Avoiding Oxygen Plasma Damage During Hard Mask Etching in Magnetic Tunnel Junction (MTJ) Fabrication Process
20200052196 ยท 2020-02-13
Inventors
Cpc classification
H01F10/3259
ELECTRICITY
H01F10/3272
ELECTRICITY
H01F41/308
ELECTRICITY
International classification
Abstract
An etch process flow for forming magnetic tunnel junction (MTJ) cells with enhanced throughput that also increases the magnetoresistive ratio and decreases critical dimension (CD) variation is disclosed. A photoresist pattern is formed on a dielectric antireflective coating (DARC), which contacts a top surface of a hard mask (HM) that is an uppermost MTJ layer. After a first ion beam etch (IBE) or reactive ion etch (RIE) transfers the pattern through the DARC, a second etch is used to transfer the pattern through the HM. The second etch includes an oxidant to passivate the pattern sidewalls and completely removes the photoresist layer because of one or both of a thicker DARC and thicker HM than in conventional processing. Accordingly, an oxygen etch typically used to remove the photoresist after the HM etch is avoided and thereby provides improved MTJ performance, especially for CDs<60 nm.
Claims
1. A method of etching a magnetic tunnel junction (MTJ) stack of layers, comprising: providing a MTJ stack of layers on a first electrode wherein the MTJ stack of layers includes a hard mask (HM) on a first stack of layers, and forming a second stack of layers comprising a dielectric antireflective coating (DARC) with a first thickness on the HM, and a photoresist layer on the DARC; forming a pattern with a critical dimension (CD) in the photoresist layer and transferring the pattern through the DARC with a first etch process that is an ion beam etch (IBE) or a reactive ion etch (RIE) wherein the pattern after the first etch process includes at least a sidewall that extends from a top surface of the DARC to a top surface of the HM; performing a second etch that is an IBE or RIE wherein the pattern in the DARC is transferred through the HM, and wherein the first thickness is sufficiently large such that the photoresist layer is entirely removed before the end of the second etch, and the sidewall extends from a DARC top surface to a top surface of the first stack of layers, and wherein the second etch comprises one or more oxidants that passivate the sidewall; and performing a third (MTJ) etch that is one or both of a RIE or IBE comprised of a noble gas and the one or more oxidants wherein the MTJ etch transfers the pattern through the first stack of layers, and stops at a top surface of the first electrode and thereby forms a plurality of MTJ cells.
2. The method of claim 1 wherein the first and second etches and the MTJ etch are all RIE or all IBE, and are performed in a first process chamber.
3. The method of claim 2 further comprised of a cleaning step that is an IBE or plasma etch performed after the MTJ etch, and wherein a plasma is generated from a gas mixture comprised of a noble gas and the one or more oxidants.
4. The method of claim 1 wherein the one or more oxidants is selected from air, 0.sub.2, methanol, ethanol, H.sub.20.sub.2, H.sub.20, N.sub.20, NH.sub.3, and CO.
5. The method of claim 1 wherein the first etch is an IBE and comprises a noble gas that is Ar, Kr, Xe, or Ne.
6. The method of claim 1 wherein the second etch is an IBE and comprises a noble gas that is Ar, Kr, Xe, or Ne.
7. The method of claim 1 wherein the first etch is a RIE and comprises a fluorocarbon or chlorocarbon.
8. The method of claim 1 wherein the second etch is a RIE and comprises a fluorocarbon or chlorocarbon.
9. The method of claim 1 wherein the first etch further comprises oxygen in order to passivate the sidewall.
10. The method of claim 1 wherein the MTJ stack of layers is formed in a magnetoresistive random access memory (MRAM), spin torque transfer (STT)-MRAM, spin torque oscillator (STO), sensor, or biosensor.
11. The method of claim 1 wherein the first stack of layers comprises a free layer (FL), a reference layer (RL), and a tunnel barrier between the FL and RL.
