Semiconductor Integrated Film Deposition

Abstract

To provide methods for enhancing the efficiency in a lithographic process for depositing a photoresist layer on a substrate using vapor phase processes.SOLUTION: A method of depositing a metal oxo photoresist using dry deposition processes comprises forming a first metal oxo film on a substrate with a first vapor phase process including a first metal precursor vapor and a first oxidant vapor, and forming a second metal oxo film over the first metal oxo film with a second vapor phase process including a second metal precursor vapor and a second oxidant vapor.SELECTED DRAWING: Figure 5

Description

[Technical Field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. patent application Ser. No. 16 / 934,730, filed Jul. 21, 2020, the entire contents of which are incorporated herein by reference.

[0002] background 1) Field TECHNICAL FIELD

[0002] Embodiments of the present disclosure relate to the field of semiconductor processing, and more particularly to methods for depositing photoresist layers on substrates using vapor phase processes. [Background technology]

[0003] 2) Description of related technologies

[0003] Lithography has been used for decades in the semiconductor industry to create 2D and 3D patterns in microelectronic devices. The lithography process involves spin-on deposition of a film (photoresist), irradiating the film in a selected pattern with an energy source (exposure), and removing (etching) the exposed (positive tone) or unexposed (negative tone) areas of the film by dissolving in a solvent. A bake is performed to drive off any remaining solvent.

[0004]

[0004] Photoresist must be a radiation-sensitive material, and upon irradiation, a chemical transformation occurs in the exposed portions of the film, allowing for a change in solubility between the exposed and unexposed areas. This change in solubility is used to remove (etch) either the exposed or unexposed areas of the photoresist. The photoresist is then developed, and the pattern can be transferred by etching into the underlying thin film or substrate. After the pattern is transferred, the remaining photoresist is removed, and this process can be repeated many times to obtain the 2D and 3D structures used in microelectronic devices.

[0005]

[0005] Several properties are important in lithography processes. These properties include sensitivity, resolution, low line edge roughness (LER), etch resistance, and the ability to form thinner layers. Higher sensitivity requires less energy to change the solubility of the as-deposited film. This increases the efficiency of the lithography process. Resolution and LER determine how narrow features can be achieved by the lithography process. Pattern transfer to form deep structures requires more etch-resistant materials. Higher etch-resistant materials also allow for thinner films. Thinner films increase the efficiency of the lithography process. Summary of the Invention

[0006]

[0006] Embodiments disclosed herein include methods for forming a metal-oxo photoresist in a vapor phase process. In one embodiment, a method for forming a photoresist layer on a substrate includes forming a first metal-oxo film on the substrate in a first vapor phase process including a first metal precursor vapor and a first oxidizer vapor, and forming a second metal-oxo film on the first metal-oxo film using a second vapor phase process including a second metal precursor vapor and a second oxidizer vapor.

[0007] In a further embodiment, a method of forming a photoresist layer on a substrate in a vacuum chamber comprises: x L y where M is a metal, R is a leaving group, L is a ligand, x is between 0 and 6, and y is between 0 and 6. The method may further include providing a metal precursor vapor into the vacuum chamber, wherein a reaction between the metal precursor vapor and the oxidant vapor results in the formation of a photoresist layer on the surface of the substrate, the photoresist layer being a metal-oxo-containing material.

[0008] In a further embodiment, a method of forming a photoresist layer on a substrate in a vacuum chamber includes initiating a deposition cycle. In one embodiment, the deposition cycle includes initiating a deposition cycle of a compound having the general formula MR x Ly (wherein M is a metal, R is a leaving group, L is a ligand, x is between 0 and 6, and y is between 0 and 6) includes providing a metal precursor vapor to a vacuum chamber. In one embodiment, the metal precursor vapor is absorbed onto a surface on the substrate. The deposition cycle can further include purging the vacuum chamber and providing an oxidizer vapor to the vacuum chamber, where a photoresist layer is formed on the surface of the substrate by a reaction between the metal precursor absorbed onto the surface on the substrate and the oxidizer vapor. In one embodiment, the photoresist layer is a metal-oxo-containing material. In one embodiment, the deposition cycle can further include purging the vacuum chamber. [Brief explanation of the drawings]

[0009] [Figure 1] 9 is a chemical formula for the synthesis of metal precursors used in vapor deposition processes to form metal-oxo films, according to embodiments of the present disclosure. [Figure 2]

[0010] 1 is a flowchart illustrating a process for forming photoresist on a substrate using a chemical vapor deposition (CVD) process, according to one embodiment of the present disclosure. [Figure 3]

[0011] 10 is a flowchart illustrating a process for forming photoresist on a substrate using an atomic layer deposition (ALD) process, according to an additional embodiment of the present disclosure. [Figure 4]

[0012] 1 is a cross-sectional view of a metal oxo photoresist on a substrate according to an embodiment of the present disclosure. [Figure 5]

[0013] 1 is a flowchart illustrating a process for forming a photoresist having a non-uniform composition through the thickness of the photoresist, according to one embodiment of the present disclosure. [Figure 6A]

[0014] 1 is a cross-sectional view of a metal-oxo photoresist on a substrate, the metal-oxo photoresist including a first layer and a second layer having different material compositions, according to an embodiment of the present disclosure. [Figure 6B]

[0015] 1 is a cross-sectional view of a metal-oxo photoresist on a substrate, the metal-oxo photoresist including multiple layers that provide a compositional gradient across the thickness of the metal-oxo photoresist, according to an embodiment of the present disclosure. [Figure 7A]

[0016] 1A is a cross-sectional view of a metal-oxo photoresist on a substrate having a non-uniform spatial composition, according to one embodiment. [Figure 7B]

[0017] FIG. 2 is a cross-sectional view of a metal oxo photoresist after exposure and development, according to one embodiment. [Figure 7C]

[0018] 1 is a cross-sectional view of an underlying substrate after pattern transfer, according to one embodiment. [Figure 8]

[0019] 6 is a cross-sectional view of a processing tool that can be used to perform the process of FIG. 2, FIG. 3, or FIG. 5 according to an embodiment of the present disclosure. [Figure 9]

[0020] 1 illustrates a block diagram of an exemplary computer system according to one embodiment of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0010]

[0021] A method for depositing photoresist on a substrate using a vapor-phase process is described herein. In the following description, numerous specific details are set forth, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes, and material regimes for depositing photoresist, in order to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that embodiments of the present disclosure may be practiced without these specific details. In other instances, well-known aspects, such as integrated circuit fabrication, have not been described in detail in order to avoid unnecessarily obscuring embodiments of the present disclosure. Furthermore, it should be understood that the various embodiments illustrated in the figures are illustrative representations and are not necessarily drawn to scale.

