TREA

Selective layer formation using deposition and removing

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Information

  • Patent Grant
  • 11804373
  • Patent Number
    11,804,373
  • Date Filed
    Friday, September 23, 2022
    a year ago
  • Date Issued
    Tuesday, October 31, 2023
    6 months ago
Information
Abstract
Methods and systems for selectively depositing dielectric films on a first surface of a substrate relative to a passivation layer previously deposited on a second surface are provided. The methods can include at least one cyclical deposition process used to deposit material on the first surface while the passivation layer is removed, thereby preventing deposition over the passivation layer.
Description
BACKGROUND
Field

The present disclosure relates generally to the field of semiconductor device manufacturing and, more particularly, to selective formation of layers employing deposition and removal of films.


Description of the Related Art

In the semiconductor industry, there is an increasing need for selective processes. For example, film growth may be desired on one surface but not on a second, different surface. These two different surfaces can comprise different materials, for example a metal and a dielectric. Good selective processes could reduce the number process steps by avoiding more complicated processes for separate patterning of the deposited material, such as photolithographic masking and patterning, thus saving time and money.


SUMMARY

In one aspect a method is provided for an atomic layer deposition (ALD) process for selectively forming a dielectric material on a first surface of a patterned substrate. The method includes providing a substrate comprising a first surface and a second surface, wherein the second surface comprises a passivation layer thereover. The method further includes conducting at least one deposition cycle comprising alternately and sequentially contacting the substrate with a first precursor and a second reactant comprising oxygen. The method further includes wherein the second reactant reacts with the first precursor to form a dielectric material on the first surface, and wherein the passivation layer is ashed by the second reactant during each deposition cycle.


In some embodiments, the method for an ALD process further includes wherein the first surface is a dielectric surface. In some embodiments, the dielectric surface comprises silicon oxide. In some embodiments, the first surface comprises a low-k material. In some embodiments, the second surface is a metal surface. In some embodiments, the metal surface comprises at least one of Co, Cu or W. In some embodiments, the dielectric material is an oxide. In some embodiments, the oxide is silicon oxide. In some embodiments, the oxide is a metal oxide.


In some embodiments, the first precursor comprises a metal precursor, a silicon precursor, or mixtures thereof. In some embodiments, the first precursor is an alkylaminosilane.


In some embodiments, the passivation layer comprises an organic material. In some embodiments, the passivation layer is selectively deposited on the second surface relative to the first surface prior to beginning the first deposition cycle. In some embodiments, the deposition cycle is repeated a plurality of times to form an oxide film of a desired thickness on the dielectric surface. In some embodiments, additional passivation layer is selectively deposited on the passivation layer between the beginning and end of each deposition cycle.


In some embodiments, the ALD process is a plasma enhanced atomic layer deposition (PEALD) process. In some embodiments, the at least one deposition cycle begins with contacting the substrate with the second reactant before contact with the first precursor. In some embodiments, the at least one deposition cycle further comprises contacting the substrate with at least one additional reactant in each cycle. In some embodiments, the second reactant further comprises plasma. In some embodiments, contacting the substrate with the second reactant further comprises activating the second reactant with plasma.


In some embodiments, the dielectric material is selectively formed on the first surface relative to the passivation layer. In some embodiments, the dielectric material is formed on the passivation layer and the dielectric material is removed from the passivation layer with the ashing of the passivation layer, thereby selectively forming the dielectric material on the first surface.


In another aspect a cyclical deposition process is provided for selectively a forming a material on a surface of a patterned substrate. The method includes providing a substrate comprising a first surface and a second surface, wherein the second surface comprises a passivation layer thereover. The method further includes conducting at least one deposition cycle comprising alternately and sequentially contacting the substrate with a first precursor and a second reactant. The second reactant reacts with the first precursor to form the material on the first surface, and the passivation layer is etched by the second reactant during each deposition cycle.


In some embodiments, the process comprises atomic layer deposition (ALD). In some embodiments, the process comprises plasma enhanced ALD (PEALD). In some embodiments, the second reactant comprises plasma-activated species. In some embodiments, the second reactant comprises oxygen, the passivation layer comprises an organic layer, and etching comprises ashing. In some embodiments, the passivation layer comprises a polymer.