12. The method of claim 1 wherein the first thickness is substantially larger than a thickness of the hard mask.
13. A method of etching a magnetic tunnel junction (MTJ) stack of layers, comprising: providing a MTJ stack of layers on a first electrode wherein the MTJ stack of layers includes a hard mask (HM) on a first stack of layers, and forming a second stack of layers comprising a dielectric antireflective coating (DARC) on the HM, and a photoresist layer on the DARC wherein the HM is a metal, alloy, or metal nitride having a first thickness; forming a pattern with a critical dimension (CD) in the photoresist layer and transferring the pattern through the DARC with a first etch process that is an ion beam etch (IBE) or a reactive ion etch (RIE) wherein the pattern after the first etch process has a sidewall that extends from a top surface of the photoresist layer to a top surface of the HM; performing a second etch that is an IBE or RIE wherein the pattern in the DARC is transferred through the HM, and wherein the first thickness is sufficiently large such that the photoresist layer is entirely removed and the sidewall extends to a top surface of the first stack of layers, and wherein the second etch comprises one or more oxidants that passivate the sidewall; and performing a third (MTJ) etch that is one or both of a RIE or IBE comprised of a noble gas and the one or more oxidants wherein the MTJ etch transfers the pattern through the first stack of layers, and extends the sidewall to a top surface of the first electrode and thereby forms a plurality of MTJ cells.
14. The method of claim 13 wherein the first and second etches and the MTJ etch are all RIE or all IBE, and are performed in a first process chamber.
15. The method of claim 14 further comprised of a cleaning step that is an IBE or plasma etch performed after the MTJ etch, and wherein a plasma is generated from a gas mixture comprised of a noble gas and the one or more oxidants.
16. The method of claim 13 wherein the one or more oxidants is selected from air, 0.sub.2, methanol, ethanol, H.sub.20.sub.2, H.sub.20, N.sub.20, NH.sub.3, and CO.
17. The method of claim 13 wherein the first etch is an IBE and comprises a noble gas that is Ar, Kr, Xe, or Ne.
18. The method of claim 13 wherein the second etch is an IBE and comprises a noble gas that is Ar, Kr, Xe, or Ne.
19. The method of claim 13 wherein the first etch is a RIE and comprises a fluorocarbon or chlorocarbon.
20. The method of claim 13 wherein the second etch is a RIE and comprises a fluorocarbon or chlorocarbon.
21. The method of claim 13 wherein the first etch further comprises oxygen in order to passivate the sidewall.
22. The method of claim 13 wherein the MTJ stack of layers is formed in a magnetoresistive random access memory (MRAM), spin torque transfer (STT)-MRAM, spin torque oscillator (STO), sensor, or biosensor.
23. The method of claim 13 wherein the DARC has a thickness substantially greater than the first thickness.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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[0027]
DETAILED DESCRIPTION
[0028] The present disclosure is an etch process that transfers a pattern in a photoresist layer sequentially through a DARC, hard mask, and underlying MTJ stack of layers to form a plurality of MTJ cells, and where the photoresist is completely removed before the end of the hard mask etch step. Only one MTJ cell is depicted in the drawings with cross-sectional views in order to simplify the drawings. A process is defined as a method that includes a plurality of steps. The resulting MTJ cells may be used in MRAM, STT-MRAM, spin torque oscillators (STO), sensors, and biosensors. In the drawings, a thickness of a layer is shown in the z-axis direction while a top surface of each layer is formed in a plane along the x-axis and y-axis directions.
[0029] In related patent application US 2016/0351798, we disclosed a process flow where a photoresist mask layer is formed directly on a hard mask, and the HM etch is then performed with conditions comprising air, oxygen, or water to generate smoother MTJ sidewalls and more uniform MTJ shapes from a top-down view. Furthermore, HM passivation with oxygen, for example, is necessary before the photoresist mask is stripped.
[0030] In related patent application Ser. No. 15/668,113, the photoresist pattern is formed on a DARC layer, and is transferred through the DARC before the HM etch. The HM etch may remove the photoresist mask layer in some embodiments, but in other embodiments, the photoresist layer is not stripped until after HM sidewall passivation.
[0031] Now we have discovered an improved process flow for the HM etch and subsequent MTJ etch that combines the HM passivation, HM etch, and photoresist removal into one step for faster throughput, and better MTJ performance in terms of less CD variation (smaller Rp_cov %), and enhanced MR ratio compared with a process of record (POR) employed by the inventors.
