Deposition of semiconductor integrated films

Abstract

Embodiments disclosed herein include methods for depositing a metal oxide photoresist using a dry deposition process. In one embodiment, the method includes: forming a first metal oxide film on the substrate using a first vapor phase process including a first metal precursor vapor and a first oxidant vapor; and forming a second metal oxide film on the first metal oxide film using a second vapor phase process including a second metal precursor vapor and a second oxidant vapor.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. patent application Ser. No. 16 / 934,730, filed Jul. 21, 2020, which is incorporated herein by reference in its entirety. Background Art

[0003] 1) Field

[0004] Various embodiments of the present disclosure relate to the field of semiconductor processing, and more particularly, to methods of depositing a photoresist layer onto a substrate using a vapor phase process.

[0005] 2) Description of related technologies

[0006] For decades, lithography has been used in the semiconductor industry to form 2D and 3D patterns in microelectronic devices. The lithography process involves spin-coating a film (photoresist), irradiating the film with a selected pattern using 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 remove any remaining solvent.

[0007] The photoresist should be a radiation-sensitive material, and upon irradiation, a chemical transformation occurs in the exposed portion of the film, which allows the solubility between the exposed and unexposed areas to change. This solubility change is exploited to remove (etch) the exposed or unexposed areas of the photoresist. The photoresist is then developed, and the pattern can be transferred to the underlying film or substrate by etching. After the pattern is transferred, the remaining photoresist is removed, and this process is repeated multiple times to provide 2D and 3D structures for use in microelectronic devices.

[0008] Several properties are important in lithographic processing. These include sensitivity, resolution, lower line-edge roughness (LER), etch resistance, and the ability to form thinner layers. The higher the sensitivity, the lower the energy required to change the solubility of the deposited film. This allows the efficiency of the lithographic process to become higher. Resolution and LER determine how narrow features can be achieved using the lithographic process. Pattern transfer to form deep structures requires materials with higher etch resistance. Materials with higher etch resistance also allow thinner films to be achieved. Thinner films increase the efficiency of the lithographic process. Summary of the Invention

[0009] Various embodiments disclosed herein include methods for forming a metal oxide (metal oxo) photoresist using a vapor phase process. In one embodiment, a method for forming a photoresist layer on a substrate includes forming a first metal oxide film on the substrate using a first vapor phase process including a first metal precursor vapor and a first oxidant vapor; and forming a second metal oxide film on the first metal oxide film using a second vapor phase process including a second metal precursor vapor and a second oxidant vapor.

[0010] In another embodiment, a method of forming a photoresist layer on a substrate in a vacuum chamber includes providing a metal precursor vapor into the vacuum chamber, wherein the metal precursor has a 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. The method may further include providing an oxidant vapor into the vacuum chamber, wherein a reaction between the metal precursor vapor and the oxidant vapor results in formation of the photoresist layer on the surface of the substrate, and wherein the photoresist layer is a metal-oxygen-containing material.

[0011] In another 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 providing a metal precursor vapor into the vacuum chamber, wherein the metal precursor has a 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. In one embodiment, the metal precursor vapor is adsorbed onto a surface above the substrate. The deposition cycle may further include: purging the vacuum chamber and providing an oxidant vapor into the vacuum chamber, wherein a reaction between the metal precursor adsorbed onto the surface above the substrate and the oxidant vapor results in the formation of the photoresist layer above the surface of the substrate. In one embodiment, the photoresist layer is a metal-oxygen-containing material. In one embodiment, the deposition cycle may further include: purging the vacuum chamber. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 is a chemical formula for the synthesis of a metal precursor for forming a metal oxide film in a vapor deposition process according to an embodiment of the present disclosure.

[0013] Figure 2 is a flow chart illustrating a process for forming a photoresist on a substrate using a chemical vapor deposition (CVD) process according to an embodiment of the present disclosure.

[0014] Figure 3 is a flow chart illustrating a process for forming a photoresist on a substrate using an atomic layer deposition (ALD) process according to further embodiments of the present disclosure.

[0015] Figure 4 is a cross-sectional view of a metal oxide photoresist on a substrate according to an embodiment of the present disclosure.

[0016] Figure 5 is a flow chart illustrating a process for forming a photoresist having a non-uniform composition throughout the thickness of the photoresist according to an embodiment of the present disclosure.

[0017] Figure 6A is a cross-sectional view of a metal oxide photoresist on a substrate according to an embodiment of the present disclosure, wherein the metal oxide photoresist includes a first layer and a second layer having different material compositions.

