CN108232007A - A kind of method that gas cluster ion beam trims the magnetic tunnel junction after being etched - Google Patents

A kind of method that gas cluster ion beam trims the magnetic tunnel junction after being etched Download PDF

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Publication number
CN108232007A
CN108232007A CN201611191829.XA CN201611191829A CN108232007A CN 108232007 A CN108232007 A CN 108232007A CN 201611191829 A CN201611191829 A CN 201611191829A CN 108232007 A CN108232007 A CN 108232007A
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magnetic tunnel
tunnel junction
gas
trimming
side wall
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张云森
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Shanghai Ciyu Information Technologies Co Ltd
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Shanghai Ciyu Information Technologies Co Ltd
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N52/00Hall-effect devices
    • H10N52/01Manufacture or treatment

Abstract

The method of magnetic tunnel junction after being etched the present invention provides a kind of trimming of gas cluster ion beam:Step 1:Hearth electrode substrate, and deposited magnetic tunnel knot multilayer film and hard mask film layer in substrate are provided;Step 2:Graphic definition magnetic tunnel junction pattern etches magnetic tunnel junction;Step 3:Gas cluster ion beam trims the magnetic tunnel junction side wall after etching to remove sidewall damage/sedimentary;Step 4:Deposit dielectrics, chemical polishing polish dielectric until the top of hard mask.Due to the lateral sputtering behavior of gas cluster ion beam, cluster or atomic energy are got at up to the every nook and cranny of magnetic tunnel junction being patterned, the damage that is covered in side wall and again sedimentary can effectively be removed, simultaneously, since the energy of each atom is very low, cluster gas atom will not bring new damage, be very beneficial for magnetic RAM magnetics, the promotion of electric property and the improvement of yield.

