CN104953026A - Method to etch non-volatile metal materials - Google Patents
Method to etch non-volatile metal materials Download PDFInfo
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- CN104953026A CN104953026A CN201510072693.XA CN201510072693A CN104953026A CN 104953026 A CN104953026 A CN 104953026A CN 201510072693 A CN201510072693 A CN 201510072693A CN 104953026 A CN104953026 A CN 104953026A
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Abstract
A method for etching a stack with an Ru containing layer disposed below a hardmask and above a magnetic tunnel junction (MTJ) stack with pinned layer is provided. The hardmask is etched with a dry etch. The Ru containing layer is etched, where the etching uses hypochlorite and/or O3 based chemistries. The MTJ stack is etched. The MTJ stack is capped with dielectric materials. The pinned layer is etched following the MTJ capping.
Description
The cross reference of related application
The application requires the U.S. Provisional Patent Application No.61/971 being entitled as " etching and metal residue after removing etching " filed an application on March 27th, 2014 according to 35U.S.C. § 119 (e), the priority of 032, is all incorporated into herein by reference at this.
Background technology
The present invention relates to and etch non-volatile materials layer at the production period of semiconductor device by mask.More specifically, the present invention relates to etching metal MTJ (MTJ) stacking.
Between semiconductor wafer processing period, metal-containing layer etch features can be passed through.During formation magnetic RAM (MRAM) or resistor type random access memory (RRAM) equipment, multiple thin metal level or film can be sequentially executed etching.For MRAM, multiple thin metal layer can be used to form magnetic tunneling junction stack.
Summary of the invention
Above-mentioned and according to object of the present invention in order to realize, provide a kind of etching with the stacking method containing layer of ruthenium, described containing layer of ruthenium be arranged on hard mask below and with the stacking top of the MTJ (MTJ) of pinprick layer.Described hard mask is used dry etching to etch.The described layer of ruthenium that contains is etched by the chemical substance used based on hypochlorite and/or ozone.Described MTJ is stacking to be etched.Described MTJ is stacking to be covered by dielectric substance.Described pinprick layer and then described MTJ covering is etched.
In another form of expression of the present invention, provide a kind of stacking method that etching comprises hard mask, described hard mask is positioned at containing on layer of ruthenium, described containing layer of ruthenium be positioned at MTJ (MTJ) on pinprick layer stacking on.Described hard mask, containing layer of ruthenium and MTJ is stacking is etched.Described MTJ is stacking to be sealed.Described pinprick layer is etched.
In another form of expression of the present invention, provide the stacking method of a kind of etching with pinprick layer, described pinprick layer is arranged on the stacking below of MTJ, the stacking below be arranged on containing layer of ruthenium of described MTJ, the described below being arranged on hard mask layer containing layer of ruthenium.Described hard mask is used dry etching to etch.The described layer of ruthenium that contains is etched.Described MTJ is stacking to be etched.Described MTJ is stacking to be covered by dielectric substance.Described pinprick layer use for noble metal selectively chemical substance etch, described chemical substance comprises the mixture of at least one in thionyl chloride/pyridine mixtures, hydrogen bromide/dimethyl sulfoxide (DMSO) (DMSO) mixture or carbon tetrachloride and dimethyl sulfoxide (DMSO), acetonitrile, benzonitrile or dimethyl formamide (DMF).
These and other features of the present invention also will describe more specifically following carrying out by reference to the accompanying drawings in of the present invention illustrating.
Accompanying drawing explanation
The present invention illustrates in an illustrative manner instead of in a limiting fashion, and reference marker similar in accompanying drawing refers to similar element, wherein:
Fig. 1 is the high level flow chart of one embodiment of the present of invention.
Fig. 2 A to Fig. 2 G is the stacking schematic diagram carrying out according to one embodiment of present invention processing.
Fig. 3 is the schematic diagram that can be used for the etch reactor etched.
Fig. 4 shows a computer system, and it is suitable for implementation in the controller used in embodiments of the invention.
Embodiment
Referring now to some preferred embodiments shown in accompanying drawing, the present invention is specifically described.In the following description, multiple detail has been enumerated to provide thorough understanding of the present invention.But to those skilled in the art, it is evident that, the present invention does not have the some or all of of these details can implement yet.In other cases, well-known processing step and/or structure are not described in detail in order to avoid optionally fuzzy the present invention.