In some embodiments, deposition is halted before the etching of the passivation layer exposes the second surface. In some embodiments, the method includes further depositing additional passivation layer over the second surface after halting the deposition and prior to continuing the deposition.


In another aspect a plasma enhanced atomic layer deposition (PEALD) process is provided for selectively forming an oxide material on a first dielectric surface of a patterned substrate. The method includes providing a substrate comprising a first dielectric surface and a second metallic surface, wherein the second metallic surface comprises an organic passivation layer thereover. The method further includes conducting at least one deposition cycle comprising alternately and sequentially contacting the substrate with a first precursor and a second reactant comprising oxygen and plasma. The second reactant reacts with the first precursor to form an oxide material on the first dielectric surface, and the organic passivation layer is ashed by the second reactant during each deposition cycle.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1A is a flow diagram illustrating a selective deposition process for depositing a material on a first surface while reducing the thickness of a passivation layer over a second surface.



FIG. 1B is a flow diagram illustrating a selective deposition process for depositing a material on a first surface while reducing the thickness of a passivation layer selectively deposited over a second surface.



FIG. 2 is a graph of some embodiments showing the thickness of a polyimide layer versus the number of cycles of oxidation performed, wherein a passivation ash rate is calculated.



FIG. 3 illustrates the selective deposition of a material on a first surface of a substrate by a cyclical deposition process, while the cyclical deposition process removes a passivation layer over a second surface.





DETAILED DESCRIPTION

Dielectric films, such as metal oxide or silicon oxide (e.g., SiO) films, have a wide variety of applications, as will be apparent to the skilled artisan, for example in integrated circuit fabrication. According to some embodiments of the present disclosure, various dielectric films, particularly oxide films, precursors, and methods for depositing such films are provided.


In some embodiments, a material is formed on a first surface of a substrate relative to a second surface by a selective deposition process. In some embodiments, the material is an oxide material. In some embodiments, a dielectric film is formed selectively using a cyclical deposition process on a dielectric surface of a substrate relative to a passivation layer on a metal surface.


For example, FIG. 1A is a flow diagram 100 illustrating a selective deposition process of depositing a material on a first surface while reducing the thickness of a passivation layer over a second surface. In the first illustrated block 102 a substrate with a first surface and a second surface is provided, wherein the second surface comprises a passivation layer thereover. In block 104 the substrate is contacted with a first reactant, and in block 106 the substrate is contacted with a second reactant. In some embodiments, blocks 104 and 106 are performed alternately and sequentially. In illustrated decision block 108, the substrate may be repeatedly exposed to the first and second reactants in blocks 104 and 106 until a material of sufficient thickness is formed. In some embodiments, a sufficiently thick material is formed and therefore blocks 104 and 106 are not repeated. In some embodiments, a sufficiently thick material is not formed and therefore blocks 104 and 106 are repeated, and the repetition of blocks 104 and 106 is referred to as a cyclical deposition process. Blocks 104 and 106 need not be in the same sequence nor identically performed in each repetition. In some embodiments, blocks 104 and 106 are performed consecutively. In some embodiments, blocks 104 and 106 are separated by one or more intermittent processes. In some embodiments, the repetition of blocks 104 and 106 are performed consecutively. In some embodiments, the repetition of blocks 104 and 106 is separated by one or more intermittent processes. In some embodiments, intermittent processes may be selected from at least one of excess reactant and byproduct removal (e.g., vacuum and/or inert gas purge), selective deposition of an additional passivation layer, additional clean up etch, repeated exposure of the same reactant prior to exposure of another reactant, and/or exposure to an additional reactant in some or all cycles. Intervening removal of excess reactant and byproduct aids in separating the supply of different reactants to minimize risk of gas phase interaction and limit the deposition reactions to surface reactions. Skilled artisans will appreciate that some interactions with residual gases may be tolerated in order to minimize duration of the intervening removal (e.g., purge) steps. Avoiding overlap in the supply of reactants to the reaction space typically reduces gas phase reactions sufficiently, and optimization of flow paths together with intervening purging can further minimize residual gas interactions. Once a desired material is thickness is formed, the selective deposition process is completed in block 110, where the material is selectively obtained on a first surface and a passivation layer with a reduced thickness is obtained on the second surface. Reactants can be precursors that leave one or more elements in the deposited film. In some embodiments, one or more reactants can serve to chemically reduce, oxidize or getter products of the deposited material.