Description

A kind of method that gas cluster ion beam trims the magnetic tunnel junction after being etched
Technical field
The present invention relates to the processing method of magnetic tunnel junction (MTJ, Magnetic Tunnel Junction) a kind of, specifically It is related to a kind of use gas cluster ion beam (GCIB, Gas Cluster Ion Beam) to the magnetic tunnel junction after etching (MTJ, Magnetic Tunnel Junction) technique that side wall is trimmed, belongs to magnetic memory manufacturing technology field.
Background technology
In recent years, using the MRAM of magnetic tunnel junction (MTJ) by it is believed that be following solid state non-volatile memory body, It has the characteristics that high-speed read-write, large capacity and low energy consumption.Ferromagnetism MTJ is usually sandwich structure, wherein the note that is magnetic Recall layer, it can change the direction of magnetization to record different data;Positioned at the tunnel barrier layer of intermediate insulation;Magnetic reference Layer, positioned at the opposite side of tunnel barrier layer, its direction of magnetization is constant.
For information can be recorded in this magnetoresistive element, it is proposed that using based on spin momentum transfer or spin-transfer torque The write method of (STT, Spin Transfer Torque) switch technology, such MRAM are known as STT-MRAM.According to magnetic polarization The difference in direction, STT-MRAM are divided into as STT-MRAM in face and vertical STT-MRAM (i.e. pSTT-MRAM), and the latter has preferably Performance.Method according to this, you can by providing spin polarized current to magnetoresistive element come the intensity of magnetization of inverting magnetization memory layer Direction.In addition, the reduction of the volume with Magnetic memory layer, write or spin polarized current that conversion operation need to be injected is also smaller. Therefore, this write method can be achieved at the same time device miniaturization and reduce electric current.
Meanwhile in view of switching electric current required when reducing MTJ element size can also reduce, so the pSTT- in terms of scale MRAM can be very good mutually to agree with state-of-the-art technology node.Therefore, it is desirable to it is that pSTT-MRAM elements are made into minimum ruler It is very little, and with extraordinary uniformity and the influence to MTJ magnetism is minimized, used preparation method can also be real Show high good and the bad rate, pinpoint accuracy, high reliability, low energy consumption and remain adapted to the temperature coefficient that data well preserve.Meanwhile Write operation is changed based on resistance state in nonvolatile memory, so as to need control thus caused to mtj memory device lifetime Destruction and shortening.However, the fluctuation of MTJ resistance may be increased by preparing a small-sized MTJ element so that pSTT-MRAM's Larger fluctuation can also be had therewith by writing voltage or electric current, can damage the performance of MRAM in this way.
In present MRAM manufacturing process, two kinds of etching technics of generally use to carry out magnetic tunnel junction it is miniature, the One kind is ion beam etching (IBE, Ion Beam Etching), and second is reactive ion etching (RIE, Reactive Ion Etching).Two kinds of lithographic techniques respectively have advantage and disadvantage, in order to obtain higher etch rate, it will usually which single ion acceleration is arrived In very high energy range, energetic ion would generally destroy crystal structure, meanwhile, because of physical sputtering or chemical etching by-product The deposition again of object can also increase, in general, after magnetic tunnel junction etching, side wall can form one layer of damaging layer/sedimentary, this The magnetism and electric property of magnetic tunnel junction will be influenced, more there is victor, it will is directly resulted in from reference layer to the short of memory layer Road, so as to be unfavorable for the raising of magnetic storage yield.
In recent years, gas cluster ion beam (GCIB, Gas Cluster Ion Beam), due to single ion low energy and horizontal stroke To splash effect, it is considered to be it is a kind of it is highly effective receive/micro- surface treating implement, device is as shown in Figure 1;Cluster gas The principle that (Gas Cluster) source generates cluster beam is to use the gas for being several times as much as standard atmospheric pressure, such as:Ar、O2、N2、CO2、NF3、 SF6Deng entering cluster by the fine nozzle 111 of a Sub-millimeter diameter occurs vacuum chamber 110, and it is swollen that ultrasonic adiabatic condensation occurs It is swollen, gas molecule, atomic collision and form cluster, cluster generally with 500 to 10,000 atoms each other by Van der Waals force combine Together;In the air-flow formed in supersonic expansion, actually only small part of gas forms cluster, and with larger hair It dissipates, therefore, it is necessary to using the blocking diverging of beam splitting collimator apparatus, the non-cluster gas in edge, the gas group that straight line is only allowed to advance Cluster leads to filter tow device (Skimmer) 112, and the collimation cluster air-flow of filtered beam device (Skimmer) 112 is immediately into high vacuum Ionization system, i.e.,:Ionization chamber 120 is ionized by the electron bombardment of hot filament (electro-dissociator 121) transmitting, is formed positively charged Cluster beam.These gas cluster ion beams are accelerated by extra electric field (accelerator 122), obtain higher-energy, into deflection magnetic Field 123, in the process, monatomic and smaller cluster ions beam will shift, and larger cluster ions are not due to having Process cavity 130 can then be entered by shifting.When cluster ions beam and 131 surface of substrate collide, cluster divides, It forms smaller cluster or atom, increases atom lateral transfer, i.e., so-called lateral splash effect (Later Sputter It Effect), will not surface generation damage simultaneously as the energy comparison of single atom is small;Such as:It is made of 2000 atoms Cluster under the conditions of 20KeV, it is only 10eV to obtain energy by atom.