[0032] In
[0033] In other embodiments (not shown), at least one additional layer may be included in the aforementioned MTJ stack such as a Hk enhancing layer (i.e. MgO) between the free layer and hard mask that enhances PMA in the free layer. The Hk enhancing layer may also be W, Mo, or an alloy thereof rather than a metal oxide.
[0034] The seed layer 11 is a single layer or a multilayer, and may be comprised of one or more of NiCr, Ta, Ru, Ti, TaN, Cu, Mg, or other materials typically employed to promote a smooth and uniform grain structure in overlying layers.
[0035] Reference layer 12 preferably has a synthetic anti-parallel (SyAP) configuration represented by AP2/Ru/AP1 where an anti-ferromagnetic coupling layer made of Ru, Rh, or Ir, for example, is sandwiched between an AP2 magnetic layer and an AP1 magnetic layer (not shown). The AP2 layer, which is also referred to as the outer pinned layer is formed on seed layer 11 while AP1 is the inner pinned layer and typically contacts the tunnel barrier 13. AP1 and AP2 layers may be comprised of CoFe, CoFeB, Co, or a combination thereof. In other embodiments, one or both of the AP1 and AP2 layers may be a laminated stack with inherent PMA such as (Co/Ni).sub.n, (CoFe/Ni).sub.n, (Co/NiFe).sub.n, (Co/Pt).sub.n, (Co/Pd).sub.n, or the like where n is the lamination number. Furthermore, a transitional layer such as CoFeB, Co, or CoFeB/Co may be inserted between the laminated stack in the AP1 layer and the tunnel barrier layer.
[0036] The tunnel barrier layer 13 is preferably a metal oxide that is one or more of MgO, TiOx, AlTiO, MgZnO, Al.sub.2O.sub.3, ZnO, ZrOx, HfOx, or MgTaO. More preferably, MgO is selected as the tunnel barrier layer because it provides the highest MR ratio, especially when sandwiched between two CoFeB layers, for example.
[0037] The free layer 14 may be Co, Fe, CoFe, or an alloy thereof with one or both of B and Ni, or a multilayer stack comprising a combination of the aforementioned compositions. In another embodiment, the free layer may have a non-magnetic moment diluting layer such as Ta or Mg inserted between two CoFe or CoFeB layers that are ferromagnetically coupled. In an alternative embodiment, the free layer has a SyAP configuration such as FL1/Ru/FL2 where FL1 and FL2 are two magnetic layers that are antiferromagnetically coupled, or is a laminated stack with inherent PMA described previously with respect to the reference layer composition.
[0038] Hard mask (HM) 15 is also referred to as a capping layer and is typically comprised of one or more of Ta, Ru, TaN, Ti, TiN, and W. In other embodiments, the HM may comprise a metal, or an alloy such as MnPt that provides substantial resistance to subsequent etching and chemical mechanical polish (CMP) processes employed during MTJ fabrication and thereby preserves CD integrity. In our POR scheme, the HM has a thickness t1 of about 480 Angstroms. In general, the hard mask is an electrical conductor, and provides high etch selectivity relative to underlying MTJ layers during an etch process that forms MTJ cells with sidewalls that stop on the bottom electrode. All layers in the MTJ stack may be deposited in a DC sputtering chamber of a sputtering system such as an Anelva C-7100 sputter deposition system that includes ultra high vacuum DC magnetron sputter chambers with multiple targets and at least one oxidation chamber. Usually, the sputter deposition process involves Ar and a base pressure between 510.sup.8 and 510.sup.9 torr.
