Catalyst-enhanced chemical vapor deposition

Abstract

1. A method for processing a substrate, the method comprising: treating the substrate with a halogen-containing catalyst, the substrate comprising a semiconductor layer, a dielectric layer disposed on the semiconductor layer, a recess formed in the dielectric layer, and a layer of a first metal disposed between the dielectric layer and the semiconductor layer, the layer of the first metal being at a bottom of the recess; and treating the substrate with a molecular inhibitor (MI) after treating the substrate with the halogen-containing catalyst, the MI coating sidewalls of the dielectric layer in the recess; and depositing a second metal on the modified surface of the layer of first metal in the recess, the MI coating the sidewalls preventing deposition of the second metal on the dielectric layer.

Description

[Technical Field]

[0001] This application claims priority to and the benefit of the filing date of U.S. Non-Provisional Patent Application No. 18 / 145,582, filed December 22, 2022, which is incorporated herein by reference in its entirety.

[0002] The present invention relates generally to methods for processing substrates, and in particular embodiments to catalyst-enhanced chemical vapor deposition. [Background technology]

[0003] Generally, semiconductor devices such as integrated circuits (ICs) are fabricated by sequentially depositing and patterning layers of dielectric, conductive, and semiconducting materials on a substrate to form a network of electronic components and interconnect elements (e.g., transistors, resistors, capacitors, metal lines, contacts, and vias) integrated into a monolithic structure. Scaling efforts to increase the number of interconnect elements per unit area face greater challenges as scaling enters nanometer-scale semiconductor device manufacturing nodes. Thus, there is a demand for three-dimensional (3D) semiconductor devices in which transistors are stacked on top of each other.

[0004] As device structures become denser and vertically evolving, the demand for precise material processing, for example during deposition and patterning, is becoming stronger. Therefore, various deposition techniques, such as chemical vapor deposition (CVD), physical vapor deposition (PVD), and atomic layer deposition (ALD), require further innovation to provide sufficient deposition rate, profile control, film conformality, and film quality, among others. Summary of the Invention [Means for solving the problem]

[0005] According to one embodiment of the present invention, a method for processing a substrate includes treating the substrate with a halogen-containing catalyst, the substrate comprising a semiconductor layer, a dielectric layer disposed on the semiconductor layer, a recess formed in the dielectric layer, and a layer of a first metal disposed between the dielectric layer and the semiconductor layer, the layer of the first metal being at a bottom of the recess, the halogen-containing catalyst modifying a surface of the layer of the first metal; and after treating the substrate with the halogen-containing catalyst, treating the substrate with a molecular inhibitor (MI), the MI coating sidewalls of the dielectric layer in the recess; and depositing a second metal on the modified surface of the layer of first metal in the recess, the MI coating the sidewalls preventing deposition of the second metal on the dielectric layer.

[0006] According to one embodiment of the present invention, a method for processing a substrate includes performing a cyclical chemical vapor deposition (CVD) process to fill a portion of a recess, the substrate including a dielectric layer having a recess and a first metal layer at a bottom of the recess, one cycle of the cyclical CVD process including treating the substrate with a halogen-containing catalyst, the halogen-containing catalyst modifying a surface of a second metal formed on the first metal layer; after treating the substrate with the halogen-containing catalyst, treating the substrate with a molecular inhibitor (MI), the MI coating sidewalls of the dielectric layer in the recess; and depositing the second metal on the first metal layer in the recess, the MI coating the sidewalls preventing deposition of the second metal on the dielectric layer.

[0007] According to one embodiment of the present invention, there is provided a method for processing a substrate, the method comprising: exposing the substrate to a first vapor comprising a halogen-containing catalyst, the substrate comprising a dielectric surface and a first metal surface, the halogen-containing catalyst modifying a surface of the first metal surface; exposing the substrate to a second vapor comprising a molecular inhibitor (MI), the MI selectively adsorbing on the dielectric surface; and selectively depositing a second metal on the modified surface of the first metal surface by chemical vapor deposition (CVD), the deposition rate on the modified surface of the first metal surface being at least 100 times greater than the deposition rate on the MI on the dielectric surface.

[0008] For a more complete understanding of the present invention, and the advantages thereof, reference should be made to the following descriptions taken in conjunction with the accompanying drawings, in which: [Brief explanation of the drawings]

[0009] [Figure 1A] 1A-1C illustrate cross-sectional views of a substrate at various stages of a chemical vapor deposition (CVD) process according to various embodiments, with FIG. 1A showing an incoming substrate comprising a first metal layer and a dielectric layer having recessed features. [Figure 1B] 1A-1C illustrate cross-sectional views of a substrate at various stages of a chemical vapor deposition (CVD) process according to various embodiments, with FIG. 1B showing the substrate after pre-treatment to expose a first metal layer. [Figure 1C] 1A-1D illustrate cross-sectional views of a substrate at various stages of a chemical vapor deposition (CVD) process according to various embodiments. [Figure 1D] 1A-1D illustrate cross-sectional views of a substrate at various stages of a chemical vapor deposition (CVD) process according to various embodiments. [Figure 1E] 1A-1D illustrate cross-sectional views of a substrate at various stages of a chemical vapor deposition (CVD) process according to various embodiments. [Figure 1F] 1A-1D illustrate cross-sectional views of a substrate at various stages of a chemical vapor deposition (CVD) process according to various embodiments. [Figure 1G]1A-1G show cross-sectional views of a substrate at various stages of a chemical vapor deposition (CVD) process according to various embodiments, with FIG. 1G showing the substrate after a second treatment with MI followed by a second treatment with a catalyst. [Figure 1H] 1A-1H show cross-sectional views of a substrate at various stages of a chemical vapor deposition (CVD) process according to various embodiments, with FIG. 1H showing the substrate after a cycle of the CVD process filling the recesses with a second metal. [Figure 2A] FIG. 2A shows a schematic representation of the stepwise area-selective surface modification of a catalyst-enhanced CVD process according to one embodiment, with FIG. 2A illustrating the selective adsorption of a catalyst onto a metal. [Figure 2B] FIG. 2B shows a schematic representation of stepwise area-selective surface modification of a catalyst-enhanced CVD process according to one embodiment, with FIG. 2B showing the selective adsorption of a molecular inhibitor (MI) onto silicon oxide. [Figure 2C] 2A-2C show schematic diagrams of stepwise area-selective surface modification of a catalyst-enhanced CVD process according to one embodiment, with FIG. 2C showing selective metal-on-metal deposition. [Figure 3A] 3A-3D illustrate process flow diagrams of methods for chemical vapor deposition (CVD) processes according to various embodiments, with FIG. 3A illustrating one embodiment. [Figure 3B] 3A-3C illustrate process flow diagrams of methods for chemical vapor deposition (CVD) processes according to various embodiments, with FIG. 3B illustrating another embodiment. [Figure 3C] 3A-3C illustrate process flow diagrams of methods of chemical vapor deposition (CVD) processes according to various embodiments, with FIG. 3C illustrating yet another embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0010] This application relates to methods for processing substrates, and more particularly, to catalyst-enhanced chemical vapor deposition (CVD) for conductive materials. Generally, conductive materials are used in semiconductor devices to enable electrical connections between various components. While copper (Cu) has been used for interconnects in integrated circuits (ICs) for decades, new conductive materials with lower electrical resistivity (e.g., Ru, Co, and W) are being tested as excellent candidates for applications such as sub-10 nm node middle-of-line (MOL) and back-of-line (BEOL) logic interconnects. Furthermore, unlike Cu, some of these new conductive materials may not require a diffusion barrier layer, which advantageously simplifies the manufacturing process. However, depositing and patterning these metal materials with sufficient selectivity for high aspect ratio (HAR) features at small scales has been challenging. Bottom-up selective metal deposition is desired to fill high HAR recesses without voids or pinch-off issues. One solution is to use molecular inhibitors during the deposition process, which may preferentially deposit metal on metal surfaces compared to, for example, inhibitor-covered dielectric surfaces. However, inhibitors may also adsorb to metal surfaces, causing impurity problems and slowing the metal deposition rate. Therefore, new methods for metal deposition with improved deposition rates may be desirable.

[0011] Embodiments of the present application disclose a catalyst-enhanced chemical vapor deposition (CVD) method using a halogen-containing catalyst and a molecular inhibitor. In various embodiments, the catalyst-enhanced CVD method may be applied to selectively deposit a second conductive material on a first conductive material to fabricate interconnects within an IC. For example, selective bottom-up filling of recesses may be possible, where deposition occurs preferentially on the surface of the first conductive material, while unwanted deposition on the dielectric material may be suppressed. In various embodiments, the catalyst-enhanced CVD method may include three steps: (1) treating the first conductive material surface with a halogen-containing catalyst (e.g., I2, CH3I, or C2H5I); (2) treating the dielectric surface with a molecular inhibitor (MI); and (3) selectively depositing the second conductive material on the first conductive material surface. The catalyst protects the first conductive material surface from unwanted MI deposition and also catalyzes a surface reaction that promotes CVD of the second conductive material. As a result, the disclosed method may advantageously improve overall deposition rates. In various embodiments, the method of catalyst-enhanced CVD may be applied as a cyclic process to fill high aspect ratio (HAR) features.

[0012] The methods described in this disclosure may be particularly advantageous for manufacturing processes for sub-15 nm node middle-of-line (MOL) and back-end-of-line (BEOL) logic interconnects and may enable the use of new metal materials such as Ru, Mo, Nb, and W for these applications. Although various embodiments of the methods are primarily described in this disclosure as CVD of metals, the methods may also be applied in other processes, such as atomic layer deposition (ALD), deposition of two or more metals or other conductive materials (e.g., metal nitrides).

[0013] Catalyst-enhanced CVD steps are described below with reference to Figures 1A-1H and Figures 2A-2C according to various embodiments. Exemplary process flow diagrams are shown in Figures 3A-3C. All figures in this disclosure are for illustrative purposes only and are not to scale, including aspect ratios of features.

[0014] 1A-1H show cross-sectional views of a substrate 100 at various stages of catalyst-enhanced CVD according to various embodiments. The selective surface modification of the catalyst-enhanced CVD process is further illustrated schematically in FIGS. 2A-2C, which are described in conjunction with FIGS. 1C-1E, respectively.

[0015] 1A shows a cross-sectional view of an incoming substrate 100. In various embodiments, the substrate 100 may be part of or include a semiconductor device, e.g., may have undergone several processing steps following conventional processing. Thus, the substrate 100 may comprise layers of semiconductors useful in various microelectronics. For example, a semiconductor structure may comprise the substrate 100 upon which various device regions are formed.

[0016] In one or more embodiments, substrate 100 may be a silicon wafer or a silicon-on-insulator (SOI) wafer. In certain embodiments, substrate 100 may comprise a silicon germanium wafer, a silicon carbide wafer, a gallium arsenide wafer, a gallium nitride wafer, or other compound semiconductor. In other embodiments, substrate 100 comprises a heterogeneous layer, such as silicon germanium-on-silicon, gallium nitride-on-silicon, or silicon carbon-on-silicon, as well as a silicon-on-silicon layer or an SOI substrate. In various embodiments, substrate 100 is patterned or embedded with other components of a semiconductor device.

[0017] 1A, the substrate 100 may include a recess 115 formed in the dielectric layer 110. In one particular embodiment, the substrate 100 may further include an etch stop layer 120 as the bottom layer of the dielectric layer 110 and a first metal layer 130 at the bottom of the recess 115. As shown in FIG. 1A, in one or more embodiments, a surface oxide layer 135 may be present on the surface of the first metal layer 130.

[0018] In various embodiments, dielectric layer 110 may comprise any other suitable dielectric material, including silicon oxide, a low-k material such as fluorinated silicon glass (FSG), a carbon-doped oxide, a polymer, a SiCOH-containing low-k material, a non-porous low-k material, a porous low-k material, a CVD low-k material, a spin-on dielectric (SOD) low-k material, or a high-k material. In certain embodiments, the critical dimension (CD) of recess 115 may be between about 10 nm and about 65 nm for via-based structures, or in other embodiments, between about 10 nm and about 100 nm for trench-based structures. In one or more embodiments, the depth of recess 115 may be between about 40 nm and about 80 nm for single damascene structures, or between about 80 nm and about 150 nm for dual damascene structures. In various embodiments, recess 115 may have an aspect ratio between about 4 and about 8 for single damascene structures, or between about 6 and about 10 for dual damascene structures.

[0019] The first metal layer 130 may include a low-resistivity metal such as copper (Cu), ruthenium (Ru), cobalt (Co), molybdenum (Mo), or tungsten (W). Although not shown in Figure 1A, in certain embodiments, the first metal layer 130 may comprise two or more stacked conductive layers. Examples of stacked conductive layers include Co metal on Cu metal (Co / Cu) and Ru metal on Cu metal (Ru / Cu).

[0020] ESL 120 may comprise a dielectric material such as silicon nitride, silicon oxynitride, silicon carbide, or silicon carbonitride. ESL 120 may be deposited using deposition techniques such as vapor deposition, including chemical vapor deposition (CVD), physical vapor deposition (PVD), and atomic layer deposition (ALD), as well as other plasma processes, such as plasma enhanced chemical vapor deposition (PECVD), sputtering, and other processes. In certain embodiments, the thickness of ESL 120 may be between 2 nm and 5 nm.

[0021] FIG. 1B shows a cross-sectional view of the substrate 100 after pre-treatment to expose the first metal layer 130 .

[0022] In various embodiments, prior to treatment with a molecular inhibitor for selective metal deposition, a pretreatment may be performed to remove the surface oxide layer 135 and expose the first metal layer 130. The pretreatment may include, for example, treating the surface oxide layer 135 with a plasma containing dihydrogen (H). In other embodiments, the pretreatment may be omitted if the substrate 100 does not already have a surface oxide present.

[0023] FIG. 1C shows a cross-sectional view of the substrate after treatment with a catalyst.

[0024] FIG. 2A illustrates the selective adsorption of a catalyst onto a metal according to one embodiment.

[0025] In FIG. 1C, the substrate 100 may be treated with a catalyst to selectively coat the exposed surface of the first metal layer 130, resulting in a modified first metal surface 140. In one embodiment, as shown in FIG. 2A, the catalyst may selectively adsorb metal only onto a dielectric surface, such as silicon oxide. With the catalyst coating the first metal layer 130, a subsequent step with a molecular inhibitor may advantageously selectively adsorb onto the dielectric layer 110. In various embodiments, the catalyst may be delivered to the substrate 100 as a vapor diluted in a noble or inert carrier gas (e.g., Ar or N), where a substrate temperature near room temperature in the microchip fabrication atmosphere (air) may be maintained. In one embodiment, this exposure to the catalyst may be carried out for 1 to 120 seconds using a heating stage or temperature ramping technique.

[0026] In various embodiments, the catalyst may comprise a halogen, and in certain embodiments, the halogen-containing catalyst may comprise an iodine (I) or bromine (Br) compound, such as an alkyl halide. In one or more embodiments, the halogen-containing catalyst may comprise I, CHI, CHI, Br, CHBr, or CHBr. In one embodiment, the halogen-containing catalyst may adsorb onto the first metal layer 130 to form a halogen-containing monolayer-modified first metal surface 140. In other embodiments, coverage of the surface of the first metal layer 130 may be only partial, or may form as more than a monolayer-modified first metal surface 140.

[0027] Although this disclosure primarily describes methods with halogen-containing catalysts, any suitable molecule that may interact with the metal precursor during CVD and promote surface reactions for metal deposition may be used. In one or more embodiments, the catalyst may be oxygen-free to prevent oxygen from interacting with the metal and potentially causing impurity issues.

[0028] FIG. 1D shows the substrate 100 after selective treatment with a molecular inhibitor (MI).

[0029] Figure 2B shows the selective adsorption of MI onto a silicon oxide surface.

[0030] In FIG. 1D, the substrate 100 may be treated with a molecular inhibitor (MI). The MI may selectively coat the exposed surface, both sidewalls, and top horizontal surfaces of the dielectric layer 110, resulting in a passivated dielectric surface 150. The presence of a catalyst as the modified first metal surface 140 can prevent unwanted MI adsorption onto the first metal layer 130. This is further illustrated in FIG. 2B, where MI adsorbs only on the silicon oxide surface. In various embodiments, the MI may be vaporized and delivered to the substrate 100 as a vapor diluted in a noble / inert carrier gas (e.g., Ar or N). In one particular embodiment, the treatment may be performed without plasma excitation at a substrate temperature between about 80° C. and about 250° C., a process chamber pressure between about 1 and 10 Torr, and an exposure time between 1 and 120 seconds.

[0031] Without wishing to be limited by any theory, treatment with MI may make the surface of the dielectric layer 110 more hydrophobic, which may be beneficial in reducing deposition of metal precursors during the metal deposition step (inhibitory effect). Therefore, the MI may be selected from molecules having hydrophobic groups (e.g., alkyl or aryl). Furthermore, such molecules are generally capable of forming stable chemical bonds with the surface of the dielectric layer 110 (e.g., Si—O—Si) and may therefore comprise silane compounds. In various embodiments, the MI includes alkylsilanes, alkoxysilanes, alkylalkoxysilanes, alkylsiloxanes, alkoxysiloxanes, alkylalkoxysiloxanes, arylsilanes, acylsilanes, arylsiloxanes, acylsiloxanes, silazanes, dimethylsilane dimethylamine (DMSDMA), trimethylsilane dimethylamine (TMSDMA), bis(dimethylamino)dimethylsilane (BDMADMS), N,O-bistrimethylsilyltrifluoroacetamide (BSTFA), or trimethylsilylpyrrole (TMS-pyrrole).

[0032] FIG. 1E shows a cross-sectional view of the substrate 100 after depositing a second metal 160 .

[0033] FIG. 2C shows selective metal-on-metal deposition.

[0034] In various embodiments, the metal deposition step may be performed using chemical vapor deposition (CVD), although other techniques, such as atomic layer deposition (ALD), may be used in other embodiments. The second metal 160 may comprise a low-resistivity metal such as Cu, Ru, Co, or W. The second metal 160 may or may not be the same material as that used for the first metal layer 130. Although not shown in FIG. 1F , in certain embodiments, multiple metals may be deposited to form an alloy or stacked conductive layer. Because the sidewalls and top surface of the dielectric layer 110 are still passivated by MI, the second metal 160 may be selectively deposited on the first metal layer 130 and grown bottom-up from the first metal layer 130.

[0035] In certain embodiments, Ru metal may be deposited by chemical vapor deposition (CVD) or atomic layer deposition (ALD) using a Ru-containing precursor. An example of a Ru-containing precursor is Ru(CO). 12 , (2,4-dimethylpentadienyl)(ethylcyclopentadienyl)ruthenium (Ru(DMPD)(EtCp)), bis(2,4-dimethylpentadienyl)ruthenium (Ru(DMPD)2), 4-dimethylpentadienyl)(methylcyclopentadienyl)ruthenium (Ru(DMPD)(MeCp)), and bis(ethylcyclopentadienyl)ruthenium (Ru(EtCp)2), as well as combinations of these with other precursors. In one embodiment, the process conditions for a Ru metal CVD process include the use of Ru(CO) without plasma excitation. 12 and CO (e.g., a gas flow ratio of about 1:1000), a substrate temperature of between about 100°C and about 250°C, a process chamber pressure of between about 1 mTorr and about 500 mTorr, and an exposure time of 400 seconds, depositing between about 10 nm and 20 nm of Ru metal on the metal surface.

[0036] Based on this catalyst-enhanced CVD method, both the metal deposition rate and selectivity can be improved by utilizing MI and a catalyst. First, the MI on the dielectric layer 110 suppresses unwanted metal deposition on the dielectric layer 110, thus improving selectivity. In addition, the presence of the catalyst on the modified first metal surface 140 promotes surface reactions, thereby promoting metal deposition, such as the formation of intermediate metal complexes. Because the catalyst is present only on the first metal layer 130 and not on the dielectric layer 110, both the deposition rate and selectivity can be improved.

[0037] In certain embodiments, the catalyst may remain on the surface after the metal deposition step as a modified second metal surface 145, as shown in FIG. 1E. In other embodiments, not shown, some or all of the catalyst may migrate to the metal (e.g., first metal layer 130 or second metal 160) or be consumed and removed from the substrate 100 as gaseous by-products. In one embodiment, any excess or residual catalyst may be desorbed from the surface by additional heat treatment. Thus, in one or more embodiments, the catalyst may be replenished by a subsequent step (e.g., FIG. 1G) before continuing with metal deposition.

[0038] 1E, the metal deposition step may fill a portion of the recess 115, for example, about one-quarter of the initial depth of the recess 115. In one embodiment, the target thickness of the second metal 160 deposited per metal deposition step may be between about 10 nm and 20 nm.

[0039] In other embodiments, the recess 115 may be completely filled in a single metal deposition step. In certain embodiments, the metal deposition step may be terminated at a specific height to avoid excessive formation of metal nuclei 165 on the dielectric layer 110. These metal nuclei 165 may be formed by adsorption of the metal precursor to the MI or by incomplete passivation of the dielectric layer 110 by the MI. Metal nuclei 165 on the dielectric layer 110, especially on the sidewalls, may cause lateral growth of the second metal 160, potentially resulting in pinch-off problems. Therefore, in various embodiments, the catalyst-enhanced CVD may be performed as a cyclic process including a metal nucleus removal etch, as described below ( FIG. 1F ), and the recess 115 may be filled through cycles of the catalyst-enhanced CVD process.

[0040] FIG. 1F shows a cross-sectional view of the substrate 100 after the metal core removal etch.

[0041] To minimize unwanted lateral metal growth, a metal nucleus removal etch can be performed after the metal deposition step to clean the sidewalls and top surface of the dielectric layer 110. It may be preferable to remove the metal nuclei 165 before they become too large and difficult to remove efficiently. As shown in FIG. 1F, after the metal nucleus removal etch, the MI and catalyst may be removed from the dielectric layer 110 and the second metal 160. In certain embodiments, the metal nucleus removal etch may be performed using reactive ion etching (RIE), for example, using plasma-excited O gas, optionally with the addition of a halogen-containing gas (e.g., Cl). In one embodiment, process conditions for O2-Cl2 RIE for metal nucleus removal etching may include etching including O2 and Cl2 (e.g., a gas flow ratio of about 100:1), a substrate temperature between about room temperature and about 370°C, plasma excitation using a capacitively coupled plasma (CCP) source (about 1200 W of RF power applied to the top electrode and between about 0 W and about 300 W of RF power applied to the bottom electrode), a process chamber pressure of about 5 mTorr, and an exposure time of 40 seconds, removing the equivalent of about 5 nm of metal nuclei. In a specific embodiment, the metal nucleus removal etching may be performed using chemical vapor etching (CVE). In another embodiment, treatment with ozone (O3) gas may be used for the metal nucleus removal etching. Ozone for ozone treatment may be generated from dioxygen (O) gas by ultraviolet excitation under the following exemplary process conditions: a process temperature between about 50°C and 200°C; a pressure range between about 500 mT and 10 Torr diluted with Ar gas; an ozone exposure time between 1 second and 60 seconds; and a 100 g / m 3 ~300g / m 3 Ozone density between 0.01 and 0.10. Ozone treatment can be applied to BEOL metallization without causing damage to low-k dielectrics and may be advantageous over O2 plasma-based RIE.

[0042] In other embodiments, not shown, metal deposition (FIG. 1E) may be achieved without metal nuclei (e.g., metal nuclei 165 in FIG. 1E) on the sidewalls of the dielectric layer 110, and in these cases, the metal nuclei removal etch may be omitted. In certain embodiments, MI may not completely stop metal deposition on the dielectric layer 110, but may substantially slow the deposition rate. In one example, the deposition rate on the first metal layer 130 may be at least 100 times the deposition rate on the dielectric layer 110. In one embodiment, MI may inhibit metal deposition by extending the incubation time of the chemical vapor deposition (CVD) of the metal on the dielectric layer 110 by 10 to 50 times.

[0043] FIG. 1G shows a cross-sectional view of substrate 100 after a second treatment with a catalyst followed by a second treatment with MI.

[0044] In various embodiments, the catalyst-enhanced CVD method may be performed as a cyclic process by repeating the steps of catalyst treatment (e.g., FIGS. 1C and 2A), selective MI treatment (e.g., FIGS. 1D and 2B), metal deposition (e.g., FIGS. 1E and 2C), and metal nucleus removal etching (e.g., FIG. 1F). As shown in FIG. 1G, after the metal nucleus removal etching (FIG. 1F), the dielectric layer 110 may be cleaned and free of any metal nuclei. Additionally, MI and catalyst that may have been present after the metal deposition step may also be removed. During the second catalyst treatment, the catalyst may interact with the surface of the second metal 160 deposited in the first cycle to form a modified second metal surface 145. During the second MI treatment, MI may cover the exposed surface, both sidewalls, and top horizontal surfaces of the dielectric layer 110, resulting in a passivated dielectric surface 150. With the replenished catalyst and MI, the substrate 100 may undergo a subsequent metal deposition step to further fill the recesses 115 with a second metal 160 .

[0045] FIG. 1H shows a cross-sectional view of substrate 100 after a cycle of a catalyst-enhanced CVD process that fills recesses 115 with a second metal 160 .

[0046] Each cycle of the selective metal deposition process may fill a portion of the recess 115 with the second metal 160 and may be repeated until the recess 115 is completely filled. In one embodiment, the impurity level (e.g., Si) in the filled recess may be below the detection limit (e.g., ±0.1 atomic %) of common techniques such as elemental analysis or X-ray photoelectron spectroscopy (XPS). Furthermore, the filled recess may be void-free. In one embodiment, the recess 115 may be completely filled with two to four cycles of the selective metal deposition process, although in other embodiments, any number of cycles may be performed. In certain embodiments, the process conditions for the selective metal deposition process steps may be adjusted for each cycle to account for the aspect ratio of the remaining recess. For example, the exposure time for metal deposition for the first cycle may be shorter than the exposure time for subsequent cycles because a larger surface area may increase the likelihood of metal nucleation on the sidewalls. In various embodiments, each step of the selective metal deposition process (e.g., FIGS. 1A-1H) may be performed within the thermal budget for the target semiconductor device fabrication, e.g., below 400°C.

[0047] 3A-3C show process flow diagrams of methods for catalyst-enhanced CVD processes according to various embodiments. The process flow can follow the diagrams discussed above (FIGS. 1C-1E) and will therefore not be described again.

[0048] In FIG. 3A, process flow 30 begins with treating a substrate with a halogen-containing catalyst, where the substrate includes a recess formed in a dielectric layer and a first metal layer within the recess (block 310, FIG. 1C). The surface of the first metal layer may be selectively coated with the halogen-containing catalyst. The substrate may be treated with a molecular inhibitor (MI) to coat the sidewalls of the dielectric layer within the recess (block 320, FIG. 1D). Thereafter, a second metal may then be selectively deposited on the first metal layer within the recess, where the MI coating the sidewalls prevents deposition of the second metal on the dielectric layer (block 330, FIG. 1E).

[0049] In FIG. 3B, a cyclical chemical vapor deposition (CVD) process 32 begins by treating a substrate with a halogen-containing catalyst to coat a metal surface (e.g., a first metal layer in a first cycle of the cyclical CVD process, and a second metal surface in a subsequent cycle) (block 312, FIG. 1C). The substrate may include a dielectric layer having a recess and a first metal layer exposed at the bottom of the recess. After treating the substrate with the halogen-containing catalyst, the substrate may then be treated with MI to coat the sidewalls of the dielectric layer in the recess (block 322, FIG. 1D). Thereafter, a second metal may then be selectively deposited on the first metal layer in the recess, where the MI covering the sidewalls prevents deposition of the second metal on the dielectric layer (block 332, FIG. 1E). These steps (blocks 312, 322, and 332) may be repeated cyclically in certain embodiments. In other embodiments, deposition of the second metal deposits second metal nuclei on portions of the sidewalls, and an additional etch may be inserted into one or more cycles of the cyclical CVD process to remove the second metal nuclei from portions of the sidewalls (block 342, FIG. 1F). In one embodiment, the cyclical CVD process partially fills the recess with the second metal, and the method further includes performing another deposition process to fill the remaining portion of the recess with the second metal or another metal. In one embodiment, the another deposition process may be a wet process, such as a metal plating process.

[0050] In FIG. 3C, another process flow 34 begins by exposing a substrate to a first vapor containing a halogen-containing catalyst, where the substrate has a recess formed in a dielectric layer and a first metal layer within the recess (block 314, FIG. 1C). The halogen-containing catalyst adsorbs to the first metal layer selectively relative to the sidewalls of the dielectric layer within the recess. The substrate may then be exposed to a second vapor containing MI (block 324, FIG. 1D), where MI selectively adsorbs to the sidewalls and the adsorbed halogen-containing catalyst prevents MI from adsorbing to the first metal layer. Thereafter, a second metal may then be selectively deposited on the first metal layer within the recess by CVD, where the deposition rate on the first metal layer is at least twice the deposition rate on the MI (block 334, FIG. 1E).

[0051] Catalyst-enhanced chemical vapor deposition (CVD) using catalysts and molecular inhibitors in various embodiments may advantageously eliminate or minimize impurity problems due to inhibitor contamination. These methods are particularly useful for vapor-phase metal deposition to fill high-aspect-ratio (HAR) recesses in applications such as sub-10 nm node middle-of-line (MOL) and back-end-of-line (BEOL) logic interconnects, where even very low levels of impurities can reduce electrical conductivity and thereby degrade device performance. While this disclosure primarily describes embodiments related to chemical vapor deposition of low-resistivity metals (e.g., Cu, Ru, Co, and W), the methods may also be applied to atomic layer deposition (ALD) or other deposition techniques. Furthermore, in certain embodiments, these methods may be used to deposit metal compounds (e.g., metal oxides and metal nitrides), and the selective metal deposition step may be followed by additional processing to convert the deposited metal to the metal compound.

[0052] Illustrative embodiments of the present invention are summarized here, with other embodiments being apparent from the specification as a whole and from the claims filed herewith. [Example]

[0053] Example 1 1. A method for processing a substrate, the method comprising: treating the substrate with a halogen-containing catalyst, the substrate comprising a semiconductor layer, a dielectric layer disposed on the semiconductor layer, a recess formed in the dielectric layer, and a layer of a first metal disposed between the dielectric layer and the semiconductor layer, the layer of the first metal being at a bottom of the recess; and treating the substrate with a molecular inhibitor (MI) after treating the substrate with the halogen-containing catalyst, the MI coating sidewalls of the dielectric layer in the recess; and depositing a second metal on the modified surface of the layer of first metal in the recess, the MI coating the sidewalls preventing deposition of the second metal on the dielectric layer.

[0054] Example 2. 2. The method of example 1, wherein the substrate further comprises a surface oxide layer on the layer of the first metal, and further comprising removing the surface oxide layer to expose the first metal layer in the recess before treating the substrate with the halogen-containing catalyst.

[0055] Example 3. 3. The method of any one of Examples 1 or 2, further comprising depositing a second metal to deposit second metal nuclei on portions of the sidewalls, and removing the second metal nuclei.

[0056] Example 4. The method of any one of Examples 1-3, wherein depositing the second metal is achieved bottom-up and without growing the second metal from the dielectric layer.

[0057] Example 5. The method of any one of Examples 1-4, wherein the halogen-containing catalyst comprises an iodine-containing compound.

[0058] Example 6 The method of any one of Examples 1 to 5, wherein the halogen-containing catalyst comprises I2, CH3I, or C2H5I.

[0059] Example 7 The method of any one of Examples 1-6, wherein the MI comprises an alkylsilane, alkoxysilane, alkylalkoxysilane, alkylsiloxane, alkoxysiloxane, alkylalkoxysiloxane, arylsilane, acylsilane, arylsiloxane, acylsiloxane, silazane, dimethylsilane dimethylamine (DMSDMA), trimethylsilane dimethylamine (TMSDMA), bis(dimethylamino)dimethylsilane (BDMADMS), N,O-bistrimethylsilyltrifluoroacetamide (BSTFA), or trimethylsilylpyrrole (TMS-pyrrole).

[0060] Example 8 The method of any one of Examples 1-7, wherein the first metal layer comprises Ru, Co, or W and the second metal comprises Cu, Ru, Co, or W.

[0061] Example 9. 1. A method for processing a substrate, the method comprising: performing a cyclical chemical vapor deposition (CVD) process to fill a portion of a recess; the substrate including a dielectric layer having a recess and a first metal layer at the bottom of the recess; one cycle of the cyclical CVD process comprising: treating the substrate with a halogen-containing catalyst, the halogen-containing catalyst modifying a surface of a second metal formed on the first metal layer; treating the substrate with a molecular inhibitor (MI) after treating the substrate with the halogen-containing catalyst, the MI coating sidewalls of the dielectric layer in the recess; and depositing the second metal on the first metal layer in the recess, the MI coating the sidewalls preventing deposition of the second metal on the dielectric layer.

[0062] Example 10. The method of example 9, wherein depositing a second metal deposits second metal nuclei on a portion of the sidewall, and wherein one of the cyclical CVD processes further includes removing the second metal nuclei from the portion of the sidewall.

[0063] Example 11 The method of any one of Examples 9 or 10, wherein the cyclical CVD process fills the recesses with a second metal.

[0064] Example 12 The method of any one of Examples 9-11, wherein the cyclical CVD process includes partially filling the recess with a second metal and further performing another deposition process to fill the remaining portion of the recess with the second metal or another metal.

[0065] Example 13 The method of one of Examples 9-12, wherein the alternative deposition process is a wet process.

[0066] Example 14. The method of any one of Examples 9-13, wherein the MI comprises silane and the second metal filling the recess does not contain detectable silicon or silane impurities.

[0067] Example 15. The method of any one of Examples 9-14, wherein the first metal layer comprises Ru, Co, or W and the second metal comprises Cu, Ru, Co, or W.

[0068] Example 16. The method of one of Examples 9-15, wherein the halogen-containing catalyst comprises I2, CH3I, or C2H5I.

[0069] Example 17. 1. A method for treating a substrate, the method comprising: exposing the substrate to a first vapor comprising a halogen-containing catalyst, the substrate comprising a dielectric surface and a first metal surface, the halogen-containing catalyst modifying a surface of the first metal surface; exposing the substrate to a second vapor comprising a molecular inhibitor (MI), the MI selectively adsorbing on the dielectric surface; and selectively depositing a second metal on the modified surface of the first metal surface by chemical vapor deposition (CVD), the deposition rate on the modified surface of the first metal surface being at least 100 times greater than the deposition rate on the MI on the dielectric surface.

[0070] Example 18. 18. The method of example 17, wherein the first metal layer comprises Ru, Co, or W and the second metal comprises Cu, Ru, Co, or W.

[0071] Example 19. 19. The method of any one of examples 17 or 18, wherein the substrate includes a recess prior to depositing the second metal, the recess having a critical dimension (CD) between 10 nm and 65 nm.

[0072] Example 20. The method of one of Examples 17-19, wherein the substrate includes a recess prior to depositing the second metal, and the recess has an aspect ratio (height to width ratio) of at least 4:1.

[0073] While the present invention has been described with reference to exemplary embodiments, this specification is not intended to be construed in a limiting sense. Various modifications and combinations of the exemplary embodiments, as well as other embodiments of the invention, will be apparent to those skilled in the art upon reference to this description. It is therefore intended that the appended claims cover any such modifications or embodiments.

Claims

1. 1. A method for processing a substrate, comprising: treating the substrate with a halogen-containing catalyst, the substrate comprising a semiconductor layer, a dielectric layer disposed on the semiconductor layer, a recess formed in the dielectric layer, and a layer of a first metal disposed between the dielectric layer and the semiconductor layer, the layer of the first metal being at a bottom of the recess, the halogen-containing catalyst modifying a surface of the layer of the first metal; treating the substrate with a molecular inhibitor (MI) after treating the substrate with the halogen-containing catalyst, the MI coating a sidewall of the dielectric layer within the recess; depositing a second metal on the modified surface of the layer of the first metal in the recess, the MI covering the sidewalls preventing deposition of the second metal on the dielectric layer; A method comprising:

2. 10. The method of claim 1, wherein the substrate further comprises a surface oxide layer on the layer of the first metal, and further comprising removing the surface oxide layer to expose the first metal layer in the recess prior to treating the substrate with the halogen-containing catalyst.

3. 2. The method of claim 1, further comprising depositing second metal nuclei on portions of the sidewalls by depositing the second metal, and removing the second metal nuclei.

4. 10. The method of claim 1, wherein depositing the second metal is accomplished bottom-up and without the second metal growing out of the dielectric layer.

5. The method of claim 1 , wherein the halogen-containing catalyst comprises an iodine-containing compound.

6. The halogen-containing catalyst is I ２ , C.H. ３ I or C ２ H ５ The method of claim 5 , comprising:

7. 2. The method of claim 1, wherein the MI comprises an alkylsilane, an alkoxysilane, an alkylalkoxysilane, an alkylsiloxane, an alkoxysiloxane, an alkylalkoxysiloxane, an arylsilane, an acylsilane, an arylsiloxane, an acylsiloxane, a silazane, dimethylsilane dimethylamine (DMSDMA), trimethylsilane dimethylamine (TMSDMA), bis(dimethylamino)dimethylsilane (BDMADMS), N,O-bistrimethylsilyltrifluoroacetamide (BSTFA), or trimethylsilylpyrrole (TMS-pyrrole).

8. The method of claim 1 , wherein the first metal layer comprises Ru, Co, or W, and the second metal comprises Cu, Ru, Co, or W.

9. 1. A method for processing a substrate, comprising: performing a cyclical chemical vapor deposition (CVD) process to fill a portion of the recess, the substrate comprising a dielectric layer having the recess and a first metal layer at a bottom of the recess, one cycle of the cyclical CVD process comprising: treating the substrate with a halogen-containing catalyst, the halogen-containing catalyst modifying a surface of a second metal formed on the first metal layer; treating the substrate with a molecular inhibitor (MI) after treating the substrate with the halogen-containing catalyst, the MI coating a sidewall of the dielectric layer within the recess; depositing the second metal on the first metal layer in the recess, the MI covering the sidewalls preventing deposition of the second metal on the dielectric layer; method.

10. 10. The method of claim 9, wherein depositing the second metal deposits second metal nuclei on the portion of the sidewall, and wherein one of the cyclical CVD processes further comprises removing the second metal nuclei from the portion of the sidewall.

11. The method of claim 9 , wherein the cyclic CVD process fills the recess with the second metal.

12. 10. The method of claim 9, wherein the cyclical CVD process includes partially filling the recess with the second metal and then performing another deposition process to fill the remaining portion of the recess with the second metal or another metal.

13. The method of claim 12 , wherein the alternative deposition process is a wet process.

14. 10. The method of claim 9, wherein the MI comprises silane and the second metal filling the recess does not contain detectable silicon or silane impurities.

15. The method of claim 9 , wherein the first metal layer comprises Ru, Co, or W, and the second metal comprises Cu, Ru, Co, or W.

16. The halogen-containing catalyst is I ２ , C.H. ３ I or C ２ H ５ 10. The method of claim 9, comprising:

17. 1. A method for processing a substrate, comprising: exposing the substrate to a first vapor comprising a halogen-containing catalyst, the substrate comprising a dielectric surface and a first metal surface, the halogen-containing catalyst modifying a surface of the first metal surface; exposing the substrate to a second vapor containing a molecular inhibitor (MI), wherein the MI selectively adsorbs onto the dielectric surface; Selectively depositing a second metal on the modified surface of the first metal surface by chemical vapor deposition (CVD), wherein the deposition rate on the modified surface of the first metal surface is at least 100 times greater than the deposition rate on the MI on the dielectric surface. method.

18. 18. The method of claim 17, wherein the first metal layer comprises Ru, Co, or W, and the second metal comprises Cu, Ru, Co, or W.

19. 18. The method of claim 17, wherein the substrate comprises a recess prior to depositing the second metal, the recess having a critical dimension (CD) between 10 nm and 65 nm.

20. 18. The method of claim 17, wherein the substrate comprises a recess prior to depositing the second metal, the recess having an aspect ratio (height to width) of at least 4:1.

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