Similar to FIG. 1A, FIG. 1B is an example flow diagram 200 illustrating the selective deposition of a material on a first surface while reducing the thickness of a passivation layer, however FIG. 1B includes selectively forming a passivation layer on a second surface. It is to be understood that any of the same or similar features or functions discussed with regard to FIG. 1A may also be applied to the same or similar features or functions of FIG. 1B. In the first illustrated block 202 a passivation layer is selectively formed on a second surface of a substrate relative to a first surface. In block 204 the substrate is contacted with a first reactant, and in block 206 the substrate is contacted with a second reactant. In illustrated decision block 208, a sufficiently thick material may be formed and therefore the material is selectively obtained on the first surface with a passivation layer of a reduced thickness as shown in block 212. If a sufficiently thick material is not yet formed and if the passivation layer is not at risk of being fully consumed by exposure to the reactants, decision block 210 illustrates that the substrate may be repeatedly and alternately exposed to the first and second reactants in blocks 204 and 206. Alternatively, if the passivation layer is at risk of being fully consumed by exposure to the reactants, decision block 210 illustrates that first illustrated block 202 may be repeated where a passivation layer is selectively formed on a second surface of a substrate relative to a first surface before the substrate is exposed to the first and second reactants in blocks 204 and 206.


In some embodiments, the cyclical deposition process is atomic layer deposition (ALD). In some embodiments, the cyclical deposition process is cyclical chemical vapor deposition (CVD). In some embodiments, the passivation layer was previously deposited on the second surface (for example, the metal surface). In some embodiments, the passivation layer is partially removed during the cyclical deposition process. During an ALD process, for example, the passivation layer may be slowly removed, such as by etching, during ALD phases. For example, for an organic (e.g., polymer) passivation layer, etching (e.g., ashing) may be accomplished during deposition phases in which oxidants are supplied, while simultaneously a dielectric film is deposited on the dielectric surface. In another example, a passivation layer is simultaneously removed while an oxide material is deposited on the dielectric surface during exposure of the substrate to a second reactant in the ALD process. The slow etching of the passivation layer may prevent deposition of the dielectric on the passivation layer and on the metal.


In some embodiments, the ALD process may be a plasma enhanced atomic layer deposition process (PEALD). In some embodiments, plasma power is provided to generate more reactive species from reactants containing oxygen. In some embodiments, reactant containing oxygen comprises O2 gas, which is subjected to plasma generating power. In some embodiments, the plasma may be generated remotely from the deposition chamber and plasma products supplied to the deposition chamber. In some remote plasma embodiments, the delivery path optimizes delivery of neutral O species while minimizing ion delivery to the substrate. In some embodiments, the plasma may be generated in situ within the deposition chamber.


In some embodiments, the first surface of the substrate comprises a dielectric surface. In some embodiments, the dielectric surface of the substrate comprises a silicon oxide (e.g., SiO2). In some embodiments, the dielectric surface of the substrate comprises a low-k material.


In some embodiments, the second surface comprises a metal surface. Unless otherwise indicated, if a surface is referred to as a metal surface herein, it may be a metal surface or a metallic surface. In some embodiments the metal or metallic surface may comprise metal, metal oxides, and/or mixtures thereof. In some embodiments the metal or metallic surface may comprise surface oxidation. In some embodiments the metal or metallic material of the metal or metallic surface is electrically conductive with or without surface oxidation. In some embodiments metal or a metallic surface comprises one or more transition metals. In some embodiments the metal or metallic surface comprises one or more of Al, Cu, Co, Ni, W, Nb, Fe. In some embodiments the metal or metallic surface comprises at least one of Co, Cu or W. In some embodiments the metal or metallic surface comprises one or more noble metals, such as Ru. In some embodiments the metal or metallic surface comprises a conductive metal oxide, nitride, carbide, boride, or combination thereof. For example, the metal or metallic surface may comprise one or more of RuOx, NbCx, NbBx, NiOx, CoOx, NbOx and WNCx. In some embodiments the substrate may comprise a metal nitride, including, but not limited to TiN and/or TaN. In some embodiments the metal surface may comprise a metal carbide, including, but not limited to TiC and/or TaC. In some embodiments the metal surface may comprise a metal chalcogenide, including, but not limited to MoS2, Sb2Te3, and/or GeTe. In some embodiments the metal surface is a TiN surface. In some embodiments the metal surface is a W surface.