[0039] As a first step in the process flow of our POR scheme, a DARC 16, and a photoresist layer 17 are sequentially formed on the top surface 15t of the hard mask by well known methods. DARC is one or more of SiO.sub.2, Si.sub.3N.sub.4, SiCOH, SiON, amorphous carbon, or black diamond with top surface 16t and thickness t2 of about 300 Angstroms, and has a refractive index that minimizes reflection of light during patternwise exposure of the photoresist layer thereby enabling more uniform island shapes with sidewalls 20 having less CD variation (more uniform w1) to be formed in the photoresist layer. A conventional patternwise exposure and developer sequence is employed to form a pattern in the photoresist layer that comprises a plurality of islands each with sidewall 20. As indicated later by a top-down view in
[0040] After patterning photoresist layer 17, the island shape with sidewall 20 is transferred through the DARC 16 and reduces the photoresist layer thickness to d Etch step 30 may be an IBE with one or more of Ar, Kr, Xe, or Ne, or may comprise RIE with a fluorocarbon or chlorocarbon gas wherein ions or plasma are directed substantially orthogonal to hard mask top surface 15t. Moreover, oxygen may be flowed into the etch chamber during the IBE or RIE, or afterward as a passivation measure to form a smoother sidewall. As a result, sidewall 20 is extended along the DARC to a top surface 15t of the hard mask 15, and CD w1 is duplicated in the DARC.
[0041] Referring to
[0042] Referring to
[0043] Regarding
[0044] In
[0045] The present disclosure anticipates that with a DARC thickness of >900 Angstroms, which is substantially larger than the HM thickness, and etch optimization such that the photoresist:DARC ER ratio is substantially greater than 1.25:1, then all of photoresist layer 17 may be removed during etch 30. In this case, the metal hard mask 15 will not be exposed to photoresist residue during subsequent etch 31p, which is expected to provide a smoother MTJ sidewall 20 after MTJ etch and lower CD variation.
[0046] In
[0047] Referring to
[0048] Sidewall angle varies from about 70 to 90 depending on the ratio of noble gas to oxidant in MTJ etch 33. For example, the sidewall angle becomes greater as the Ar/CH.sub.3OH flow rate ratio becomes closer to 1:1. Moreover, the HM and DARC etch rates slow with increasing oxidant content in the MTJ etch which means higher selectively with respect to underlying MTJ layers. In other words, a DARC thickness t4, where t4<t3, may remain after the MTJ etch when using noble gas/oxidant flow rate ratios proximate to 1:1. In other embodiments when IBE or RIE is employed with pure noble gas, or with a noble gas/oxidant ratio of around 10:1 or higher, all of the DARC may be consumed and a top portion of the HM 15 may also be etched away during the MTJ etch. Generally, the higher risk of MTJ sidewall damage with higher oxidant content in the MTJ etch must be balanced with the benefit of higher etch selectivity when determining the optimum noble gas/oxidant flow rate ratio.
[0049] Another important consideration is that IBE or RIE with pure noble gas has a more pronounced shadow effect in which small gaps between adjacent MTJ sidewalls are more difficult to clean out (remove all residue), especially in locations proximate to bottom electrode top surface 10t. Therefore, at least a limited amount of oxidant is desirable in the MTJ etch 33 to prevent unwanted erosion of the bottom electrode 10. According to one preferred embodiment, the noble gas/oxidant flow rate ratio should be between 98:2 and 1:1.
[0050] In some embodiments, all etch steps 30, 31p, 33 may be performed in the same etch chamber within a sputter deposition mainframe to enhance throughput. When a RIE process chamber is employed for one or more of the aforementioned etch steps, there is an upper electrode, a lower electrode (electrostatic chuck) on which one or more wafers are held in place, and a gap between each wafer and upper electrode (not shown). Preferably, a first RF power between 600 and 3000 Watts is applied to the upper electrode, and a second RF power from 400 to 3000 Watts is applied to the lower electrode in order to generate and sustain plasma in the gap between the two electrodes. In addition, the RIE chamber pressure must be sufficiently high enough to sustain a stable plasma, but is not more than 3 mTorr.
[0051] MTJ etch 33 typically comprises a main etch portion during a first period of time that ends when an end point is reached. As described in related patent application Ser. No. 15/668,113, an optical emission spectroscopy (OES) system may be employed to monitor the progress of RIE etching in real time. In one preferred embodiment, the flow rate ratio of noble gas/oxidant is increased during the over etch portion to minimize chemical damage to MTJ sidewalls. In addition, RF power during the over etch portion may be decreased to 75 Watts or less at both of the upper and lower electrodes to minimize the amount of bottom electrode material that is etched, and redeposited on MTJ sidewall 20.