[0018] Figure 6B is a cross-sectional view of a metal oxide photoresist on a substrate according to an embodiment of the present disclosure, wherein the metal oxide photoresist includes multiple layers that provide a composition gradient through the thickness of the metal oxide photoresist.

[0019] Figure 7A is a cross-sectional view of a metal oxide photoresist on a substrate having a non-uniform spatial composition according to an embodiment.

[0020] Figure 7B is a cross-sectional view of a metal oxide photoresist after exposure and development according to an embodiment.

[0021] Figure 7C is a cross-sectional view of an underlying substrate after pattern transfer according to an embodiment.

[0022] Figure 8 It is possible to implement the embodiment according to the present disclosure Figure 2 、 Figure 3 or Figure 5 Cross-sectional view of a processing tool for the process in FIG.

[0023] Figure 9 A block diagram of an exemplary computer system according to an embodiment of the present disclosure is shown. DETAILED DESCRIPTION

[0024] This article describes a method for depositing a photoresist on a substrate using a vapor phase process. In the following description, many specific details, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD) processes and material schemes for depositing photoresist, are set forth to provide a thorough understanding of the embodiments of the present disclosure. It will be apparent to those skilled in the art that the embodiments of the present disclosure can be practiced without these specific details. In other cases, well-known aspects (such as integrated circuit manufacturing) are not described in detail to avoid unnecessarily obscuring the embodiments of the present disclosure. In addition, it is to be understood that the various embodiments shown in the drawings are illustrative representations and are not necessarily drawn to scale.

[0025] As background, the efficiency of photoresist systems used for extreme ultraviolet (EUV) lithography is low. That is, existing photoresist material systems for EUV lithography require high doses in order to provide the required solubility switch that allows the photoresist material to be developed. Due to the increased sensitivity to EUV radiation, organic-inorganic hybrid materials (e.g., metal oxide material systems) have been proposed as material systems for EUV lithography. Such material systems typically include metals (e.g., Sn, Hf, Zr, etc.), oxygen and carbon. Metal oxide molecules are sometimes referred to as nanoparticles. Metal oxide organic-inorganic hybrid materials have also been shown to provide lower LER and higher resolution, both of which are properties required to form narrow features.

[0026] Currently, a metal oxide material system is disposed on a substrate using a wet process. The metal oxide material system is dissolved in a solvent and is distributed on a substrate (e.g., a wafer) using a wet chemical deposition process (such as a spin coating process). Wet chemical deposition of photoresist has several disadvantages. One disadvantage of wet chemical deposition is the production of a large amount of wet process byproducts. Wet process byproducts are undesirable, and the semiconductor industry is actively working to reduce wet process byproducts as much as possible. In addition, wet chemical deposition can lead to unevenness problems. For example, spin-on deposition can provide a photoresist layer with uneven thickness or uneven distribution of metal oxide molecules. In addition, it has been shown that the metal oxide photoresist material system loses thickness after exposure, which is troublesome in lithography processing. In addition, in the spin coating process, the percentage of metal in the photoresist is fixed and not easy to adjust.

[0027] Therefore, various embodiments of the present disclosure provide a vacuum deposition process for providing a metal oxide photoresist layer. The vacuum deposition process addresses the aforementioned shortcomings of the wet deposition process. In particular, the vacuum deposition process provides the following advantages: 1) eliminates the generation of wet process byproducts; 2) provides a highly uniform photoresist layer; 3) prevents thickness reduction after exposure; 4) provides a mechanism for adjusting the metal percentage in the photoresist; and 5) enables the formation of a photoresist layer having a tailored, non-uniform material composition throughout the thickness of the photoresist layer.

[0028] The ability to form a customized and non-uniform material composition throughout the thickness of the photoresist layer produces improved properties of the photoresist. For example, the bottom portion of the photoresist layer that interfaces with the underlying substrate can be a material composition with higher adhesion strength. In addition, the bottom portion of the photoresist layer can be engineered to have a lower sensitivity to radiation. In negative tone resists, lower sensitivity can help prevent scumming after the development of the photoresist. Scumming can refer to the presence of residual photoresist material that is not removed from the pattern after development. Multiple embodiments may also include a gradient material composition throughout the thickness of the photoresist. Grading the material composition can be used to control the exposure latitude curve of the photoresist. This allows control of the development profile of the photoresist and / or can be used to provide optical proximity correction (OPC). OPC is typically implemented by changing the pattern in the mask. However, multiple embodiments disclosed herein allow OPC technology to be implemented by changing the composition of the photoresist. Therefore, OPC changes can be implemented without changing the photolithography mask, thus being a more economical solution.