For the ease of understanding, Fig. 1 is the high level flow chart of the technique used in one embodiment of the invention.Provide and there is stacking substrate, this is stacking have the below that is configured in hard mask and the stacking top of MTJ (MTJ) containing ruthenium (Ru) layer.Hard mask is etched or is opened (step 104).Hypochlorite (hypochlorite) and/or the chemical etches (step 108) based on ozone is used containing layer of ruthenium.MTJ is stacking to be etched (step 112).MTJ through etching is stacking to be sealed (step 116).Pinned magnetic layer is etched (step 120).Such pinned magnetic layer is described in " development of the MTJ MRAM of IBM: demonstrate chip to 16-Mb MRAM from the first knot " (Development ofthe magnetic tunnel junction MRAM at IBM:From first junctions to a 16-Mb MRAM demonstrator chip) literary composition of IBM J.RES. & DEV. periodical phase the 50th volume January the 1st in 2006, and it is all incorporated into herein by reference.
embodiment
Fig. 2 A is the viewgraph of cross-section of stacking 200, and it is used to magnetic RAM (MRAM) in this embodiment.In the present embodiment, the bottom of stacking 200 is formed in tantalum beryllium (TaBe) layer 204 on substrate.Platinum manganese (PtMn) layer 208 is formed on TaBe layer 204.First ferro-cobalt (CoFe) layer 212 is formed on PtMn layer 208.First ruthenium (Ru) layer 216 is formed on a CoFe layer 212.2nd CoFe layer 220 is formed on a Ru layer 216.First magnesia (MgO) layer 224 is formed on the 2nd CoFe layer 220.3rd CoFe layer 228 is formed on a MgO layer 224.2nd MgO layer 232 is formed on the 3rd CoFe layer 228.Titanium (Ti) layer 236 is formed on the 2nd MgO layer 232.4th CoFe layer 240 is formed on Ti layer 236.First tantalum (Ta) layer 248 is formed on the 4th CoFe layer 240.2nd Ru layer 252 is formed on the first tantalum layer 248.Second tantalum layer 256 is formed on the 2nd Ru layer 252.The mask comprising titanium nitride (TiN) layer 260 and silicon nitride (SiN) layer 264 is formed pattern on the 2nd Ta layer 256.In this embodiment, comprise a CoFe layer 212 and a Ta layer 248 and the layer between the first cobalt iron layer 212 and the first tantalum layer 248 and form MTJ (MTJ) layer 268.PtMn layer 208 and TaBe layer 204 form pinprick layer 270.This pinprick layer 270 can be formed by other materials.
In one embodiment, all process can be carried out in a single plasma etch.Fig. 3 is the schematic diagram that can be used for the etch reactor (etch reactor) implementing the present embodiment.In one or more embodiment of the present invention, etch reactor 300 is included in the gas distribution plate 306 in the etched cavity that sealed by chamber wall 350, and this gas distribution plate 306 has gas feed and chuck 308.In etched cavity 349, it is formed with stacking substrate 304 and is positioned on the top of chuck 308.Chuck 308 can provide bias voltage to keep substrate 304 or another kind of chucking power can be used to keep substrate 304 from ESC source 348 as electrostatic chuck (ESC).Provide a kind of thermal source 310 of the lamp that such as generates heat with heating of metal layer.Precursor gas body source 324 is connected to etched cavity 349 by distribution plate 306.
Fig. 4 shows the high level block diagram of computer system 400, and this computer system 400 is suitable for implementation in the controller 335 used in embodiments of the invention.Computer system can have multiple physical form, and its scope is from integrated circuit, printed circuit board (PCB) and small hand held devices to huge super computer.Computer system 400 comprises one or more processor 402, and electronic display unit 404 (for display graphics, text and other data), main storage 406 can be comprised further (such as, random asccess memory (RAM)), memory device 408 (such as, hard disk drive), mobile storage means 410 (such as, CD drive), user interface facilities 412 (such as, keyboard, touch-screen, keypad, mouse or other indicating equipments etc.) and communication interface 414 (such as, radio network interface).Communication interface 414 allows software and data to transmit by being connected between computer system 400 and external equipment.System can also comprise the communications infrastructure 416 (such as, communication bus, crossbar (cross-over bar) or network), and aforesaid equipment/module is connected to this communications infrastructure 416.
The information transmitted via communication interface 414 can be the signal form by communication connection, described signal is such as electronics, electromagnetism, light sensation or other signals that can be received by communication interface 414, and described communication connection is carried signal and can is the communication connection using electric wire or cable, optical fiber, telephone wire, cellular phone link, radio frequency link and/or other communication ports to realize.According to such communication interface, can expect, one or more processor 402 can receive information or can state on the implementation in the process of method step to network output information by automatic network.In addition, embodiment of the method for the present invention can perform individually on a processor or such as internet can be combined in teleprocessing unit network on perform, the process of described teleprocessing unit shared portion.