[0052] As depicted in
[0053] In an alternative embodiment, etch step 34 comprises a plasma etch wherein a plasma is generated with a RF or DC power 100 Watts and pure noble gas or with a combination of noble gas and one or more oxidants described previously. The plasma is directed orthogonal to the substrate (=90) in an etch chamber that may be in the same mainframe as employed for the subsequent encapsulation process. In all embodiments, etch step 34 is incorporated in the MTJ etch process flow as a cleaning measure to ensure that MTJ sidewalls and substrate top surface 10t are substantially free of residue. The wafer on which the plurality of MTJ cells is fabricated is typically rotated during an IBE step but is not rotated during a RIE or plasma etch.
[0054] Referring to
[0055] Thereafter, a chemical mechanical polish (CMP) process is performed to form a top surface 25t on the encapsulation layer that is coplanar with HM top surface 15t. Thus, the CMP process removes any material above a plane that includes the HM top surface.
[0056] Referring to
[0057] Thereafter, a top electrode layer comprised of a plurality of parallel conductive lines (not shown) is formed by a conventional method on the MTJ cells and encapsulation layer 25 as appreciated by those skilled in the art. A first top electrode line may contact a top surface of MTJ cells 1a, 1c while a second top electrode line contacts top surface in MTJ cells 1b, 1d. Conductive lines in the top electrode layer are preferably formed along the y-axis direction that is orthogonal to the conductive lines along the x-axis direction in the bottom electrode layer.
[0058] According to a second embodiment of the etch process flow of the present disclosure, HM thickness t2 in the POR scheme may be increased to t5 in HM 15x as illustrated in
[0059] Referring to
[0060] Thereafter, the etch process of the present disclosure comprises MTJ etch 33 and an optional IBE or plasma cleaning step 34 before encapsulation and planarization steps provide a plurality of MTJ cells including MTJ cell 1a that is surrounded by encapsulation layer 25 as shown in
[0061] The present disclosure also anticipates an alternative embodiment where a combination of a thicker DARC 16X and thicker HM 15X may be employed to ensure photoresist 17 is completely removed at the end of the HM etch 31p. For example, in the experiment described below, DARC thickness t3 may be substantially larger than the HM thickness t5 while both t3 and t5 are considerably higher than conventional thickness values of t2 and t1, respectively, for DARC and HM layers.
[0062] We have demonstrated the benefits of the combined physical/chemical etch process of the present disclosure with results from an experiment where a series of MTJ cells with various diameters (w1 in
[0063] In both cases, the Ta/DARC etch steps were performed with a RIE comprised of 50 sccm CF.sub.4. The Ta/DARC etching was performed in two steps with an intermediate passivation step comprised of H.sub.2O or O.sub.2 treatment, or exposing the wafer to air. The MTJ etch for both examples was a RIE comprising 97.5:2.5 Ar/CH.sub.3OH flow rate ratio, a RF power of 1500 Watts (upper electrode), 1100 Watts (lower electrode), a 15 sccm flow rate for the combined gas mixture, and a 3 mTorr pressure. An annealing step at 400 C. was performed for about 2 hours after an encapsulation process was used to isolate adjacent MTJ cells.
[0064] Results are shown in
[0065] Referring to
[0066] Our results confirm that when a HM etch includes an oxidant to passivate HM sidewalls and there is sufficient DARC thickness and HM thickness to guarantee no photoresist layer remains after the HM etch, then MR ratio and Rp_cov % are improved while maintaining other MTJ performance values including thermal stability and the RA product. Ideally, all etch steps and the encapsulation process should be done in one platform having multi-chambers, including a dedicated chamber for each of the HM and MTJ RIE steps, IBE for HM, MTJ, or sidewall cleaning, a plasma etch chamber for MTJ sidewall cleaning, and PVD/CVD chamber for encapsulation. Practically, there may be three separate platforms with one each assigned to RIE for HM and RIE for MTJ, IBE and PVD, and plasma etching and PVD.
[0067] While this disclosure has been particularly shown and described with reference to, the preferred embodiment thereof, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of this disclosure.