CN106601906B - The preparation method and application of InP resistance-change memory material - Google Patents
The preparation method and application of InP resistance-change memory material Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000000137 annealing Methods 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 4
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000004377 microelectronic Methods 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007772 electrode material Substances 0.000 description 4
- 238000004549 pulsed laser deposition Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 235000008434 ginseng Nutrition 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004151 rapid thermal annealing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
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- 229910052905 tridymite Inorganic materials 0.000 description 1
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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
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- 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
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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
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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
- H10N70/041—Modification of switching materials after formation, e.g. doping
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Abstract
The invention discloses a kind of preparation method and application of InP resistance-change memory material, belong to microelectronic manufacturing technology field.The preparation method comprises the following steps: 1) being packed into monocrystalline InP piece as target in pulse laser equipment cavity；2) substrate that surface is deposited with electrode is packed into pulse laser equipment cavity；3) it will be vacuumized in pulse laser equipment cavity；4) substrate is heated；5) using the method for pulse laser deposition in deposition on substrate InP film；6) substrate 600~800 DEG C of annealing under vacuum conditions that will deposited InP film, obtains InP resistance-change memory material after cooling.InP resistance-change memory material has good storage characteristics, and the resistance-variable storing device based on storage material preparation has memory window mouth width, and data hold time is long, the high feature of durability.
Description
Technical field
The invention belongs to microelectronic manufacturing technology field more particularly to a kind of preparation method of InP resistance-change memory material and
Using.
Background technique
With flourishing for portable consumer electronics product, capacity and integration density of the people to nonvolatile memory
Propose increasingly higher demands.In order to improve the integration density of memory, device size constantly reduces, and multilevel storage technology obtains
It must be more and more widely used, 3D Stack Technology is increasingly becoming research hotspot.However, object is moved towards in the diminution of device size at last
The limit is managed, the reliability of multilevel storage technology and other properties also all have many problems, and 3D technology is then because facing material
Material selection, device architecture, technique realize that the challenge of many arduousnesses such as difficulty also will not temporarily be promoted rapidly, therefore, in order to realize
The higher density of data storage, smaller cost of bit are badly in need of a kind of novel storage with CMOS technology highly compatible
Device structure.Resistance-variable storing device (RRAM) due to simple device architecture, compact storage array, excellent storage performance and with it is existing
There is the high compatibility of CMOS technology, becomes most potential one of solution.From 1967, Simons and Verderber were sent out
Now and have studied Au/SiO2After the electric resistance changing behavior of/Al structure, by gradualling mature for more than 40 years film preparing technologies
With the development of non-volatile memory technology, more and more thin-film materials suitable for resistance-variable storing device are reported, and by industry
Applied to trial-production of storage chip, including perovskite, metal oxide, solid electrolyte material, organic material etc..Find synthesis
The technical issues of resistance-change memory material haveing excellent performance is those skilled in the art's urgent need to resolve.
Summary of the invention
For the deficiency of existing memory, the present invention provides a kind of preparation methods of InP resistance-change memory material, and will system
Standby InP resistance-change memory material is applied in resistive memory, the preparation method of InP resistance-change memory material, including following step
It is rapid:
(1) it is packed into monocrystalline InP piece as target in pulse laser equipment cavity；
(2) substrate that surface is deposited with electrode is packed into pulse laser equipment cavity；；
(3) it will be vacuumized in pulse laser equipment cavity, vacuum degree is 5 × 10-8Pa；
(4) substrate is heated to 350~450 DEG C；
(5) using the method for pulse laser deposition in deposition on substrate InP film；
(6) quick thermal annealing process will be carried out under the substrate vacuum condition that deposited InP film, finally obtains InP resistive
Storage material.
Further, the substrate in the step (2) is insulative inorganic material.
Further, the pulse laser deposition parameter in the step (5) are as follows: the spacing of target and substrate is 6~8cm, is swashed
1~5Hz of working frequency of light, energy force density are 1~3J/cm2。
Further, the InP film that deposition obtains in the step (5) with a thickness of 10~500nm.
Further, step (6) rapid thermal anneal process are as follows: 600~800 DEG C of annealing temperature, annealing time 5~120
Second.
InP resistance-change memory material is used to prepare InP-base resistive memory, preparation step are as follows: by InP resistance-change memory material
Surface covers hard mask plate, and hard mask plate is then placed in magnetron sputtering apparatus with a thickness of 100nm, deposit metal electrodes, removal
Mask plate obtains InP-base resistive memory.