Selectivity


Selectivity can be given as a percentage calculated by [(deposition on first surface)-(deposition on second surface)]/(deposition on the first surface). Deposition can be measured in any of a variety of ways. In some embodiments deposition may be given as the measured thickness of the deposited material. In some embodiments deposition may be given as the measured amount of material deposited.


In some embodiments selectivity is greater than about 10%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99% or even greater than about 99.5%. In embodiments described herein, the selectivity can change over the duration or thickness of a deposition.


In some embodiments deposition of the dielectric, such as an oxide, only occurs on the first dielectric surface and does not occur on the passivation layer over the second metal surface. In some embodiments deposition on the first surface of the substrate relative to the passivation layer is at least about 80% selective, which may be selective enough for some particular applications. In some embodiments the deposition on the first surface of the substrate relative to the passivation layer is at least about 50% selective, which may be selective enough for some particular applications. In some embodiments the deposition on the first surface of the substrate relative to the passivation layer is at least about 10% selective, which may be selective enough for some particular applications.


In some embodiments the passivation layer may be selectively formed on the metal surface prior to selective deposition of the dielectric material on the dielectric surface. For example, in some embodiments, a passivation layer may be blanket deposited on a patterned substrate, and patterned and etched by traditional processes to leave the passivation layer selectively where the subsequent deposition is to be avoided, such as over a metal surface. In other embodiments, a passivation layer may be selectively deposited on a metal layer. Selective deposition of a passivation layer may be carried out, for example, as described below, and as described in US Patent Publication No. 2017-0352533 A1 (application Ser. No. 15/170,769) or US Patent Publication No. 2017-0352550 A1 (application Ser. No. 15/486,124), the entire disclosure of each of which is incorporated by reference herein in its entirety.


As noted above, the selective formation of the passivation layer over metal surfaces need not be 100% selective in order to achieve 100% selectivity. For example, the passivation layer deposition may be partially selective such that it is formed to be thicker over the metal surface than over the dielectric surface. A subsequent short, timed etch of the passivation material may be conducted for a duration to expose the dielectric surface while leaving some passivation layer covering the metal surface.


ALD Process


According to some embodiments, a dielectric film is deposited on a first surface of a substrate with an oxygen based ALD process. In some embodiments, the deposited dielectric film may be, for example, silicon oxide (e.g., SiO2) or other metal oxide that can be grown with a PEALD process. In some embodiments, the deposited dielectric film can comprise SiO2, TiO2, ZrO2, HfO2, Nb2O5, Ta2O5, WO3, NiO and combinations thereof. The second surface of the substrate may be covered by a passivation layer. In some embodiments, the passivation layer is an organic layer. The organic passivation layer may be a polymer, such as polyimide or polyamide.


In some embodiments, an oxide material film is deposited on a first surface of a substrate with an oxygen based ALD process. In some embodiments, the deposited oxide material film may be a conductive oxide film. For example, in some embodiments the conductive oxide film is an indium tin oxide (ITO) film. In some embodiments, the deposited oxide material film may be a dielectric film, as described herein.


In some embodiments, the passivation layer inhibits oxide material film and/or dielectric film deposition there. However, in some embodiments, the passivation layer does not inhibit deposition of the oxide material film or dielectric film, that is, the oxide material film or dielectric film chemistry may not be selective as between the underlying dielectric substrate surface and the passivation layer. This is due to the fact that conditions are selected to ensure some removal of the passivation layer during the ALD process, thus undercutting and removing any deposition of the oxide material film or dielectric film over the passivation layer. As the passivation layer is sacrificial, the passivation layer is slowly removed (e.g., etched) during one of the cyclical deposition phases. For example, in an ALD sequence, an organic (e.g., polymer) passivation layer may be slowly ashed by an oxidant phase of the ALD sequence, which prevents oxide material film or dielectric film growth on the passivation layer. In another example, in an ALD sequence, a passivation layer is removed during exposure of the substrate to a second reactant in the ALD process, which prevents oxide material film or dielectric film growth on the passivation layer. Relative to the growth over the passivation layer, the oxide material film or dielectric film is deposited normally (non-selectively, or with low selectivity) on the dielectric surface. Regardless of whether the oxide material film or dielectric material is deposited normally or selectively on the dielectric surface, slowly etching (e.g., ashing) the sacrificial passivation layer by an oxidant phase of the ALD sequence has the end effect of selectively forming the oxide material film or dielectric material on the dielectric substrate relative to the passivation layer. Thus, using the process of FIG. 1A or 1B can effectively increase selectivity of the formation of the oxide material film or dielectric film.