[0029] In addition to providing composition control of the thickness of the photoresist, a plurality of embodiments can also provide composition control throughout the substrate surface. For example, the photoresist at the center of the substrate can have a sensitivity different from that at the edge of the substrate. This spatially inhomogeneous composition is particularly beneficial in processing plasma inhomogeneity. In particular, in many plasma processes, due to the discontinuity of the plasma sheath (plasma sheath) near the edge of the substrate, the critical dimension (critical dimension, CD) control of large radius substrates is challenging. When plasma inhomogeneity can be solved by the composition variation in the photoresist, improved CD control is provided.

[0030] Various embodiments disclosed herein provide various vacuum deposition processes comprising a 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).

[0031] In one embodiment, a vacuum deposition process relies on a chemical reaction between a metal precursor and an oxidant. The metal precursor and the oxidant are evaporated into a vacuum chamber. The metal precursor reacts with the oxidant to form a photoresist layer containing metallic oxides on the surface of the substrate. In some embodiments, the metal precursor and the oxidant are supplied to the vacuum chamber together. In other embodiments, the metal precursor and the oxidant are supplied to the vacuum chamber in alternating pulses. In an ALD or PE-ALD process, a purge of the vacuum chamber may be provided between pulses of the metal precursor and the oxidant.

[0032] In one embodiment, the metal precursor may have the general formula MR x L y M is a metal center, R is a leaving group, and L is a ligand. In one embodiment, x may be between 0 and 6, and y may be between 0 and 6. The metal precursor may be synthesized using any chemical reaction process. For example, a general reaction such as Figure 1 As shown in the figure, the compound SnR x X y (where X is Cl or Br) can react with various ligands to form the metal precursor SnR x L y It should be understood that the Sn metal center can be replaced by any suitable metal atom. In one embodiment, the L ligand is responsible for reacting with the oxidant to form a metallo-oxygen molecule, and the R leaving group is released during exposure (e.g., EUV exposure) during the patterning process. Therefore, the sensitivity of the photoresist can be at least partially affected by the choice of the leaving group R.

[0033] The selection of metal center M, leaving group R and ligand L has facilitated the different material properties of metal oxide photoresist.For example, the change of M, R and L can provide different sensitivities to radiation, different adhesion properties, different structural properties (that is, making it possible to form high aspect ratio patterns), different etch selectivities and many other properties.Therefore, photoresist can be specifically customized according to desired purpose.In addition, the use of vacuum deposition process allows to change one or more of M, R and L through the thickness of photoresist to provide non-uniform material properties in photoresist, as will be described in more detail below.

[0034] In a specific embodiment, M is Sn. However, it should be understood that M can be any suitable 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.

[0035] In one embodiment, the ligand L can be a variety of chemical structures. In one embodiment, the ligand L can be a pseudohalide ligand. Pseudohalides can include, but are not limited to, CN, CNO, SCN, N3, or SeCN.

[0036] In one embodiment, a suitable class of ligands L for metal precursors is a monodentate ligand comprising a N donor atom. The binding mode to the metal center M is shown in molecule I. Such monodentate ligands may include cyclic ligands. Some examples of such ligands L are provided in molecules II-V.

[0037]

[0038]

[0039] In one embodiment, the ligand L can also be a bidentate or monodentate ligand containing a 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-XVIII.

[0040]

[0041]

[0042]

[0043] In one embodiment, the ligand L can also be a bidentate ligand comprising one N donor atom and one O donor atom, wherein the donor atoms are bound to the metal center M. The binding mode of such a ligand to the metal center M is shown in molecule XIX. Examples of such ligands are shown in molecules XX-XXIV.

[0044]

[0045]

[0046] In one embodiment, the ligand L may also comprise N donor atoms that donate to more than one metal center. Examples of binding modes for such ligands are shown in molecules XXV-XXVII.

[0047]

[0048] In one embodiment, the ligand L may also comprise an H donor atom. Examples of such ligands are shown in molecule XXVIII.

[0049] MH (XXVIII)

[0050] 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 an alkyl (C1-C10), an alkenyl (interior or terminal), an alkynyl (interior or terminal), an aryl or a carbenes. 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 a donor atom.