The beneficial effects of the present invention are: the present invention deposits InP resistance-change memory material, energy using pulsed laser deposition technique
Enough stoichiometric ratios for keeping material well, the defect state of thin-film material is improved by making annealing treatment, improves resistive
The transformation consistency of memory.The resistive memory based on InP resistance-change memory material of preparation has memory window mouth width, data
Retention time is long, the high feature of durability.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of InP resistance-change memory material；
Fig. 2 is the structural schematic diagram of InP-base resistive memory；
Fig. 3 is the I-V test curve figure of Ag/InP/Pt resistance-variable storing device device prepared by embodiment 1；
Fig. 4 is the durability test result of Ag/InP/Pt resistance-variable storing device device prepared by embodiment 1；
Fig. 5 is the resistance iterated integral between the circulation and circulation of Ag/InP/Pt resistive memory prepared by embodiment 1
Cloth；
Fig. 6 is the data holding ability test result of Ag/InP/Pt resistive memory prepared by embodiment 1.
Specific embodiment
The present invention provides a kind of preparation method and application of InP resistance-change memory material, below in conjunction with drawings and examples
The present invention is described in detail, but the present invention is not limited thereto.
Each layer film thickness and area size shape do not reflect actual proportions in figure, and purpose is in the schematically illustrate present invention
Hold.
Fig. 1 is the preparation method flow chart of InP resistance-change memory material:
Step 101: being packed into monocrystalline InP piece as target in pulse laser equipment cavity；
Step 102: the substrate of surface depositing electrode is packed into pulse laser equipment cavity；
Step 103: 5 × 10 will be evacuated in pulse laser equipment cavity-8Pa；
Step 104: heating substrate is to 350~450 DEG C；
Step 105: using the method for pulse laser deposition in deposition on substrate InP film；
Step 106: the substrate of InP film will be deposited in 600~800 DEG C of progress, 5~120 seconds quick thermal annealing process,
Finally obtain InP resistance-change memory material.
Fig. 2 is the resistive memory structural schematic diagram prepared based on InP resistance-change memory material, specifically: substrate material
201, substrate material is monocrystalline silicon, and there is the silicon oxide layer 300nm of thermal oxide growth in face on the monosilicon, and silicon oxide layer plays electric exhausted
The effect of edge prevents from generating leakage current in substrate；It is the adhesive layer Ti material 202 of electrode and substrate on substrate 201, bonding
The presence of layer makes the performance of device more stable；It is Pt lower metal electrode material 203 in Ti adhesion-layer materials 202；203 layers above
It is InP resistive material 204；InP resistive material 204 is above upper electrode layer 205, upper electrode material can for various metals or
Alloy conductive material.
Embodiment 1
The preparation method and application of InP resistance-change memory material, specifically include:
1) preparation method of InP resistance-change memory material, preparation step are as follows: InP target is fixed on to the target of PLD cavity
In the support of position, then surface is deposited with to the Si/SiO of Pt/Ti electrode2Substrate is packed into the intracorporal sample carrier of pulse laser equipment cavity
On, the spacing of adjustment target substrate is 7cm, and vacuum in the cavity of PLD equipment is then extracted into 5 × 10 using molecular pump-8Pa makes
Sample carrier is heated to 400 DEG C with electric furnace heating wire, uses the KrF excimer laser that wavelength is 248nm as laser source, setting swashs
Light device parameter are as follows: pulse frequency 5Hz, single pulse energy 240mJ, energy density 1.8J/cm2, then start laser and start
Deposition on substrate InP resistance-change memory material, sedimentation time 20 minutes, InP resistance-change memory material with a thickness of 65nm, deposition is completed
The InP resistance-change memory material being grown on substrate is taken out from PLD cavity afterwards and is put into rapid thermal anneler progress rapid thermal annealing
Processing 600 DEG C of annealing temperature, annealing time 60 seconds, takes out substrate from quick anneal oven, obtains InP resistive and deposit after cooling
Store up material.
2) the resistive memory preparation based on InP resistance-change memory material, preparation step are as follows: by what is 1) prepared
InP resistance-change memory material surface covers hard mask plate, and hard mask plate is then placed in magnetron sputtering apparatus having a size of 100nm, sinks
Product Ag metal electrode, removes mask plate, obtains Ag/InP/Pt resistive memory.
Fig. 3 is the I-V test curve figure of Ag/InP/Pt resistive memory prepared by embodiment 1, can from figure
Prepared device has low shift voltage without point activation out, and big on-off ratio is expected to be used for multidigit storage skill
Art.