In some embodiments, before deposition of the oxide material film or dielectric film is performed but after the passivation layer is formed, any passivation layer remaining on the dielectric surface can be removed with a plasma pretreatment with suitable parameters. In some embodiments, rather than a separate process to remove any passivation material from over the dielectric surface, any passivation layer remaining on the dielectric surface is removed by initial phases of the ALD process, including oxidation phase, or by simply conducting the oxidation phase of the ALD process before initiating the full ALD process wherein after the thinner passivation layer on dielectric is completely ashed the oxide material film or dielectric film deposition process begins. Thus, the ALD sequence may start with the second reactant, including oxidant, to serve for a short timed etch of undesired passivation material from the first surface, without removal of all the passivation material from the second surface, before selective deposition on the first surface.


In some embodiments, the oxidation phase of the ALD process is a plasma process in a PEALD sequence. In some embodiments, the plasma is oxygen based. For example, the plasma may be generated in O2 gas or a mixture of O2 and a noble gas, such as Ar. In some embodiments the plasma may be generated in a gas comprising oxygen, or may otherwise comprise excited oxygen species. In some embodiments, the oxidation phase of the ALD process is a non-plasma oxidation process (e.g., H2O or O3).


In some embodiments plasma, for example oxygen containing plasma, may be generated by applying RF power of from about 10 W to about 2000 W, from about 50 W to about 1000 W, from about 100 W to about 500 W, from about 30 W to 100 W, or about 100 W in some embodiments. In some embodiments the RF power density may be from about 0.02 W/cm2 to about 2.0 W/cm2, or from about 0.05 W/cm2 to about 1.5 W/cm2. The RF power may be applied to a reactant that flows during the plasma contacting time, that flows continuously through the reaction chamber, and/or that flows through a remote plasma generator. Thus in some embodiments the plasma is generated in situ, while in other embodiments the plasma is generated remotely. In some embodiments a showerhead reactor is utilized and plasma is generated in situ between a susceptor (on top of which the substrate is located) and a showerhead plate. In some embodiments the gap between the susceptor and showerhead plate is from about 0.1 cm to about 20 cm, from about 0.5 cm to about 5 cm, or from about 0.8 cm to about 3.0 cm.


The thickness of the oxide film that can be formed on dielectric surface before the passivation layer is completely removed depends on the passivation layer initial thickness, ash rate of the passivation layer, and the growth rate of the oxide deposition process. For example, FIG. 2 demonstrates that with an ash rate of ˜0.2 Å/cycle, a 20 nm sacrificial polyimide layer on a metal surface, and a growth per cycle (GPC) of 1 Å/cycle, 50 nm of SiO2 may be deposited on a dielectric surface by applying 500 cycles of the oxygen based PEALD process. FIG. 2 shows the ash rate of polyimide when exposed to oxidant phases in which argon is supplied at 700 sccm, O2 is supplied at 100 sccm, pressure is kept at 2 Torr, plasma power is set to 100 W, substrate temperature is maintained at 100° C., and each oxidant phase includes 1 second of O2 plasma and 1 second of purge. The PEALD would include one phase of the above oxidant phase alternated with supply of a silicon precursor and purge, where the silicon precursor is selected for adsorption on the dielectric or growing silicon oxide film and to react with the oxidant phases to form silicon oxide. In other embodiments, oxidant phases can be alternated with a supply of one or more metal precursor phase(s) and attendant purge phase(s), where the metal precursor is selected to adsorb on the dielectric surface or the growing metal oxide film and to react to with the oxidant phases to form the desired oxide.


In some embodiments, optimization of the etch rate of the sacrificial passivation layer can be tuned so that growth of the oxide material film or dielectric film does not result in net deposition on the passivation layer during the ALD process. In some embodiments, the incubation time for deposition on the passivation layer is sufficiently long enough that a desired oxide layer thickness is deposited on the dielectric surface. In some embodiments a thick enough passivation layer is formed over the metal surface such that a sufficiently thick oxide film may be deposited over the dielectric surface using the ALD process without further depositing another passivation film layer, i.e., without fully consuming the initial passivation layer.