[0011]

[0022] To provide context, photoresist systems used in extreme ultraviolet (EUV) lithography suffer from low efficiency. Existing photoresist material systems for EUV lithography require high dosages to provide the solubility switch necessary to enable development of the photoresist material. Organic-inorganic hybrid materials (e.g., metal-oxo material systems) have been proposed as material systems for EUV lithography due to their enhanced sensitivity to EUV radiation. Such materials systems typically contain a metal (e.g., Sn, Hf, Zr, etc.), oxygen, and carbon. Metal-oxo molecules are sometimes referred to as nanoparticles. Metal-oxo-based organic-inorganic hybrid materials have also been shown to provide lower LER and higher resolution, properties necessary for forming narrow features.

[0012]

[0023] Metal-oxo material systems are currently deposited on substrates using wet processes. They are dissolved in a solvent and distributed across a substrate (e.g., a wafer) using a wet-chemical deposition method, such as spin-coating. Wet-chemical deposition of photoresists has several drawbacks. One downside is the generation of large amounts of wet by-products. These are undesirable, and the semiconductor industry is actively working to reduce them as much as possible. Furthermore, wet-chemical deposition can cause non-uniformity issues. For example, spin-on deposition can produce photoresist layers with uneven thickness or uneven distribution of metal-oxo molecules. Furthermore, metal-oxo photoresist material systems have been shown to suffer from post-exposure thickness loss, which is troublesome in lithography processes. Furthermore, in spin-on processes, the percentage of metal in the photoresist is fixed and cannot be easily adjusted.

[0013]

[0024] Thus, embodiments of the present disclosure provide a vacuum deposition process for providing a metal-oxo photoresist layer. The vacuum deposition process addresses the shortcomings of the wet deposition process described above. In particular, the vacuum deposition process has the following advantages: 1) it eliminates the generation of wet by-products; 2) it provides a highly uniform photoresist layer; 3) it resists thickness loss after exposure; 4) it provides a mechanism for adjusting the percentage of metal in the photoresist; and 5) it allows for the formation of a photoresist layer with a tailored, non-uniform material composition throughout the thickness of the photoresist layer.

[0014]

[0025] The ability to create a tailored, non-uniform material composition throughout the thickness of a photoresist layer results in improved photoresist properties. For example, the bottom of the photoresist layer, which interfaces with the underlying substrate, can be a material composition with higher adhesion strength. Furthermore, the bottom of the photoresist layer can be designed to be less sensitive to radiation. In negative-tone resists, reduced sensitivity can be useful to prevent scumming after photoresist development. Scumming can refer to the presence of residual photoresist material that is not removed from the pattern after development. Embodiments can also include a functionally graded material composition throughout the thickness of the photoresist. A gradient in material composition can be used to control the exposure latitude curve of the photoresist. This allows for control of the photoresist development profile and / or can be used to provide optical proximity correction (OPC). OPC is typically performed by modifying the pattern of a mask. However, the embodiments disclosed herein enable OPC techniques to be performed by modifying the composition of the photoresist. As such, OPC modifications can be performed without modifying the photolithography mask, providing a more economical solution.

[0015]

[0026] In addition to providing compositional control through the thickness of the photoresist, embodiments may also provide compositional control across the entire surface of the substrate. For example, photoresist at the center of the substrate may have a different sensitivity than photoresist at the edge of the substrate. Such spatially non-uniform composition is particularly useful for addressing plasma non-uniformities. In particular, in many plasma processes, critical dimension (CD) control of large-radius substrates is difficult due to discontinuities in the plasma sheath near the edge of the substrate. Improved CD control is provided when plasma non-uniformities can be explained by variations in the composition of the photoresist.

[0016]

[0027] Embodiments disclosed herein provide various vacuum deposition processes that involve the reaction of a metal precursor with an oxidant. In a first embodiment, the vacuum deposition process can be a chemical vapor deposition (CVD) process. In a second embodiment, the vacuum deposition process can be an atomic layer deposition (ALD) process. In some embodiments, the vacuum deposition process can be a thermal process. In other embodiments, the vacuum deposition process can be a plasma-enhanced (PE) deposition process (e.g., PE-CVD or PE-ALD).

[0017]

[0028] In one embodiment, the vacuum deposition process relies on a chemical reaction between a metal precursor and an oxidizer. The metal precursor and oxidizer are vaporized into a vacuum chamber. The metal precursor reacts with the oxidizer to form a metal-oxo-containing photoresist layer on the surface of the substrate. In some embodiments, the metal precursor and oxidizer are provided together in the vacuum chamber. In other embodiments, the metal precursor and oxidizer are provided in alternating pulses in the vacuum chamber. In an ALD or PE-ALD process, a purge of the vacuum chamber can be provided between pulses of the metal precursor and oxidizer.

[0018]

[0029] In one embodiment, the metal precursor has the general formula MR x L ywhere M is the metal center, R is a leaving group, and L is a ligand. In one embodiment, x can be between 0 and 6, and y can be between 0 and 6. The metal precursor can be synthesized using any chemical reaction process. For example, a general reaction is shown in Figure 1. As shown, the compound SnR x X y where X is Cl or Br) can be reacted with various ligands to give the metal precursor SnR x L y It should be understood that the Sn metal center can be replaced with any suitable metal atom. In one embodiment, the L ligand serves to react with an oxidizing agent to form a metal-oxo molecule, and the R leaving group is released during exposure (e.g., EUV exposure) during the patterning process. Thus, the sensitivity of the photoresist can be influenced, at least in part, by the selection of the leaving group R.

[0019]

[0030] The selection of the metal center M, the leaving group R, and the ligand L drives different material properties of the metal-oxo photoresist. For example, modifications to M, R, and L can provide different sensitivity to radiation, different adhesion properties, different structural properties (i.e., to enable high aspect ratio patterning), different etch selectivities, among many other properties. Thus, the photoresist can be specifically tailored for a desired purpose. Furthermore, using a vacuum deposition process, one or more of M, R, and L can be modified throughout the thickness of the photoresist to provide non-uniform material properties within the photoresist, as described in more detail below.

[0020]

[0031] In certain embodiments, M is Sn. However, it should be understood that M can be any suitable metallic element such as, but not limited to, Sn, Hf, Zr, Co, Cr, Mn, Fe, Cu, Ni, Mo, W, Ta, Os, Re, Pd, Pt, Ti, V, In, Al, Sb, Bi, Te, As, Ge, Se, Cd, Ag, Pd, Au, Er, Yb, Pr, La, Na, or Mg.

[0021]

[0032] In one embodiment, the ligand L can be a number of different chemical structures. In one embodiment, the ligand L can be a pseudohalide ligand. Pseudohalides include, but are not limited to, CN, CNO, SCN, N3, or SeCN.

[0022]

[0033] In one embodiment, one class of ligands L suitable for metal precursors are monodentate ligands containing an N donor atom. The binding mode to the metal center M is shown in molecule I. Such monodentate ligands can include cyclic ligands. Examples of some such ligands L are provided in molecules II through V. TIFF0007723515000001.tif115170

[0023]

[0034] In one embodiment, the ligand L can also be a bidentate or monodentate ligand containing an N, O, S, or P donor atom. The binding modes of such ligands to the metal center are shown in molecules VI and VII. In molecules VI and VII, X and Y can be N, O, S, or P. Examples of such ligands are shown in molecules VIII to XVIII. TIFF0007723515000002.tif254170TIFF0007723515000003.tif137170

[0024]

[0035] In molecules VI and VII, X and Y can be N, O, S, or P. Examples of such ligands are shown in molecules VIII to XVIII. Examples of such ligands are shown in molecules XX to XXIV. TIFF0007723515000004.tif186170

[0025]

[0036] In one embodiment, ligand L may also contain N donor atoms donating to multiple metal centers. Examples of binding modes of such ligands are shown in molecules XXV through XXVII. TIFF0007723515000005.tif124170

[0026]

[0037] In one embodiment, the ligand L may also contain an H donor atom. An example of such a ligand is shown in molecule XXVIII. TIFF0007723515000006.tif14170

[0027]

[0038] In one embodiment, the leaving group R described herein can include many different suitable molecules. For example, the leaving group can include one or more of alkyl (C1-C10), alkenyl (internal or terminal), alkynyl (internal or terminal), aryl, or carbene. The leaving group R can be linear, branched, or cyclic. In one embodiment, the leaving group R can also include Si, Ge, or Sn as the donor atom.

[0028]

[0039] Examples of suitable alkyls are given in molecules XXIX and XXX. TIFF0007723515000007.tif32170

[0029]

[0040] Examples of suitable alkenyls are provided in molecules XXXI to XXXIII. TIFF0007723515000008.tif53170

[0030]

[0041] Examples of suitable alkynyl groups are described in molecule XXXIV. TIFF0007723515000009.tif17170

[0031]

[0042] Examples of suitable aryls are described in molecules XXXV and XXXVI. TIFF0007723515000010.tif48170

[0032]

[0043] Examples of suitable carbenes are described in molecules XXXVII and XXXVIII. TIFF0007723515000011.tif58170

[0033]

[0044] Examples of leaving groups R containing Si, Ge, or Sn as the donor atom are shown in molecules XXXIX to XLI, where X is Si, Ge, or Sn. TIFF0007723515000012.tif56170

[0034]

[0045] In further embodiments, the metal precursor may also include a stannylene precursor. Molecule XLII is an example of a general stannylene precursor. The ligand L may be any of the ligands L described above or a general amine (NR2). The leaving group R may include any of the leaving groups R described above. TIFF0007723515000013.tif25170

[0035]

[0046] In yet another embodiment, the metal precursor can also be a general metal precursor, such as that shown in molecule XLIII. R can include any of the leaving groups R described above, and the metal center M can be any metal element, such as, but not limited to, Sn, Hf, Zr, Co, Cr, Mn, Fe, Cu, Ni, Mo, W, Ta, Os, Re, Pd, Pt, Ti, V, In, Al, Sb, Bi, Te, As, Ge, Se, Cd, Ag, Pd, Au, Er, Yb, Pr, La, Na, or Mg. Such general metal precursors can be used in combination with the metal precursors described above. TIFF0007723515000014.tif28170

[0036]

[0047] Referring now to FIG. 2, a flowchart illustrating a process 220 for depositing a metal-oxo photoresist on a substrate surface is provided in accordance with an embodiment of the present disclosure. Process 220 can be described as a CVD or PE-CVD process. In a CVD process, the chemical reaction is thermally driven, while in a PE-CVD process, the chemical reaction can be enhanced by the presence of a plasma. In a PE-CVD process, a hydrocarbon can also be flowed into the chamber during plasma-assisted deposition to incorporate more carbon into the film. When the plasma is on during deposition and there are hydrocarbon molecules in the chamber, this can add more carbon to the film. The carbon can be in the form of MC (M=metal). MC (such as Sn—C) can be functionalized upon exposure. The hydrocarbon can be a carbon-containing molecule such as CH₂=CH₂, acetylene, CH₄, propylene, etc.

[0037]

[0048] In one embodiment, process 220 can begin with operation 221, which includes providing a metal precursor vapor to a vacuum chamber containing a substrate. The metal precursor vapor can include a metal precursor such as those described in more detail above. For example, the metal precursor can be a metal precursor having the general formula MR x L y where x and y are each between 0 and 6.

[0038]

[0049] In one embodiment, the metal center M can include one or more of Sn, Hf, Zr, Co, Cr, Mn, Fe, Cu, Ni, Mo, W, Ta, Os, Re, Pd, Pt, Ti, V, In, Sb, Al, Bi, Te, As, Ge, Se, Cd, Ag, Pb, Au, Er, Yb, Pr, La, Na, and Mg. The leaving group R can include one or more of alkyl, alkenyl (internal or terminal), alkynyl (internal or terminal), aryl, or carbene. The leaving group R can also include a Si donor atom, a Ge donor atom, or a Sn donor atom. In one embodiment, the leaving group R can be linear, branched, or cyclic. In one embodiment, the ligand L may include a pseudohalide, a monodentate ligand with N donor atoms, a monodentate or bidentate ligand with N, O, S, and / or P donor atoms, a bidentate ligand with one N donor atom and one O donor atom, or a ligand with N donor atoms or hydrogen atoms donating to multiple metal centers M.

[0039]

[0050] In other embodiments, the metal precursor may include a stannylene precursor or a general metal precursor such as shown in molecule XLIII. It should be understood that multiple metal precursor vapors may be provided to the vacuum chamber. For example, the first metal precursor may include Sn, and the second metal precursor may include Hf. In such embodiments, the resulting metal oxo photoresist may contain two or more different types of metal atoms. In one embodiment, the metal precursor vapor may be diluted with a carrier gas. The carrier gas may be an inert gas such as Ar, N2, or He.

[0040]

[0051] In one embodiment, process 220 may continue with operation 222, which includes providing an oxidizer vapor to the vacuum chamber. In one embodiment, the oxidizer vapor may include a carbon skeleton with reactive groups at both ends of the carbon skeleton. The reactive groups initiate a reaction with the metal precursor, resulting in the formation of a metal-oxo photoresist on the substrate. In one embodiment, the oxidizer vapor may include water or ethylene glycol. In one embodiment, the oxidizer vapor may be diluted with a carrier gas. The carrier gas may be an inert gas, such as Ar, N, or He.