[0051] Examples of suitable alkyl groups are provided in molecules XXIX and XXX.

[0052]

[0053] Examples of suitable alkenyl groups are provided in molecules XXXI-XXXIII.

[0054]

[0055] Examples of suitable alkynyl groups are provided in molecule XXXIV.

[0056]

[0057] Examples of suitable aryl groups are provided in Molecules XXXV and XXXVI.

[0058]

[0059] Examples of suitable carbenes are provided in Molecules XXXVII and XXXVIII.

[0060]

[0061] Examples of leaving groups R comprising Si, Ge or Sn as donor atoms are shown in molecules XXXIX-XLI, where X is Si, Ge or Sn.

[0062]

[0063] In another embodiment, the metal precursor may also include a stannylene precursor. Molecule XLII is an example of a universal stannylene precursor. The ligand L can be any of the ligands L described above or a universal amine (NR2). The leaving group R can include any of the leaving groups R described above.

[0064]

[0065] In another embodiment, the metal precursor can also be a universal 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 universal metal precursors can be used in combination with the above-mentioned metal precursors.

[0066]

[0067] Now refer to Figure 2 According to an embodiment of the present disclosure, a flow chart is provided showing a process 220 for depositing a metal oxide photoresist on a substrate surface. 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, hydrocarbons can also flow into the chamber during plasma-assisted deposition to incorporate more carbon into the film. When the plasma is turned on during deposition, and if there are hydrocarbon molecules in the chamber, more carbon can be incorporated into the film. One form of carbon can be MC (M=metal). MC (e.g., Sn-C) can be sensitive to exposure. The hydrocarbon can be a carbon-containing molecule such as, for example, CH2=CH2, acetylene, CH4, propylene, etc.

[0068] In one embodiment, process 220 may begin with operation 221, which includes providing a metal precursor vapor into a vacuum chamber containing a substrate. The metal precursor vapor may include a metal precursor, such as those described in more detail above. For example, the metal precursor may have the general formula MR x L y , where x and y are both between 0 and 6.

[0069] In one embodiment, the metal center M may 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 may include one or more of an alkyl, an alkenyl (inside or end), an alkynyl (inside or end), an aryl or a carbene. The leaving group R may also include a Si donor atom, a Ge donor atom or a Sn donor atom. In one embodiment, the leaving group R may be linear, branched or cyclic. In one embodiment, the ligand L may comprise a pseudohalide, a monodentate ligand having a N donor atom, a monodentate or bidentate ligand having a N, O, S and / or P donor atom, a bidentate ligand having one N donor atom and one O donor atom, a ligand having an N donor atom that donates to more than one metal center M, or a hydrogen atom.

[0070] In other embodiments, the metal precursor may comprise a stannylene precursor or a universal metal precursor, such as shown in molecule XLIII. In addition, it should be understood that more than one metal precursor vapor may be provided to the vacuum chamber. For example, the first metal precursor may comprise Sn and the second metal precursor may comprise Hf. In such an embodiment, the resulting metal oxide photoresist may comprise two or more different types of metal atoms. In one embodiment, the metal precursor vapor may be diluted by a carrier gas. The carrier gas may be an inert gas such as Ar, N2, or He.

[0071] In one embodiment, process 220 may continue with operation 222, which includes providing an oxidant vapor into the vacuum chamber. In one embodiment, the oxidant vapor may include a carbon backbone having reactive groups at opposite ends of the carbon backbone. The reactive groups initiate a reaction with the metal precursor, which results in the formation of a metal oxide photoresist on the substrate. In one embodiment, the oxidant vapor may include water or ethylene glycol. In one embodiment, the oxidant vapor may be diluted by a carrier gas. The carrier gas may be an inert gas such as Ar, N2, or He.

[0072] In one embodiment, process 220 may continue with optional operation 223, which includes treating the metal oxide photoresist layer with a plasma. In one embodiment, the plasma treatment may include generating a plasma from one or more inert gases (such as Ar, N2, He, etc.). In one embodiment, the one or more inert gases may also be mixed with one or more oxygen-containing gases (such as O2, CO2, CO, NO, NO2, H2O, etc.). In one embodiment, the vacuum chamber may be purged prior to operation 223. The purge may include a pulse of an inert gas (such as Ar, N2, He, etc.).