In some embodiments, a selective passivation layer deposition and the selective ALD process are performed in an iterative manner, for example such using the process described in FIG. 1B. This iterative process may enable the thickness of the passivation layer to be replenished after the ALD process is performed, therefore allowing subsequent ALD processes to be performed. For example, if the passivation layer is ashed away in 100 cycles or if the incubation on passivation layer is 100 cycles before the deposited oxide begins to form on the passivation layer faster than it can be removed by undercutting, 90 cycles of a first ALD process may be performed to selectively deposit the oxide on the dielectric surface, deposition of a subsequent passivation layer over the previous passivation layer may be performed, and a second 90 cycles of the ALD process may be performed. In some embodiments, this iterative process may be repeated as many times as desired to obtain a desired oxide layer thickness on the dielectric surface. A person of ordinary skill in the art would appreciate that the number of iterative processes necessary would vary depending on a number of factors such as, for example, the thickness of the deposited oxide desired, the thickness of the passivation layer, and the ash rate or incubation period of the passivation layer.


In some embodiments, the PEALD deposition may be carried out essentially as described above. In other embodiments, the substrate is alternately and sequentially contacted with a first reactant comprising elements to be included in the deposited material, such as a metal or silicon, and a second reactant comprising oxygen, and a second plasma reactant. In some embodiments the second plasma reactant does not comprise oxygen species. In some embodiments no reactants comprising oxygen species are used other than the second reactant. The plasma and precursors (i.e. the first and second reactants) may be provided in pulses separated by a removal process (e.g., purge) in which excess reactant and reaction byproducts, if any, are removed from the reaction space. In some embodiments, a PEALD deposition process begins with the plasma pulse followed by the precursors, and the reaction sequence, or deposition cycle, may be repeated a desired number of times (A):

A×(plasma pulse/purge/precursors/purge)


In some embodiments the deposition cycle begins with the non-plasma precursors, which is then followed by the plasma pulse.


According to some embodiments, PEALD processes utilized may be any suitable oxygen based plasma processes. In some embodiments, the deposited dielectric film is an oxide film. In some embodiments, the deposited dielectric film is a metal oxide film. In some embodiments, the deposited dielectric film may be selected from the group consisting of SiO2, TiO2, ZrO2, HfO2, Nb2O5, Ta2O5, WO3 and NiO. In some embodiments, the deposited dielectric film is silicon oxide. In some embodiments, an oxide precursor is an alkylaminosilane, which is used to deposit silicon oxide films.


In some embodiments, an oxide film is selectively formed on a first dielectric surface of a substrate relative to a second, different metal or metallic surface of the substrate by an oxygen-based PEALD process. For example, silicon oxide may be selectively deposited by oxygen-based PEALD on a low-k dielectric surface (e.g., silicon oxide-based surface) relative to a metal surface.



FIG. 3 shows a schematic of some embodiments, wherein a substrate 302 comprises a first surface of a first structure 304 (for example, a dielectric surface of a dielectric layer) and a second surface of a second structure 306 that has a different material composition (for example, a metal surface of a metal layer, such as a cobalt, copper or tungsten surface) further comprising an initial passivation layer 308A having a first thickness (for example, 20 nm of a polyimide organic layer), in which a material 312 is selectively deposited on the first surface relative to the second surface (due to selectively relative to the overlying initial passivation layer 308A). In some embodiments the selectively deposited material 312 is an oxide material. In some embodiments, the oxide material is a dielectric material. In examples described herein, the dielectric oxide is a film of silicon oxide. As can be seen in FIG. 3, after one or more cycles of a selective deposition process 310 (for example, 500 cycles of an oxygen based PEALD silicon oxide deposition process), the material 312 (for example, 50 nm of SiO) is deposited over the first surface of the first structure 304 and the remaining passivation layer 308B has decreased to a second thickness (for example, 10 nm of a polyimide organic layer). In some embodiments, the selective deposition process halts before all of the initial passivation layer is removed. In some embodiments, after the selective deposition process is completed, the reduced thickness of the remaining passivation layer 308B may be subsequently removed (for example, by ashing) without deposition to expose the second surface of the second structure 306.