[0041]

[0052] In one embodiment, process 220 may continue with optional operation 223, which includes treating the metal-oxo photoresist layer with a plasma. In one embodiment, the plasma treatment may include a plasma generated from one or more inert gases such as Ar, N, He, or the like. In one embodiment, the one or more inert gases may also be mixed with one or more oxygen-containing gases such as O, CO, CO, NO, NO, HO, or the like. In one embodiment, the vacuum chamber may be purged prior to operation 223. The purging may include a pulse of an inert gas such as Ar, N, He, or the like.

[0042]

[0053] In one embodiment, process 220 can be performed with operation 221 and operation 222 being performed simultaneously. That is, providing a metal precursor vapor to the vacuum chamber and providing an oxidizer vapor to the vacuum chamber can occur simultaneously. After a metal-oxo photoresist film of a desired thickness is formed, process 220 can be stopped. In one embodiment, optional plasma treatment operation 223 can be performed after a metal-oxo photoresist film having a desired thickness is formed.

[0043]

[0054] In other embodiments, process 220 can be performed in a pulsed manner. That is, a pulse of metal precursor vapor can be provided to the vacuum chamber, followed by a pulse of oxidizer vapor. In one embodiment, a cycle including a pulse of metal precursor vapor and a pulse of oxidizer vapor can be repeated multiple times to provide a metal-oxo photoresist film of a desired thickness. In one embodiment, the order of the cycles can be switched. For example, the oxidizer vapor can be pulsed first, and the metal precursor vapor can be pulsed second.

[0044]

[0055] In one embodiment, the pulse duration of the metal precursor vapor can be substantially similar to the pulse duration of the oxidizer vapor. In other embodiments, the pulse duration of the metal precursor vapor can be different from the pulse duration of the oxidizer vapor. In one embodiment, the pulse duration can be between 0 seconds and 1 minute. In certain embodiments, the pulse duration can be between 1 second and 5 seconds.

[0045]

[0056] In one embodiment, each repetition of the cycle uses the same process gas. In other embodiments, the process gas can be changed between cycles. For example, a first cycle can utilize a first metal precursor vapor, and a second cycle can utilize a second metal precursor vapor. Subsequent cycles can continue alternating between the first and second metal precursor vapors. In one embodiment, multiple oxidizer vapors can be alternated between cycles in a similar manner.

[0046]

[0057] In one embodiment, the optional plasma treatment of operation 223 may be performed after every cycle. That is, each cycle may include a pulse of metal precursor vapor, a pulse of oxidant vapor, and a plasma treatment. In an alternative embodiment, the optional plasma treatment of operation 223 may be performed after multiple cycles. In yet another embodiment, the optional plasma treatment operation 223 may be performed after the completion of every cycle (i.e., as a post-treatment).

[0047]

[0058] In one embodiment, process 220 can be a thermal process or a plasma process. In the case of a thermal process, the reaction between the metal precursor vapor and the oxidant vapor can be thermally driven. Such an embodiment can be referred to as a CVD process. In the case of a plasma process, a plasma can be struck during one or both of operations 221 and 222. In such cases, the presence of the plasma can enhance the chemical reaction used to form the metal-oxo photoresist. Such an embodiment can be referred to as a PE-CVD process. In one embodiment, any plasma source can be used to form the plasma. For example, the plasma source can include, but is not limited to, a capacitively coupled plasma (CCP) source, an inductively coupled plasma (ICP) source, a remote plasma source, or a microwave plasma source.

[0048]

[0059] In one embodiment, the vacuum chamber utilized in process 220 may be any suitable chamber capable of providing a pressure below atmospheric pressure. In one embodiment, the vacuum chamber may include temperature control capabilities for controlling the temperature of the chamber walls and / or for controlling the temperature of the substrate. In one embodiment, the vacuum chamber may also include features for providing a plasma in the chamber. A more detailed description of a suitable vacuum chamber is provided below with respect to FIG. 7.

[0049]

[0060] In one embodiment, the substrate may be temperature controlled during process 220. For example, the temperature of the substrate may be between about 0° C. and about 500° C. In a particular embodiment, the substrate may be held at a temperature between room temperature and 150° C. In one embodiment, the temperature of the substrate may be controlled to provide a substrate temperature between about 0° C. and about 100° C.

[0050]

[0061] Referring now to FIG. 3, a flowchart illustrating a process 340 for depositing a metal-oxo photoresist on a substrate surface is provided in accordance with an additional embodiment of the present disclosure. Process 340 can be described as an ALD or PE-ALD process. In an ALD process, the chemical reaction is thermally driven, while in a PE-ALD process, the chemical reaction can be enhanced by the presence of a plasma. In a PE-ALD process, a hydrocarbon can also be flowed into the chamber during plasma-assisted deposition to incorporate more carbon into the film. When the plasma is on during deposition and there are hydrocarbon molecules in the chamber, this can add more carbon to the film. The carbon can be in the form of MC (M=metal). MC (such as Sn—C) can be functionalized upon exposure. The hydrocarbon can be a carbon-containing molecule such as CH₂=CH₂, acetylene, CH₄, propylene, etc.

[0051]

[0062] In one embodiment, process 340 can begin with operation 341, which includes providing a metal precursor vapor to a vacuum chamber containing a substrate. In one embodiment, the metal precursor vapor can include molecules having one or more metal atoms. The metal precursor vapor can include metal precursors such as those described in more detail above. For example, the metal precursor can be a metal having the general formula MR x L y where x and y are each between 0 and 6.

[0052]

[0063] In one embodiment, the metal center M can include one or more of Sn, Hf, Zr, Co, Cr, Mn, Fe, Cu, Ni, Mo, W, Ta, Os, Re, Pd, Pt, Ti, V, In, Sb, Al, Bi, Te, As, Ge, Se, Cd, Ag, Pb, Au, Er, Yb, Pr, La, Na, and Mg. The leaving group R can include one or more of alkyl, alkenyl (internal or terminal), alkynyl (internal or terminal), aryl, or carbene. The leaving group R can also include a Si donor atom, a Ge donor atom, or a Sn donor atom. In one embodiment, the leaving group R can be linear, branched, or cyclic. In one embodiment, the ligand L may include a pseudohalide, a monodentate ligand with N donor atoms, a monodentate or bidentate ligand with N, O, S, and / or P donor atoms, a bidentate ligand with one N donor atom and one O donor atom, or a ligand with N donor atoms or hydrogen atoms donating to multiple metal centers M.

[0053]

[0064] In other embodiments, the metal precursor may include a stannylene precursor or a general metal precursor such as shown in molecule XLIII. It should be understood that multiple metal precursor vapors may be provided to the vacuum chamber. For example, the first metal precursor may include Sn, and the second metal precursor may include Hf. In such embodiments, the resulting metal oxo photoresist may contain two or more different types of metal atoms. In one embodiment, the metal precursor vapor may be diluted with a carrier gas. The carrier gas may be an inert gas such as Ar, N2, or He.

[0054]

[0065] In one embodiment, the metal precursor vapor is absorbed onto the surface of the substrate. In one embodiment, substantially a monolayer of the metal precursor may be provided on the surface of the substrate. However, in other embodiments, several layers of the metal precursor vapor may be absorbed onto the surface of the substrate.

[0055]

[0066] In one embodiment, process 340 may continue with operation 342, which includes purging the vacuum chamber. In one embodiment, the purging process removes residual metal precursor vapor and any by-products from the vacuum chamber. The purging process may include a pulse of an inert gas, such as Ar, N, or He.

[0056]

[0067] In one embodiment, process 340 may continue with operation 343, which includes providing an oxidizer vapor to the vacuum chamber. The oxidizer vapor reacts with the metal precursor absorbed on the surface to form a metal-oxo photoresist layer on the surface of the substrate. Because the metal precursor is absorbed on the surface of the substrate, the reaction may be considered self-limiting. In one embodiment, the oxidizer vapor may include a carbon skeleton with reactive groups at both ends of the carbon skeleton. The reactive groups initiate a reaction with the metal precursor, resulting in the formation of a metal-oxo photoresist on the substrate. In one embodiment, the oxidizer vapor may include water or ethylene glycol. In one embodiment, the oxidizer vapor may be diluted with a carrier gas. The carrier gas may be an inert gas such as Ar, N2, or He.

[0057]

[0068] In one embodiment, the pulse duration of the metal precursor vapor can be substantially similar to the pulse duration of the oxidizer vapor. In other embodiments, the pulse duration of the metal precursor vapor can be different from the pulse duration of the oxidizer vapor. In one embodiment, the pulse duration can be between 0 seconds and 1 minute. In certain embodiments, the pulse duration can be between 1 second and 5 seconds.

[0058]

[0069] In one embodiment, process 340 may continue with operation 344, which includes purging the vacuum chamber. In one embodiment, the purging process removes residual oxidizer vapor and any by-products from the vacuum chamber. The purging process may include a pulse of an inert gas, such as Ar, N, or He.

[0059]

[0070] In one embodiment, process 340 may continue with optional operation 345, which includes treating the metal-oxo photoresist layer with a plasma. In one embodiment, the plasma treatment may include a plasma generated from one or more inert gases, such as Ar, N, He, etc. In one embodiment, the one or more inert gases may also be mixed with one or more oxygen-containing gases, such as O, CO, CO, NO, NO, HO, etc.

[0060]

[0071] In one embodiment, treatment operations 341 through 344 may define a cycle of process 340. An embodiment may include repeating the cycle multiple times to provide a metal-oxo photoresist film having a desired thickness. In one embodiment, optional plasma treatment operation 345 may be performed after each cycle. That is, each cycle may include a metal precursor vapor pulse, a purge, an oxidizer vapor pulse, a purge, and a plasma treatment. In other embodiments, optional plasma treatment operation 345 may be performed after multiple cycles. In other embodiments, optional plasma treatment operation 345 may be performed after multiple cycles.

[0061]

[0072] In one embodiment, each repetition of the cycle uses the same process gas. In other embodiments, the process gas can be changed between cycles. For example, a first cycle can utilize a first metal precursor vapor, and a second cycle can utilize a second metal precursor vapor. Subsequent cycles can continue alternating between the first and second metal precursor vapors. In one embodiment, multiple oxidizer vapors can be alternated between cycles in a similar manner.

[0062]

[0073] In one embodiment, process 340 can be a thermal process or a plasma process. In the case of a thermal process, the reaction between the metal precursor vapor and the oxidizer vapor can be thermally driven. Such an embodiment may be referred to as an ALD process. In the case of a plasma process, a plasma can be struck during one or both of operations 341 and 343. In such cases, the presence of the plasma can enhance the chemical reaction used to form the metal-oxo photoresist. Such an embodiment may be referred to as a PE-ALD process. In one embodiment, any plasma source can be used to form the plasma. For example, the plasma source can include, but is not limited to, a CCP source, an ICP source, a remote plasma source, or a microwave plasma source.

[0063]

[0074] In one embodiment, the vacuum chamber utilized in process 340 may be any suitable chamber capable of providing a pressure below atmospheric pressure. In one embodiment, the vacuum chamber may include temperature control capabilities for controlling the temperature of the chamber walls and / or for controlling the temperature of the substrate. In one embodiment, the vacuum chamber may also include features for providing a plasma within the chamber. A more detailed description of a suitable vacuum chamber is provided below with respect to FIG. 7.

[0064]

[0075] In one embodiment, the substrate may be temperature controlled during process 340. For example, the temperature of the substrate may be between about 0° C. and about 500° C. In a particular embodiment, the substrate may be held at a temperature between room temperature and 150° C. In one embodiment, the temperature of the substrate may be controlled to provide a substrate temperature between about 0° C. and about 100° C.

[0065]

[0076] 4, a cross-sectional view of a metal-oxo photoresist layer 470 on a substrate 401 is shown, according to one embodiment. In one embodiment, the metal-oxo photoresist layer 470 can be disposed on the substrate 401 using a process such as process 340 or process 220. The metal-oxo photoresist layer 470 can have a substantially uniform composition throughout the thickness of the metal-oxo photoresist layer. However, it should be understood that a metal-oxo photoresist can include more than one type of metal center, M. Such an embodiment can be provided by flowing multiple types of metal precursors into the vacuum chamber simultaneously or in alternating pulses.

[0066]

[0077] It should be understood that embodiments are not limited to substantially uniform metal-oxo photoresist layers. For example, the composition of the metal-oxo photoresist layer can be adjusted by the thickness of the metal-oxo photoresist layer. For example, the metal center can be changed, the percentage of metal can be altered, or the carbon concentration can be changed, among other changes.

[0067]

[0078] Varying the composition of the metal-oxo photoresist layer through its thickness is made possible by the vacuum deposition process used to form the metal-oxo photoresist. For example, the metal precursor vapor or oxidant vapor can be varied (e.g., different molecules can be used, different vapor flow rates can be used, etc.) at different points in the deposition of the metal-oxo photoresist. This is a significant improvement over existing wet-based spin on processes, which are limited to having a substantially uniform material composition throughout the thickness of the photoresist layer.

[0068]

[0079] Thus, the disclosed embodiments enable enhanced tunability to optimize metal-oxo photoresist layers for various applications. For example, the first few nanometers (e.g., the first 10 nm or less) of a metal-oxo photoresist layer on a substrate can have a different composition than the rest of the film. This allows the remainder of the metal-oxo photoresist to be optimized for dose, while the lower portion can be tuned for improved adhesion, sensitivity to EUV photons, or sensitivity to developing chemistries to improve post-lithography pattern control (e.g., scum), as well as defects and resistance to collapse / lift-off. In other embodiments, a composition gradient can be provided through the thickness of the metal-oxo photoresist. A gradient in material composition can be used to control the exposure latitude curve of the photoresist. This allows for control of the photoresist development profile and / or can be used to provide OPC. The gradient can also be optimized for the pattern type. For example, pillars may require improved adhesion, while line / space patterns may allow for lower adhesion while tuning for improved dose.

[0069]

[0080] Referring now to FIG. 5 , a flowchart illustrating a process 550 for depositing a metal-oxo photoresist on a substrate surface is provided in accordance with an additional embodiment of the present disclosure. In process 550, the material composition of the metal-oxo photoresist is non-uniform throughout the thickness of the metal-oxo photoresist. Process 550 can begin with operation 551, which includes forming a first metal-oxo film on the substrate in a first gas-phase process. In one embodiment, the first gas-phase process can include a first metal precursor vapor and a first oxidizer vapor. In one embodiment, the first gas-phase process can include a CVD or PE-CVD process similar to process 220 described above. In a further embodiment, the first gas-phase process can include an ALD or PE-ALD process similar to process 340 described above. The first metal precursor vapor can include any of the metal precursor vapors described in more detail above.

[0070]

[0081] In one embodiment, process 550 can continue with operation 552, which includes forming a second metal-oxo film on the first metal-oxo film with a second gas-phase process including a second metal precursor vapor and a second oxidizer vapor. In one embodiment, the second gas-phase process can include a CVD or PE-CVD process similar to process 220 described above. In a further embodiment, the second gas-phase process can include an ALD or PE-ALD process similar to process 340 described above. In one embodiment, the second metal precursor vapor and / or the second oxidizer vapor can be different from the first metal precursor vapor and the first oxidizer vapor. Thus, the second metal-oxo film can have a different composition than the first metal-oxo film.

[0071]

[0082] In some embodiments, only two distinct metal-oxo film layers are provided. An example of such an embodiment is shown in FIG. 6A. As shown, a photoresist layer including a first metal-oxo film 671 and a second metal-oxo film 672 is disposed on a substrate 601. In one embodiment, the first metal-oxo film 671 is an interface layer that provides improved adhesion to the substrate 601. The first metal-oxo film 671 may have a thickness of about 10 nm or less.

[0072]

[0083] In other embodiments, the photoresist layer may include multiple distinct metal-oxo film layers. An example of such an embodiment is shown in FIG. 6B. As shown, the photoresist layer includes multiple distinct metal-oxo film layers 671-678 having different compositions. Such an embodiment may be formed using process 550, which includes additional vapor-phase processes for each layer. In the illustrated embodiment, each of layers 671-678 is substantially uniform in thickness. However, it should be understood that embodiments may include metal-oxo film layers having non-uniform thicknesses.

[0073]

[0084] In one embodiment, process 550 may further include optional plasma treatment of the metal-oxo film(s). In one embodiment, the plasma treatment may be performed after deposition of both the first and second metal-oxo films. Alternatively, the plasma treatment may be performed after deposition of each metal-oxo film. That is, the first metal-oxo film may be deposited, followed by a plasma treatment before depositing the second metal-oxo film. In one embodiment, the plasma treatment may include a plasma generated from one or more inert gases, such as Ar, N, He, etc. In one embodiment, the one or more inert gases may also be mixed with one or more oxygen-containing gases, such as O, CO, CO, NO, NO, HO, etc.

[0074]

[0085] Providing metal-oxo photoresist films using a gas-phase process, such as those described in the above embodiments, offers significant advantages over wet chemical methods. One such advantage is the removal of wet by-products. Gas-phase processes eliminate liquid waste and simplify by-product removal. Furthermore, gas-phase processes provide more uniform photoresist layers. Uniformity in this sense can refer to thickness uniformity across the wafer and / or the uniformity of the distribution of the metal components of the metal-oxo film. In particular, CVD, PE-CVD, ALD, and PE-ALD processes have been shown to provide excellent thickness uniformity and component uniformity.

[0075]

[0086] Furthermore, the use of gas-phase processes allows for fine tuning of the proportion of metal in the photoresist and the composition of the metal in the photoresist. The percentage of metal can be changed by increasing / decreasing the flow rate of the metal precursor into the vacuum chamber and / or by changing the pulse length of the metal precursor / oxidizer. The use of gas-phase processes also allows for the inclusion of multiple different metals in the metal-oxo film. For example, a single pulse of two different metal precursors can be used, or alternating pulses of two different metal precursors can be used. The use of gas-phase processes also allows for the formation of metal-oxo films with different material compositions to tailor the photoresist for a desired application.

[0076]

[0087] Furthermore, metal-oxo photoresists formed using gas-phase processes have been shown to be more resistant to thickness loss after exposure. Without being bound to a particular mechanism, the resistance to thickness loss is believed to be due, at least in part, to reduced carbon loss upon exposure.

[0077]

[0088] In addition to compositional variation with photoresist thickness, embodiments may also provide spatial compositional variation. Spatial compositional variation may refer to variation at different points across a substrate. For example, the composition of the photoresist at the center of the substrate may be different from the composition of the photoresist at the edge of the substrate. In particular, the concentration of the photosensitive component in the photoresist may be varied across the surface. Such spatial compositional variation is also possible with dry deposition processes; that is, spatial compositional variation is not possible using conventional wet processes (such as spin coating).

[0078]

[0089] 7A-7C, a series of cross-sectional views illustrating a process for forming a photoresist having spatial compositional variations, according to one embodiment, are shown. Referring now to FIG. 7A, a cross-sectional view of a substrate 701 is shown, according to one embodiment. In one embodiment, a first layer 702 is provided on the substrate. The first layer 702 is a layer that is patterned using a photoresist layer 780. In one embodiment, the photoresist layer 780 may be deposited on the first layer 702 using a vacuum deposition process, similar to the embodiments above.

[0079]

[0090] To provide spatial composition variation, the showerhead 790 of the processing tool can distribute process gas at a non-uniform flow rate. For example, the outer edges of the showerhead 790 can be adjusted to provide an increased flow rate of process gas compared to the center of the showerhead 790. For a known CD bias (center to edge) in a plasma etch process, the dry deposition process can be adjusted to create a reverse bias in a lithography step. For example, the center of the photoresist 780 can have a concentration of the photosensitive component Δ0, and the edge of the photoresist 780 can have a concentration of the photosensitive component Δ0+Δ.

[0080]

[0091] 7B, a cross-sectional view of photoresist 780 after exposure and patterning is shown, according to one embodiment. As shown, the center of photoresist 780 has a dimension CD, and the edge of photoresist 780 has a dimension CD+ΔCD. The resulting dimensional differences in patterned photoresist 780 can be attributed to different sensitivities due to spatial compositional variations.

[0081]

[0092] 7C, a cross-sectional view of the substrate after the photoresist pattern has been transferred to the first layer 702 is shown, according to one embodiment. As shown, the resulting structure in the first layer 702 has the same CD at the center and edge of the substrate 701. Despite the plasma non-uniformity due to the dimensional changes shown in FIG. 7B, uniform dimensions of the first layer 702 are produced. Thus, embodiments enable improved CD uniformity by using a photoresist with a gradient across the substrate (e.g., from center to edge).

[0082]

[0093] In the above embodiment, the substrate may be a wafer, such as a silicon wafer. However, it should be understood that such dry photoresist deposition and development processes are also suitable for other substrates. For example, if the substrate is a reticle, the above process can also be used. Typically, photoresist is deposited on the reticle substrate by spin coating. The square plate of the reticle makes uniform photoresist deposition particularly challenging. This is because surface tension effects from the corners of the mask make it difficult to systematically and consistently control the photoresist thickness. Similar problems arise during wet development processes. Significant challenges with pattern collapse also exist, as the liquid does not easily roll off the edges of the mask as it does with circular wafers. Furthermore, most reticles currently in production require a "topcoat" (i.e., a charge dissipation layer (CDL)) on the photoresist layer. This topcoat is also deposited using a spin coating process, further complicated by complex thickness non-uniformity effects.

[0083]

[0094] Accordingly, embodiments disclosed herein include a dry deposition process for photoresist and CDL deposition on reticle substrates. Dry deposition allows for greater control over thickness uniformity, avoiding the problems noted above. Furthermore, the tools required for the dry deposition process already exist in many facilities. This potentially removes spin-coating tools dedicated to reticle fabrication, which are typically older platforms that are poorly designed, prone to defects, and have a large facility footprint.

[0084]

[0095] 8 is a schematic diagram of a vacuum chamber configured to perform vapor deposition of a metal-oxo photoresist according to an embodiment of the present disclosure. Vacuum chamber 800 includes a grounded chamber 805. A substrate 810 is loaded through opening 815 and clamped to a temperature-controlled chuck 820.

[0085]

[0096] Process gases are supplied to the interior of the chamber 805 from gas sources 844 via respective mass flow controllers 849. In certain embodiments, a gas distribution plate 835 provides distribution of the process gases 844, such as metal precursors, oxidizers, and inert gases. The chamber 805 is evacuated via an exhaust pump 855.

[0086]

[0097] When RF power is applied during processing of the substrate 810, a plasma is formed in the chamber processing region above the substrate 810. A bias power RF generator 825 is coupled to the temperature-controlled chuck 820. The bias power RF generator 825 provides bias power to energize the plasma as needed. The bias power RF generator 825 may have a low frequency, for example, between about 2 MHz and 60 MHz, and in certain embodiments, is in the 13.56 MHz band. In certain embodiments, the vacuum chamber 800 includes a third bias power RF generator 826, with a frequency in the 2 MHz band, connected to the same RF match 827 as the bias power RF generator 825. A source power RF generator 830 is coupled to the plasma generating element (e.g., gas distribution plate 835) via a match (not shown) to provide source power to energize the plasma. The source RF generator 830 may have a frequency, for example, between 100 and 180 MHz, and in certain embodiments, is in the 162 MHz band. As substrate diameters change over time to 150 mm, 200 mm, 300 mm, etc., it is common in the art to normalize the source and bias power of a plasma etching system to the substrate area.

[0087]

[0098] Vacuum chamber 800 is controlled by a controller 870. Controller 870 may include a CPU 872, a memory 873, and an I / O interface 874. CPU 872 may perform processing operations within vacuum chamber 800 according to instructions stored in memory 873. For example, one or more processes, such as processes 220, 340, and 550 described above, may be performed in the vacuum chamber by controller 870.

[0088]

[0099] FIG. 9 illustrates a schematic diagram of an exemplary form of a machine, computer system 900, within which a set of instructions for causing the machine to perform any one or more of the method statements described herein may be executed. In alternative embodiments, the machine may be connected (e.g., networked) to other machines in a local area network (LAN), an intranet, an extranet, or the Internet. The machine may function as a server or a client machine in a client-server network environment, or as a peer machine in a peer-to-peer (or distributed) network environment. The machine may be a personal computer (PC), a tablet PC, a set-top box (STB), a personal digital assistant (PDA), a mobile phone, a web appliance, a server, a network router, switch, or bridge, or any machine capable of executing a set of instructions (sequential or otherwise) that define operations to be performed by the machine. Furthermore, while a single machine is shown, the term "machine" should also be interpreted to include any collection of machines (e.g., computers) that individually or jointly execute a set (or sets) of instructions to perform any one or more of the methodologies described herein.

[0089]

[0100] The exemplary computer system 900 includes a processor 902, a main memory 904 (e.g., read-only memory (ROM), flash memory, dynamic random access memory (DRAM) such as synchronous DRAM (SDRAM) or Rambus DRAM (RDRAM), etc.), a static memory 906 (e.g., flash memory, static random access memory (SRAM), MRAM, etc.), and a secondary storage device 918 (e.g., a data storage device), which communicate with each other via a bus 930.

[0090]

[0101] Processor 902 represents one or more general-purpose processing devices, such as a microprocessor, a central processing unit, etc. More specifically, processor 902 may be a complex instruction set computing (CISC) microprocessor, a reduced instruction set computing (RISC) microprocessor, a very long instruction word (VLIW) microprocessor, a processor implementing other instruction sets, or a processor implementing a combination of instruction sets. Processor 902 may also be one or more special-purpose processing devices, such as an application-specific integrated circuit (ASIC), a field-programmable gate array (FPGA), a digital signal processor (DSP), a network processor, etc. Processor 902 is configured to execute processing logic 926 for performing the operations described herein.

[0091]

[0102] Computer system 900 may further include a network interface device 908. Computer system 900 may include a video display device 910 (e.g., a liquid crystal display (LCD), a light emitting diode display (LED), or a cathode ray tube (CRT)), an alphanumeric input device 912 (e.g., a keyboard), a cursor control device 914 (e.g., a mouse), and a signal generating device 916 (e.g., a speaker).

[0092]

[0103] The secondary memory 918 may include a machine-accessible storage medium (or more specifically, a computer-readable storage medium) 932 on which is stored one or more sets of instructions (e.g., software 922) that embody any one or more of the methodologies or functions described herein. The software 922 may reside, completely or at least partially, within the main memory 904 and / or processor 902, which also constitute machine-readable storage media, while being executed by the computer system 900. This software 922 may also be transmitted or received over the network 920 via the network interface device 908.

[0093]

[0104] While the illustrated embodiment depicts the machine-accessible storage medium 932 as a single medium, the term "machine-readable storage medium" should be understood to include a single medium or multiple media (e.g., a centralized database or a distributed database, and / or associated caches and servers) that store one or more sets of instructions. The term "machine-readable storage medium" should also be taken to include any medium capable of storing or encoding a set of instructions that are executed by a machine, causing the machine to perform any one or more of the methods of the present invention. Accordingly, the term "machine-readable storage medium" should be taken to include, but is not limited to, solid-state memory, optical media, and magnetic media.

[0094]

[0105] According to one embodiment of the present disclosure, a machine-accessible storage medium has stored thereon instructions that cause a data processing system to execute a method for depositing a metal-oxo photoresist on a substrate. The method includes vaporizing a metal precursor into a vacuum chamber and vaporizing an oxidizer into the vacuum chamber. The metal precursor and the oxidizer can be provided to the vacuum chamber sequentially or simultaneously. A reaction between the metal precursor and the oxidizer results in the formation of a metal-oxo photoresist on the substrate. The metal-oxo photoresist can be treated with a plasma treatment in some embodiments.

[0095]

[0106] Thus, a method for forming a metal-oxo photoresist using a vapor phase process has been disclosed.

Claims

1. 1. A method of forming a photoresist layer on a substrate, comprising: forming a first metal-oxo film on the substrate using a first gas-phase process including a first metal precursor vapor and a first oxidizer vapor, wherein flow rates of the first metal precursor vapor and the first oxidizer vapor are non-uniform across a surface of the substrate; forming a second metal-oxo film on the first metal-oxo film using a second gas phase process including a second metal precursor vapor and a second oxidizer vapor, wherein flow rates of the second metal precursor vapor and the second oxidizer vapor are non-uniform across the surface of the substrate; and A method comprising:

2. The method of claim 1 , wherein the material composition of the first metal-oxo film is different from the material composition of the second metal-oxo film.

3. The method of claim 1 , wherein the first metal-oxo film has a thickness of about 5 nm or less.

4. The method of claim 3 , wherein the first metal precursor vapor is different from the second metal precursor vapor and / or the first oxidant vapor is different from the second oxidant vapor.

5. 10. The method of claim 1, wherein the first gas-phase process and the second gas-phase process are a chemical vapor deposition (CVD) process, a plasma-enhanced CVD (PE-CVD) process, an atomic layer deposition (ALD) process, or a plasma-enhanced ALD (PE-ALD) process.

6. The method of claim 1 , wherein the substrate temperature is between about 0° C. and about 100° C.

7. The method of claim 1 , wherein the adhesive strength of the first metal-oxo film is greater than the adhesive strength of the second metal-oxo film.

8. 10. The method of claim 1, further comprising forming a plurality of additional metal-oxo films on the second metal-oxo film, wherein the first metal-oxo film, the second metal-oxo film, and the plurality of additional metal-oxo films provide a compositional gradient.

9. 1. A method of forming a photoresist layer on a substrate in a vacuum chamber, comprising: providing a metal precursor vapor into the vacuum chamber, the metal precursor having the general formula MR ｘ L ｙ wherein M is a metal, R is a leaving group, L is a ligand, x is between 0 and 6, and y is between 0 and 6; providing an oxidizer vapor into the vacuum chamber, wherein a reaction between the metal precursor vapor and the oxidizer vapor results in the formation of the photoresist layer on the surface of the substrate, the photoresist layer being a metal-oxo-containing material, and wherein flow rates of the metal precursor vapor and the oxidizer vapor over a center of the substrate are different from flow rates of the metal precursor vapor and the oxidizer vapor proximate an edge of the substrate; A method comprising:

10. 10. The method of claim 9, further comprising striking a plasma in the vacuum chamber during one or both of providing the metal precursor vapor in the vacuum chamber and providing the oxidizer vapor in the vacuum chamber.

11. 10. The method of claim 9, further comprising treating the photoresist layer with a plasma.

12. 10. The method of claim 9, wherein the ligand comprises a pseudohalide, a monodentate ligand containing a nitrogen donor atom, a bidentate ligand containing one or more of a nitrogen donor atom, an oxygen donor atom, a sulfur donor atom, and a phosphorus donor atom, a ligand having a nitrogen donor atom donating to multiple metal centers, or a hydrogen ligand.

13. 10. The method of claim 9, wherein the leaving group comprises one or more of an alkyl, alkenyl, alkynyl, aryl, carbene, or the leaving group comprises silicon, germanium, or tin as a donor atom.

14. 1. A method of forming a photoresist layer on a substrate in a vacuum chamber, comprising: Initiating a deposition cycle comprising: providing a metal precursor vapor in the vacuum chamber, the metal precursor having the general formula MR ｘ L ｙ wherein M is a metal, R is a leaving group, L is a ligand, x is between 0 and 6, and y is between 0 and 6, wherein the metal precursor vapor is absorbed onto a surface on the substrate, and a flow rate of the metal precursor vapor over the center of the substrate is different from a flow rate of the metal precursor vapor proximate an edge of the substrate; purging the vacuum chamber; providing an oxidizer vapor into the vacuum chamber, wherein a reaction between the metal precursor absorbed on the surface of the substrate and the oxidizer vapor results in the formation of the photoresist layer on the surface of the substrate, the photoresist layer being a metal-oxo-containing material, and wherein a flow rate of the oxidizer vapor over a center of the substrate is different from a flow rate of the oxidizer vapor proximate an edge of the substrate; purging the vacuum chamber; and initiating the deposition cycle comprising:

15. The method of claim 14 further comprising repeating the deposition cycle multiple times.

16. The method of claim 14 further comprising striking a plasma in the vacuum chamber during the deposition cycle.

17. 15. The method of claim 14, wherein the ligand comprises a pseudohalide, a monodentate ligand containing a nitrogen donor atom, a bidentate ligand containing one or more of a nitrogen donor atom, an oxygen donor atom, a sulfur donor atom, and a phosphorus donor atom, a ligand having a nitrogen donor atom donating to multiple metal centers, or a hydrogen ligand.

18. 15. The method of claim 14, wherein the leaving group comprises one or more of an alkyl, alkenyl, alkynyl, aryl, carbene, or the leaving group comprises silicon, germanium, or tin as a donor atom.

19. The deposition cycle comprises: The method of claim 14 further comprising treating the photoresist layer with a plasma.

20. 20. The method of claim 19, further comprising treating the photoresist layer with a plasma after repeating the deposition cycle multiple times.

Images