[0073] In one embodiment, process 220 may be performed such that operations 221 and 222 are performed simultaneously. That is, the supply of the metal precursor vapor into the vacuum chamber and the supply of the oxidant vapor into the vacuum chamber may be performed simultaneously. After forming a metal oxide photoresist film having a desired thickness, process 220 may be stopped. In one embodiment, an optional plasma treatment operation 223 may be performed after forming the metal oxide photoresist film having a desired thickness.

[0074] In other embodiments, process 220 may be performed in a pulsed manner. That is, a pulse of metal precursor vapor may be provided to the vacuum chamber first, followed by a pulse of oxidant vapor. In one embodiment, a cycle comprising pulses of metal precursor vapor and pulses of oxidant vapor may be repeated multiple times to provide a metal oxide photoresist film having a desired thickness. In one embodiment, the order of the cycles may be switched. For example, the oxidant vapor may be pulsed first, followed by the metal precursor vapor.

[0075] In one embodiment, the pulse duration of the metal precursor vapor may be substantially similar to the pulse duration of the oxidant vapor. In other embodiments, the pulse duration of the metal precursor vapor may be different from the pulse duration of the oxidant vapor. In one embodiment, the pulse duration may be between 0 seconds and 1 minute. In a specific embodiment, the pulse duration may be between 1 second and 5 seconds.

[0076] In one embodiment, each repetition of the cycle uses the same process gas. In other embodiments, the process gas may be changed between cycles. For example, a first cycle may utilize a first metal precursor vapor, and a second cycle may utilize a second metal precursor vapor. Subsequent cycles may continue to alternate between the first metal precursor vapor and the second metal precursor vapor. In one embodiment, multiple oxidant vapors may be alternated between cycles in a similar manner.

[0077] In one embodiment, the optional plasma treatment of operation 223 may be performed after each cycle. That is, each cycle may include a pulse of metal precursor vapor, a pulse of oxidant vapor, and plasma treatment. In another 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 all cycles are completed (that is, as a post-treatment).

[0078] In one embodiment, process 220 can be a thermal treatment or a plasma process. In the case of a thermal treatment, the reaction between the metal precursor vapor and the oxidant vapor can be driven by heat. This 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 a case, the presence of the plasma can enhance the chemical reaction used to form the metal oxide photoresist. This 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.

[0079] In one embodiment, the vacuum chamber utilized in process 220 may be any suitable chamber capable of providing sub-atmospheric pressure. In one embodiment, the vacuum chamber may include temperature control features for controlling chamber wall temperature and / or for controlling substrate temperature. 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 .

[0080] 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 maintained 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.

[0081] Now refer to Figure 3 According to another embodiment of the present disclosure, a flow chart is provided showing a process 340 for depositing a metal oxide photoresist on a surface of a substrate. 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, hydrocarbons can also flow into the chamber during plasma-assisted deposition to incorporate more carbon into the film. When the plasma is turned on during deposition, and if there are hydrocarbon molecules in the chamber, more carbon can be incorporated into the film. One form of carbon can be MC (M=metal). MC (e.g., Sn-C) can be sensitive to light exposure. The hydrocarbon can be a carbon-containing molecule such as, for example, CH2=CH2, acetylene, CH4, propylene, etc.

[0082] In one embodiment, process 340 may begin with operation 341, which includes providing a metal precursor vapor into a vacuum chamber containing a substrate. In one embodiment, the metal precursor vapor may include molecules having one or more metal atoms. The metal precursor vapor may include a metal precursor, such as those described in more detail above. For example, the metal precursor may have the general formula MR x L y , where x and y are both between 0 and 6.

[0083] In one embodiment, the metal center M may 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 may include one or more of an alkyl, an alkenyl (inside or end), an alkynyl (inside or end), an aryl or a carbene. The leaving group R may also include a Si donor atom, a Ge donor atom or a Sn donor atom. In one embodiment, the leaving group R may be linear, branched or cyclic. In one embodiment, the ligand L may comprise a pseudohalide, a monodentate ligand having a N donor atom, a monodentate or bidentate ligand having a N, O, S and / or P donor atom, a bidentate ligand having one N donor atom and one O donor atom, a ligand having an N donor atom that donates to more than one metal center M, or a hydrogen atom.

[0084] In other embodiments, the metal precursor may comprise a stannylene precursor or a universal metal precursor, such as shown in molecule XLIII. In addition, it should be understood that more than one metal precursor vapor may be provided to the vacuum chamber. For example, the first metal precursor may comprise Sn and the second metal precursor may comprise Hf. In such an embodiment, the resulting metal oxide photoresist may comprise two or more different types of metal atoms. In one embodiment, the metal precursor vapor may be diluted by a carrier gas. The carrier gas may be an inert gas such as Ar, N2, or He.