In some embodiments, the PEALD process disclosed may accomplish selective formation of silicon oxide or other oxides on dielectric surfaces. In some embodiments, the PEALD process disclosed may accomplish a reduction in the number of steps for forming desired patterns in various device manufacturing process flows, relative to convention patterning processes.


It will be understood by those of skill in the art that numerous and various modifications can be made without departing from the spirit of the present invention. The described features, structures, characteristics and precursors can be combined in any suitable manner. Therefore, it should be clearly understood that the forms of the present invention are illustrative only and are not intended to limit the scope of the present invention. All modifications and changes are intended to fall within the scope of the invention, as defined by the appended claims.

Claims
  • 1. A method of selectively forming a dielectric material on a first surface of a substrate, the method comprising: providing a substrate comprising a first surface and a second surface, wherein the second surface comprises a passivation layer thereover; andconducting a cyclical deposition process to selectively form a dielectric material on the first surface, wherein the cyclical deposition process comprises deposition cycles, wherein at least one deposition cycle of the deposition cycles comprises separately contacting the substrate with a precursor and a reactant to form the dielectric material on the first surface, and wherein passivation of the passivation layer on the second surface is removed during the at least one deposition cycle.
  • 2. The method of claim 1, further comprising depositing additional passivation over the passivation layer between two of the deposition cycles.
  • 3. The method of claim 1, wherein the cyclical deposition process is halted before the second surface is exposed by removal of the passivation of the passivation layer.
  • 4. The method of claim 1, wherein the passivation of the passivation layer on the second surface is removed in each of the deposition cycles of the cyclical deposition process that include contacting the substrate with the reactant.
  • 5. The method of claim 1, further comprising selectively depositing the passivation layer on the second surface relative to the first surface prior to beginning a first deposition cycle of the at least one deposition cycle.
  • 6. The method of claim 1, wherein the dielectric material comprises an oxide film.
  • 7. The method of claim 6, wherein the oxide film is a silicon oxide film.
  • 8. The method of claim 6, wherein the oxide film is a metal oxide film.
  • 9. The method of claim 1, wherein said contacting the substrate with the reactant comprises activating the reactant with plasma.
  • 10. The method of claim 1, wherein the cyclical deposition process is a plasma enhanced atomic layer deposition process.
  • 11. The method of claim 1, wherein the first surface is a dielectric surface and the second surface is a metal surface.
  • 12. The method of claim 11, wherein the metal surface comprises at least one of Co, Cu or W.
  • 13. The method of claim 1, wherein the reactant comprises oxygen.
  • 14. The method of claim 1, wherein the passivation layer comprises a polymer.
  • 15. The method of claim 1, wherein the passivation layer comprises an organic material.
  • 16. The method of claim 1, wherein the at least one deposition cycle begins with contacting the substrate with the reactant before contacting the substrate with the precursor.
  • 17. A plasma enhanced method for selectively forming an oxide material on a dielectric surface of a substrate, the plasma enhanced method comprising: providing a substrate comprising a dielectric surface and a metallic surface, wherein the metallic surface comprises a passivation layer thereover; andconducting deposition cycles to selectively form an oxide material on the dielectric surface, at least one deposition cycle of the deposition cycles comprising separately contacting the substrate with a precursor and a reactant to form the oxide material on the dielectric surface, wherein the reactant comprises oxygen and plasma, and wherein passivation of the passivation layer on the metallic surface is removed by the reactant during the at least one deposition cycle.
  • 18. The plasma enhanced method of claim 17, further comprising depositing passivation material over the metallic surface between a first deposition cycle of the deposition cycles and a last deposition cycle of the deposition cycles.
  • 19. The plasma enhanced method of claim 17, wherein the passivation of the passivation layer is removed in each of the deposition cycles that comprises contacting the substrate with the reactant.
  • 20. The plasma enhanced method of claim 17, wherein the passivation layer comprises a polymer.
CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No. 17/113,383, filed Dec. 7, 2020, which is a continuation of U.S. patent application Ser. No. 16/399,328, filed Apr. 30, 2019, now U.S. Pat. No. 10,872,765, which claims priority to U.S. Provisional Patent Application No. 62/666,039, filed May 2, 2018, the disclosures of each of which are incorporated herein by reference in their entireties for all purposes.

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