Term " non-transitory computer-readable medium " is generally used to refer to the medium of such as main storage, additional storage, removable storage and memory device (such as hard disk, flash memory, hard drive memory, CD-ROM and other forms of permanent memory) and so on, and must not be interpreted as the temporary theme containing such as carrier wave or signal and so on.The example of computer code comprises the machine code such as produced by compiler, and comprises the file of the more high-level code performed by computer using interpreter.Computer-readable medium can also be transmitted by the computer data signal be embodied in carrier wave and be expressed as by the computer code of the executable command sequence of processor.
Hard mask is etched or is opened (step 104).In this instance, hard mask is tantalum (Ta) layer 256.SiN layer 264 and TiN layer 260 are used as the mask etching Ta layer 256.In this embodiment, plasma etching is used to etching Ta layer 256.In this embodiment, use Cl can be adopted
2as the dry etching of etching gas.Fig. 2 B is by the viewgraph of cross-section of stacking 200 after etching at tantalum layer 256.
2nd Ru layer 252 uses the chemical substance based on hypochlorite and/or ozone to carry out etching (step 108).In one embodiment, plasma etching can be used to the etching of the provided chemical substance based on hypochlorite and/or ozone.In another embodiment, the chemical substance based on hypochlorite and ozone can be used to wet etching.In such embodiments, before etching the 2nd Ru layer 252, dilution hydrogen fluoride (dHF) prerinse can be used to remove silicon oxide residues (silicon oxide residue).Clorox (NaClO) aqueous solution can be used in wet etching to etch the 2nd Ru layer 252.In this instance, Ru etching is the wet etching using the NaClO aqueous solution.Other hypochlorite etch processs be included in pH>12 without the perchloric acid (HClO) in sodium (Na) solution; Organic hypochlorite R-hypochlorous acid (R-OCl) in organic solvent; Containing the alkyls (-CH of R
3. – CH
2cH
3,-C (CH
3)
3deng), cycloalkanes base class (cycloalkly) or aromatic carbonyl (acromatic carbonyl).Fig. 2 C is that the 2nd Ru layer 252 is by the viewgraph of cross-section of stacking 200 after etching.The example of the Ru wet etching containing ozone water solution containing pH>12 is used to comprise the saturated NaOH of ozone (ozone saturated NaOH), NH
4oH or tetramethyl oxyammonia (tetramethyammoniumhydroxide) solvent.
MTJ stacking 268 is undertaken etching (step 112) by the recess entering pinprick layer.This recess allows the Capping operation of follow-up use dielectric (dielectric) to seal the interface of MTJ and pinprick layer.In this embodiment, low bias voltage ion sputtering is used to etch described MTJ stacking 268.In this embodiment, the gas used in this step is made up of argon gas (Ar) substantially.Preferably, low bias voltage provides the bias voltage between 10 to 500 volts.More preferably, low bias voltage is between 20 to 300 volts.Most preferably, low bias voltage is between 100 to 200 volts.Find there is no chemical corrosion gas and only have the low-voltage ion of inertia bombarding gas (inert bombardment gas) to sputter to provide MTJ to pile up the MTJ that decreases to etch unexpectedly.Chemical corrosion gas is the gas with utilizing chemical reaction to carry out the composition etched.Inertia bombarding gas does not use chemical reaction to etch, and only uses physical bombardment to etch.Fig. 2 D is that the 2nd MTJ stacking 268 is by the viewgraph of cross-section of stacking 200 after etching.
