Selective metal-on-metal deposition process

Abstract

Methods and reactor systems for selectively depositing a material on a surface of a substrate are disclosed. An exemplary method includes selectively treating a second surface to form a passivation layer on the second surface, and selectively depositing a metal material on a first surface to form a selectively deposited metal.

Description

Technical Field

[0001] This disclosure generally relates to a method for selectively forming a material on a first surface of a substrate relative to a second surface on the substrate. More specifically, this disclosure relates to a method for selectively depositing a material by selectively forming a passivation layer on the surface of the substrate. Background Technology

[0002] Metals, or metallic films or layers, are used in a wide variety of applications. For example, metallic films can be used to form conductive regions or barrier layers. Such metallic films can be used to form various electronic devices, such as semiconductor devices and photovoltaic devices.

[0003] In some device fabrication processes, it may be desirable to form material only on certain areas of a surface. This is typically achieved by depositing a continuous film of material and subsequently patterning the continuous film using photolithography and etching steps. This photolithography and etching process can be time-consuming and expensive. Furthermore, this process may not provide the precision or resolution required for many applications.

[0004] Recently, efforts have been made to develop selective deposition techniques to reduce the number of steps in patterning deposited materials, lower processing costs, and allow for the formation of relatively small selectively deposited material regions. While some selective deposition techniques work relatively well, there is a general expectation to develop improved selective deposition techniques that provide the desired selectivity and properties of the deposited material.

[0005] Any discussion of the problems and solutions described in this section is included in this disclosure for the purpose of providing background information only. This should not be construed as an admission that any or all of the discussions are prior art or known at the time of making this invention. Summary of the Invention

[0006] This summary is provided to introduce some concepts that can be presented in a simplified form. Exemplary concepts are described in more detail in the following detailed description. This summary is not intended to identify key or essential features of the claimed subject matter; nor is it necessarily intended to limit the scope of the claimed subject matter.

[0007] As described in more detail below, various embodiments of this disclosure relate to methods for selectively depositing material on a surface or region of a substrate surface. Examples of this disclosure can be used to selectively deposit metals on a metallic surface relative to a nonmetallic or oxide surface. As a particular example, a method can be used to selectively deposit a metal, such as molybdenum, on a copper surface.

[0008] Exemplary methods include providing a substrate comprising a first surface and a second surface, the first surface comprising copper, performing a pre-deposition process to activate the first surface, selectively treating the second surface to form a passivation layer on the second surface, and selectively depositing a molybdenum material on the first surface to form a selectively deposited molybdenum material. According to examples of these embodiments, the second surface comprises an insulating material, such as an oxide of a metal or quasi-metal. According to aspects of these embodiments, the first surface comprises one or more of copper metal or its oxide. According to another aspect, the method further includes the step of performing a post-deposition process. The post-deposition process may be configured to form the treated molybdenum material and / or remove the passivation layer material from the second surface. Performing the post-deposition process may include forming an activating material by a hydrogen-containing gas. According to another aspect, the step of selectively depositing the molybdenum material includes a cyclic deposition process. For example, the cyclic deposition process may include a pulse providing a reducing agent, a pulse providing a molybdenum precursor, and a provision of hydrogen. The reducing agent may be or include a two-electron donor molecule. The hydrogen provision step may be continuous in one or more cycles of the cyclic deposition process, or may be continuous in the method. According to another example, the pressure in the reaction chamber during hydrogen supply, prior to the pulses providing the reducing agent and the pulses providing the molybdenum precursor, is higher than the pressure in the reaction chamber during the pulses providing the reducing agent and / or higher than the pressure in the reaction chamber during the pulses providing the molybdenum precursor. For example, the pressure in the reaction chamber during hydrogen supply, prior to the pulses providing the reducing agent and the pulses providing the molybdenum precursor, may be at least four times higher than the pressure in the reaction chamber during the pulses providing the reducing agent and / or higher than the pressure in the reaction chamber during the pulses providing the molybdenum precursor. According to another example, the pre-deposition process includes forming an activating material from a hydrogen-containing gas. According to another aspect, selectively treating the second surface includes providing an aminosilane to the reaction chamber.

[0009] According to another embodiment, a reactor system is provided. An exemplary reactor system includes a reaction chamber, a molybdenum precursor source, a reducing agent source, a hydrogen source, at least one passivation layer precursor source, and a controller coupled to the reaction chamber. The controller may be configured to perform a pre-deposition treatment process, selectively treat a second surface to form a passivation layer on the second surface, and selectively deposit molybdenum material on a first surface to form selectively deposited molybdenum material, and / or perform other steps as described herein. The reactor system may include multiple reaction chambers. One or more steps performed by the controller may be performed in one or more of the multiple reaction chambers.

[0010] For the purpose of summarizing the invention and its advantages relative to the prior art, certain objects and advantages of the invention may have been described above. It should be understood, of course, that not all of these objects or advantages may necessarily be achieved according to any particular embodiment of the invention. Therefore, for example, those skilled in the art will recognize that the invention may be embodied or implemented in a manner that achieves or optimizes one or more advantages taught or suggested herein, without necessarily achieving other objects or advantages that may be taught or suggested herein.

[0011] All these embodiments are intended to fall within the scope of this disclosure. Those skilled in the art will readily appreciate these and other embodiments from the following detailed description of certain embodiments with reference to the accompanying drawings. The invention is not limited to any particular embodiment disclosed. Attached Figure Description

[0012] Embodiments of this disclosure can be more fully understood when considered in conjunction with the following illustrative drawings, and by referring to the detailed description and claims.

[0013] Figure 1 A method according to an exemplary embodiment of the present disclosure is shown.

[0014] Figures 2 to 5 The structure formed according to the example of this disclosure is shown.

[0015] Figure 6 A schematic diagram of a reactor system according to an example of this disclosure is shown.

[0016] Figure 7 A schematic diagram of a reactor system with multiple reaction chambers according to an example of this disclosure is shown.

[0017] Figure 8 Another structure based on an example of this disclosure is shown.

[0018] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements may be exaggerated relative to other elements to aid in understanding the embodiments shown in this disclosure. The illustrations presented herein are not necessarily intended to be actual views of any particular material, structure, or system, but are merely representations for describing embodiments of this disclosure. Detailed Implementation

[0019] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific embodiments and / or uses disclosed herein, as well as their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited to the specific embodiments described below.

[0020] As described in more detail below, various embodiments of this disclosure provide methods for selectively depositing material on one surface relative to another surface. The methods described herein can be used to form structures that can be used, for example, to form electronic devices, such as semiconductor devices, microelectromechanical systems (MEMS), photonic devices, etc.

[0021] As used herein, the term substrate can refer to any one or more underlying materials that can be used to form or on which devices, circuits, or films are formed. A substrate may comprise a bulk material, such as silicon (e.g., single-crystal silicon), other group IV materials (e.g., germanium), or other semiconductor materials (e.g., group II-VI or III-V semiconductor materials), and may comprise one or more layers overlying or underlying the bulk material. Furthermore, a substrate may include various features formed within or on at least a portion of the substrate layers, such as recesses, protrusions, etc. For example, a substrate may comprise a semiconductor material. An exemplary substrate includes a first surface of a first material and a second surface of a second material, wherein the first material and the second material are different. As a specific example, the first material and / or the first surface may be or include copper and / or its oxides, and the second material and / or the second surface may be or include an insulating material, such as a dielectric material.

[0022] As used herein, a structure may be or include a substrate as described herein. A structure may include a substrate and one or more layers covering the substrate, such as one or more layers formed by the methods according to this disclosure.

[0023] As used herein, the terms film and / or layer can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers can include two-dimensional materials, three-dimensional materials, nanoparticles, partially or entirely molecular layers, or partially or entirely atomic layers or atomic and / or molecular clusters. A film or layer can consist partially or entirely of a plurality of dispersed atoms on a substrate surface and / or embedded in the substrate and / or embedded in a device fabricated on the substrate. A film or layer can include a material or layer having pinholes and / or isolation islands.

[0024] As used herein, the term metallic surface can refer to a surface that includes metallic components, including but not limited to metal surfaces (e.g., elemental metals or metal alloys), metal oxide surfaces, metal silicide surfaces, metal nitride surfaces, metal carbide surfaces, mixtures thereof, etc. The term metallic surface can also include the surface of a natural oxide of a metallic material.

[0025] As used herein, the term silicon surface or silicon-containing surface may refer to a surface that includes silicon and may include additional elements. Exemplary silicon-containing materials include, for example, silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, silicon carbonitride, and mixtures thereof.

[0026] As used herein, oxide surfaces may include metal oxides or quasi-metal oxides. Exemplary oxide surfaces include silicon oxide, metal oxides, silicon carbide, etc.

[0027] The term cyclic deposition process or cyclic deposition process can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate, and includes processing techniques such as atomic layer deposition (ALD), molecular layer deposition (MLD), cyclic chemical vapor deposition (cyclic CVD), and hybrid cyclic deposition processes including ALD and cyclic CVD components. In some cases, a cyclic deposition process may include continuously flowing one or more precursors, reactants, or inert gases and pulsed other precursors or reactants. The term MLD can refer to a vapor deposition process in which one or more deposition cycles are performed in a processing chamber. Typically, during each cycle, an organic precursor is chemisorbed onto the deposition surface (e.g., the substrate surface or the surface of a previously deposited underlying layer, such as material from a previous MLD cycle), typically forming a monolayer that does not readily react with another organic precursor (i.e., a self-limiting reaction). Subsequently, if desired, another precursor (e.g., another organic precursor) can be subsequently introduced into the processing chamber to form the desired organic material on the deposition surface. In addition, a purging step may be used during each cycle to remove excess organic precursors from the processing chamber and / or remove reaction byproducts from the processing chamber after the desired organic material has been formed.

[0028] As used herein, the term "purge" can refer to the process of supplying an inert or substantially inert gas to a reaction chamber between two potentially interacting gas pulses. For example, a purging process using, for instance, an inert gas (e.g., a rare gas) can be provided between a precursor pulse and a reactant pulse to reduce gas-phase interactions between the precursor and reactant that might otherwise occur. It should be understood that purging can be performed temporally, spatially, or both. For example, in the case of temporal purging, purging steps can be used, for instance, in a temporal sequence of supplying a precursor to the reaction chamber, supplying a purge gas to the reaction chamber, and supplying a reactant or another precursor to the reaction chamber, wherein the substrate on which the deposited layer is located remains stationary. In the case of spatial purging, the purging step can take the form of moving the substrate from (e.g., continuously) a first position supplying the precursor through a purge gas curtain to (e.g., continuously) a second position supplying the reactant or other precursor.

[0029] In this disclosure, "continuous" or "sequential" can refer to a step that does not break the vacuum, is not interrupted as a timeline, does not involve any material intervention, does not change the processing conditions, immediately follows as the next step, or, in some embodiments and depending on the situation, a discrete physical or chemical structure that, apart from the two structures, has no intervention between them.

[0030] Furthermore, in this disclosure, any two numbers of a variable may constitute a feasible range of the variable, and any indicated range may include or exclude endpoints. Additionally, any value of the indicated variable (whether or not it is indicated by the term "approx.") may refer to an exact value or an approximation and include equivalents, and may refer to an average, median, representative value, multi-value, etc. For example, the term "approx." may refer to + / - 20%, 10%, 5%, 2%, or 1% of a value. In some embodiments, the terms "comprising," "including," "consisting of," and "having" independently mean generally or broadly comprising, including, substantially consisting of, or consisting of in some embodiments. In this disclosure, the meaning of any definition does not necessarily exclude the common and customary meanings in some embodiments.

[0031] Although numerous exemplary materials are given throughout the embodiments of this disclosure, it should be noted that the chemical formulas given for each exemplary material should not be construed as limiting, and the non-limiting exemplary materials given should not be limited by the given exemplary stoichiometry.

[0032] As described above, various examples of this disclosure relate to the selective formation of material on one surface relative to another surface. The selectivity of forming or depositing material can refer to a relatively high amount of material formed or deposited on a surface relative to another surface. For example, the selectivity of deposition on surface A relative to surface B can be given as a percentage calculated as [(deposition on surface A) - (deposition on surface B)] / (deposition on surface A). Deposition can be measured in any of a variety of ways. For example, deposition can be given as a measured thickness of the deposited material or as a measured amount of the deposited material (e.g., weight).

[0033] As described in more detail below, in the embodiments described herein, selective deposition of the passivation layer may be performed on the second surface (B) relative to the first surface (A). Subsequently, a first material may be selectively deposited on the first surface (A) relative to the passivation layer (B). In some embodiments, the selectivity is greater than about 10%, or greater than about 50%, or greater than about 75%, or greater than about 85%, or greater than about 90%, or greater than about 93%, or greater than about 95%, or greater than about 98%, or greater than about 99%, or even greater than about 99.5%.

[0034] In some embodiments, deposition occurs only on one surface and not on the other. It should be understood that a partially selective process can produce a fully selective structure, for example, through post-deposition treatment.

[0035] Now turn to the attached image. Figure 1A method 100 for selectively depositing material on the surface of a substrate according to an embodiment of the present disclosure is shown. The method 100 includes the steps of: providing a substrate 102 in a reactor reaction chamber, performing a pre-deposition process 104, selectively treating (passivating) a second surface 106, selectively depositing molybdenum material 108, and (optionally) performing a post-deposition process 110.

[0036] During step 102, a substrate is provided in the reaction chamber. The reaction chamber may be a stand-alone reaction chamber or part of a cluster tool, such as the cluster tool described in more detail below. The reaction chamber may include a substrate heater to heat the substrate to the temperatures described herein. Alternatively or additionally, the reaction chamber may include rapid thermal processing equipment (such as a lamp) to heat the substrate.

[0037] The reaction chamber may be configured to perform all or some of the steps of method 100. In some embodiments of this disclosure, the first reaction chamber may be configured to perform one or more steps of method 100, and additional reaction chambers may be used for other steps of method 100. However, in other embodiments of this disclosure, the first reaction chamber may be configured to perform all steps of method 100.

[0038] Reactors and associated reaction chambers capable of performing one or more steps of method 100 include atomic / molecular layer deposition (ALD / MLD) reaction chambers, plasma-enhanced atomic layer deposition (PEALD) reaction chambers, and chemical vapor deposition (CVD) reaction chambers, equipped with suitable devices and means for providing precursors. According to some embodiments, a spray-head reaction chamber may be used. According to some embodiments, a plasma reaction chamber, such as a PEALD reaction chamber, may be used. In such embodiments, the plasma may be direct, remote, or near the substrate. In some embodiments, the reactor is a spatial ALD reactor, wherein the substrate moves or rotates during processing. In some cases, the reactor is a thermal reactor.

[0039] In some embodiments, a batch reactor may be used. In some embodiments, a vertical batch reactor is utilized, wherein the boats rotate during processing. For example, a vertical batch reactor may include a reaction chamber and a lift configured and arranged to move boats configured to support a batch of 10 to 200 substrates into or out of the reaction chamber.

[0040] In other embodiments, the batch reactor comprises a small batch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 wafers. In some embodiments where a batch reactor is used, the inter-wafer non-uniformity is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

[0041] Method 100 can optionally be carried out in a reactor and associated reaction chambers forming a cluster tool. In a cluster tool, each reaction chamber can be dedicated to a single type of process, such that the temperature of the reaction chamber in each module can be kept constant, which can increase throughput compared to reaction chambers where the substrate is heated to the processing temperature before each run. Additionally, in a cluster tool, the time required to pump the reaction space to the desired processing pressure level between substrates can be reduced. In some embodiments of this disclosure, the stand-alone reactor can be equipped with a loading lock. In this case, cooling the reaction space between runs may not be necessary.

[0042] Figure 2 A substrate 200 that can be supplied during step 102 is shown. The substrate 200 supplied during step 102 may include a first surface 202 and a second surface 204. The first surface 202 may include a first material 206, and the second surface 204 may include a second material 208 different from the first material 206. For example, the first surface 202 may be or include a metal, such as copper. In some cases, the first material 206 or the first surface 202 is a metallic surface. In some cases, the first surface may include multiple metallic materials. For example, the first surface may include a pad or barrier layer material and a filler material, such as a metal (e.g., copper) or a metal alloy.

[0043] The second surface 204 and / or the second material 208 may be or include silicon. For example, the second surface 204 may be or include silicon, a silicon surface having a natural oxide (also in the form of silicon oxide) formed thereon, SiCHO, SiO x The second surface and / or the second material may be, or may include, an insulating material, such as a dielectric material. The dielectric material may be a material with a relatively low dielectric constant, such as silicon oxide, or a material with a high dielectric constant, such as (e.g., transition) metal oxides, such as hafnium oxide.

[0044] Once the substrate is loaded into the appropriate reaction chamber, it can be heated to a suitable temperature, for example, for degassing or for subsequent step 104. For instance, the substrate can be heated to a temperature of about 150°C to about 250°C or about 250°C to about 400°C. During step 102, the pressure within the reaction chamber can be between about 100 mTorr and 1 Torr, or between 200 mTorr and 800 mTorr.

[0045] During step 104, a pre-deposition process for activating the first surface is performed. The pre-deposition process step 104 may include, for example, exposing the surface of the substrate to a hydrogen-containing gas. For example, step 104 may include forming an activating material from the hydrogen-containing gas. The hydrogen-containing gas may be or include hydrogen (H2). The hydrogen-containing gas may be provided alone or in combination with another gas (e.g., a purge gas or a carrier gas). In some cases, the hydrogen-containing gas may be provided to the reaction chamber along with an inert gas such as argon. According to an example, a nitrogen-containing gas is not provided to the reaction chamber during step 104. According to another example, the activating material provided during step 104 may be formed using direct, indirect, or remote plasma. In some cases, remote or indirect plasma may be preferred. The temperature during step 104 may be as described above in conjunction with step 102. The pressure within the reaction chamber during step 104 may be between about 1 and about 5 Torr or between about 5 and about 10 Torr.

[0046] During step 106, the second surface is selectively processed to form a passivation layer on the second surface. Figure 3 The structure 300 is shown, including a passivation layer 302 covering the second surface 204.

[0047] According to examples of this disclosure, the passivating material is or includes a polymer or small molecule inhibitor. According to further examples, the passivating material is or includes an organic material.

[0048] Various precursors and reactants can be used to deposit passivating materials. Exemplary passivating material precursors and / or reactants include polyimide precursors, SAM precursors, small molecule inhibitor precursors, and regioselective deposition precursors. In some cases, passivating materials are selectively deposited using passivating material precursors (e.g., small molecule inhibitor precursors).

[0049] Exemplary small molecule inhibitor precursors include silylating agents and / or aminosilanes. The silylating agents / aminosilanes according to this disclosure can be provided in the gas phase. In some embodiments, the silylating agents / aminosilanes include one or more of the following: (N,N-dimethylamino)trimethylsilane, allyltrimethylsilane, bis(dimethylamino)dimethylsilane, bis(dimethylamino)diethylsilane, halosilanes such as trimethylchlorosilane or octadecyltrichlorosilane, imidazoles such as N-(trimethylsilyl)imidazolium, silazanes such as hexamethyldisilazane, silylamines such as N-(trimethylsilyl)dimethylamine or 1,1,1-trimethoxy-N,N-dimethylsilaneamine, or pyrroles such as 1-(triisopropylsilyl)pyrrole. The substrate can be contacted with a sufficient amount of passivating agent for a sufficient duration such that the top surface is selectively blocked by the silicon material.

[0050] During step 106, the temperature inside the reaction chamber may be between about 100°C and about 200°C, or between about 200°C and about 400°C. The pressure inside the reaction chamber may be between about 0 Torr and about 5 Torr, or between about 5 Torr and about 20 Torr.

[0051] The thickness of the passivation layer (e.g., passivation layer 302) on the second surface 204 can be between about 0.1 nm and about 2.5 nm, or between about 2.5 nm and about 7.5 nm. The selectivity of the first material deposited on the second surface relative to the first surface can be as described above.

[0052] During step 108, a metal, such as molybdenum, is selectively deposited on the first surface 202. Figure 4 Structure 400 is shown, which includes a metallic material (e.g., molybdenum) 402 formed to cover the first material 206.

[0053] Step 108, which involves selectively depositing molybdenum material on a first surface relative to a second surface, may include a cyclic deposition process. Step 108 may include providing a metal precursor, providing a reducing agent, and providing hydrogen (H2). These steps may be separated by a purging step. In some cases, the cyclic deposition process includes a pulse providing a reducing agent, a pulse providing a molybdenum precursor, and providing hydrogen, wherein the reducing agent is different from hydrogen. The duration of the pulse may be, for example, between about 0.5 ms and about 60 seconds or between about 0.5 ms and about 10 seconds. In some cases, hydrogen may also be pulsed into the reaction chamber. For example, hydrogen may be pulsed between the pulse providing the molybdenum precursor and the pulse providing the reducing agent. In some cases, the hydrogen providing step is continuous in one or more cycles of the cyclic deposition process—for example, in one or more (e.g., all) of steps 104-110. In some cases, step 108 includes, in the following order: providing hydrogen, a pulse providing a reducing agent, a first purging, a pulse providing the molybdenum precursor, and a second purging. As described above, hydrogen may be continuously provided in at least one cycle (e.g., all cycles of method 100 and / or one or more (e.g., all) steps) and stopped after the second purging. According to another example, at least one cyclic or cyclic deposition process includes providing hydrogen before the pulse providing the reducing agent and the pulse providing the molybdenum precursor.

[0054] According to another example, the pressure within the reaction chamber can be varied to obtain deposited molybdenum with desired properties. For example, the pressure within the reaction chamber during hydrogen supply, prior to the pulses providing the reducing agent and the pulses providing the molybdenum precursor, can be higher than the pressure within the reaction chamber during the pulses providing the reducing agent and / or higher than the pressure within the reaction chamber during the pulses providing the molybdenum precursor. In some cases, the pressure within the reaction chamber during hydrogen supply, prior to the pulses providing the reducing agent and the pulses providing the molybdenum precursor, can be at least four times higher than the pressure within the reaction chamber during the pulses providing the reducing agent and / or higher than the pressure within the reaction chamber during the pulses providing the molybdenum precursor.

[0055] Suitable exemplary metal precursors for use in step 108 include a metal and one or more ligands. For example, the ligand may include one or more of the following: alkyl, alkoxide, diketide, acetamidine, formamidinide, guanidine, amide, alkoxyamine, aryl, cyclopentadienyl, and halogen. Specific exemplary metal precursors include metal halides and metal oxide halides, such as one or more of molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), molybdenum trichloride (V) (MoOCl3), molybdenum tetrachloride (VI) (MoOCl4), and / or molybdenum dichloride (IV) (MoO2Cl2).

[0056] Exemplary reducing agents suitable for use during step 108 include molecules containing a two-electron donor or a two-electron donor molecule. In some cases, the reducing agent contains a molecule having a cyclic structure. In some cases, the reducing agent contains cyclohexadiene. In some cases, the reducing agent (e.g., a cyclic structure) includes at least one C1-C4 alkyl group thereon. In some cases, the reducing agent (e.g., a cyclic structure) includes one or more—e.g., two or more (e.g., C1-C4) alkylsilyl groups, such as trimethylsilyl. In some cases, the reducing agent includes a molecule containing two or more C-C double bonds and one or more alkylsilyl groups. As a specific example, the reducing agent is or includes 1-methyl-2,5-di-trimethylsilylcyclohex-1,4-diene. After the selective molybdenum deposition step 108, the passivation step 106 can be repeated to allow for the reapplication of the passivation material.

[0057] During the post-deposition processing step 110, the treated molybdenum material can be formed and the passivation layer material can be removed from the second surface. Figure 5 The structure 500 with the passivation layer material removed is shown. Figure 8 Another structure 800 is shown, which includes (e.g., treated) molybdenum 802 selectively formed on a first surface 804, the first surface 804 including a barrier layer or liner layer 806 (e.g., a metal nitride, such as TiN, TaN, MoN, Ru) and a bulk metallic surface 808 (e.g., copper). Surface 810 can be any second surface material described herein.

[0058] Similar to step 104, post-deposition processing step 110 may include exposing the surface of the substrate to a hydrogen-containing gas. For example, step 110 may include forming an activating material from the hydrogen-containing gas. The hydrogen-containing gas may be or include hydrogen (H2). The hydrogen-containing gas may be provided alone or in combination with another gas (e.g., a purge gas or a carrier gas). In some cases, the hydrogen-containing gas may be provided to the reaction chamber along with an inert gas such as argon. According to another example, the activating material provided during step 110 may be formed using direct, indirect, or remote plasma. In some cases, remote or indirect plasma may be preferred. The temperature and pressure within the reaction chamber during step 110 may be as described above in conjunction with step 104.

[0059] Now for reference Figure 6 In various examples, reactor system 600 includes a reaction chamber 604, a base 606 for holding substrate 630 during processing, a gas distribution system 608 (e.g., spray nozzles) for distributing one or more precursors and / or reactants to the surface of substrate 630, one or more precursor or reactant sources 610, 612, and / or 613, and / or carrier gas and / or purge gas source 614, fluidly coupled to reaction chamber 604 via corresponding lines 616, 618, 619, and 620 and corresponding valves or controllers 622, 623, 625, and 626. Substrate 630 may include a substrate or structure as described herein. Purge gas / carrier gas 624 from gas source 614 may flow to and through reaction chamber 604 to act as a carrier gas, and / or purge or remove any excess reactants or other unwanted materials from reaction chamber 604. Sources 610, 612, and 613 may include containers and precursors or reactants as described herein. For example, source 610 may include a container and a metal precursor 615; source 612 may include a container and hydrogen 617; source 613 may include a container and a reducing agent 621. Reactor system 600 may include other sources. Reactor system 600 may also include a vacuum source 628 fluidly coupled to reaction chamber 604. Vacuum source 628 may be configured to evacuate reactants, purge gases, or other materials from reaction chamber 604.

[0060] The reactor system 600 also includes a controller 652. The controller 652 can be configured to perform various functions and / or steps as described herein. The controller 652 may include one or more microprocessors, memory elements, and / or switching elements to perform various functions. Although shown as a single unit, the controller 652 may alternatively include multiple devices. The controller 652 can be used to control airflow (e.g., by monitoring flow and controlling valves 622, 623, 625, and / or 626), motors, heaters, cooling devices, and / or vacuum sources 628 to perform various processes (e.g., method 100). Furthermore, when the system includes two or more reaction chambers, as described in more detail below, the two or more reaction chambers may be coupled to the same / shared controller.

[0061] Figure 7 A reactor system 700 is shown comprising multiple reaction chambers 702-708, each reaction chamber being... Figure 6 An example of reaction chamber 604 is provided. Reaction chambers 702-708 may be disposed around and / or coupled to transfer chamber 710, which includes a transfer tool 712 for transferring a substrate between reaction chambers 702-708 and load-locking chamber 714, and between reaction chambers 702-708 (e.g., through transfer chamber 710). For example, substrate 630 may be disposed in different chambers for different steps of the methods described herein. For example, one of reaction chambers 702-708 may be used to form a passivation layer as described herein, another of reaction chambers 702-708 may be used to selectively deposit molybdenum, another of reaction chambers 702-708 may be used for pretreatment, and another of reaction chambers 702-708 may be used for post-treatment as described herein. Other configurations are also possible, such that one or more steps of method 100 or 800 are performed in a single reaction chamber.

[0062] The exemplary embodiments described above do not limit the scope of the invention, as these embodiments are merely examples of embodiments of the invention, the scope of which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to fall within the scope of the invention. In fact, various modifications to this disclosure, such as alternative useful combinations of the described elements, in addition to those shown and described herein, will become apparent to those skilled in the art from the description. These modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for selectively depositing a material on the surface of a substrate, the method comprising the steps of: A substrate is provided, the substrate including a first surface and a second surface, the first surface including copper; Perform a pre-deposition process to activate the first surface; The second surface is selectively treated to form a passivation layer on the second surface; as well as Molybdenum material is selectively deposited on the first surface to form selectively deposited molybdenum material.

2. The method according to claim 1, wherein, The first surface comprises one or more of copper metal or its oxides.

3. The method of claim 1, further comprising the steps of performing a post-deposition processing procedure to form a treated molybdenum material and removing the passivation layer material from the second surface.

4. The method according to claim 3, wherein, The post-deposition treatment process includes the formation of an activating substance from hydrogen-containing gas.

5. The method according to claim 1, wherein, The selective deposition of molybdenum materials involves a cyclic deposition process.

6. The method according to claim 5, wherein, At least one cycle of the cyclic deposition process includes: A pulse that provides the reducing agent; Provides pulses for molybdenum precursors; and Provides hydrogen.

7. The method according to claim 6, wherein, The molybdenum precursor includes one or more of the following: molybdenum tetrachloride (MoCl4), molybdenum pentachloride (MoCl5), molybdenum trichloride (V) (MoOCl3), molybdenum tetrachloride (VI) (MoOCl4), or molybdenum dichloride (IV) (MoO2Cl2).

8. The method according to claim 6, wherein, The reducing agent includes a two-electron-donor molecule.

9. The method according to claim 6, wherein, The reducing agent has a cyclic structure.

10. The method according to claim 6, wherein, The reducing agent comprises a molecule containing two or more C-C double bonds and one or more alkylsilyl groups.

11. The method according to claim 6, wherein, The reducing agent includes 1-methyl-2,5-di-trimethylsilylcyclohexyl-1,4-diene.

12. The method according to claim 6, wherein, The hydrogen supply step is continuous in one or more cycles of the cyclic deposition process.

13. The method according to claim 6, wherein, The at least one cycle includes providing hydrogen before the pulse providing the reducing agent and the pulse providing the molybdenum precursor.

14. The method according to claim 13, wherein, The pressure in the reaction chamber during hydrogen supply is higher than the pressure during the pulse of reducing agent supply and higher than the pressure during the pulse of molybdenum precursor supply, both before the pulse of reducing agent supply and the pulse of molybdenum precursor supply.

15. The method according to claim 14, wherein, The pressure in the reaction chamber during hydrogen supply is at least four times higher than the pressure during the pulse of reducing agent supply and the pressure during the pulse of molybdenum precursor supply, both before the pulse of reducing agent supply and the pulse of molybdenum precursor supply.

16. The method according to claim 6, wherein, The at least one cycle comprises, in the following order: Provide hydrogen; A pulse that provides the reducing agent; First purging; Provides pulses for molybdenum precursors; and Second purging.

17. The method according to claim 16, wherein, The supply of hydrogen is continuous in the at least one cycle and stops after the second purging.

18. The method according to claim 1, wherein, The pre-deposition process includes the formation of an activating substance from hydrogen-containing gas.

19. The method according to claim 1, wherein, Selectively treating the second surface includes supplying an aminosilane to the reaction chamber.

20. The method according to claim 1, wherein, The second surface includes an insulating material.

Images