Invention content
The magnetic tunnel junction side wall after etching is trimmed using gas cluster ion beam the present invention provides a kind of Method, include the following steps:
Step 1:Hearth electrode substrate, and deposited magnetic tunnel knot multilayer film and hard mask film layer in substrate are provided;
Step 2:Graphic definition magnetic tunnel junction pattern etches magnetic tunnel junction;
Step 3:Gas cluster ion beam is used to be trimmed to remove side wall to the magnetic tunnel junction side wall after being etched Damage and/or sedimentary;
Step 4:Deposit dielectrics, chemical polishing polish dielectric until the top of hard mask film layer.
Further, gas is Ar, N used by gas cluster ion beam2、O2、CO、CO2、NO、N2O、NO、NO2、NH3、 H2、He、Ne、Xe、CF4、SF6、NF3、CHF3、CH2F2And CH4In one or several kinds.
Further, the accelerating potential range of gas cluster ion beam is 3KeV~60KeV.
Further, the irradiation dose range of gas cluster ion beam is 5 × 1013ions/cm2~5 × 1018ions/ cm2
Further, gas cluster ion beam vertical incidence or incident using the irradiation angle less than 45 degree.
Further, irradiation angle selects 5 degree, 10 degree or 15 degree.
Further, in step 3, after being trimmed to side wall, one layer of side wall protective layer is deposited immediately.
Further, the material of side wall protective layer is selected from SiN, SiCN or SiC.
Further, side wall protective layer is obtained using chemical vapor deposition or atomic layer deposition.
Beneficial effects of the present invention:It is provided by the invention it is a kind of using gas cluster ion beam to the magnetic tunnel after etching The method that road knot side wall is trimmed, due to the lateral sputtering behavior of GCIB, cluster or atomic energy get at and reach what is be patterned The every nook and cranny of magnetic tunnel junction can effectively remove the damage that is covered in side wall and again sedimentary, simultaneously as each The energy of atom is very low, and cluster gas atom will not bring new damage, is very beneficial for magnetic RAM magnetics, electricity Learn the promotion of performance and the improvement of yield.
Description of the drawings
Fig. 1 is the knot of device that gas cluster ion beam of the present invention trims the magnetic tunnel junction side wall after etching Structure schematic diagram;
Fig. 2 is the technique that the present invention trims the magnetic tunnel junction side wall after etching using gas cluster ion beam Flow chart;
Fig. 3 is to provide the hearth electrode substrate of CMP planarization in the preferred embodiment of the present invention, and shape successively on it Schematic diagram into after magnetic tunnel junction multilayer film and hard mask film layer;
Fig. 4 is the schematic diagram after being performed etching to magnetic tunnel junction in the preferred embodiment of the present invention;
Fig. 5 to Fig. 8 is in the preferred embodiment of the present invention, and the side wall of magnetic tunnel junction is trimmed in GCIB radiation Schematic diagram;
Fig. 9 is in the preferred embodiment of the present invention, after being trimmed using GCIB to the side wall of magnetic tunnel junction Schematic diagram;
Figure 10 is in the preferred embodiment of the present invention, deposits the schematic diagram after one layer of side wall protective layer;
Figure 11 be the present invention a preferred embodiment in, deposit dielectrics, and it is chemically-mechanicapolish polished until Schematic diagram after at the top of hard mask;
Shown in figure:Vacuum chamber, 111- nozzles occur for 100- gas cluster ion beam flatening process devices, 110- clusters (Nozzle), 112- filter beam devices (Skimmer), 120- ionization chambers, 121- electro-dissociators, 122- accelerators, 123- magnetic deflection fields, 130- process cavities, 131- substrates (wafer console), 210- hearth electrode substrates, 220- magnetic tunnel junction multilayer films, 230- are covered firmly Mould film layer, 240- sidewall damages/sedimentary, 250- side wall protective layers, 260- dielectrics.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below in conjunction with the accompanying drawings to the present invention Specific embodiment be described in detail.It should be noted that attached drawing of the present invention uses using the form of simplification and non-essence Accurate ratio, only for the purpose of facilitating and clarifying the purpose of the embodiments of the invention.
It is provided by the invention a kind of the magnetic tunnel junction side wall after etching to be trimmed using gas cluster ion beam Technique, due to the lateral sputtering behavior of GCIB, cluster or atomic energy are got at up to each of the magnetic tunnel junction being patterned Corner can effectively remove the damage that is covered in side wall and again sedimentary, simultaneously as the energy of each atom is very Low, cluster gas atom will not bring new damage.It is very beneficial for magnetic RAM magnetics, the promotion of electric property, With the improvement of yield.Its forming step is as follows, as shown in Figure 2:
Step 1:Hearth electrode substrate 210, and deposited magnetic tunnel knot multilayer film 220 and hard mask film in substrate are provided Layer 230, as shown in Figure 3;
Wherein, the overall thickness of magnetic tunnel junction (MTJ) multilayer film 220 is 15nm~40nm, can be by reference layer, potential barrier Layer and memory layer the Bottom Pinned structures being superimposed upwards successively either by memory layer, barrier layer and reference layer according to The secondary Top Pinned structures being superimposed upwards.
Further, reference layer has magnetic polarization invariance, is face inner mold (iSTT-MRAM) or vertical (pSTT- according to it MRAM) structure is different.The reference layer of face inner mold (iSTT-MRAM) generally has (IrMn or PtMn)/CoFe/Ru/CoFe Structure, preferred overall thickness are 10~30nm;The reference layer of vertical-type (pSTT-MRAM) generally has TbCoFe or [Co/Pt]nCo/Ru/[CoPt]mSuperlattice multilayer film structure, preferred overall thickness are 8~20nm.
Further, barrier layer is nonmagnetic metal oxide, preferably MgO or Al2O3, thickness is 0.5nm~3nm.
Further, memory layer polarizes with variable magnetic, is face inner mold (iSTT-MRAM) or vertical (pSTT- according to it MRAM) institute is different again for structure.The memory layer of face inner mold iSTT-MRAM is generally CoFe/CoFeB or CoFe/NiFe, preferred thick Spend for 2nm~6nm, vertical-type pSTT-MRAM memory layers be generally CoFeB, CoFe/CoFeB, Fe/CoFeB, CoFeB (Ta, W, Mo)/CoFeB, preferred thickness are 0.8nm~2nm.
The thickness of hard mask film layer 230 is 20nm~100nm, selects Ta, TaN, W or WN etc. to be obtained in halogen plasma-based It obtains and more preferably carves profile.
Step 2:220 pattern of graphic definition magnetic tunnel junction etches magnetic tunnel junction 220, as shown in Figure 4;More into one Step ground, this step can be divided into the following steps:
(1) 220 pattern of graphic definition magnetic tunnel junction, and pattern is shifted to the top of magnetic tunnel junction 220;It crosses herein Cheng Zhong, using a photoetching once etch (LE, lithography-etching) or Twi-lithography twice etching (LELE, Lithography-etching-lithography-etching method) is completed the definition to magnetic tunnel junction 220 and is covered firmly Reactive ion (RIE) etching of mould film layer 230, and remaining polymer is removed using RIE techniques simultaneously, so that pattern is transferred to The top of magnetic tunnel junction 220.
(2) magnetic tunnel junction 220 is performed etching;
Wherein, etching technics may be used reactive ion etching (RIE, Reactive Ion Etching) and/or from Beamlet etches (IBE, Ion Beam Etching).IBE is mainly used as ion source using Ar, Kr or Xe etc.;RIE is mainly used CH3OH、CH4/Ar、C2H5OH、CH3OH/Ar or CO/NH3Deng as main etching gas;And use emission spectrometer (OES, Optical Emission Spectroscopy) or ion microprobe (SIMS, Second Ion Mass Spectroscopy) judge etching terminal signal.
Step 3:Gas cluster ion beam trims the magnetic tunnel junction side wall after etching to remove side wall damage Wound/sedimentary 240, as shown in Figures 5 to 9;Due to the lateral sputtering behavior of GCIB, cluster or atomic energy are got at up to by pattern The every nook and cranny of the magnetic tunnel junction of change, Fig. 5 to Fig. 8 arrive at the different zones of the magnetic tunnel after etching, cluster for cluster Generate the schematic diagram laterally sputtered;Wherein, gas used by gas cluster ion beam (GCIB, Gas Cluster Ion Beam) Body is Ar, N2、O2、CO、CO2、NO、N2O、NO、NO2、NH3、H2、He、Ne、Xe、CF4、SF6、NF3、CHF3、CH2F2And CH4In One or several kinds, the accelerating potential of GCIB are differed for 3KeV to 60KeV, and irradiation dose (irradiation dose) is 5 × 1013To 5 × 1018ions/cm2Differ.
Preferably, it usually selects GCIB vertical incidence or selects the irradiation angle (irradiation of low-angle angle:θ), such as:5 degree, 10 degree or 15 degree etc..
Preferably, one layer of side wall protective layer 250 can be deposited immediately after side wall trims technique, as shown in Figure 10, Its material is selected from SiN, SiCN or SiC etc., generally use chemical vapor deposition (CVD, Chemical Vapor Deposition) or the mode of atomic layer deposition (ALD, Atomic Layer Deposition) is realized.
Step 4:Deposit dielectrics 260, chemical polishing polish dielectric until the top of hard mask film layer 230, such as Figure 11 It is shown;Wherein, dielectric 260 is SiO2Or low-k (low-k) dielectric, such as:HSQ, MSQ or SiOCH etc.;
More specifically, low-k (low-k) dielectric refers to dielectric constant (k) less than silica (k=3.9) Material, in the specific implementation, low-k materials can be hydrogeneous silicate (Hydrogen Silsequioxane, HSQ, k=2.8 ~3.0), containing Si-CH3Functional group salt containing methane-siliconic acid (Methylsilsesquioxane, MSQ, k=2.5~ 2.7), the hybrid organic siloxane polymer synthesized by the comprehensive hydrogeneous silicates HSQ and MSQ of salt containing methane-siliconic acid (Hybrid Organic Siloxane Polymer, HOSP) film (k=2.5), porous SiOCH films (k=2.3~ 2.7), it might even be possible to using organics such as the porosity silicates (Porous Silicate) of ultralow dielectric (k≤2.0) High-molecular compound and the porous SiOCH films that dielectric constant (k) is 1.9.
The preferred embodiment of the present invention described in detail above.It should be appreciated that those of ordinary skill in the art without Creative work is needed according to the present invention can to conceive and makes many modifications and variations.Therefore, all technologies in the art Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Technical solution, all should be in the protection domain being defined in the patent claims.