Sealed (step 116) by depositing the conformal insulator layer 272 be made up of dielectric substance through the MTJ stacking 268 of etching.This cover layer 272 by the MTJ stacked package opened to keep the stacking injury avoiding the etching bottom that will be caused by subsequent treatment of MTJ.It is equally important that the process of the etch processes of succeeding layer with etching MTJ stacking 268 is also separated by cover layer.Two kinds of common injury classifications on MTJ comprise: the etch products on MTJ sidewall deposits again, and it causes MTJ short circuit, and react to reduce magnetic with MTJ layer etching chemistry.Therefore, in traditional technique, when all stacking by intectate etch time, MTJ is stacking impaired.The etch processes of any damage MgO or CoFeB is all not received, comprises based on water (H
2o), the chemistry of oxygen, halogen or plasma system etching.Select suitable cover layer that the MTJ be opened can be made to avoid fault in follow-up processing flow or deterioration.Therefore, window is opened to carry out various process (comprising the process of those and MgO/CoFeB non-compatible) to etch succeeding layer and the electricity/magnetic attribute maintaining MTJ is avoided reducing by desirable cover layer.Various isolation cover layer can be used for selection, such as: based on dielectric film, SiN, SiC, SiCN, SiO of silicon
2, SiOC, SiOCH
3, SiOCHxCH
3, Si; Based on dielectric film (carbon, polymer), the nitride (BN) of carbon.In this instance, show with SiO
2with the cover layer of SiN.Plasma is by SiH
4and O
2formed with etched stacking on deposit SiO
2layer.In another embodiment, deposited SiN layer.Fig. 2 E deposited SiO
2sedimentary deposit 272 after stacking 200 viewgraph of cross-section.
Sedimentary deposit 272 is etched back (being opened) to make PtMn layer 208 below expose, and the sidewall of MTJ stacking 268 keeps sealing.In this embodiment, CF
4open process with Ar plasma to be used to open described sedimentary deposit.Fig. 2 F is the viewgraph of cross-section of stacking 200 after sedimentary deposit 272 has been opened.The bottom of sedimentary deposit 272 is completely removed.The sidewall of sedimentary deposit 272 can be thinned but keep sealing described MTJ stacking 268.
Pinprick layer 270 is etched (step 120).In one embodiment, pinprick layer 270 is etched by dry plasma etch.In another embodiment, pinprick layer 270 uses wet etching to be etched.Example comprises the pyridine (pyridine) of different proportion and thionyl chloride (SOCl
2) mixture, and the dilution mixture thing in organic solvent includes but not limited to acetonitrile (acetonitrile).Hydrogen bromide (HBr) and dimethyl sulfoxide (DMSO) (DMSO) mixture are also used to etch PtMn and the pinprick layer containing other noble metals.Carbon tetrachloride (CCl
4) be also used to etch PtMn and the pinprick layer containing other noble metals with the mixture of at least one in DMSO, acetonitrile, benzonitrile (benzonitrile) or dimethyl formamide (DMF).Fig. 2 G is that pinprick layer 270 is by the viewgraph of cross-section of stacking 200 after etching.The additional treatment step such as removing sedimentary deposit 272 and so on can be used to form stacking 202 in a mram.
Some embodiments of the present invention provide the advantage being much better than prior art.Such as, the sealing of MTJ stacking 268 eliminates MTJ stacking 268 in pinprick layer etching (step 120) period institute's damaged.In addition, use low bias voltage ion sputtering to replace chemical etching or high bias voltage ion sputtering to stacking 268 etchings of MTJ, create a further reduction the damage to MTJ stacking 268.The chemical etching of MTJ stacking 268 can damage some layers of MTJ stacking 268.Find unexpectedly, low bias voltage ion sputtering can cause stacking 268 material re-deposition of less MTJ.Because deposition materials can cause layer short circuit again, the minimizing of the MTJ material therefore deposited again improves equipment quality.Remove such deposition materials again and may damage MTJ layer.The magnetic of MRAM can not be changed with being hoped to the infringement of MTJ stacking 268.Use and found with being expected to provide a kind of optional etch improved for Ru layer 284 based on chemical etches the 2nd Ru layer 248 of hypochlorous acid and/or ozone, this requires a kind of etch recipe being different from formula for etching MTJ stacking 268.Ru is unusual inertia.Hypochlorous acid is the strong oxidizer needed for oxidation inert Ru.Different causing stacking 268 infringements of less MTJ with optional etching and deposit again in these two steps.In other embodiments, MTJ stacking 268 can comprise other layers or with another order or can have more or less layer.MTJ stacking 268 is the requisite forms forming MRAM.
Although the present invention describes according to several preferred embodiment, have and fall into change within scope of the present invention, displacement, amendment and various substitute equivalents.Shall also be noted that the many alternative existing and realize method and apparatus of the present invention.Therefore, accompanying claim is interpreted as comprising all these changes in true spirit of the present invention and scope, displacement and various substitute equivalents.
Claims (20)
1. etching is with containing the stacking method of ruthenium (Ru) layer, described containing layer of ruthenium be arranged on hard mask below and with the stacking top of the MTJ (MTJ) of pinprick layer, described method comprises:
Use the described hard mask of dry etching etching;
Etching is described containing layer of ruthenium, and wherein, described etching uses based on hypochlorite and/or ozone (O
3) chemical substance;
Etch described magnetic tunneling junction stack;
Dielectric substance is used to cover described magnetic tunneling junction stack; And
And then described MTJ covers, and etches described pinprick layer.
