Surface modification for metal-containing photoresist deposition

Abstract

To provide a method, apparatus, and system for improving adhesion between a substrate and a metal-containing photoresist.SOLUTION: Receiving a substrate in a reaction chamber, the substrate having an exposed first material on a surface thereof, the first material comprising a silicon-based material and / or a carbon-based material; generating a plasma comprising chemical functional groups from a plasma generating gas source that is substantially free of silicon; Exposing the substrate to a plasma to modify the substrate surface by forming bonds between the first material and chemical functional groups of the plasma, and depositing a metal-containing photoresist on the modified surface of the substrate, wherein the bonds between the first material and the chemical functional groups of the plasma improve adhesion between the substrate and the metal-containing photoresist.SELECTED DRAWING: Figure 5

Description

[Background technology]

[0001] [Incorporated by reference] A PCT application is filed concurrently herewith as part of this application. Each application to which this application claims the benefit or priority identified in the concurrently filed PCT application is incorporated herein by reference in its entirety for all purposes.

[0002] As semiconductor manufacturing continues to advance, feature sizes continue to shrink, requiring new processing methods. One area of ​​advancement is patterning, for example, with metal-containing photoresist materials (including, but not limited to, materials sensitive to EUV radiation).

[0003] The Background Art set forth herein is intended to present the contents of the present disclosure generally, and the inventions of the presently named inventors are not admitted expressly or impliedly as prior art to the present disclosure to the extent that they are described in this Background Art section and in a descriptive manner that does not constitute prior art at the time of filing. Summary of the Invention

[0004] Various embodiments herein relate to methods, apparatus, and systems for processing semiconductor substrates that improve adhesion between the substrate and a metal-containing photoresist.

[0005] In one aspect of the disclosed embodiments, a method for improving adhesion between a substrate and a metal-containing photoresist is provided, the method including: (a) providing a substrate having a surface including a first material, the first material including a silicon-based material and / or a carbon-based material; (b) generating a plasma from a plasma-generating gas source, the plasma-generating gas source being substantially silicon-free and the plasma including chemical functional groups; (c) exposing the substrate to the plasma to modify the surface of the substrate by forming bonds between the first material and the chemical functional groups of the plasma; and (d) after (c), depositing a metal-containing photoresist on the modified surface of the substrate, wherein the bonds between the first material and the chemical functional groups of the plasma improve adhesion between the substrate and the metal-containing photoresist.

[0006] In various embodiments, one or more specific plasma generating gas sources may be used. In many cases, the plasma generating gas source may include at least one organic species. For example, in some embodiments, the plasma generating gas source may include carbon dioxide. In these or other embodiments, the plasma generating gas source may include carbon monoxide. In these or other embodiments, the plasma generating gas source may include water vapor. In these or other embodiments, the plasma generating gas source may include alcohol vapor. In these or other embodiments, the plasma generating gas source may include a halogen gas. In these or other embodiments, the plasma generating gas source may include diatomic oxygen (O) and / or ozone (O). In these or other embodiments, the plasma generating gas source may include hydrogen peroxide (H). In these or other embodiments, the plasma may include one or more chemical functional groups selected from the group consisting of O radicals, OH radicals, CO radicals, Cl radicals, Br radicals, I radicals, and combinations thereof.

[0007] In various embodiments, the plasma-generating gas source is substantially free of active nitrogen. In these or other embodiments, the plasma-generating gas source may further include an inert gas and / or hydrogen (H).

[0008] A variety of different plasma configurations may be used. In some cases, the plasma may be generated remotely and delivered to a reaction chamber where the substrate is exposed to the plasma. In other cases, the plasma may be generated in-situ in a reaction chamber where the substrate is exposed to the plasma.

[0009] The first material on the substrate may have a particular composition. For example, in some cases, the first material may include amorphous carbon, spin-on carbon, spin-on glass, silicon carbide, or silicon oxycarbide. In some cases, the first material includes amorphous silicon, silicon oxide, silicon nitride, or silicon oxynitride.

[0010] The methods herein may be used to promote the formation of specific bond structures. In various embodiments, bonding of the first material with the chemical functional groups of the plasma promotes the formation of metal-oxygen bonds on the substrate surface while depositing the metal-containing photoresist in (d), thereby improving adhesion between the substrate and the metal-containing photoresist. In certain embodiments, exposure of the substrate to the plasma may form C=O bonds, C—OH bonds, C—Cl bonds, C—Br bonds, CI bonds, Si—O bonds, Si—OH bonds, Si—Cl bonds, Si—Br bonds, Si—I bonds, or combinations thereof. In various embodiments, depositing a metal-containing photoresist on the modified surface of the substrate forms C—O-metal bonds and / or Si—O-metal bonds.

[0011] The methods described herein may be performed using one or more reaction chambers. The one or more reaction chambers may also be used for deposition, etching, substrate processing, etc. For example, in some cases, (c) may occur after the first material is deposited on the substrate, in the reaction chamber in which the first material is deposited on the substrate. In these or other embodiments, (c) and (d) may occur in the same reaction chamber.

[0012] In some embodiments, the method may further include, prior to (d), exposing the substrate to a second plasma comprising an inert gas, wherein exposing the substrate to the second plasma increases the surface area of ​​the substrate, which can further improve adhesion between the first material and the metal-containing photoresist.

[0013] In some embodiments, the first material can be a hard mask material. In some embodiments, the first material can be a porous interfacial layer. In various embodiments, the plasma-generating gas source can include carbon dioxide, and the method can further include waiting at least about 3 hours between exposing the substrate to the plasma in (c) and depositing the metal-containing photoresist in (d). In some embodiments, exposing the substrate to the plasma in (c) modifies only the top 5 Å or less of the first material. In various embodiments, exposing the substrate to the plasma in (c) does not result in increased formation of photoresist scum when the metal-containing photoresist is developed.

[0014] In some cases, specific process conditions may be used. For example, in some cases, the plasma generating gas source includes carbon dioxide, and the plasma may be generated at a pressure of about 5-100 mTorr and an RF power of about 50-1,000 W. In some cases, the plasma generating gas source includes water, and the plasma may be generated at a pressure of about 5-300 mTorr and an RF power of about 100-2,000 W. In various embodiments, the plasma generating gas source may flow at a rate of about 100-5,000 sccm between (b) and (c). In these or other embodiments, (c) may occur at a temperature of about 20-100°C. In some embodiments, the method may further include applying a bias of up to about 100 V to the substrate while the substrate is exposed to the plasma in (c) or while the substrate is exposed to the second plasma prior to (c), where application of the bias to the substrate attracts ions to the substrate surface, thereby roughening the substrate surface. In some such cases, the bias applied to the substrate may be between about 0 and 50V.

[0015] In another aspect of the disclosed embodiments, a system for improving adhesion between a substrate and a metal-containing photoresist is provided, the system comprising at least one reaction chamber, at least one plasma generator, at least one inlet for providing gas and / or plasma to the at least one reaction chamber, and a controller having at least one processor configured to control the at least one reaction chamber, the at least one plasma generator, and the at least one inlet to effect any of the claimed methods or methods otherwise described herein.

[0016] In a further aspect of the disclosed embodiments, a system for improving adhesion between a substrate and a metal-containing photoresist comprises at least one reaction chamber, at least one plasma generator, at least one inlet for providing gas and / or plasma to the at least one reaction chamber, and a controller having at least one processor, wherein the at least one processor controls the at least one reaction chamber, the at least one plasma generator, and the at least one inlet to (a) cause the at least one reaction chamber to receive a substrate having a surface including a first material, the first material including a silicon-based material and / or a carbon-based material; (b) generate a plasma including chemical functional groups from a plasma-generating gas source; (c) provide the plasma in the at least one reaction chamber, wherein a surface of the substrate is modified by bonds formed between the first material and the chemical functional groups of the plasma; and (d) after (c), provide a metal-containing photoresist in the at least one reaction chamber, wherein the metal-containing photoresist deposits on the modified surface of the substrate, and wherein the bonds between the first material and the chemical functional groups of the plasma improve adhesion between the substrate and the metal-containing photoresist.

[0017] In some such embodiments, the at least one processor controls the at least one inlet to provide the plasma and the metal-containing photoresist to one particular one of the at least one reaction chambers, hi other embodiments, the at least one processor controls the at least one inlet to provide the plasma and the metal-containing photoresist to two different ones of the at least one reaction chambers.

[0018] In a further aspect of the disclosed embodiments, a structure is provided comprising: a substrate; a first material deposited on the substrate, the first material being silicon-based or carbon-based and having a modified surface including hydroxyl groups; and a metal-containing photoresist deposited on the modified surface of the first material, wherein the metal-containing photoresist and the modified surface form metal-oxygen-silicon bonds and / or metal-oxygen-carbon bonds. [Brief explanation of the drawings]

[0019] [Figure 1A] 1A and 1B illustrate a semiconductor substrate when subjected to a patterning operation, particularly illustrating defect problems that may arise. [Figure 1B] 1A and 1B illustrate a semiconductor substrate when subjected to a patterning operation, particularly illustrating defect problems that may arise. [Figure 1C] 1A and 1B illustrate a semiconductor substrate when subjected to a patterning operation, particularly illustrating defect problems that may arise. [Figure 1D] 1A and 1B illustrate a semiconductor substrate when subjected to a patterning operation, particularly illustrating defect problems that may arise. [Figure 1E] 1A and 1B illustrate a semiconductor substrate when subjected to a patterning operation, particularly illustrating defect problems that may arise. [Figure 1F] 1A and 1B illustrate a semiconductor substrate when subjected to a patterning operation, particularly illustrating defect problems that may arise.

[0020] [Figure 2A] 1 shows a semiconductor substrate when subjected to a patterning operation according to various embodiments herein. [Figure 2B] 1 shows a semiconductor substrate when subjected to a patterning operation according to various embodiments herein. [Figure 2C] 1 shows a semiconductor substrate when subjected to a patterning operation according to various embodiments herein. [Figure 2D] 1 shows a semiconductor substrate when subjected to a patterning operation according to various embodiments herein. [Figure 2E] 1 shows a semiconductor substrate when subjected to a patterning operation according to various embodiments herein. [Figure 2F] 1 shows a semiconductor substrate when subjected to a patterning operation according to various embodiments herein.

[0021] [Figure 3A] Due to the embodiment in which the substrate is exposed to a plasma generated from water, various chemical species may be present on or near the substrate surface when the substrate is subjected to a patterning operation. [Figure 3B] Due to the embodiment in which the substrate is exposed to a plasma generated from water, various chemical species may be present on or near the substrate surface when the substrate is subjected to a patterning operation. [Figure 3C] Due to the embodiment in which the substrate is exposed to a plasma generated from water, various chemical species may be present on or near the substrate surface when the substrate is subjected to a patterning operation.

[0022] [Figure 4A] Due to the embodiment in which the substrate is exposed to a plasma generated from carbon dioxide, various chemical species may be present on or near the substrate surface when the substrate undergoes a patterning operation. [Figure 4B] Due to the embodiment in which the substrate is exposed to a plasma generated from carbon dioxide, various chemical species may be present on or near the substrate surface when the substrate undergoes a patterning operation. [Figure 4C] Due to the embodiment in which the substrate is exposed to a plasma generated from carbon dioxide, various chemical species may be present on or near the substrate surface when the substrate undergoes a patterning operation. [Figure 4D]Due to the embodiment in which the substrate is exposed to a plasma generated from carbon dioxide, various chemical species may be present on or near the substrate surface when the substrate undergoes a patterning operation.

[0023] [Figure 5] A processing station that can be used to deposit material and / or expose a substrate to a plasma, according to various embodiments.

[0024] [Figure 6] A multi-station processing tool that can be used to deposit material, expose a substrate to a plasma, and / or perform other operations described herein. [Figure 7] A multi-station processing tool that can be used to deposit material, expose a substrate to a plasma, and / or perform other operations described herein.

[0025] [Figure 8] An inductively coupled plasma processing apparatus that can be used to expose a substrate to a plasma and / or perform other operations described herein.

[0026] [Figure 9] A semiconductor process cluster architecture comprising various modules that may be configured to expose a substrate to a plasma and / or perform other operations described herein.

[0027] [Figure 10] Experimental results investigating the effect of different plasma treatments on water contact angle.

[0028] [Figure 11] Experimental results investigating the effect of time on water contact angle following carbon dioxide-based plasma treatment.

[0029] [Figure 12] Experimental results investigating the effect of time on dose versus size following carbon dioxide-based plasma treatment. DETAILED DESCRIPTION OF THE INVENTION

[0030] In the following description, several specific details are set forth in order to provide a thorough understanding of the present embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been shown in detail in order to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with specific embodiments, it will be understood that no limitation of the disclosed embodiments is intended. The terms resist and photoresist are used interchangeably herein.

[0031] In semiconductor manufacturing, patterning of thin films is often a critical step. Patterning requires lithography. In traditional photolithography (such as 193 nm photolithography), patterning is achieved by emitting photons from a photon source onto a mask, printing a pattern onto a light-sensitive photoresist, thereby causing a chemical reaction in the photoresist that, after development, removes certain portions of the photoresist to form the pattern.

[0032] Leading-edge nodes (as defined by the International Technology Roadmap for Semiconductors) include 22 nm, 16 nm, and beyond. At the 16 nm node, for example, a typical via or line width in a damascene structure is typically about 30 nm or less. Scaling of features in advanced semiconductor integrated circuits (ICs) and other devices is a lithography-driven drive to improve resolution.

[0033] Extreme ultraviolet (EUV) lithography can expand lithography technology by moving to shorter image source wavelengths than are achievable with conventional photolithography methods. State-of-the-art lithography tools (also called scanners) can use EUV light sources with wavelengths of approximately 10-20 nm or 11-14 nm (e.g., 13.5 nm). EUV radiation is strongly absorbed by a wide range of solid and liquid materials, including quartz and water vapor, and therefore operates in a vacuum.

[0034] EUV lithography utilizes EUV resists that can be patterned with EUV light to form masks for use in etching underlying layers. In some cases, the EUV resists are polymeric chemically amplified resists (CARs) formed by liquid spin-on techniques. An alternative to CARs are metal-containing EUV photoresist films that can be directly photopatterned. Such resist films may be formed by (wet) spin-on techniques and are available from Inpria, Inc. of Corvallis, Oregon, and may be, for example, those described in U.S. Patent Publications US 2017 / 0102612 and US 2016 / 0116839, which are incorporated herein by reference for their disclosure of at least photopatternable metal oxide-containing films, or may be dry-deposited as described in PCT Application No. US 19 / 31618, filed May 9, 2019, entitled "METHODS FOR MASKING EUV PATTERNABLE HARD MASKS," which discloses at least the composition and patterning of directly photopatternable metal oxide films to form EUV resist masks, the disclosures of which are incorporated herein by reference. These directly photopatternable EUV resists may be composed of or include metals and their organometallic oxides / hydroxides and other derivatives that have high EUV absorption. Upon EUV exposure, EUV photons and generated secondary electrons initiate a chemical reaction (SnO xThese organometallic resists are highly promising in that they promote EUV photon adsorption, generate secondary electrons, and / or exhibit enhanced etch selectivity relative to underlying film stacks and device layers.

[0035] Although the techniques herein are presented for patterning applications using metal-containing resists sensitive to EUV radiation, embodiments are not so limited. In general, the techniques herein are broadly applicable to a variety of patterning applications using metal-containing resists. That is, in various embodiments, the deposited metal-containing resist material may be sensitive to radiation other than EUV radiation (such as radiation at conventional lithography wavelengths).

[0036] Current metal-containing resist materials (as well as other resist materials) often suffer from poor adhesion to the underlayer. The underlayer can be a variety of materials, such as amorphous carbon, spin-on carbon, spin-on glass, amorphous silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, etc. In many cases, the underlayer is a hard mask layer. In various cases, the underlayer is a silicon-based material or a carbon-based material. Other elements that may be present include, for example, oxygen, nitrogen, and hydrogen.

[0037] To overcome adhesion problems, a relatively thick adhesion layer (sometimes called an underlayer) is often provided between the underlayer and the resist layer. The adhesion layer promotes high-quality adhesion between the underlayer and the resist layer, thereby reducing the risk of delamination of these layers during subsequent processing. Alternatively or additionally, in some cases, the resist layer may be deposited to include an adhesion promoter in the resist material. In another approach used with conventional chemically amplified resists, the underlayer may be exposed to hexamethyldisilazane (HMDS) in vapor form prior to resist deposition to improve adhesion between the underlayer and the resist.

[0038] However, these techniques can cause significant problems during pattern transfer, as shown in Figures 1A-1F, which depict semi-finished semiconductor substrates in the course of several patterning operations. Figure 1A shows a semiconductor substrate 101 having an underlayer 102 formed thereon. The underlayer 102 may include any of the underlayer materials described above. After the underlayer 102 is formed on the substrate 101, an adhesion layer 103 is formed on the underlayer 102, as shown in Figure 1B. In one example, the adhesion layer 103 is spin-on carbon or spin-on glass and is deposited to a thickness of approximately 5-10 nm. Next, a resist layer 104 is deposited on the adhesion layer 103, as shown in Figure 1C. After deposition, the resist layer 104 is exposed to radiation in a lithography operation to form exposed regions 104a and unexposed regions 104b, as shown in Figure 1D. The resist layer 104 is then developed, thereby removing the unexposed regions 104b while leaving the exposed regions 104a on the substrate 101, as shown in Figure 1E. The exposed regions 104a of the resist layer 104 are then used as a mask to etch recessed features through the adhesion layer 103 and down to the underlying layer 102, as shown in Figure 1F. In other examples, depending on the materials used, the exposed regions 104a may be removed, leaving unexposed regions 104b.

[0039] The presence of the adhesion layer 103 often leads to the formation of defects, such as the foot defect 105 and bridge defect 106 shown in FIG. 1F. The foot defect 105 can occur when the adhesion layer 103 and the underlying layer 102 are etched, but the etched feature does not meet sufficient dimensional or uniformity requirements. For example, the foot defect 105 shown in FIG. 1F has a non-uniform width throughout the adhesion layer 103, resulting in insufficient width through some depth of the adhesion layer 103 and the underlying layer 102, resulting in a reduction in the critical dimension of the etched feature. In this case, the bottom of the etched feature has a smaller critical dimension than its top, which is undesirable (e.g., because the bottom of the feature is too narrow). The bridge defect 106 can occur when the adhesion layer 103 is not etched through its entire thickness. If this occurs, the formation of a recessed feature in the underlying layer 102 is prevented. These foot defects 105 and bridge defects 106 can cause not only feature defects (eg, missing vias and holes), but also incomplete openings and incomplete electrical connections.

[0040] In various cases, foot and bridge defects can occur due to insufficient etching of the adhesion layer, which results from photoresist scum. Photoresist scum can be caused by interdiffusion of elements between the photoresist and the underlying layer. When a conventional chemically amplified resist is used, the adhesion layer can be a relatively thin layer formed by exposing the underlayer to a hexamethyldisilazane (HMDS) vapor priming process. The HMDS vapor priming process improves adhesion between the underlayer and the resist layer due to the presence of silicon and / or nitrogen provided by the HMDS. However, the silicon and / or nitrogen from the HMDS (and / or other adhesion layer materials) can result in a significant amount of photoresist scum after the resist layer is developed. Photoresist scum generally refers to materials (e.g., resist material and materials that react with the resist material) that are undesirably left on the substrate after the resist layer is developed. Such materials are often left near the bottom of recessed features, especially in the bottom corners. Photoresist scum, for example, frequently causes the formation of foot and bridge type defects because it exhibits a lower etch rate than other materials being etched at the same time. This can be particularly problematic when the underlying material contains carbon or other materials that are etched by O2-based chemistries that are ineffective at removing silicon and nitrogen.

[0041] To avoid the defect problems associated with the method shown in FIGS. 1A-1F, a separate surface treatment can be performed to improve adhesion between the underlayer and the resist layer without increasing the formation of photoresist scum. The surface treatment may have the advantage of reducing dose-to-size, as further described below. FIGS. 2A-2F illustrate an exemplary process. FIG. 2A depicts a substrate 201 having an underlayer 202 formed thereon. The underlayer 202 may include any of the underlayer materials described above. After the underlayer 202 is deposited, the substrate 201 is exposed to a plasma generated from a plasma-generating gas source to form a thin layer of a modified material 203 on the top surface of the underlayer 202, as shown in FIG. 2B. The modified material 203 is typically very thin (e.g., about 1-5 monolayers thick or about 1-2 monolayers thick). This may correspond to a modified material thickness of about 2-5 Å. The thickness of the modified material 203 is greatly exaggerated in FIGS. 2B-2F for illustrative purposes. In various cases, exposure of the substrate to the plasma modifies only the top 5 Å or less of the underlying layer 202 .

[0042] The plasma contains chemical functional groups that modify the surface of the foundation layer 202. A variety of different types of chemical functional groups may be used.

[0043] In some embodiments, the plasma generating gas source includes oxygen or other oxygen-containing species, and the plasma includes oxygen radicals and / or oxygen-containing radicals (e.g., O radicals, OH radicals, CO radicals, etc.) that can react with the underlying layer 202. In some embodiments, the plasma generating gas source includes one or more halogen gases, such as chlorine (Cl), bromine (Br), or iodine (I), and the plasma includes chlorine radicals, bromine radicals, iodine radicals, or combinations thereof. The reaction to form the modified material 203 may be self-limiting.

[0044] Exposure of the substrate to the plasma can result in the formation of bonds between the underlying layer 202 and chemical functional groups in the plasma. For example, in some cases where the underlying layer 202 includes silicon and / or carbon and the plasma-generating gas includes oxygen or other oxygen-containing species, exposure of the underlying layer 202 to the plasma can result in the formation of bonds between (1) carbon and / or silicon from the underlying layer 202 and (2) oxygen from the chemical functional groups in the plasma. That is, exposure of the underlying layer 202 to the plasma can result in the formation of C-O bonds (and in some cases C-OH bonds), Si-O bonds (and in some cases Si-OH bonds), or a combination thereof, depending on the material of the underlying layer 202 and the composition of the plasma. Similarly, in some cases where the underlying layer 202 includes silicon and / or carbon and the plasma-generating gas includes a halogen gas, exposure of the underlying layer 202 to the plasma can result in the formation of bonds between (1) carbon and / or silicon from the underlying layer 202 and (2) halogen from the chemical functional groups in the plasma. In this case, exposure of the underlayer 202 to plasma may result in the formation of C-halogen bonds (e.g., C-Cl bonds, C-Br bonds, CI bonds, etc.), Si-halogen bonds (e.g., Si-Cl bonds, Si-Br bonds, Si-I bonds, etc.), or combinations thereof. The plasma treatment results in highly stable bonds between the underlayer 202 and the modified material 203. In some cases, the modified material 203 includes -OH terminations, -O terminations, -Cl terminations, -Br terminations, and / or -I terminations.

[0045] In some embodiments, as further described below in connection with FIG. 4C , the modified material 203 is further modified after its initial formation. This further modification involves converting some or all of the —O terminations (or other terminations present on the substrate surface) to —OH terminations. This further modification may be achieved by exposing the substrate to moisture (e.g., HO) and / or another hydroxyl-containing species. In certain examples, the further modification simply involves ensuring that there is a waiting period (e.g., 3 hours or more, possibly 3-24 hours) after exposure of the underlying material 202 to the plasma and before deposition of the resist layer 204, during which the substrate is exposed to air (or other moisture / hydroxyl-containing environment).

[0046] After the modifying material 203 is formed, the resist layer 204 is deposited as shown in FIG. 2C. The resist layer 204 is a metal-containing resist material as described above. During deposition of the resist layer 204, bonding of chemical functional groups (e.g., oxygen, halogen, etc.) from the plasma with the underlayer 202 improves adhesion between the substrate (e.g., carbon and / or silicon of the underlayer 202) and the resist layer 204 (e.g., metal atoms of the resist layer 204). For example, if the modifying material 203 contains -OH terminations, metal from the resist layer 204 (or the metal-containing precursor used to form the resist layer 204) may react with the -OH terminations in the modifying material 203, thereby forming O-metal bonds. For example, if the underlayer 202 contains silicon, deposition of the resist layer 204 may result in the formation of Si-O-metal bonds. Similarly, if the underlayer 202 contains carbon, deposition of the resist layer may result in the formation of C-O-metal bonds. In another example where the modifying material 203 includes a -halogen termination, the highly active -halogen termination is believed to readily displace metal from the resist layer 204 (or a metal-containing precursor used to form the resist layer 204) to form C-metal bonds and / or Si-metal bonds. The resulting bond structure provides excellent adhesion between the underlayer 202 and the resist layer 204. Furthermore, the excellent adhesion is achieved without the introduction of additional silicon or nitrogen, which can cause significant photoresist scumming problems and result in significant defects.

[0047] Next, substrate 201 is exposed to radiation in a lithography operation to form exposed portions 204a and unexposed portions 204b of resist layer 204, as shown in FIG. 2D. Resist layer 204 is then developed to remove unexposed portions 204b while leaving exposed portions 204a on substrate 201, as shown in FIG. 2E. Wet or dry development methods may be used. After development, the recessed features defined by exposed portions 204a of resist layer 204 extend through modified material 203 to underlying material 202, as shown in FIG. 2F. Because modified material 203 is very thin and substantially silicon- and nitrogen-free, it does not cause the defect problem described in connection with FIG. 1F. This is a significant improvement.

[0048] In addition to preventing the defects described in connection with FIGS. 1A-1F and 2A-2F, the techniques described herein can provide the additional benefit of reducing dose-to-size. Generally, it is desirable to create a target amount of cross-linking within a resist layer to achieve acceptable lithography and etching results. Some of this cross-linking may be achieved by exposing the photoresist to EUV radiation. However, it is also generally desirable to minimize the amount of EUV radiation irradiated onto a substrate, e.g., to reduce dose-to-size. The techniques described herein have been shown to advantageously reduce the amount of EUV radiation required to achieve a target degree of cross-linking within a resist layer. These results are further explained in the Experimental Section below.

[0049] 3A-3C depict an embodiment in which an underlayer is modified by exposing the underlayer to a water-generated plasma. FIG. 3A shows the material present in underlayer 302 prior to modification. In this particular example, underlayer 302 is a carbon-containing, ashable hardmask material, although it is understood that other carbon- and silicon-based materials may be used in other cases with similar effectiveness.

[0050] 3B shows the underlying layer 302 undergoing modification and materials present in the nearby plasma 310 while the substrate is exposed to the plasma 310. As noted above, in this example, the plasma 310 is generated from water and therefore contains HO, H radicals, OH radicals, and ions. The plasma 310 breaks C=C bonds on the top surface of the underlying layer 302, forming active CO-OH groups at the α-carbon positions.

[0051] 3C shows the materials present on the substrate during the initial stages of depositing resist layer 304 on underlying material 302. In this example, resist layer 304 is a tin-based organometallic material, although other metal-containing resist materials may be used. As resist layer 304 is deposited, the metal in the metal-containing resist precursor reacts with CO—OH groups, thereby forming CO—Sn bond structures that fully bond the tin in resist layer 304 to the carbon in underlying layer 302. Further cross-linking may occur as the complete resist layer 304 is deposited, forming, for example, Sn—O—Sn bond structures. Further cross-linking may occur during a subsequent heating step in which the resist layer is exposed to elevated temperatures.

[0052] In some embodiments in which the plasma is generated from water, one or more of the following reaction conditions may be used: The pressure of the reaction chamber may be about 5-300 mTorr, and in some cases, about 100-200 mTorr. The RF power used to generate the plasma may be about 100-2000 W, and in some cases, about 500-1000 W. Water may be provided at a flow rate of about 100-5000 sccm, and in some cases, about 100-500 sccm. The substrate may be placed on a temperature-controlled substrate support. The substrate support may be maintained at a temperature of about 20-100°C, and in some cases, about 20-30°C, during exposure of the substrate to the plasma. A bias of, for example, up to about 50 V may be applied to the substrate during plasma processing. Experimental results for such embodiments are described in the Experimental Section below.

[0053] 4A-4D depict an embodiment in which an underlayer is modified by exposing the underlayer to a plasma generated from carbon dioxide. Figure 4A shows the material present in underlayer 402 before modification. In this example, underlayer 402 is a carbon-containing ashable hardmask material, although it is understood that other carbon- and silicon-based materials may be used in other cases with similar effect.

[0054] 4B shows the underlying layer 402 undergoing modification and the material present in the nearby plasma 410 while the substrate is exposed to the plasma 410. The plasma 410 breaks C=C bonds on the top surface of the underlying layer 402 and inserts CO groups at the α-carbon positions.

[0055] 4C shows materials present in the underlayer 402 and nearby atmosphere 411 during a period of time after the underlayer 402 is exposed to the plasma and before the resist layer 404 is deposited. Moisture (HO) present in atmosphere 411 reacts with CO groups on the surface of the underlayer 402, thereby forming active CO—OH groups. As noted above, in certain embodiments, a waiting period is used after modification of the underlayer and before deposition of the resist layer to ensure that the underlayer 402 is properly saturated with CO—OH groups and / or other hydroxyl terminations.

[0056] 4D shows the materials present on the substrate during the initial stages of deposition of resist layer 404. In this example, resist layer 404 is a tin-based organometallic material, although other metal-containing resist materials may be used. As resist layer 404 is deposited, the metal in the metal-containing resist precursor reacts with CO—OH groups (or other hydroxyl-terminated groups), thereby forming CO—Sn bond structures that bond the tin in resist layer 404 to the carbon in underlying layer 402. Further cross-linking occurs as the complete resist layer 404 is deposited, forming, for example, Sn—O—Sn bond structures. Further cross-linking may occur in a subsequent heating step, as described above.

[0057] In some embodiments in which the plasma is generated from carbon dioxide, one or more of the following reaction conditions may be used: The pressure of the reaction chamber may be about 5-100 mTorr, and in some cases, about 10-30 mTorr. The RF power used to generate the plasma may be about 50-1000 W, and in some cases, about 100-200 W. The carbon dioxide may be provided at a flow rate of about 100-5000 sccm, and in some cases, about 100-500 sccm. The substrate may be placed on a temperature-controlled substrate support. The substrate support may be maintained at a temperature of about 20-100°C, and in some cases, about 20-30°C, during exposure of the substrate to the plasma. A bias of, for example, up to about 50 V may be applied to the substrate during plasma processing. Experimental results for such embodiments are described in the Experimental Section below.

[0058] While exemplary processing conditions are provided in connection with Figures 3A-3C and 4A-4D, it is understood that similar or different processing conditions may be used in other embodiments in which the plasma is generated from different or additional species (e.g., halogens or other species). Generally, regardless of the plasma composition, one or more of the following processing conditions may be used in various embodiments: The pressure of the reaction chamber may be about 5-500 mTorr, about 5-300 mTorr, about 5-100 mTorr, about 10-30 mTorr, or about 100-200 mTorr. The RF power used to generate the plasma may be about 50-3000 W, about 50-2000 W, about 50-1000 W, about 500-1000 W, about 100-2000 W, or about 100-200 W. A bias may be applied to the substrate, if desired. When a vial is used, the bias may be about 0-500V, about 0-100V, or about 0-50V. The bias may be at least about 1V. The plasma may be generated at a duty cycle of about 20-100%. The gas used to generate the plasma may flow at a rate of about 100-6000sccm, about 100-5000sccm, about 100-1000sccm, or about 100-500sccm. The substrate support may be maintained at a temperature of about 10-120°C, about 20-100°C, about 20-50°C, or about 20-30°C. The substrate may be exposed to the plasma for one continuous period or for multiple discontinuous periods. In some cases, the total period during which the substrate is exposed to the plasma may be about 5-60 seconds or about 10-20 seconds. When the substrate is exposed to the plasma for multiple discrete periods, each plasma exposure period may be about 1-10 seconds. The number of exposure periods may be about 1-50.

[0059] The processing conditions may be controlled to achieve a desired density of -O, -OH, -Cl, -Br, and / or -I terminations on the modified material / underlayer. For example, pressure, gas flow rates and composition ratios, RF power, temperature, and other processing conditions described above may be controlled for this purpose.

[0060] The plasma may be generated in several different ways. In some cases, the plasma is generated remotely and delivered to a chamber / processing space where the substrate is exposed to the plasma. In some cases, the plasma is generated directly in-situ in the chamber / processing space where the substrate is exposed to the plasma. A variety of different types of plasma may be used. In some cases, the plasma is a capacitively coupled plasma. In some cases, the plasma is an inductively coupled plasma.

[0061] The plasma may be generated from several different plasma generating gas sources (e.g., gas / vaporized liquid from which the plasma is generated). Figures 3A-3C relate to an embodiment in which the plasma generating gas source is water, and Figures 4A-4D relate to an embodiment in which the plasma generating gas source is carbon dioxide. In another embodiment, the plasma generating gas source may include both water and carbon dioxide. A variety of other plasma generating gas sources may be used that generate plasmas of desired chemical functional groups. For example, in some cases, the plasma generating gas source may be water (HO), carbon dioxide (CO), carbon monoxide (CO), alcohol (C), or the like. x H y It may include one or more of OH and its substituted forms (specific examples include substituted and unsubstituted forms of methanol, ethanol, propanol, butanol, etc.), diatomic oxygen (O), ozone (O), hydrogen peroxide (H), O), chlorine (Cl), bromine (Br), iodine (I), and the like.

[0062] In some embodiments, the plasma generating gas source includes at least one reactive species that includes only oxygen (e.g., O2, O3, etc.). In some embodiments, the plasma generating gas source includes at least one reactive species that includes only oxygen and hydrogen (e.g., HO, HO, etc.). In some embodiments, the plasma generating gas source includes at least one reactive species that includes only carbon and oxygen (e.g., CO, CO2, etc.). In some embodiments, the plasma generating gas source includes at least one reactive species that includes only carbon, hydrogen, and oxygen (e.g., C x H yThe plasma generating gas source includes at least one reactive species containing OH. Often, the plasma generating gas source includes at least one organic species. In some cases, the plasma generating gas source includes at least one diatomic halogen species.

[0063] In many cases, the plasma-generating gas source may further include H2 and / or inert species (Ar, He, Ne, Kr, Xe, and / or N2). The inert species may be ionized in the plasma, and the ions may bombard the substrate surface, increasing the surface area and roughness of the underlying layer. This increased surface area / roughness provides additional sites where the metal of the resist layer can adhere to the carbon and / or silicon of the underlying layer, for example, through the C-O-metal, Si-O-metal, C-metal, and / or Si-metal bonds described above. Thus, the ion bombardment serves to increase the density of these bonds at the interface between the underlying layer and the resist layer, thereby enhancing adhesion between these layers. In some cases, the inert gas and reactive species in the plasma-generating gas source may be provided to the plasma simultaneously. In other cases, the substrate may be exposed to a first plasma containing an inert gas and then a second plasma containing reactive chemical functionalities in the plasma-generating gas source, with the two plasmas provided at different times. In this case, exposure to the inert gas to increase the surface area / roughness may occur (1) during deposition of the underlying material (e.g., at least during the final stages of this deposition so that the top surface of the underlying material is affected), or (2) after deposition of the underlying material but before exposing the substrate to the plasma.

[0064] Another technique that can be used to increase the surface area to provide additional bonding opportunities is to deposit a thin porous interfacial layer between the underlayer and the resist layer. In this case, the thin porous interfacial layer is a plasma-modified layer. Therefore, details described herein regarding the modification of the underlayer may also apply to the modification of the thin porous interfacial layer. In various embodiments, the thin porous interfacial layer may be a low-density amorphous carbon material. If used, it may be about 2-10 nm thick and / or about 1.0-1.3 g / cm. 3The thin porous interfacial layer may be formed by PECVD.

[0065] The plasma generating gas source may be substantially free of certain elements known to cause photoresist scum and related defects. For example, the plasma generating gas source may be substantially free of silicon and silicon-containing species. In these or other cases, the plasma generating gas source may be substantially free of reactive nitrogen-containing species. As used herein, the term "substantially free" means that the relevant species are not intentionally provided and, if present, are present in only trace amounts. Because the plasma generating gas is substantially free of these species, exposure of the substrate to the plasma does not increase the formation of photoresist scum when metal-containing photoresists are developed. This is significantly different from other surface modifications, including exposure to HMDS, for example. HMDS contains silicon and nitrogen, which leads to the formation of much photoresist scum and the defects shown in Figure 1F.

[0066] One advantage of the technology herein is that it breaks the trade-off between (1) achieving sufficient adhesion between the underlying layer and the metal-containing photoresist and (2) preventing the formation of photoresist scum and associated foot and bridge defects. Previous techniques for improving adhesion between related layers relied on silicon-containing materials (and in some cases silicon- and nitrogen-containing materials), which often cause photoresist scum and associated defects. The plasma treatment described herein promotes high-quality adhesion between the underlying layer and the metal-containing photoresist and achieves this adhesion without the formation of photoresist scum or associated defects. Furthermore, the plasma promotes increased cross-linking within the metal-containing photoresist, thereby reducing the amount of EUV radiation required to achieve the desired amount of cross-linking. In other words, the increased cross-linking caused by exposure of the substrate to the plasma advantageously reduces the dose-to-size ratio.

[0067] While this disclosure relates to lithographic patterning techniques and materials exemplified by EUV lithography, it should be understood that it is also applicable to other next-generation lithography technologies. In addition to EUV, which includes the standard 13.5 nm EUV wavelength currently in use and under development, the radiation source most relevant to such lithography is DUV (deep ultraviolet). DUV generally refers to the use of 248 nm or 193 nm excimer laser sources, X-rays (which officially include EUV, which has a narrower energy range than the X-ray range), and E-beams (which can include a wide range of energies). Particular methods may depend on the specific materials and applications used for the semiconductor substrate and final semiconductor device. Thus, the methods described herein are merely examples of methods and materials that may be used in the present technology. Device

[0068] The techniques described herein may be implemented in a variety of apparatuses, which generally include at least a reaction chamber, a plasma generator, inlets and outlets for supplying and removing materials from the reaction chamber, respectively, a substrate support for supporting a substrate during processing, and a controller configured to perform the methods described herein.

[0069] In some embodiments, the reaction chamber may be located in a stand-alone tool dedicated to exposing substrates to plasma. In other embodiments, the reaction chamber may be located in a separate tool used for other purposes, such as deposition, etching, and / or other substrate processing. In that case, the reaction chamber may be the same reaction chamber used to perform deposition, etching, or other substrate processing, or the reaction chamber may be a different chamber physically connected to the rest of the tool via suitable hardware. In some cases, the reaction chamber may process one substrate at a time. In other cases, the reaction chamber may process multiple substrates at a time. In certain embodiments, the reaction chamber may have multiple stations, each configured to process substrates simultaneously with the other stations. This opens up many possibilities.

[0070] In one example, the reaction chamber used to expose the substrate to the plasma is the same as the reaction chamber used to deposit the underlayer. In one example, the reaction chamber may be a chamber configured to perform an evaporation deposition technique, such as chemical vapor deposition and / or atomic layer deposition. In another example, the reaction chamber used to expose the substrate to the plasma is the same as the reaction chamber used to deposit a metal-containing photoresist, which may also be deposited by an evaporation deposition technique, such as chemical vapor deposition and / or atomic layer deposition, or by a wet technique, such as a spin-on film. In some cases, the deposition of the underlayer, the exposure of the underlayer to the plasma, and the deposition of the metal-containing photoresist may all occur in the same reaction chamber.

[0071] 5-9 depict various different apparatus that may be used to implement the techniques described herein. FIG. 5 schematically illustrates an embodiment of a processing station 500 that may be used to expose a substrate to a plasma and / or deposit a material (e.g., an underlying material and / or a metal-containing photoresist) using atomic layer deposition (ALD) and / or chemical vapor deposition (CVD), either of which may be plasma-enhanced. For simplicity, processing station 500 is depicted as a stand-alone processing station having a processing chamber body 502 for maintaining a low-pressure environment, although it will be appreciated that multiple processing stations 500 may be included in a common processing tool environment. Furthermore, it will be appreciated that in some embodiments, one or more hardware parameters of processing station 500 (including those described in more detail below) may be programmably adjusted by one or more computer controllers.

[0072] The processing station 500 is in fluid communication with a reactant delivery system 501 for supplying process gases to a distribution showerhead 506. The reactant delivery system 501 includes a mixing vessel 504 for mixing and / or conditioning the process gases delivered to the showerhead 506. One or more mixing vessel inlet valves 520 may control the introduction of process gases into the mixing vessel 504. Similarly, a showerhead inlet valve 505 may control the introduction of process gases to the showerhead 506.

[0073] Some reactants, such as BTBAS, may be stored in liquid form prior to vaporization and delivery to a subsequent processing station. For example, the embodiment of FIG. 5 includes an evaporation point 503 for vaporizing the liquid reactant delivered to a mixing vessel 504. In some embodiments, the evaporation point 503 may be a heated vaporizer. The reactant vapor produced in such a vaporizer may condense in downstream delivery lines. Exposure of an incompatible gas to the condensed reactant may form small particles. These small particles can clog piping, interfere with valve operation, and contaminate the substrate. Some approaches to address these issues include sweeping and / or evacuating the delivery lines to remove residual reactants. However, sweeping the delivery lines may increase the cycle time of the processing station and reduce the throughput of the processing station. Thus, in some embodiments, the delivery lines downstream of the evaporation point 503 may be heat traced. In some examples, the mixing vessel 504 may also be heat traced. In one non-limiting example, the piping downstream of the evaporation point 503 has an increasing temperature profile ranging from about 100° C. to about 150° C. at the mixing vessel 504 .

[0074] In some embodiments, the reactant liquid may be vaporized in a liquid injector. For example, the liquid injector may inject pulses of liquid reactant into a carrier gas stream upstream of the mixing vessel. In some situations, the liquid injector may vaporize the reactant by switching the liquid from high pressure to low pressure. In other situations, the liquid injector may atomize the liquid into dispersed droplets, which may then be vaporized in a heated feed tube. It will be appreciated that small droplets evaporate faster than large droplets, reducing the delay between liquid injection and complete evaporation. Rapid evaporation may reduce the length of piping downstream from the evaporation point 503. In some situations, the liquid injector may be attached directly to the mixing vessel 504. In other situations, the liquid injector may be attached directly to the showerhead 506.

[0075] In some embodiments, a liquid flow controller upstream of the evaporation point 503 may be provided to control the mass flow rate of liquid for evaporation and delivery to the processing station 500. For example, the liquid flow controller (LFC) may include a thermal mass flow meter (MFM) located downstream thereof. The plunger valve of the LFC may then be adjusted in response to a feedback control signal provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, stabilizing the liquid flow rate using feedback control can take more than one second, which may extend the time to dispense the liquid reactant. Thus, in some embodiments, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some embodiments, the LFC may be dynamically switched from the feedback control mode to the direct control mode by deactivating the sense tube and PID controller of the LFC.

[0076] The showerhead 506 distributes process gases toward the substrate 512. In the embodiment shown in Figure 5, the substrate 512 is located below the showerhead 506 and is shown resting on a pedestal 508. It will be appreciated that the showerhead 506 may have any suitable shape and may have any suitable number and arrangement of ports for distributing process gases to the substrate 512.

[0077] In some embodiments, a microspace 507 is located below the showerhead 506. Performing plasma exposure, ALD, and / or CVD processes in the microspace rather than the full volume of the processing station can reduce reactant exposure and sweep times, reduce the time to change processing conditions (e.g., pressure, temperature, etc.), and limit exposure of the processing station robot to processing gases. Exemplary microspace sizes include, but are not limited to, volumes of 0.1 to 2 liters. This microspace also impacts productivity throughput. As the deposition rate per cycle decreases, cycle time also decreases. In certain cases, the latter effect can be significant enough to increase overall module throughput for a given target film thickness.

[0078] In some embodiments, the pedestal 508 may be raised or lowered to expose the substrate 512 to the microcavity 507 and / or to modify the deposition in the microcavity 507. For example, during a substrate transfer phase, the pedestal 508 may be lowered to allow the substrate 512 to be loaded onto the pedestal 508. During a deposition process phase or a plasma exposure process phase, the pedestal 508 may be raised to position the substrate 512 within the microcavity 507. In some embodiments, the microcavity 507 may completely surround the substrate 512 and a portion of the pedestal 508 to form a region of high flow impedance during substrate processing operations.

[0079] If desired, the pedestal 508 may be raised or lowered during a process step to adjust the process pressure, reactant concentration, etc. within the microcavity 507. In situations where the process chamber body 502 remains at base pressure during processing, the microcavity 507 may be evacuated by lowering the pedestal 508. Exemplary ratios of microcavity:processing chamber volume include, but are not limited to, volume ratios of 1:500 to 1:10. It will be appreciated that in some embodiments, the pedestal height may be programmably adjusted by a suitable computer controller.

[0080] In other situations, adjusting the height of the pedestal 508 may allow the plasma density to be changed during plasma activation and / or plasma treatment operations involved in a process. The pedestal 508 may be lowered during another substrate transfer step to allow removal of the substrate 512 from the pedestal 508 at the end of the associated process step.

[0081] While the exemplary microcavity variation described herein refers to a height-adjustable pedestal, it will be appreciated that in some embodiments, the position of the showerhead 506 may be adjusted relative to the pedestal 508 to change the volume of the microcavity 507. Furthermore, it will be appreciated that the vertical position of the pedestal 508 and / or the showerhead 506 may be changed by any suitable mechanism within the scope of the present disclosure. In some embodiments, the pedestal 508 may include a rotation axis for rotating the orientation of the substrate 512. It will be appreciated that in some embodiments, one or more of these exemplary adjustments may be programmatically implemented by one or more suitable computer controllers.

[0082] Returning to the embodiment shown in FIG. 5 , the showerhead 506 and pedestal 508 are in electrical communication with an RF power source 514 and matching network 516 for powering plasmas (such as those used to modify the underlying material and those used during other processing steps in the same chamber). In some embodiments, the plasma energy may be controlled by controlling one or more of the process station pressure, gas concentration, RF source power, RF source frequency, and timing of plasma power pulses. For example, the RF power source 514 and matching network 516 may be operated at any suitable power to generate a plasma having a desired composition of radical species. Examples of suitable powers are included above. Similarly, the RF power source 514 may provide RF power at any suitable frequency. In some embodiments, the RF power source 514 may be configured to independently control high-frequency RF power and low-frequency RF power. Examples of low-frequency RF frequencies include, but are not limited to, frequencies between 50 and 500 kHz. Examples of high-frequency RF frequencies include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be adjusted individually or continuously to provide plasma energy for surface reactions. In one non-limiting example, the plasma power may be intermittently pulsed to reduce ion collisions with the substrate surface, as opposed to a continuously powered plasma.

[0083] In some embodiments, the plasma may be monitored in situ by one or more plasma monitors. In some situations, plasma power may be monitored by one or more voltage and current sensors (e.g., VI probes). In other situations, plasma density and / or process gas concentration may be measured by one or more solid-state optical emission spectroscopy (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, OES sensors may be used in a feedback loop to provide programmatic control of plasma power. In some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.

[0084] In some embodiments, the plasma may be controlled by input / output control (IOC) sequence instructions. In one example, instructions for setting plasma conditions for a plasma processing step may be included in a corresponding plasma activation recipe step of a deposition processing recipe. In some cases, process recipe steps may be arranged sequentially such that all instructions for a deposition processing step are executed simultaneously with that processing step. In some embodiments, instructions for setting one or more plasma parameters may be included in a recipe step prior to the plasma processing step. For example, a first recipe step may include instructions for setting the flow rates of an inert gas and / or a reactive gas, instructions for setting a plasma generator to a power setpoint, and a time delay instruction for the first recipe step. A subsequent second recipe step may include instructions for turning on the plasma generator and a time delay instruction for the second recipe step. A third recipe step may include instructions for turning off the plasma generator and a time delay instruction for the third recipe step. It will be appreciated that these recipe steps may be further subdivided and / or repeated in any suitable manner within the scope of the present disclosure.

[0085] In some deposition processes, plasma firing lasts for periods of about several seconds or longer. In certain embodiments, shorter plasma firing periods may be used. These may be about 10 microseconds to 1 second (typically about 20 to 80 microseconds), with 50 microseconds being a specific example. Such very short RF plasma firing periods require extremely rapid plasma stabilization. To achieve this, the plasma generator may be configured so that the impedance match is set to a specific voltage while allowing the frequency to float. Traditionally, RF plasmas are generated at an RF frequency of about 13.56 MHz. In various embodiments disclosed herein, the frequency can float to values ​​different from this standard value. By floating the frequency while fixing the impedance match at a predetermined voltage, the plasma can stabilize much more quickly, which can be a very important result when using very short plasma firing periods associated with some types of deposition cycles or other processing cycles.

[0086] In some embodiments, the pedestal 508 may be temperature controlled by a heater 510. Additionally, in some embodiments, pressure control of the deposition processing station 500 may be provided by a butterfly valve 518. As shown in the embodiment of Figure 5, the butterfly valve 518 throttles back a vacuum provided by a downstream vacuum pump (not shown). However, in some embodiments, pressure control of the processing station 500 may be adjusted by modifying the flow rates of one or more gases introduced into the processing station 500.

[0087] Multiple processing stations may be included in a multi-station processing tool environment, such as that shown in FIG. 6 , which depicts a schematic diagram of an embodiment of a multi-station processing tool. Processing apparatus 600 employs an integrated circuit fabrication chamber 663 that includes multiple fabrication processing stations. Each of the multiple fabrication processing stations may be used to perform a processing operation on a substrate held on a wafer holder, such as a pedestal, at a particular processing station. In the embodiment of FIG. 6 , integrated circuit fabrication chamber 663 is shown having four processing stations 651, 652, 653, and 654. Other similar multi-station processing apparatuses may have more or fewer processing stations depending on the embodiment and, for example, the desired level of parallel wafer processing, size / space constraints, cost constraints, etc. Also shown in FIG. 6 is a substrate handler robot 675. Substrate handler robot 675 operates under the control of a system controller 690 and may be configured to move substrates from a wafer cassette (not shown in FIG. 6 ) through a loading port 680 to one of processing stations 651, 652, 653, and 654 within integrated circuit fabrication chamber 663.

[0088] 6 also depicts an embodiment of a system controller 690 used to control the processing conditions and hardware states of processing device 600. System controller 690 may include one or more memory devices, one or more mass storage devices, and one or more processors as described herein.

[0089] RF subsystem 695 may generate and deliver RF power to integrated circuit fabrication chamber 663 via radio frequency input port 667. In certain embodiments, integrated circuit fabrication chamber 663 may include input ports in addition to radio frequency input port 667 (the additional input ports are not shown in FIG. 6 ). Thus, integrated circuit fabrication chamber 663 may use eight RF input ports. In certain embodiments, processing stations 651-654 of integrated circuit fabrication chamber 165 may each use a first input port and a second input port, where the first input port may deliver signals having a first frequency and the second input port may deliver signals having a second frequency. The use of dual frequencies may result in enhanced plasma characteristics.

[0090] As noted above, a multi-station processing tool may include one or more processing stations. FIG. 7 shows a schematic diagram of an embodiment of a multi-station processing tool 700 including an input load lock 702 and an output load lock 704, either or both of which may include a remote plasma source. A robot 706 is configured to transfer substrates or wafers at atmospheric pressure from a cassette loaded via a pod 708 to the input load lock 702 through an atmospheric port 710. The substrate is placed on a pedestal 712 in the input load lock 702 by the robot 706, the atmospheric port 710 is closed, and the load lock is pumped down. If the input load lock 702 includes a remote plasma source, the substrate may be exposed to a remote plasma treatment in the load lock before being introduced into the processing chamber 714. Additionally, the substrate may be heated in the input load lock 702, for example, to remove moisture and adsorbed gases. A chamber transfer port 716 to the processing chamber 714 then opens, and another robot (not shown) places the substrate on a pedestal in the first station shown within the reactor for processing. While the embodiment depicted in Figure 7 includes a load lock, it will be appreciated that in some embodiments, direct substrate entry into the processing station may be provided. In various embodiments, an immersion gas is introduced into the station when the substrate is placed on the pedestal 712 by the robot 706.

[0091] The illustrated processing chamber 714 includes four processing stations, numbered 1 through 4 in the embodiment shown in FIG. 7 . Each station has a heated pedestal (718 for station 1) and a gas line inlet. It will be appreciated that in some embodiments, each processing station may have different or multiple purposes. For example, in some embodiments, a processing station may be switchable between an ALD process mode and a PEALD process mode, or between a plasma treatment mode and a deposition mode. Additionally or alternatively, in some embodiments, the processing chamber 714 may include one or more pairs of plasma treatment stations and a deposition station. While the illustrated processing chamber 714 includes four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, the processing chamber may have five or more stations, while in other embodiments, the processing chamber may have three or fewer stations.

[0092] FIG. 7 depicts an embodiment of a wafer transport system 790 for transporting substrates within the processing chamber 714. In some embodiments, the wafer transport system 790 may transport substrates between various processing stations and / or between processing stations and load locks. It will be appreciated that any suitable wafer transport system may be used. Non-limiting examples include a wafer carousel and a wafer transport robot. FIG. 7 also depicts an embodiment of a system controller 750 used to control the processing conditions and hardware states of the processing tool 700. The system controller 750 may include one or more memory devices 756, one or more mass storage devices 754, and one or more processors 752. The processor 752 may include a CPU or computer, analog and / or digital input / output connections, a stepper motor controller board, etc. In some embodiments, the system controller 750 includes machine-readable instructions for performing operations, such as those described herein.

[0093] In some embodiments, system controller 750 controls the operation of processing tool 700. System controller 750 executes system control software 758, which is stored on mass storage device 754, loaded into memory device 756, and executed on processor 752. Alternatively, control logic may be hard-coded in system controller 750. Application-specific integrated circuits, programmable logic devices (e.g., field-programmable gate arrays (FPGAs)), or the like may be used for these purposes. In the following description, where "software" or "code" is used, functionally equivalent hard-coded logic may be used. System control software 758 may include instructions for controlling the timing, mixture of gases, gas flow rates, chamber and / or station pressures, chamber and / or station temperatures, substrate temperatures, target power levels, RF power levels, substrate pedestal, chuck and / or susceptor positions, and other parameters of a particular process performed by processing tool 700. System control software 758 may be configured in any suitable manner. For example, various processing tool component subroutines or control objects may be created to control the operation of the processing tool components used to perform the various processing tool processes. The system control software 758 may be coded in any suitable computer-readable programming language.

[0094] FIG. 8 schematically illustrates a cross-sectional view of an inductively coupled plasma processing apparatus 800 according to certain embodiments of the present disclosure. An example of a suitable reactor that can be used to implement the techniques described herein is the Kiyo™ reactor manufactured by Lam Research Corporation of Fremont, California. The inductively coupled plasma processing apparatus 800 includes an overall processing chamber structurally defined by a chamber wall 801 and a window 811. The chamber wall 801 may be made of stainless steel or aluminum. The window 811 may be made of quartz or other dielectric material. An optional internal plasma grid 850 divides the overall processing chamber into an upper subchamber 802 and a lower subchamber 803. The plasma grid 850 may include a single grid or multiple individual grids. In many embodiments, the plasma grid 850 may be removed, utilizing the chamber space consisting of the subchambers 802 and 803.

[0095] The chuck 817 is located near the bottom inner surface of the lower sub-chamber 803. The chuck 817 is configured to receive and hold a semiconductor wafer 819. The chuck 817 can be an electrostatic chuck for supporting the wafer 819 when it is present. In some embodiments, an edge ring (not shown) surrounds the chuck 817 and has an upper surface that is substantially flush with the upper surface of the wafer 819 when the wafer 819 is on the chuck 817. The chuck 817 also includes an electrostatic electrode for desorption of the wafer. For this purpose, a filter and a DC clamp power supply (not shown) may be provided. Other control systems may be provided for lifting the wafer 819 from the chuck 817. The chuck 817 can be charged using an RF power supply 823. The RF power supply 823 is connected to a matching circuit 821 through a connection 827. The matching circuit 821 is connected to the chuck 817 through a connection 825. In this manner, the RF power supply 823 is connected to the chuck 817.

[0096] Coil 833 is positioned above window 811. Coil 833 is made of a conductive material and includes at least one turn. The exemplary coil 833 shown in FIG. 8 has three turns. A cross section of coil 833 is symbolized, with the "X" indicating the coil extending into the page and the "●" indicating the coil extending out of the page. RF power source 841 is configured to provide RF power to coil 833. Generally, RF power source 841 is connected to matching circuit 839 through connection 845. Matching circuit 839 is connected to coil 833 through connection 843. In this manner, RF power source 841 is connected to coil 833. Optionally, a Faraday shield 849 is positioned between coil 833 and window 811. Faraday shield 849 is maintained at a distance from coil 833. Faraday shield 849 is positioned directly above window 811. The coil 833, the Faraday shield 849, and the window 811 are each configured to be substantially parallel to one another. The Faraday shield can prevent metals or other species from depositing on the dielectric window of the plasma chamber.

[0097] Process gases may be supplied through a primary inlet port 860 and / or a secondary inlet port 870 (sometimes referred to as STG) located in the upper chamber. A vacuum pump (e.g., a single-stage or two-stage mechanical dry pump and / or a turbomolecular pump 840) may be used to draw process gases from the process chamber and maintain pressure within the plasma processing device 800 during plasma processing operations using a closed-loop controlled flow restriction device, such as a throttle valve (not shown) or a pendulum valve (not shown).

[0098] During operation of the apparatus, one or more reaction gases may be supplied through the injection ports 860 and / or 870. In certain embodiments, gases may be supplied only through the primary injection port 860 or only through the secondary injection port 870. In some cases, the injection ports may be replaced with showerheads. The Faraday shield 849 and / or the optional grid 850 may include internal channels and holes that allow process gases to be supplied to the chamber. Either or both of the Faraday shield 849 and the optional grid 850 may function as a showerhead for the supply of process gases.

[0099] Radio frequency power is supplied to coil 833 from RF power supply 841 to cause an RF current to flow through coil 833. The RF current flowing through coil 833 creates an electromagnetic field around coil 833. The electromagnetic field generates an induced current within upper subchamber 802. Physical and chemical interactions of the various generated ions and radicals with wafer 819 selectively etch or process features on the wafer.

[0100] If a plasma grid 850 is used such that both the upper subchamber 802 and the lower subchamber 803 are present, induced currents act on the gas present in the upper subchamber 802 to generate an electron-ion plasma in the upper subchamber 802. The optional internal plasma grid 850, if present, may function to limit the number of hot electrons in the lower subchamber 803. In some embodiments, the apparatus is designed and operated such that the plasma present in the lower subchamber 803 is an ion-ion plasma. In other embodiments, the apparatus may be designed and operated such that the plasma present in the lower subchamber 803 is an electron-ion plasma. Internal plasma grids and ion-ion plasmas are further described in U.S. Patent Application No. 14 / 082,009, filed November 15, 2013, entitled "INTERNAL PLASMA GRID FOR SEMICONDUCTOR FABRICATION," and U.S. Patent No. 9,245,761, each of which is incorporated herein by reference in its entirety.

[0101] Volatile by-products may be removed from the lower sub-chamber 803 through port 822. The chuck 817 disclosed herein may operate at elevated temperatures, between about 30 and 250°C. In some cases, the chuck 817 may operate at lower temperatures, for example, when actively cooled. In such cases, the chuck 817 may operate at a desired relatively low temperature. The temperature will depend on the processing operation and the particular recipe. In some embodiments, the chamber 801 may operate at a pressure between about 1 and 95 mTorr. In certain embodiments, the pressure may be higher.

[0102] Chamber 801 may be coupled to equipment (not shown) when installed in a clean room or manufacturing facility. The equipment includes plumbing to provide process gases, vacuum, temperature control, and environmental particle control. These equipment are coupled to chamber 801 when installed in the target manufacturing facility. Additionally, chamber 801 may be coupled to a transfer chamber that allows a robot to transfer semiconductor wafers into and out of chamber 801 using typical automation.

[0103] In some embodiments, a system controller 830 (which may include one or more physical or logical controllers) controls the operation of some or all of the processing chambers. The system controller 830 may include one or more memory devices and one or more processors. The processor may include a central processing unit (CPU) or computer, analog and / or digital input / output connections, a stepper motor controller board, and other similar components. Instructions for performing appropriate control operations are executed in the processor. These instructions may be stored in a memory device associated with the system controller 830 or may be provided over a network. In certain embodiments, the system controller 830 executes system control software.

[0104] In some cases, system controller 830 controls gas concentrations, wafer movement, and / or power supplied to coil 833 and / or electrostatic chuck 817. System controller 830 may control gas concentrations, for example, by opening or closing associated valves to generate one or more inlet gas flows that provide the required reactants at appropriate concentrations. Wafer movement may be controlled, for example, by moving a wafer positioning system as desired. Power supplied to coil 833 and / or chuck 817 may be controlled to provide specific RF power levels. Similarly, if an internal grid 850 is used, the RF power applied to the grid may be adjusted by system controller 830.

[0105] The system controller 830 may control these and other aspects based on sensor outputs (e.g., when power, potential, pressure, etc., reaches a certain threshold), timing of actions (e.g., opening a valve at a particular time in a process), or received commands from a user. Exemplary controllers are further described below.

[0106] FIG. 9 illustrates a semiconductor process cluster architecture with various modules interfacing with a vacuum transfer module (VTM) 938. The arrangement of transfer modules that "transfer" wafers between multiple containment facilities and processing modules may be referred to as a "cluster tool architecture" system. An airlock 930 (also known as a load lock or transfer module) is shown inside the VTM 938 with four processing modules 920a-920d, each of which can be individually optimized to perform various manufacturing processes. By way of example, processing modules 920a-920d may be implemented to perform substrate exposure to plasma, etching, deposition, ion implantation, wafer cleaning, sputtering, and / or other semiconductor processes. One or more processing modules (any of 920a-920d) may be implemented as disclosed herein and used to expose substrates to plasma, deposit materials, and / or etch materials as described herein. The airlock 930 and processing modules 920 may be referred to as "stations." Each station has a facet 936 that connects the station to a VTM 938. Within each facet, sensors 1-18 are used to detect the passage of a wafer 926 as it moves between the respective stations.

[0107] A robot 922 transfers wafers 926 between stations. In one embodiment, the robot 922 has one arm, and in another embodiment, the robot 922 has two arms, each arm having an end effector 924 for picking up a wafer, such as wafer 926, for transfer. In the atmospheric transfer module (ATM) 940, a front-end robot 932 is used to transfer wafers 926 from cassettes or front-opening integrated pods (FOUPs) 934 in a load port module (LPM) 942 to the airlock 930. A module center 928 in the process module 920 is one location for placing wafers 926. An aligner 944 in the ATM 940 is used to align the wafers.

[0108] In an exemplary processing method, a wafer is placed into one of the FOUPs 934 within the LPM 942. A front-end robot 932 transfers the wafer from the FOUP 934 to an aligner 944, which allows the wafer 926 to be properly centered before being etched or processed. After the wafer 926 is aligned, it is moved by the front-end robot 932 to the airlock 930. The airlock module is capable of matching the environment between the ATM and the VTM, allowing the wafer 926 to move between the two pressure environments without damage. The wafer 926 is moved by the robot 922 from the airlock module 930 through the VTM 938 to one of the processing modules 920a-920d. To accomplish this wafer transfer, the robot 922 uses an end effector 924 on each arm. Once processed, the wafer 926 is moved by the robot 922 from the processing modules 920a-920d to the airlock module 930. From here, the wafer 926 may be moved by the front-end robot 932 to one of the FOUPs 934 or to the aligner 944 .

[0109] It should be noted that the computer controlling the wafer movement may be dedicated to the cluster architecture, or may be located outside the cluster architecture at the manufacturing site, or may be located at a remote location and connected to the cluster architecture through a network.

[0110] In some embodiments, the controller may be part of a system, such as may be part of the examples described above. Such systems include semiconductor processing equipment with processing tools, chambers, processing platforms, and / or specific processing components (such as wafer pedestals and gas flow systems). These systems may be integrated with electronics for controlling operations before, during, and after processing of semiconductor wafers or substrates. Electronics may refer to a "controller" that can control various components or subcomponents of the system. Depending on the processing requirements and / or the type of system, the controller may be programmed to control the processes disclosed herein, including supplying process gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid supply settings, position operation settings, and wafer transfer to and from the tool and other transport tools and / or load locks connected or coupled to the specific system.

[0111] Generally, a controller may be defined as an electronic device having various integrated circuits, logic, memory, and / or software that receive instructions, issue instructions, control operations, enable cleaning operations, enable endpoint measurements, etc. Integrated circuits may include chips in firmware format that store program instructions, digital signal processors (DSPs), chips defined as application-specific integrated circuits (ASICs), and / or one or more microprocessors or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various personalizations (or program files) that define operational parameters for performing a particular process on or for a semiconductor wafer or for a system. In some embodiments, the operational parameters may be part of a recipe defined by a process engineer to accomplish one or more processing steps in the manufacture of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / or wafer dies.

[0112] In some embodiments, the controller may be part of or coupled to a computer integrated with, coupled to, or otherwise networked to the system. For example, the controller may be in the “cloud” that enables remote access of wafer processing or may be all or part of a fab host computer system. The computer enables remote access to the system to monitor the progress of manufacturing operations, examine the history of past manufacturing operations, and examine trends or performance metrics from multiple manufacturing operations to modify parameters of a current process, set up processing steps following a current process, or initiate a new process. In some examples, a remote computer (e.g., a server) can provide process recipes to the system over a network, including a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and / or settings, which are then communicated from the remote computer to the system. In some examples, the controller receives instructions in the form of data specifying parameters for each processing step to be performed during one or more operations. It should be understood that the parameters are specific to the type of process being performed and the type of tool the controller is configured to connect to or control. Thus, as described above, the controller may be distributed, for example, by including one or more separate controllers networked together and cooperating toward a common purpose, such as the processes and controls described herein. An example of a controller distributed for such a purpose would be one or more integrated circuits in the chamber that are located remotely (e.g., at the platform level or as part of a remote computer) and communicate with one or more integrated circuits that cooperate to control the process in the chamber.

[0113] Without limitation, example systems may include plasma processing chambers or modules, plasma etch chambers or modules, deposition chambers or modules, spin rinse chambers or modules, metal plating chambers or modules, cleaning chambers or modules, bevel edge etch chambers or modules, physical vapor deposition (PVD) chambers or modules, chemical vapor deposition (CVD) chambers or modules, atomic layer deposition (ALD) chambers or modules, atomic layer etch (ALE) chambers or modules, ion implantation chambers or modules, track chambers or modules, and any other semiconductor processing systems related to or used in the fabrication and / or manufacturing of semiconductor wafers.

[0114] As noted above, depending on the process steps being performed by the tool, the controller may be in communication with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, nearby tools, tools installed throughout the factory, a main computer, another controller, or tools used to transport materials to and from tool locations and / or load ports in a semiconductor manufacturing factory to transport wafer containers. experiment

[0115] FIG. 10 presents experimental results regarding the effect of exposing a substrate to different plasma treatments. Specifically, FIG. 10 shows the effect of different plasma treatments on the water contact angle. The water contact angle is a measure of the hydrophilicity of the surface and also indicates the relative concentration of hydroxyl groups present on the substrate surface. A lower water contact angle indicates greater hydrophilicity and a higher concentration of hydroxyl groups on the substrate surface. In these examples, the underlayer modified by exposure to plasma was a carbon-based ashable hard mask material.

[0116] Before exposing the substrate to plasma, the substrate exhibited a water contact angle of approximately 70°, indicating a highly hydrophobic surface. This data is shown in Figure 10, labeled "Before Treatment." The "After CO" results are the water contact angles after exposing the substrate to plasma generated from carbon dioxide. In this case, the water contact angle decreased from approximately 70° to approximately 22°. The "After H2O" results are the water contact angles after exposing the substrate to plasma generated from water. In this case, the water contact angle decreased from approximately 70° to 0°. Both plasma treatments resulted in a significant decrease in the water contact angle, indicating that the surface is significantly more hydrophilic due to modifications to the substrate surface during plasma exposure.

[0117] FIG. 11 presents experimental data examining the effect of waiting time on the water contact angle following plasma treatment in which a substrate is exposed to carbon dioxide-generated plasma. In this example, the water contact angle decreased during the first 35 minutes of waiting time and then began to increase. Without wishing to be bound by theory or mechanism of action, the initial decrease in water contact angle after exposure of the substrate to a carbon dioxide-based plasma is attributed to increased moisture adsorption from the environment onto the modified material on the substrate surface, as described with respect to FIG. 4C. Moisture efficiently converts many CO groups on the substrate surface to more reactive CO—OH groups. CO—OH groups are more hydrophilic than CO groups, resulting in a decrease in the water contact angle during the initial waiting period. As noted above, in certain embodiments, a waiting period may be introduced between exposure of the substrate to plasma and deposition of the metal-containing photoresist, such that the metal-containing photoresist is deposited when the substrate surface is substantially saturated with hydroxyl groups. In other embodiments, the substrate may be exposed to water vapor after exposure to plasma to saturate the substrate surface with hydroxyl groups.

[0118] Figure 12 presents experimental data examining the effect of waiting time on dose versus size following a plasma treatment in which a substrate was exposed to a carbon dioxide-generated plasma. Results are shown for two different substrates. In each case, dose versus size decreased with time after exposure to the carbon dioxide-based plasma. As discussed with respect to Figure 11, it is believed that moisture present in the atmosphere to which the substrate was exposed during the waiting period adsorbs onto the substrate surface, converting many of the CO groups to more reactive CO-OH groups. These highly reactive groups promote increased crosslinking with the metal-containing photoresist, thereby reducing the amount of EUV radiation required to achieve the desired degree of crosslinking. Because the aqueous plasma treatment has the effect of saturating the substrate surface with the desired CO-OH groups, it is expected that the same results as shown in Figures 11 and 12 will be obtained without the need for a waiting period between plasma treatment and deposition of the metal-containing photoresist. It is expected that these same results will also be seen with silicon-based underlayer materials (e.g., by substituting carbon for silicon, if desired). Conclusion

[0119] Although the above embodiments have been described in some detail for clarity of understanding, it will be apparent that certain changes and modifications may be made within the scope of the appended claims. It should be noted that there are many other ways of implementing the processes, systems, and apparatus of the present embodiments. Therefore, the present embodiments should be considered illustrative rather than restrictive, and should not be limited to the details set forth herein.

Claims

1. 1. A method for improving adhesion between a substrate and a metal-containing photoresist, comprising: (a) providing the substrate having a surface comprising a first material, the first material comprising a silicon-based material and / or a carbon-based material; (b) generating a plasma from a plasma-generating gas source, the plasma-generating gas source being substantially free of silicon, and the plasma comprising chemical functional groups; (c) exposing the substrate to the plasma to modify the surface of the substrate by forming bonds between the first material and chemical functional groups of the plasma; (d) after (c), depositing the metal-containing photoresist on the modified surface of the substrate, wherein the bonding between the first material and the chemical functional groups of the plasma improves adhesion between the substrate and the metal-containing photoresist.

2. 10. The method of claim 1, The method, wherein the plasma-generating gas source comprises water vapor.

3. 10. The method of claim 1, The method, wherein the plasma-generating gas source comprises at least one organic species.

4. 4. The method of claim 3, The method, wherein the plasma-generating gas source comprises carbon dioxide.

5. 4. The method of claim 3, The method wherein the plasma-generating gas source comprises carbon monoxide.

6. 4. The method of claim 3, The method, wherein the plasma-generating gas source comprises alcohol vapor.

7. 10. The method of claim 1, The method, wherein the plasma-generating gas source comprises a halogen gas.

8. 10. The method of claim 1, The plasma generating gas source is diatomic oxygen (O 2 ) and / or ozone (O 3 ) a method comprising:

9. 10. The method of claim 1, The plasma generating gas source is hydrogen peroxide (H 2 O 2 ) a method comprising:

10. 10. The method of claim 1, The method, wherein the plasma comprises one or more chemical functional groups selected from the group consisting of O radicals, OH radicals, CO radicals, Cl radicals, Br radicals, I radicals, and combinations thereof.

11. 11. The method of any one of claims 1 to 10, The method, wherein the plasma generating gas source is substantially free of activated nitrogen.

12. 11. The method of any one of claims 1 to 10, The plasma generating gas source may further comprise an inert gas and / or hydrogen (H 2 ) a method comprising:

13. 11. The method of any one of claims 1 to 10, The method wherein the plasma is generated remotely and the substrate is transported to a reaction chamber where it is exposed to the plasma.

14. 11. The method of any one of claims 1 to 10, The method wherein the plasma is generated in-situ in a reaction chamber where the substrate is exposed to the plasma.

15. 11. The method of any one of claims 1 to 10, The method, wherein the first material comprises amorphous carbon, spin-on carbon, spin-on glass, silicon carbide, or silicon oxycarbide.

16. 11. The method of any one of claims 1 to 10, The method, wherein the first material comprises amorphous silicon, silicon oxide, silicon nitride, or silicon oxynitride.

17. 11. The method of any one of claims 1 to 10, the bonding between the first material and the chemical functional groups of the plasma promotes the formation of metal-oxygen bonds on the surface of the substrate while depositing the metal-containing photoresist in (d), thereby improving adhesion between the substrate and the metal-containing photoresist.

18. 11. The method of any one of claims 1 to 10, wherein exposing the substrate to the plasma forms a C═O bond, a C—OH bond, a C—Cl bond, a C—Br bond, a C—I bond, a Si—O bond, a Si—OH bond, a Si—Cl bond, a Si—Br bond, a Si—I bond, or a combination thereof.

19. 11. The method of any one of claims 1 to 10, The method, wherein depositing the metal-containing photoresist on the modified surface of the substrate forms C—O-metal and / or Si—O-metal bonds.

20. 11. The method of any one of claims 1 to 10, (c) occurs after the first material is deposited on the substrate in the reaction chamber in which the first material was deposited on the substrate.

21. 11. The method of any one of claims 1 to 10, A method wherein (c) and (d) occur in the same reaction chamber.

22. The method of any one of claims 1 to 10, further comprising: (d) exposing the substrate to a second plasma comprising an inert gas, wherein exposing the substrate to the second plasma increases a surface area of ​​the substrate.

23. 11. The method of any one of claims 1 to 10, The method, wherein the first material is a hard mask material.

24. 11. The method of any one of claims 1 to 10, The method, wherein the first material is a porous interfacial layer.

25. 11. The method of any one of claims 1 to 10, The method, wherein the plasma-generating gas source comprises carbon dioxide, and the method further comprises waiting at least about 3 hours between exposing the substrate to the plasma in (c) and depositing the metal-containing photoresist in (d).

26. 11. The method of any one of claims 1 to 10, The method of claim 1, wherein exposing the substrate to the plasma in (c) modifies only the top 5 Å or less of the first material.

27. 11. The method of any one of claims 1 to 10, The method, wherein exposing the substrate to the plasma in (c) does not result in an increase in the formation of photoresist scum when the metal-containing photoresist is developed.

28. 11. The method of any one of claims 1 to 10, The method, wherein the plasma generating gas source comprises carbon dioxide and the plasma is generated at a pressure of about 5-100 mTorr and an RF power of about 50-1,000 W.

29. 11. The method of any one of claims 1 to 10, The method, wherein the plasma-generating gas source comprises water, and the plasma is generated at a pressure of about 5-300 mTorr and an RF power of about 100-2,000 W.

30. 11. The method of any one of claims 1 to 10, The method wherein the plasma generating gas source flows at a rate of about 100-5000 sccm between (b) and (c).

31. 11. The method of any one of claims 1 to 10, (c) occurs at a temperature of about 20-100°C.

32. The method of any one of claims 1 to 10, further comprising: applying a bias of up to about 100 V to the substrate while the substrate is exposed to the plasma in (c) or while the substrate is exposed to a second plasma prior to (c), wherein applying the bias to the substrate attracts ions to the surface of the substrate, thereby roughening the surface of the substrate.

33. 33. The method of claim 32, The method wherein the bias applied to the substrate is between about 0 and 50V.

34. 1. A system for improving adhesion between a substrate and a metal-containing photoresist, comprising: at least one reaction chamber; at least one plasma generator; at least one inlet for providing gas and / or plasma to said at least one reaction chamber; a controller having at least one processor, said at least one processor configured to control said at least one reaction chamber, said at least one plasma generator, and said at least one inlet to produce the method of claims 1 to 33 or any of the methods described herein; A system comprising:

35. 1. A system for improving adhesion between a substrate and a metal-containing photoresist, comprising: at least one reaction chamber; at least one plasma generator; at least one inlet for providing gas and / or plasma to said at least one reaction chamber; a controller having at least one processor, the at least one processor controlling the at least one reaction chamber, the at least one plasma generator, and the at least one inlet; (a) receiving a substrate having a surface comprising a first material in the at least one reaction chamber, the first material comprising a silicon-based material and / or a carbon-based material; (b) generating a plasma containing chemical functional groups from a plasma-generating gas source; (c) providing the plasma in the at least one reaction chamber, wherein the surface of the substrate is modified by bonds formed between the first material and chemical functional groups of the plasma; (d) after (c), providing the metal-containing photoresist in the at least one reaction chamber, wherein the metal-containing photoresist is deposited on the modified surface of the substrate, and wherein the bonding between the first material and chemical functional groups of the plasma is configured to improve adhesion between the substrate and the metal-containing photoresist; A system comprising:

36. 36. The system of claim 35, The system, wherein the at least one processor controls the at least one inlet to provide the plasma and the metal-containing photoresist to one particular one of the at least one reaction chambers.

37. 36. The system of claim 35, The system, wherein the at least one processor controls the at least one inlet to provide the plasma and the metal-containing photoresist to two different ones of the at least one reaction chamber.

38. A structure comprising: A substrate; a first material deposited on the substrate, the first material being silicon-based or carbon-based and including a modified surface containing hydroxyl groups; a metal-containing photoresist deposited on the modified surface of the first material, wherein the metal-containing photoresist and the modified surface form metal-oxygen-silicon and / or metal-oxygen-carbon bonds; and A structure comprising:

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