Fig. 4 be embodiment 1 prepared by Ag/InP/Pt resistive memory durability test as a result, from figure data
It can be seen that prepared device device resistance after 10000 loop tests is shown good still without any decline sign
Good durability.
Fig. 5 is the resistance iterated integral between the circulation and circulation of Ag/InP/Pt resistive memory prepared by embodiment 1
Cloth, Cong Tuzhong data can be seen that prepared device has excellent transition parameters consistency.
Fig. 6 is the data holding ability test result of Ag/InP/Pt resistive memory prepared by embodiment 1, from figure
Middle data can be seen that prepared device by 106High low resistance state shows that the device has without significant change after the reading of s
It is non-volatile.
In the present invention, pulse laser deposition process parameter can be conventional pulse laser deposition plating parameter, certainly its
The equipment that it prepares film can also be used for the present invention, and deposition thickness can be with STOCHASTIC CONTROL；Substrate is not limited to silicon wafer, other insulation nothings
Machine material base can also be used for the present invention, but annealing conditions can be adjusted according to material therefor and substrate properties；Lower electrode material
Material is not limited to Pt metal, and upper electrode material is not limited to Ag metal, can also be with other conductive materials.The deposition of upper/lower electrode
Technology is not limited to magnetron sputtering, other physical vapour deposition (PVD)s or chemical vapor deposition method can also be with.
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although passing through ginseng
According to the preferred embodiment of the present invention, invention has been described, it should be appreciated by those of ordinary skill in the art that can
To make various changes to it in the form and details, without departing from the appended claims limited range.
Claims (4)
- The preparation method of 1.InP resistance-change memory material, which comprises the following steps:(1) it is packed into monocrystalline InP piece as target in pulse laser equipment cavity；(2) substrate that surface is deposited with electrode is packed into pulse laser equipment cavity；(3) it will be vacuumized in pulse laser equipment cavity, vacuum degree is 5 × 10-8Pa；(4) substrate is heated to 350~450 DEG C；(5) using the method for pulse laser deposition in deposition on substrate InP film；The pulse laser deposition parameter are as follows: target Spacing with substrate is 6~8cm, 1~5Hz of working frequency of laser, and energy force density is 1~3J/cm2；The thickness of gained InP film Degree is 10~65nm；(6) quick thermal annealing process will be carried out under the substrate vacuum condition that deposited InP film, obtains InP resistance-change memory material.
- 2. the preparation method of InP resistance-change memory material according to claim 1, it is characterised in that: in the step (2) Substrate is insulative inorganic material.
- 3. the preparation method of InP resistance-change memory material according to claim 1, it is characterised in that: fast in the step (6) Speed heat annealing process are as follows: 600~800 DEG C of annealing temperature, annealing time 5~120 seconds.
- 4. a kind of application of InP resistance-change memory material that method described in claim 1 is prepared in resistance-variable storing device, Be characterized in that: InP resistance-change memory material is used to prepare InP-base resistive memory, preparation step are as follows: by InP resistance-change memory material Expect that surface covers hard mask plate, hard mask plate is then placed in magnetron sputtering apparatus with a thickness of 100nm, and deposit metal electrodes are gone Except mask plate, InP-base resistive memory is obtained.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101499529A (en) * | 2009-02-26 | 2009-08-05 | 复旦大学 | Indium phosphide cathode material for lithium ion battery and method for producing the same |
| CN102185107A (en) * | 2011-05-10 | 2011-09-14 | 中山大学 | Resistance-type random storage component and preparation method thereof |
| CN104103755A (en) * | 2014-07-14 | 2014-10-15 | 上海交通大学 | Sodium bismuth titanate thin film system based resistance random access memory and preparation method thereof |
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| KR20090006468A (en) * | 2007-07-11 | 2009-01-15 | 삼성전자주식회사 | Phase-change material, sputter target comprising the phase-change material, method of forming phase-change layer using the sputter target and method of manufacturing phase-change random access memory comprising the phase-change layer |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101499529A (en) * | 2009-02-26 | 2009-08-05 | 复旦大学 | Indium phosphide cathode material for lithium ion battery and method for producing the same |
| CN102185107A (en) * | 2011-05-10 | 2011-09-14 | 中山大学 | Resistance-type random storage component and preparation method thereof |
| CN104103755A (en) * | 2014-07-14 | 2014-10-15 | 上海交通大学 | Sodium bismuth titanate thin film system based resistance random access memory and preparation method thereof |
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