Claims (10)

  1. A kind of 1. method for trimming the magnetic tunnel junction after being etched, which is characterized in that using gas cluster ion beam to etching Magnetic tunnel junction later is trimmed.
  2. 2. a kind of method for trimming the magnetic tunnel junction after being etched according to claim 1, which is characterized in that including such as Lower step:
    Step 1:Hearth electrode substrate, and deposited magnetic tunnel knot multilayer film and hard mask film layer on the substrate are provided;
    Step 2:Graphic definition magnetic tunnel junction pattern, etches the magnetic tunnel junction;
    Step 3:Gas cluster ion beam is used to be trimmed to remove side wall to the magnetic tunnel junction side wall after being etched Damage and/or sedimentary;
    Step 4:Deposit dielectrics, chemical polishing polish the dielectric until the top of the hard mask film layer.
  3. A kind of 3. method for trimming the magnetic tunnel junction after being etched according to claim 2, which is characterized in that the gas Gas is Ar, N used by body cluster ions beam2、O2、CO、CO2、NO、N2O、NO、NO2、NH3、H2、He、Ne、Xe、CF4、SF6、 NF3、CHF3、CH2F2And CH4In one or several kinds.
  4. A kind of 4. method for trimming the magnetic tunnel junction after being etched according to claim 2, which is characterized in that the gas The accelerating potential range of body cluster ions beam is 3KeV~60KeV.
  5. A kind of 5. method for trimming the magnetic tunnel junction after being etched according to claim 2, which is characterized in that the gas The irradiation dose range of body cluster ions beam is 5 × 1013ions/cm2~5 × 1018ions/cm2
  6. A kind of 6. method for trimming the magnetic tunnel junction after being etched according to claim 2, which is characterized in that the gas Body cluster ions beam vertical incidence is incident using the irradiation angle less than 45 degree.
  7. A kind of 7. method for trimming the magnetic tunnel junction after being etched according to claim 6, which is characterized in that the spoke Irradiation angle selects 5 degree, 10 degree or 15 degree.
  8. A kind of 8. method for trimming the magnetic tunnel junction after being etched according to claim 2, which is characterized in that step 3 In, after being trimmed to the side wall, one layer of side wall protective layer is deposited immediately.
  9. A kind of 9. method for trimming the magnetic tunnel junction after being etched according to claim 8, which is characterized in that the side The material of wall protective layer is selected from SiN, SiCN or SiC.
  10. 10. a kind of method for trimming the magnetic tunnel junction after being etched according to claim 8, which is characterized in that described Side wall protective layer is obtained using chemical vapor deposition or atomic layer deposition.
CN201611191829.XA 2016-12-21 2016-12-21 A kind of method that gas cluster ion beam trims the magnetic tunnel junction after being etched Pending CN108232007A (en)

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CN111490152A (en) * 2019-01-28 2020-08-04 上海磁宇信息科技有限公司 Method for manufacturing subminiature magnetic random access memory array
CN111490151A (en) * 2019-01-28 2020-08-04 上海磁宇信息科技有限公司 Method for manufacturing subminiature magnetic random access memory array
CN111864058A (en) * 2020-07-29 2020-10-30 浙江驰拓科技有限公司 Preparation method of storage bit and preparation method of MRAM
CN111864059A (en) * 2020-07-29 2020-10-30 浙江驰拓科技有限公司 Preparation method of storage bit and preparation method of MRAM
WO2020228579A1 (en) * 2019-05-16 2020-11-19 浙江驰拓科技有限公司 Manufacturing method for mram device
CN112635658A (en) * 2019-09-24 2021-04-09 浙江驰拓科技有限公司 Method for preparing magnetic random access memory
CN112740431A (en) * 2018-09-25 2021-04-30 应用材料公司 Method of forming top contact of magnetic tunnel junction
CN113458875A (en) * 2021-06-21 2021-10-01 武汉大学深圳研究院 Cluster ion beam high-temperature polishing method and device with wide target temperature controllable range
CN113838883A (en) * 2020-06-24 2021-12-24 中芯国际集成电路制造(上海)有限公司 Semiconductor structure and method for forming semiconductor structure

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CN112740431A (en) * 2018-09-25 2021-04-30 应用材料公司 Method of forming top contact of magnetic tunnel junction
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CN113838883A (en) * 2020-06-24 2021-12-24 中芯国际集成电路制造(上海)有限公司 Semiconductor structure and method for forming semiconductor structure
CN111864058A (en) * 2020-07-29 2020-10-30 浙江驰拓科技有限公司 Preparation method of storage bit and preparation method of MRAM
CN111864059A (en) * 2020-07-29 2020-10-30 浙江驰拓科技有限公司 Preparation method of storage bit and preparation method of MRAM
CN111864058B (en) * 2020-07-29 2023-04-18 浙江驰拓科技有限公司 Preparation method of storage bit and preparation method of MRAM
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