase change film material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103887430A CN103887430A (en) | 2014-06-25 |
| CN103887430B true CN103887430B (en) | 2016-10-26 |
Family
ID=50956244
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610788846.5A Active CN106206943B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase change film material and preparation method thereof |
| CN201610794092.4A Active CN106252508B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase-change thin film material and preparation method thereof |
| CN201410123117.9A Active CN103887430B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase-change film material and preparation method thereof |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610788846.5A Active CN106206943B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase change film material and preparation method thereof |
| CN201610794092.4A Active CN106252508B (en) | 2014-03-28 | 2014-03-28 | Nitrogen-doped modified phase-change thin film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN106206943B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104393171A (en) * | 2014-11-17 | 2015-03-04 | 江苏理工学院 | Nitrogen-doped nano thin film material for rapid high-stability phase change memory and preparation method thereof |
| CN104659209B (en) * | 2015-02-09 | 2017-09-29 | 江苏理工学院 | GeSb-based nitrogen-doped nano film material for phase change memory and preparation method thereof |
| CN104681720A (en) * | 2015-02-09 | 2015-06-03 | 江苏理工学院 | SbSe-based nitrogen-doped nano thin film material for phase change memory and preparation method thereof |
| CN106374042A (en) * | 2016-09-26 | 2017-02-01 | 江苏理工学院 | Nitrogen-doped Sb nano phase change thin film material and preparation method and application thereof |
| CN108365091A (en) * | 2018-01-05 | 2018-08-03 | 江苏理工学院 | A kind of Zn10Sb90 nano phase change thin-film materials and preparation method thereof for mixing oxygen |
| CN108615811A (en) * | 2018-04-27 | 2018-10-02 | 江苏理工学院 | A kind of lanthanide-doped ZnSb nano phase change materials and preparation method thereof |
| CN110335941B (en) * | 2019-07-03 | 2023-08-18 | 芯盟科技有限公司 | Phase change memory structure and forming method thereof |
| CN111968865A (en) * | 2020-07-17 | 2020-11-20 | 太原理工大学 | In-situ nitrogen-doped metal oxide supercapacitor electrode and preparation method thereof |
| CN114277350A (en) * | 2021-12-28 | 2022-04-05 | 东北大学 | Nano high-temperature protective coating with stable structure and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101582485A (en) * | 2009-06-15 | 2009-11-18 | 中国科学院上海微***与信息技术研究所 | Doping modified phase change material and phase change storage unit containing same and preparation method thereof |
| CN102751435A (en) * | 2011-04-21 | 2012-10-24 | 中国科学院上海微***与信息技术研究所 | Phase change storage material and preparation method thereof |
| CN102800807A (en) * | 2012-08-23 | 2012-11-28 | 同济大学 | Oxygen-doped nanometre thin-film material for low-power-consumption and high-reliability phase change memory as well as preparation and application of thin-film material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7115927B2 (en) * | 2003-02-24 | 2006-10-03 | Samsung Electronics Co., Ltd. | Phase changeable memory devices |
| KR100857466B1 (en) * | 2007-05-16 | 2008-09-08 | 한국전자통신연구원 | Phase change nonvolatile memory device using sb-zn alloy and method for preparing the same |
| US7491573B1 (en) * | 2008-03-13 | 2009-02-17 | International Business Machines Corporation | Phase change materials for applications that require fast switching and high endurance |
-
2014
- 2014-03-28 CN CN201610788846.5A patent/CN106206943B/en active Active
- 2014-03-28 CN CN201610794092.4A patent/CN106252508B/en active Active
- 2014-03-28 CN CN201410123117.9A patent/CN103887430B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101582485A (en) * | 2009-06-15 | 2009-11-18 | 中国科学院上海微***与信息技术研究所 | Doping modified phase change material and phase change storage unit containing same and preparation method thereof |
| CN102751435A (en) * | 2011-04-21 | 2012-10-24 | 中国科学院上海微***与信息技术研究所 | Phase change storage material and preparation method thereof |
| CN102800807A (en) * | 2012-08-23 | 2012-11-28 | 同济大学 | Oxygen-doped nanometre thin-film material for low-power-consumption and high-reliability phase change memory as well as preparation and application of thin-film material |
Non-Patent Citations (1)
| Title |
|---|
| "Crystallization characteristics of nitrogen-doped Sb2Te3 films for PRAM application";MS Kim等;《Ceramics International》;20080425;第34卷(第4期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103887430A (en) | 2014-06-25 |
| CN106206943B (en) | 2019-01-25 |
| CN106206943A (en) | 2016-12-07 |
| CN106252508B (en) | 2018-06-08 |
| CN106252508A (en) | 2016-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103887430B (en) | Nitrogen-doped modified phase-change film material and preparation method thereof | |
| CN106374041B (en) | A kind of Sb70Se30/SiO2Multi-layer nano composite phase-change thin-film material and its preparation method and application | |
| CN106449972B (en) | A kind of Ti-Sb nano phase change thin-film material and its preparation method and application | |
| CN104659209B (en) | GeSb-based nitrogen-doped nano film material for phase change memory and preparation method thereof | |
| CN104681720A (en) | SbSe-based nitrogen-doped nano thin film material for phase change memory and preparation method thereof | |
| Fang et al. | Low-Frequency Noise in Oxide-Based $(\hbox {TiN}/\hbox {HfO} _ {x}/\hbox {Pt}) $ Resistive Random Access Memory Cells | |
| CN102832341B (en) | Al-Sb-Se nano-phase change thin film material and preparation method and application thereof | |
| CN106374043A (en) | Si-Sb-Se nano phase-change thin film material and preparation method and application thereof | |
| CN102800807B (en) | Oxygen-doped nanometre thin-film material for low-power-consumption and high-reliability phase change memory as well as preparation and application of thin-film material | |
| CN106953006A (en) | A kind of SiO2Doping Sb nano phase change thin-film materials and preparation method thereof and purposes | |
| CN106410025A (en) | Oxygen-doped Sb nanometer phase change thin-film materials and preparation method thereof and application thereof | |
| CN104393171A (en) | Nitrogen-doped nano thin film material for rapid high-stability phase change memory and preparation method thereof | |
| CN107768516A (en) | Y Sb Te phase-change materials, phase-changing memory unit and preparation method thereof | |
| CN105304815B (en) | A kind of multi-layer nano composite film material and preparation method thereof for low power consumption phase changing memory | |
| CN107342362A (en) | A kind of Mg Sb Se nano phase change films and preparation method thereof | |
| CN105742489B (en) | A kind of Zr for phase transition storage adulterates Ge2Sb2Te5Thin-film material and preparation method thereof | |
| CN106098934A (en) | One mixes oxygen GeSb nano phase change thin film and its preparation method and application | |
| Liu et al. | Memory effect of sol–gel derived V-doped SrZrO3 thin films | |
| CN106374042A (en) | Nitrogen-doped Sb nano phase change thin film material and preparation method and application thereof | |
| CN110137349B (en) | Vanadium dioxide-Sb-rich phase-change thin film material and preparation method thereof | |
| CN113072915A (en) | Sb based on oxygen doping2Te3Phase change material, phase change memory and preparation method | |
| CN107768518B (en) | A kind of Al/Ge for phase transition storage10Sb90Class superlattices phase change film material and preparation method | |
| CN106960907B (en) | A kind of rare earth Er doping Ge2Sb2Te5Phase transiting storing thin-film material and preparation method thereof | |
| Hsu et al. | A study of negative resistance effect of CuxO RRAM fabricated by using a sol-gel method | |
| CN112786782B (en) | Sb-Si for phase change memory 3 N 4 Thin film material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |