Flexible monomers for smooth polymer surfaces

Abstract

Embodiments of this disclosure relate to a method for selectively depositing a metal after using a fluid polymer to protect a substrate surface within a feature. A first metal layer is deposited by physical vapor deposition (PVD). The semiconductor substrate surface is exposed to one or more monomers to form a fluid and flexible polymer film on the first metal layer within at least one feature. The fluid polymer film is formed on the first metal layer at the bottom. One or more monomers are selected from one or more difunctional amines, difunctional aldehydes, difunctional cyanates, difunctional ketones, and difunctional alcohols. At least a portion of the first metal layer is selectively removed from the top surface and at least one sidewall. The fluid polymer film is removed.

Description

[Technical Field]

[0001]

[0001] Embodiments of the present disclosure relate to a selective deposition method facilitated by a fluid polymer. More specifically, embodiments of the present disclosure relate to a method for selectively depositing a metal after the use of a fluid polymer to protect a substrate surface within a feature. [Background technology]

[0002]

[0002] Gap-filling processes are integrated with several semiconductor manufacturing processes. Gap-filling processes can be used to fill gaps (or features) with insulating or conductive materials. For example, shallow trench isolation, intermetallic insulating layers, passivation layers, and dummy gates are all typically implemented by gap-filling processes.

[0003]

[0003] As device dimensions continue to shrink (e.g., limit dimensions less than 20 nm, less than 10 nm, and even less) and the thermal balance decreases, the limitations of conventional deposition processes make it increasingly difficult to fill the space without defects.

[0004]

[0004] A selective tungsten filling process has been introduced in which tungsten can be selectively deposited on a tungsten seed layer. Unfortunately, these processes require a minimum seed layer thickness. Known PVD processes can provide the required seed layer thickness, but selective tungsten filling processes deposit tungsten material on any exposed seed layer. In addition, there is no known method for selectively depositing metal on a metal or metal silicide without damaging the substrate metal or metal silicide.

[0005]

[0005] Therefore, there is a need for a method to protect the metal or metal silicide within the feature in order to enable bottom-up filling by a selective deposition process. [Overview of the project]

[0006]

[0006] One or more embodiments of the present disclosure relate to a method for forming a semiconductor device. The method involves depositing a first metal layer on the surface of a semiconductor substrate having at least one feature formed thereon by physical vapor deposition (PVD), wherein the at least one feature has at least one opening having a width, at least one sidewall, and a bottom, the feature depth of the at least one feature extends from the top to the bottom, and the first metal layer is formed on the top, at least one sidewall, and the bottom, and depositing the first metal layer and forming a fluid polymer film on the first metal layer within the at least one feature, the semiconductor substrate surface 1 The method involves exposing a semiconductor substrate surface to one or more monomers, wherein a fluid polymer film is formed on a first metal layer on the bottom, and one or more monomers are selected from one or more difunctional amines, difunctional aldehydes, difunctional cyanates, difunctional ketones, and difunctional alcohols, selectively removing at least a portion of the first metal layer from the top surface and at least one side wall, and removing the fluid polymer film to expose the first metal layer on the bottom of at least one feature.

[0007]

[0007] Further embodiments of the present disclosure relate to methods for manufacturing semiconductor devices. In one or more embodiments, the method comprises depositing a first metal layer on a substrate surface on which at least one feature is formed, wherein the at least one feature includes at least one opening, at least one sidewall, and a bottom, and the feature depth of the at least one feature extends from the top to the bottom, and the first metal layer is formed on the top, on at least one sidewall, and on the bottom, and depositing the first metal layer, and exposing the substrate surface to one or more monomers to form a fluid polymer film on the first metal layer in at least one feature, wherein the fluid polymer The film is formed on a first metal layer on the bottom, and one or more monomers are selected from one or more difunctional amines, difunctional aldehydes, difunctional cyanates, difunctional ketones, and difunctional alcohols, and the process includes exposing the substrate surface to one or more monomers, selectively removing the first metal layer from the top surface and at least one side wall, removing a fluid polymer film to expose the first metal layer on the bottom of at least one feature, and selectively depositing a second metal layer on the first metal layer to fill at least one feature.

[0008]

[0008] To enable a detailed understanding of the above-described features of the Disclosure, a more specific description of the Disclosure, which has been briefly summarized above, can be obtained by referring to embodiments. Some of these embodiments are shown in the accompanying drawings. However, it should be noted that the accompanying drawings illustrate only typical embodiments of the Disclosure, as the Disclosure may also permit other equally valid embodiments, and therefore should not be considered to limit the scope of the Disclosure.

[0009]

[0009] In the following attached drawings in which the same elements are indicated by the same reference numerals, the embodiments described herein are merely examples and not limiting. [Brief explanation of the drawing]

[0010] [Figure 1]

[0010] Shows a process flow diagram of a method according to one or more embodiments. [Figure 2]

[0011] Shows a cross-sectional view of a semiconductor substrate according to one or more embodiments. [Figure 3]

[0012] Shows a cross-sectional view of a semiconductor substrate according to one or more embodiments. [Figure 4]

[0013] Shows a cross-sectional view of a semiconductor substrate according to one or more embodiments. [Figure 5]

[0014] Shows a cross-sectional view of a semiconductor substrate according to one or more embodiments. [Figure 6]

[0015] Shows a cross-sectional view of a semiconductor substrate according to one or more embodiments. [Figure 7]

[0016] Shows a cross-sectional view of a semiconductor substrate according to one or more embodiments. [Figure 8]

[0017] Is a schematic top view of an exemplary multi-chamber processing system according to one or more embodiments.

DETAILED DESCRIPTION OF THE INVENTION

[0011]

[0018] Before describing some exemplary embodiments of the present disclosure, it should be understood that the present disclosure is not limited to the details of the configurations or process steps presented in the following description. The present disclosure can have other embodiments and can be practiced or executed in various ways.

[0012]

[0019] The term "about" as used in this document means "approximately" or "almost" and means a variation of up to ±15% of the numerical value in light of the stated numerical value or range. For example, values that differ by a difference of ±14%, ±10%, ±5%, ±, 2%, ±1%, ±0.5%, or ±0.1% satisfy the definition of about.

[0013]

[0020] As used in this specification and the appended claims, the terms "substrate" or "wafer" refer to the surface or a portion of the surface on which the process acts. It will also be understood by those skilled in the art that, unless the context clearly indicates otherwise, a reference to a substrate may refer only to a portion of the substrate. Further, a reference to deposition on a substrate can mean both a bare substrate and a substrate having one or more films or features deposited or formed thereon.

[0014]

[0021] As used herein, "substrate" refers to any substrate or the surface of a material formed on a substrate on which film processing is performed during a manufacturing process. For example, the substrate surface on which processing can be performed can include materials such as silicon, silicon oxide, strained silicon, silicon on insulator (SOI), carbon-doped silicon oxide, amorphous silicon, doped silicon, germanium, and gallium arsenide, depending on the application, as well as any other materials such as metals, metal nitrides, metal alloys, and other conductive materials. The substrate includes, but is not limited to, semiconductor wafers. The substrate can be exposed to a pretreatment process to polish, etch, reduce, oxidize, hydroxylate, anneal, and / or bake the substrate surface. In addition to directly performing film processing on the surface of the substrate itself, in the present disclosure, any of the disclosed film processing steps can be performed on an underlying layer formed on the substrate, as will be disclosed in more detail below, and the term "substrate surface" is intended to include an underlying layer as indicated by the context. Thus, for example, when a film / layer or a partial film / layer is deposited on the substrate surface, the exposed surface of the newly deposited film / layer becomes the substrate surface.

[0015]

[0022] As used herein, the term "substrate surface" refers to any substrate surface on which a layer can be formed. The substrate surface can have one or more features formed therein, one or more layers formed thereon, and combinations thereof. The shape of a feature may be any suitable shape, including but not limited to protrusions, grooves, holes, and vias (circular or polygonal). The term “feature” as used in this context refers to any intentional irregularity on a surface. Suitable examples of features include, but are not limited to, grooves with a top, two sidewalls, and a bottom extending into the substrate, vias with one or more sidewalls extending into the substrate and reaching a bottom, and slot vias.

[0016]

[0023] As used in this book and the attached claims, the term “selectively” refers to a process that acts on a first surface with a greater effect than a second surface. Such a process is described as acting “selectively” on the first surface than on the second surface. The term “over” as used in this way does not mean the physical orientation of one surface over the other, but rather the relationship between the thermodynamic or mechanical properties of the chemical reaction of one surface and the other.

[0017]

[0024] The term "on" indicates direct contact between elements. The term "direct" indicates direct contact between elements without an intervening element.

[0018]

[0025] As used in this document and the attached claims, terms such as “precursor,” “reactant,” and “reactive gas” are interchangeable and refer to any gas species that can react with the substrate surface.

[0019]

[0026] Embodiments of this disclosure advantageously provide a method for selectively depositing metal after using a fluid polymer to protect the substrate surface within a feature. One or more embodiments advantageously provide a method for removing metallic material from the fields and sidewalls of a feature without removing the fluid polymer from the bottom surface of the substrate. The remaining fluid polymer has a smooth surface. Further embodiments advantageously provide a method for selectively depositing metal gap filler in a bottom-up manner.

[0020]

[0027] Embodiments of this disclosure are illustrated by drawings showing processes and substrates according to one or more embodiments of this disclosure. The processes, schemes, and resulting substrates shown are merely illustrative of the disclosed processes, and those skilled in the art will understand that the disclosed processes are not limited to the illustrated applications.

[0021]

[0001] Referring to the drawings, this disclosure relates to a selective deposition method 100 for gap-filling material. Figure 1 shows a process flow diagram of the selective deposition method 100 according to one or more embodiments of this disclosure. Figures 2 to 7 show a device 200 having a substrate surface in which at least one feature is formed during processing according to one or more embodiments of this disclosure. Figure 8 is a schematic top view of an exemplary multi-chamber processing system for performing the method according to one or more embodiments.

[0022]

[0028] Figure 2 shows a semiconductor device 200 having a substrate surface 205. The aforementioned substrate surface refers to the exposed surface of the substrate on which a process can be performed. The substrate surface 205 has at least one feature 210 formed inside. Although only three features are shown in the drawing, those skilled in the art will understand that multiple features are each similarly affected by the disclosed method.

[0023]

[0029] At least one feature 210 has an aperture width w O The feature has an opening 212, which is formed in the top surface 215 of the device 200. The feature 210 also has one or more side walls 214, with a feature depth D extending from the top surface 215 to the bottom 216. Although the drawings show straight and vertical side walls, the disclosed method may also be carried out with inclined side walls, irregular side walls, or inwardly recessed side walls.

[0024]

[0030] In one or more embodiments, the device 200 shown in Figure 2 consists of material 220 on material 210. Those skilled in the art will understand that the top surface 215, side walls 214, and bottom 216 may each consist of one or more similar or different materials. For example, the lower part of a side wall 214 may be formed from a first material, while the upper part of the same side wall 214 may consist of a second material. Similarly, a thin layer may be deposited on the top surface 215 without forming an obvious portion of the side wall 214. In one or more embodiments, the bottom 216 may consist of a different material 210 than that of the side walls 214.

[0025]

[0031] In one or more embodiments, the opening width w of the opening 212 O The wavelength is approximately 50 nm or less, approximately 30 nm or less, approximately 20 nm or less, approximately 10 nm or less, or approximately 7 nm or less. In one or more embodiments, the aperture width w O This range is approximately 8nm to 20nm.

[0026]

[0032] In one or more embodiments, the feature depth D of feature 210 is approximately 5 nm or more, approximately 10 nm or more, approximately 20 nm or more, approximately 50 nm or more, approximately 60 nm or more, approximately 75 nm or more, approximately 100 nm or more, approximately 200 nm or more, approximately 300 nm or more, approximately 400 nm or more, or approximately 450 nm or more. In one or more embodiments, the feature depth D is in the range of approximately 5 nm to approximately 500 nm.

[0027]

[0033] As used in this document, the term “feature” refers to any intentional irregularity of a surface. Suitable examples of features include, but are not limited to, trenches or vias with a top, two sidewalls, and a bottom, and peaks with a top and two sidewalls. Features can have any suitable aspect ratio (the ratio of the depth of a feature to the width of a feature). In one or more embodiments, the aspect ratio of at least one feature 210 is approximately 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, or 40:1 or greater.

[0028]

[0034] For simplicity, when referring to Figures 3-7, we will be referring to the portion of feature 210 shown in Figure 2. For example, device 200 shown in Figure 3 is referred to as having a bottom 216. For clarity in the presented figures, the reference numbers for the portion of feature 210 are not shown in Figures 3-7.

[0029]

[0035] Referring to Figures 1 and 2-7, in one or more embodiments, Method 100 begins with an optional step 105 for pre-treating the substrate. The pre-treatment in step 105 may be any suitable pre-treatment known to those skilled in the art. Suitable pre-treatments include, but are not limited to, preheating, washing, immersion, removal of native oxides, or deposition of a contact layer (e.g., titanium silicide (TiSi)) or a capping layer (e.g., TiSiN). In one or more embodiments, a layer such as titanium silicide or titanium silicon nitride (TiSiN), or another metal silicide, is deposited in step 105.

[0030]

[0036] Figure 3 shows an exemplary device 200 after an optional step 105. The device 200 includes a bottom formed from the substrate 210, as well as side walls and a top formed from the layer 220. In one or more embodiments, the substrate 210 includes a conductive material, and the layer 220 includes a dielectric. Those skilled in the art will understand that the disclosed process may be performed on different materials, and / or the illustrated layers may be arranged in different ways.

[0031]

[0037] Method 100 continues to cycle 110. In cycle 110, a layer of metallic material 240 is formed at the bottom 216 of at least one feature 210 of device 200. Cycle 110 includes a series of steps, each of which may be performed sequentially and repeated. Some of the steps are arbitrary within each cycle. A given arbitrary step may be performed periodically as needed (every other cycle, every 5 cycles, or every 100 cycles) based on predetermined parameters, or it may not be performed at all during each cycle.

[0032]

[0038] As shown in FIG. 3, cycle 110 starts from an optional step 112. In 112, the metal material 240 is deposited on the substrate surface 205 of the device 200. The metal material 240 has a bottom thickness at the bottom 216, an upper thickness at the upper surface 215, and / or a sidewall thickness at the sidewall 214. The metal material may include any suitable material known to those skilled in the art. In one or more embodiments, the metal material 240 includes one or more of tungsten (W), ruthenium (Ru), nickel (Ni), titanium (Ti), molybdenum (Mo), cobalt (Co), or tantalum (Ta). In some embodiments, the first metal layer 240 is formed at the bottom of at least one feature and reacts with the semiconductor substrate surface 210 to form a metal silicide. In one or more embodiments, the metal silicide is tungsten silicide (WSi x ), ruthenium silicide (RuSi x ), nickel silicide (NiSi x ), titanium silicide (TiSi x ), molybdenum silicide (MoSi x ), cobalt silicide (CoSi x ), or tantalum silicide (TaSi x ), including one or more of them.

[0033]

[0039] The metal material 240 can be deposited by any suitable method. In one or more embodiments, the metal material 240 can be deposited by physical vapor deposition (PVD). In these embodiments, as shown in FIG. 3, the sidewall thickness is smaller than the upper thickness and the bottom thickness. In one or more embodiments, the upper thickness is greater than the bottom thickness.

[0034]

[0040] Those skilled in the art will understand that the disclosed method may begin with a metallic material 240 already formed on the substrate surface 205 of the device 200, after which the device is provided. Thus, step 112 is disclosed as an optional step. As used herein and in the appended claims, the term “provided” means that the substrate is made available for processing (e.g., placed in a processing chamber).

[0035]

[0041] Cycle 110 continues to step 114. As shown in Figure 4, in step 114, the fluid polymer film 250 is formed on the metallic material 240 within a feature 210 of the device 200. The polymer film 250 has a polymer thickness less than or equal to the feature depth D. In other words, as a fluid film (described later), the polymer film is entirely contained within the feature 210 and is not present on the top surface 215 of the device 200. In one or more embodiments, the polymer film has a thickness in the range of about 1 nm to about 10 nm, or about 2 nm to about 5 nm. In some embodiments, the thickness of the polymer film 250 is in the range of 1% to 99%, 1% to 80%, or 2% to 20% of the depth D of at least one feature 210.

[0036]

[0042] In the disclosed method, processing parameters and reactants may be selected to limit the conformality of the deposited material, thereby enabling the deposited material to better fill features on the substrate. A fluid material is a material that, under appropriate conditions, will flow by gravity to lower parts of the substrate surface and / or by capillary action into narrow CD spaces of grooves or other features.

[0037]

[0043] In one or more embodiments, forming a polymer film involves exposing a surface to one or more monomers. In one or more embodiments, the monomers consist of, substantially composed of, or composed of a single, bifunctional monomer, each having a different functional group. In this way, one functional group of one monomer molecule reacts with another functional group of a different monomer molecule. Those skilled in the art can recognize this as polymer "A".

[0038]

[0044] In one or more embodiments, one or more monomers include, substantially consist of, or consist of one or more of the following: amines having a difunctional group, aldehydes having a difunctional group, cyanates having a difunctional group, ketones having a difunctional group, and alcohols having a difunctional group.

[0039]

[0045] In one or more embodiments, the amine is of the formula H2N-(CH x ) n It has -NH2, where n is an integer in the range of 1 to 20 and x is 1 or 2. In one or more embodiments, the aldehyde is of the formula OHC-(CH x ) m The cyanate has the formula NCO-(CH), where m is an integer in the range of 2 to 20 and x is 1 or 2. In one or more embodiments, the cyanate has the formula NCO-(CH). x ) p -OCN has the formula ROC-(CH₂). x ) q The alcohol has the formula HOC-(CH x ) r -COH has a function where r is an integer between 2 and 20, and x is 1 or 2.

[0040]

[0046] In one or more embodiments, amines, aldehydes, cyanates, ketones, and alcohols contain carbon atoms. In one or more embodiments, the monomers described herein may be linear, branched, cyclic, saturated, or unsaturated. The monomers described herein do not contain reactive groups in the chemical polymerization processes described herein.

[0041]

[0047] In certain embodiments, the monomer may be selected from one or more of the following: TIFF2026524861000002.tif62170

[0042]

[0048] In one or more embodiments, the monomer is substantially composed of two bifunctional monomers, each having the same functional group. In this way, the functional group of one monomer reacts with the functional group of the second monomer. Those skilled in the art can recognize this as an "AB" polymer.

[0043]

[0049] In one or more embodiments, flexible monomers used to produce the selective protective polymer film 250 can form oligomers at a higher rate during polymerization compared to rigid monomers. Therefore, in one or more embodiments, the polymerization process proceeds through monomer, oligomer, and polymer stages. Polymer formation depends on the local concentration of the monomers. In one or more embodiments, monomers A and B are used, which can only bond with A and B, and not with A and with B. Therefore, during the purging and pumping stages, the concentration of A decreases significantly, especially in the field / wall regions 214, 215. In this case, when monomer B is introduced, only oligomers are formed on the field / wall regions 214, 215 where the concentration of monomer A is very low. Due to the difference in pumping and purging efficiency between the field / walls 214, 215 and the bottom 216 of feature 210, the concentration of monomer A at the bottom 216 of feature 210 is higher than the concentration at the field / walls 214, 215. The higher concentration of A monomer at the bottom 216 of feature 210 leads to the formation of oligomers or polymers with a higher molecular weight, together with the introduced B monomer. These oligomers and polymers will continue to grow at the bottom 216 of feature 210 throughout the process cycle. In one or more embodiments, when a B monomer with a lower molecular weight is used, even if the BAB oligomer is formed in the fields / walls 214, 215 where the concentration of A is low, it will be more volatile compared to the higher oligomer (BABAB, etc.) formed at the bottom 216 of feature 210. This minimizes the amount of polymer residue in the fields / walls 214, 215.

[0044]

[0050] The benzene ring has an electrical advantage in activating aldehyde functional groups during bonding with amines. When two aldehyde groups are located at the 1,4 positions of the benzene ring, the monomer is a hard or rigid monomer. When the monomer reacts with 1,4-diaminobenzene, a hard polymer with a rough surface within the features is formed.

[0045]

[0051] Therefore, in one or more embodiments, when two aldehyde groups are located at the 1,3 positions of benzene, it is a flexible monomer, and a flexible polymer film 250 is formed. The flexible polymer film 250 has a lower glass transition temperature compared to films formed from rigid polymers. Therefore, in one or more embodiments, particularly T g When the temperature is lower than the process temperature, a smooth polymer surface, flexibility, and a lower glass transition temperature (T) are obtained. g A polymer film 250 having ) is advantageously formed.

[0046]

[0052] In one or more embodiments, the use of flexible monomers increases the chances of oligomer formation (e.g., ABAB or ABABAB). Flexible monomers also enable smooth surfaces within feature 210 with easy packing and packing density. Flexible monomers also reduce polymer residue in the field / wall 214, 215 region due to the volatility of the oligomer and its fluidity within the feature. This improvement eliminates polymer residue in the field 215 and sidewall 214, improving process efficiency. In one or more embodiments, the quality of the semiconductor device is improved when there is little to no residue in the field 215 and wall 214 region.

[0047]

[0053] While not intended to be theoretically restrictive, the polymer formed and deposited as a polymer film 250 is considered to have the flexibility to fill the bottom of the feature 210. In one or more embodiments, the polymer is fluid during deposition and further processing.

[0048]

[0054] As mentioned above, the polymer film 250 is fluid. It has been found that controlling the size of the obtained oligomers is necessary to control the "fluidity" of the obtained polymer film 250.

[0049]

[0055] Therefore, in one or more embodiments, the polymer film 250 is formed on a substrate maintained at a temperature in the range of 0°C to 400°C. In one or more embodiments, the substrate is maintained at a temperature of about 0°C or higher, about 30°C or higher, about 50°C or higher, about 100°C or higher, about 200°C or higher, or about 300°C or higher. In one or more embodiments, the substrate is maintained at a temperature of about 400°C or lower, about 300°C or lower, about 200°C or lower, about 100°C or lower, about 50°C or lower, or about 30°C or lower.

[0050]

[0056] Furthermore, other process parameters can be controlled during the formation of the polymer film 250. Examples of controllable parameters include, but are not limited to, the pressure of the processing chamber, the selection of monomers, the use of an inert diluent or carrier gas, the partial pressure of the monomers, the pulse sequence of the monomers, and the pause period that allows the polymer material to flow.

[0051]

[0057] Cycle 110 continues to step 116. As shown in Figure 5, in step 116, at least a portion of the metallic material 240 is selectively removed. The metallic material 240 is removed from the top surface 215 without substantially affecting any material beneath the polymer film. A process used in this manner that does not "substantially affect" the material layer does not cause any reduction in volume, thickness, or composition. Those skilled in the art will understand that while a portion of the metallic material 240 is removed, the polymer film 250 acts as an etching stop layer.

[0052]

[0058] In one or more embodiments, step 116 also removes a portion of the metallic material 240 from the sidewall 214. In one or more embodiments, some of the metallic material 240 present in the sidewall 214 below the upper surface of the polymer film 250 may remain without being removed.

[0053]

[0059] In one or more embodiments, selective removal of the metallic material 240 is performed by exposing the substrate surface 205 of the device 200 to NF3 radicals. In one or more embodiments, selective removal of the metallic material 240 is performed by exposing the substrate surface 205 to a fluorine-based plasma or a chlorine-based plasma. In one or more embodiments, the substrate is maintained at a temperature in the range of 80°C to 150°C.

[0054]

[0060] In one or more embodiments, selective removal of the metallic material 240 is carried out by a series of steps, which include oxidizing the metallic material 240 and then exposing the oxidized material to a metal halide to etch the oxidized material. In one or more embodiments, when the metallic material includes tungsten, the metal halide includes WCl5.

[0055]

[0061] Cycle 110 continues to an optional step 118. As shown in Figure 6, in step 118, the polymer film 250 is removed so as to expose the metal material 240 beneath the polymer film 250. In one or more embodiments, the removal of the polymer film 250 is complete, with little or no residue remaining.

[0056]

[0062] In one or more embodiments, the polymer film 250 is removed by exposing the substrate surface 205 of the device 200 to hydrogen (H2) plasma treatment. In one or more embodiments, the polymer film 250 is removed by exposure to a high-temperature, thermal O2 atmosphere.

[0057]

[0063] In one or more embodiments, the removal of the polymer film 250 is performed by exposing the substrate surface 205 of the device 200 to one or more heat treatments or hydrogen (H2) plasma treatments. In one or more embodiments, after removing the metallic material 240 from the top surface 215 and side walls 214, the polymer may be thermally removed by heating to 350°C to 500°C under vacuum. In other embodiments, after removing the metallic material 240 from the top surface 215 and side walls 214, the polymer may also be removed by hydrogen (H2) plasma at a temperature in the range of 100°C to 300°C for a time in the range of 2 to 30 seconds.

[0058]

[0064] Cycle 110 continues to an optional step 119. In step 119, although not shown, the substrate surface 105 may be optionally cleaned. The cleaning process may be any suitable process for cleaning the surface of a metallic material. In one or more embodiments, the cleaning process does not oxidize the metallic surface.

[0059]

[0065] In one or more embodiments, at the end of cycle 110, the surface of the metallic material 240 is free of any contaminants or residues from the polymer layer 240. More specifically, in one or more embodiments, the surface of the metallic material 240 is free of carbon or oxygen residues. In one or more embodiments, if method 100 includes repeated cycles 110 (see below), there are no contaminants or residues between the metallic material 240 deposited in subsequent cycles. In one or more embodiments, if method 100 includes the deposition of a second metallic material 260 (see below), there are no contaminants or residues between the metallic material 240 and the second metallic material 260.

[0060]

[0066] In one or more embodiments, this is achieved by a residue-free removal process in step 118. In one or more embodiments, this is achieved by performing a cleaning process in step 119. In one or more embodiments, during the removal of the polymer layer 250, the monomers are selected to contain no oxygen atoms that could oxidize the surface of the metal material 240.

[0061]

[0067] Method 100 proceeds to measurement point 120. At point 120, the substrate is evaluated to determine whether the metallic material 240 has reached a predetermined thickness or whether a predetermined number of cycles 110 have been performed. If the conditions are met, Method 100 proceeds to step 130. If the conditions are not met, Method 100 returns to step 112, which is the beginning of cycle 110. In these embodiments, where cycle 110 is repeated to form additional material, those skilled in the art will understand that step 112 is often performed to deposit the required additional metallic material. In one or more embodiments, the predetermined thickness is in the range of about 2 nm to about 10 nm.

[0062]

[0068] Method 100 proceeds to an optional step 130, in which the metallic material 240 may optionally be etched, although this is not shown. In one or more embodiments, the metallic material 240 is etched to remove the portion of the metallic material 240 that extends to the sidewall 214. When etched, the metallic material 240 also thins out on the bottom 216 of the feature 210. Thus, it will be understood by those skilled in the art that the metallic material 240 may be deposited to a bottom thickness greater than desired in the final product in order to provide sacrificial material that will be removed when etching the metallic material from the sidewall 214.

[0063]

[0069] Method 100 is followed by an optional step 140. As shown in Figure 7, in step 140, the second metallic material 260 is selectively deposited on the metallic material 240. The deposition process is selective to the surface of the metallic material 240 rather than to other substrate surface materials (e.g., layer 220). The selective deposition process provides a gap-filling material comprising the second metallic material 260, which is formed in a bottom-up manner without lateral deposition from the sidewalls 214. In one or more embodiments, the second metallic material is deposited without forming any voids or seams within the second metallic material 260.

[0064]

[0070] In one or more embodiments, the metallic material 240 and the second metallic material 260 contain the same metal. In one or more embodiments, the metallic material 240 and the second metallic material 260 contain different metals. In one or more embodiments, the first metallic material 240 contains or is substantially composed of tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co), nickel (Ni), titanium (Ti), and tantalum (Ta).

[0065]

[0071] The method may end after step 140, or it may proceed to any post-processing in any step 150. The optional post-processing step 150 may be, for example, a process to change the properties of the film (e.g., annealing or plasma treatment), a further film deposition process to grow an additional film (e.g., an additional ALD or CVD process), or a further etching process to form a desired predetermined device structure. In one or more embodiments, the optional post-processing step 150 may be a process to change the properties of the deposited film. In one or more embodiments, the optional post-processing step 150 includes annealing the device 200. In one or more embodiments, the annealing is performed at a temperature of about 300°C or higher, about 400°C or higher, about 500°C or higher, about 600°C or higher, about 700°C or higher, about 800°C or higher, about 900°C or higher, or about 1000°C or higher. The annealing environment of one or more embodiments includes one or more of the following: an inert gas (e.g., molecular nitrogen (N2), argon (Ar)), a reducing gas (e.g., molecular hydrogen (H2) or ammonia (NH3)), or an oxidizing agent, but not limited to oxygen (O2), ozone (O3), or a peroxide. Annealing can be performed for any suitable length of time. In one or more embodiments, the substrate is annealed for a predetermined time in the range of about 15 seconds to about 90 minutes, or about 1 minute to about 60 minutes.

[0066]

[0072] Figure 8 shows a schematic top view of an example of a multi-chamber processing system 400 according to an embodiment of the present disclosure. The processing system 400 generally includes a factory interface 402, load lock chambers 404, 406, transfer chambers 408, 410 with their respective transfer robots 412, 414, holding chambers 416, 418, and processing chambers 420, 422, 424, 426, 428, 430. As will be described in detail in this document, wafers in the processing system 400 can be processed in various chambers and transferred between various chambers without exposing the wafers to the ambient environment outside the processing system 400 (e.g., the ambient air environment that may be present in the factory). For example, wafers can be processed in various chambers and transferred between various chambers in a low-pressure (e.g., about 300 Torr or less) or vacuum environment without disrupting the low-pressure or vacuum environment during various processes performed on the wafers in the processing system 400. Thus, the processing system 400 can provide an integrated solution for processing a portion of wafers.

[0067]

[0073] Examples of processing systems that can be appropriately modified in accordance with the teachings provided herein include integrated processing systems or other suitable commercially available processing systems. Other processing systems (including those from other manufacturers) may be adapted to benefit from the embodiments described herein.

[0068]

[0074] In the example shown in Figure 8, the factory interface 402 includes a docking station 440 and a factory interface robot 442 to facilitate wafer transfer. The docking station 440 is configured to receive one or more forward-opening unified pods (FOUPs) 444. In some examples, each factory interface robot 442 generally includes a blade 448 located at one end of the factory interface robot 442, configured to transfer wafers from the factory interface 402 to load lock chambers 404, 406.

[0069]

[0075] The load lock chambers 404 and 406 have ports 450 and 452 connected to the factory interface 402, respectively, and ports 454 and 456 connected to the transfer chamber 408, respectively. The transfer chamber 408 further has ports 458 and 460 connected to the holding chambers 416 and 418, respectively, and ports 462 and 464 connected to the processing chambers 420 and 422, respectively. Similarly, the transfer chamber 410 has ports 466 and 468 connected to the holding chambers 416 and 418, respectively, and ports 470, 472, 474, and 476 connected to the processing chambers 424, 426, 428, and 430, respectively. Ports 454, 456, 458, 460, 462, 464, 466, 468, 470, 472, 474, and 476 may be slit valve openings equipped with slit valves to allow wafers to pass through, for example, by transfer robots 412 and 414, and to provide a seal between each chamber to prevent gas from passing between them. Generally, any port is open for wafer transfer; otherwise, the port is closed.

[0070]

[0076] The load lock chambers 404, 406, transfer chambers 408, 410, holding chambers 416, 418, and processing chambers 420, 422, 424, 426, 428, 430 may be fluidly connected to gas and pressure control systems (not shown). The gas and pressure control system may include one or more gas pumps (e.g., turbopumps, cryopumps, roughing pumps), a gas source, various valves, and conduits fluidly connected to various chambers. During operation, the factory interface robot 442 transfers the wafer from the FOUP 444 to the load lock chamber 404 or 406 via port 450 or 452. The gas and pressure control system then pumps down the load lock chamber 404 or 406. The gas and pressure control system further maintains the transfer chambers 408, 410 and the holding chambers 416, 418 in an internal low-pressure or vacuum environment (which may include an inert gas). Thus, the pumping down of the load lock chamber 404 or 406 facilitates the passage of the wafer between, for example, the atmospheric environment of the factory interface 402 and the low-pressure or vacuum environment of the transfer chamber 408.

[0071]

[0077] With the wafer in load lock chamber 404 or 406 being pumped down, the transfer robot 412 transfers the wafer from load lock chamber 404 or 406 to transfer chamber 408 via port 454 or 456. The transfer robot 412 can then transfer the wafer to either processing chamber 420 or 422 via ports 462 or 464 for processing, or to holding chambers 416 or 418 via ports 458 or 460 to hold for further transfer. Similarly, the transfer robot 414 can access the wafer in holding chamber 416 or 418 via port 466 or 468 and transfer the wafer to or between any of processing chambers 424, 426, 428, or 430 via ports 470, 472, 474, or 476 for processing, and to holding chambers 416 or 418 via ports 466 or 468 to hold for further transfer. Wafer transfer and holding within and between various chambers can be performed in a low-pressure or vacuum environment provided by a gas and pressure control system.

[0072]

[0078] Processing chambers 420, 422, 424, 426, 428, and 430 can be any suitable chamber for processing wafers. In some embodiments, processing chamber 420 can perform an annealing process, processing chamber 422 can perform a cleaning process, and processing chambers 424, 426, 428, and 430 can perform an epitaxial growth process. In some examples, processing chamber 422 can perform a cleaning process, processing chamber 420 can perform an etching process, and processing chambers 424, 426, 428, and 430 can perform their respective epitaxial growth processes. Processing chamber 422 can be any suitable pre-cleaning chamber. Processing chamber 420 can be any suitable etching chamber.

[0073]

[0079] The system controller 490 is connected to the processing system 400 to control the processing system 400 or its components. For example, the system controller 490 can control the operation of the processing system 400 by using direct control of the chambers 404, 406, 408, 416, 418, 410, 420, 422, 424, 426, 428, and 430 of the processing system 400, or by controlling controllers associated with the chambers 404, 406, 408, 416, 418, 410, 420, 422, 424, 426, 428, and 430. During operation, the system controller 490 enables data acquisition and feedback from each chamber to adjust the performance of the processing system 400.

[0074]

[0080] The system controller 490 generally includes a central processing unit (CPU) 492, memory 494, and support circuitry 496. The CPU 492 may be any form of general-purpose processor available for use in an industrial environment. Memory 494, or non-temporary computer-readable media, is accessible by the CPU 492 and may be one or more types of memory, such as random access memory (RAM), read-only memory (ROM), floppy disks, hard disks, or other forms of local or remote digital storage. Support circuitry 496 is connected to the CPU 492 and may include a cache, clock circuitry, input / output subsystems, power supply, etc. The various methods disclosed herein can generally be implemented by the CPU 492 executing computer instruction code stored in memory 494 (or the memory of a particular process chamber) under the control of the CPU 492, for example, as software routines. Once the computer instruction code is executed by the CPU 492, the CPU 492 controls each chamber to execute processes according to various schemes.

[0075]

[0081] Other processing systems can also be configured in other ways. For example, more or fewer processing chambers can be connected to the transfer device. In the illustrated example, the transfer device includes transfer chambers 408, 410 and holding chambers 416, 418. In other examples, more or fewer transfer chambers (e.g., one transfer chamber) and / or more or fewer holding chambers (e.g., no holding chambers) may be implemented as transfer devices within the processing system.

[0076]

[0082] The process may generally be stored as a software routine in the memory of the system controller 1190, and when executed by the processor, causes the process chamber to execute the process of the present disclosure. The software routine may also be stored and / or executed by a second processor (not shown) located remotely from the hardware controlled by the processor. Some or all of the methods of the present disclosure can also be performed in hardware. Thus, the process may be implemented in software and executed using a computer system in hardware (e.g., application-specific integrated circuits or other types of hardware implementations), or in a combination of software and hardware. When executed by the processor, the software routine transforms a general-purpose computer into a dedicated computer (controller) that controls the chamber operation so that the process can be executed.

[0077]

[0083] Embodiments of this disclosure relate to non-temporary computer-readable media. In one or more embodiments, the non-temporary computer-readable media includes instructions that, when executed by a controller of a processing chamber, cause the processing chamber to perform a step of any of the methods described herein (e.g., Method 100). In one or more embodiments, the controller causes the processing chamber to perform the step of Method 100. In one or more embodiments, the controller causes the processing chamber to perform a step of forming a polymer film on a substrate surface (Step 114). In one or more embodiments, the controller causes the processing chamber to perform a step of removing a metallic material (Step 116).

[0078]

[0084] To describe the relationship between one element or feature and another as shown in the drawings, spatially relative terms such as “beneath,” “below,” “lower,” “above,” and “upper” may be used in this document for ease of explanation. These spatially relative terms are intended to encompass different orientations of the device in use or operation, in addition to the orientation shown in the drawing. Therefore, for example, if the device in the drawing is upside down, an element described as “below” or “beneath” another element or feature would be located “above” that other element or feature. Thus, the exemplary term “below” can encompass both above and below directions. Devices may be oriented in other ways (rotated 90 degrees or in other directions), and the spatially relative descriptions used in this document should be interpreted accordingly.

[0079]

[0085] In the context of describing the materials and methods discussed in this book (particularly in the context of the claims below), the use of “a” and “an,” “the,” and similar referents should be interpreted as encompassing both singular and plural, unless otherwise indicated in this book or unless the context clearly contradicts this interpretation. Enumerations of numerical ranges in this book are merely intended as abbreviations to refer individually to each specific value within that range, unless otherwise indicated in this book, and each specific value is incorporated in this book as if it were individually listed. All methods described in this book may be performed in any appropriate order, unless otherwise indicated in this book or unless the context clearly contradicts this interpretation. Any and all examples or exemplary language provided in this book (e.g., “such as”) are merely intended to better describe the materials and methods and do not limit their scope unless otherwise specified in the claims. Nothing in this document should be interpreted as indicating that any element not specified in the claims is essential for carrying out the disclosed materials and methods.

[0080]

[0086] Throughout this document, any reference to “one embodiment,” “a particular embodiment,” “one or more embodiments,” or “embodiments” means that the specific features, structures, materials, or properties described in relation to an embodiment are included in at least one embodiment of this disclosure. Therefore, phrases such as “in one or more embodiments,” “a particular embodiment,” “in one embodiment,” or “in an embodiment” appearing in various parts of this document do not necessarily refer to the same embodiment of this disclosure. In one or more embodiments, the specific features, structures, materials, or properties are combined in any and appropriate manner.

[0081]

[0087] While the disclosures in this book are described with reference to specific embodiments, it should be understood that these embodiments are merely illustrative of the principles and applications of the disclosure. Those skilled in the art will see that various modifications and variations can be made to the methods and apparatus of the disclosure without departing from the spirit and scope of the disclosure. Therefore, the disclosure is intended to include modifications and variations that fall within the scope of the appended claims and their equivalents.

Claims

1. A method for manufacturing semiconductor devices, A first metal layer is deposited on the surface of a semiconductor substrate having at least one feature formed thereon by physical vapor deposition (PVD), wherein the at least one feature has at least one opening having a width, at least one side wall, and a bottom, the feature depth of the at least one feature extends from the top surface to the bottom, and the first metal layer is formed on the top surface, on the at least one side wall, and on the bottom. Exposing the semiconductor substrate surface to one or more monomers in order to form a fluid polymer film on the first metal layer within at least one feature, wherein the fluid polymer film is formed on the first metal layer on the bottom, and the one or more monomers are selected from one or more of difunctional amines, difunctional aldehydes, difunctional cyanates, difunctional ketones, and difunctional alcohols, Selectively removing at least a portion of the first metal layer from the upper surface and the at least one side wall, and To expose the first metal layer on the bottom of the at least one feature, the fluid polymer film is removed. Methods that include...

2. The method according to claim 1, wherein the first metal layer comprises one or more of tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co), nickel (Ni), titanium (Ti), and tantalum (Ta).

3. The method according to claim 2, wherein the first metal layer formed on the bottom of the at least one feature reacts with the semiconductor substrate surface to form a metal silicide.

4. The aforementioned metal silicide is tungsten silicide (WSi ｘ ), ruthenium silicide (RuSi ｘ ), nickel silicide (NiSi ｘ ), Titanium silicide (TiSi ｘ ), molybdenum silicide (MoSi ｘ ), cobalt silicide (CoSi ｘ ), or tantalum silicide (TaSi ｘ The method according to claim 3, comprising one or more of the following.

5. The method according to claim 1, further comprising selectively depositing a second metal layer on the first metal layer to fill the at least one feature.

6. The method according to claim 5, wherein the second metal layer comprises one or more of tungsten (W), molybdenum (Mo), ruthenium (Ru), cobalt (Co), nickel (Ni), titanium (Ti), or tantalum (Ta).

7. The method according to claim 5, wherein the first metal layer and the second metal layer are the same.

8. The method according to claim 1, wherein the surface of the semiconductor substrate is exposed to one or more monomers at a temperature in the range of 30°C to 400°C.

9. The amine has the formula H ２ N-(CH ｘ ) ｎ -NH ２ where n is an integer in the range of 1 to 20 and x is 1 or 2, the method according to claim 1.

10. The aforementioned aldehyde is of the formula OHC-(CH ｘ ) ｍ The method according to claim 1, wherein -CHO is an integer in the range of 2 to 20, and x is 1 or 2.

11. The aforementioned cyanate is of the formula NCO-(CH ｘ ) ｐ The method according to claim 1, wherein the OCN is an integer in the range of 2 to 20, and x is 1 or 2.

12. The method according to claim 1, wherein the fluid polymer film has flexibility suitable for filling the bottom of the at least one feature.

13. The method according to claim 1, wherein the portion of the first metal layer is selectively removed at a temperature in the range of 100°C to 400°C.

14. The method according to claim 13, wherein selectively removing the portion of the first metal layer includes exposing the semiconductor substrate surface to a fluorine-based plasma or a chlorine-based plasma.

15. Removing the aforementioned fluid polymer film involves heat treatment or hydrogen (H) treatment of the semiconductor substrate surface. ２ The method according to claim 1, comprising exposure to one or more of the plasma treatments.

16. The method according to claim 1, comprising repeating the steps of forming a fluid polymer film on the first metal layer, selectively removing at least a portion of the first metal layer from the top surface and the at least one side wall, and removing the fluid polymer film.

17. The method according to claim 1, wherein the feature depth is in the range of about 5 nm to about 500 nm.

18. The method according to claim 1, wherein the polymer has a thickness less than or equal to the feature depth.

19. The method according to claim 18, wherein the thickness is in the range of about 1% to about 99% of the feature depth.

20. A method for forming a semiconductor device, A method for depositing a first metal layer on a substrate surface on which at least one feature is formed, wherein the at least one feature includes at least one opening, at least one side wall, and a bottom, the feature depth of the at least one feature extends from the top surface to the bottom, and the first metal layer is formed on the top surface, on the at least one side wall, and on the bottom. Exposing the substrate surface to one or more monomers in order to form a fluid polymer film on the first metal layer within at least one feature, wherein the fluid polymer film is formed on the first metal layer on the bottom, and the one or more monomers are selected from one or more of difunctional amines, difunctional aldehydes, difunctional cyanates, difunctional ketones, and difunctional alcohols, Selectively removing the first metal layer from the upper surface and the at least one side wall, To expose the first metal layer on the bottom of at least one feature, remove the fluid polymer film, and To fill at least one of the features, a second metal layer is selectively deposited on the first metal layer. Methods that include...

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