2. method according to claim 1, wherein, described MTJ etching uses the low bias sputtering of plasma, and described plasma is formed from inert gas but not chemical corrosion gas.
3. method according to claim 2, wherein, described low bias sputtering provides the bias voltage of 10 to 500 volts.
4. method according to claim 3, wherein, etching is described provides wet etching containing layer of ruthenium.
5. method according to claim 4, wherein, described magnetic tunneling junction stack comprises at least one ferro-cobalt (CoFe) layer and at least one magnesium oxide (MgO) layer.
6. method according to claim 5, wherein, described pinprick layer comprises at least one platinum manganese (PtMn) layer.
7. method according to claim 6, wherein, etch described hard mask, etching described containing layer of ruthenium, to etch described magnetic tunneling junction stack, cover described magnetic tunnel junction and etch described pinprick layer be perform in single plasma processing chambers.
8. method according to claim 7, wherein, etches described magnetic tunneling junction stack and uses inertia bombarding gas, which provide the physical bombardment not having chemical corrosion gas.
9. method according to claim 8, wherein, the dielectric substance of described covering is the dielectric substance based on silicon.
10. method according to claim 1, wherein, etching is described provides wet etching containing layer of ruthenium.
11. methods according to claim 1, wherein, described magnetic tunneling junction stack comprises at least one ferro-cobalt (CoFe) layer and at least one magnesium oxide (MgO) layer.
12. methods according to claim 1, wherein, described pinprick layer comprises at least one platinum manganese (PtMn) layer.
13. methods according to claim 1, wherein, etch described hard mask, etching described containing layer of ruthenium, to etch described magnetic tunnel junction, cover described magnetic tunnel junction and etch described pinprick layer be perform in single plasma processing chamber.
14. methods according to claim 1, wherein, etch described magnetic tunneling junction stack and use inertia bombarding gas, which provide the physical bombardment not having chemical corrosion gas.
15. methods according to claim 1, wherein, the dielectric substance of described covering is the dielectric substance based on silicon.
16. 1 kinds of etchings comprise the stacking method of hard mask, and described hard mask is positioned at containing on layer of ruthenium, described containing layer of ruthenium be positioned at MTJ (MTJ) on pinprick layer stacking on, described method comprises:
Etch described hard mask, described containing layer of ruthenium and described magnetic tunneling junction stack;
Seal described magnetic tunneling junction stack; And
Etch described pinprick layer.
17. methods according to claim 16, wherein, etch the low bias sputtering that described magnetic tunneling junction stack uses plasma, described plasma is formed from inert gas but not chemical corrosion gas, wherein, described low bias sputtering provides the bias voltage of 10 to 500 volts.
18. methods according to claim 16, wherein, described magnetic tunneling junction stack comprises at least one ferro-cobalt (CoFe) layer and at least one magnesium oxide (MgO) layer.
19. methods according to claim 16, wherein, use the dielectric substance based on silicon to carry out the described magnetic tunneling junction stack of described sealing.
20. 1 kinds of stacking methods etched with pinprick layer, described pinprick layer is arranged on the below of magnetic tunneling junction stack, and described magnetic tunneling junction stack is arranged on the below containing layer of ruthenium, the described below being arranged on hard mask layer containing layer of ruthenium, and described method comprises:
Use the described hard mask of dry etching etching;
Etching is described containing layer of ruthenium;
Etch described magnetic tunneling junction stack;
Dielectric substance is used to cover described magnetic tunneling junction stack; And
Use for noble metal selectively pinprick layer described in chemical etches, comprise thionyl chloride (SOCl
2the mixture of at least one in)/pyridine mixtures, hydrogen bromide (HBr)/dimethyl sulfoxide (DMSO) (DMSO) mixture or carbon tetrachloride and dimethyl sulfoxide (DMSO), acetonitrile, benzonitrile or dimethyl formamide (DMF).
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| Application Number | Priority Date | Filing Date | Title |
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| US201461971032P | 2014-03-27 | 2014-03-27 | |
| US61/971,032 | 2014-03-27 | ||
| US14/325,190 | 2014-07-07 | ||
| US14/325,190 US9257638B2 (en) | 2014-03-27 | 2014-07-07 | Method to etch non-volatile metal materials |
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| CN104953026B CN104953026B (en) | 2017-11-14 |
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