[0085] In one embodiment, the metal precursor vapor is adsorbed onto the surface of the substrate. In one embodiment, a single layer of the metal precursor may be provided substantially above the surface of the substrate. However, in other embodiments, several layers of the metal precursor vapor may be adsorbed onto the surface of the substrate.

[0086] In one embodiment, process 340 may continue with operation 342, which includes purging the vacuum chamber. In one embodiment, the purge process removes residual metal precursor vapor and any byproducts from the vacuum chamber. The purge process may include a pulse of an inert gas such as Ar, N2, He, etc.

[0087] In one embodiment, process 340 may continue with operation 343, which includes providing an oxidant vapor into a vacuum chamber. The oxidant vapor reacts with the surface-adsorbed metal precursor to form a metal oxide photoresist layer on the surface of the substrate. Since the metal precursor is adsorbed to the surface of the substrate, the reaction can be considered self-limiting. In one embodiment, the oxidant vapor may include a carbon backbone having reactive groups at opposite ends of the carbon backbone. The reactive groups initiate a reaction with the metal precursor, which results in the formation of a metal oxide photoresist on the substrate. In one embodiment, the oxidant vapor may include water or ethylene glycol. In one embodiment, the oxidant vapor may be diluted by a carrier gas. The carrier gas may be an inert gas such as Ar, N2 or He.

[0088] In one embodiment, the pulse duration of the metal precursor vapor may be substantially similar to the pulse duration of the oxidant vapor. In other embodiments, the pulse duration of the metal precursor vapor may be different from the pulse duration of the oxidant vapor. In one embodiment, the pulse duration may be between 0 seconds and 1 minute. In a specific embodiment, the pulse duration may be between 1 second and 5 seconds.

[0089] In one embodiment, process 340 may continue with operation 344, which includes purging the vacuum chamber. In one embodiment, the purge process removes residual oxidant vapor and any byproducts from the vacuum chamber. The purge process may include a pulse of an inert gas such as Ar, N2, He, etc.

[0090] In one embodiment, process 340 may continue with optional operation 345, which includes treating the metal oxide 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, N2, He, etc.). In one embodiment, the one or more inert gases may also be mixed with one or more oxygen-containing gases (such as O2, CO2, CO, NO, NO2, H2O, etc.). In one embodiment, treatment operations 341 to 344 may define a cycle of process 340. Various embodiments may include repeating the cycle multiple times to provide a metal oxide 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 pulse of metal precursor vapor, a purge, a pulse of oxidant vapor, 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 all cycles are completed (that is, as a post-processing).

[0091] In one embodiment, each repetition of the cycle uses the same process gas. In other embodiments, the process gas may be changed between cycles. For example, the first cycle may utilize a first metal precursor vapor, while the second cycle may utilize a second metal precursor vapor. Subsequent cycles may continue to alternate between the first metal precursor vapor and the second metal precursor vapor. In one embodiment, multiple oxidant vapors may be alternated between cycles in a similar manner.

[0092] In one embodiment, process 340 may 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 may be thermally driven. This embodiment may be referred to as an ALD process. In the case of a plasma process, a plasma may be struck during one or both of operations 341 and 343. In such a case, the presence of the plasma may enhance the chemical reaction used to form the metal oxide photoresist. This embodiment may be referred to as a PE-ALD process. In one embodiment, any plasma source may be used to form the plasma. For example, the plasma source may include, but is not limited to, a CCP source, an ICP source, a remote plasma source, or a microwave plasma source.

[0093] In one embodiment, the vacuum chamber utilized in process 340 may be any suitable chamber capable of providing a sub-atmospheric pressure. In one embodiment, the vacuum chamber may include temperature control features for controlling chamber wall temperature and / or for controlling substrate temperature. 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 .

[0094] 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 maintained 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.

[0095] Now refer to Figure 4 , according to one embodiment, a cross-sectional view of a metal oxide photoresist layer 470 on a substrate 401 is shown. In one embodiment, the metal oxide photoresist layer 470 can be disposed on the substrate 401 using a process such as process 340 or process 220. The metal oxide photoresist layer 470 can have a substantially uniform composition throughout the thickness of the metal oxide photoresist layer. However, it should be understood that the metal oxide photoresist can contain more than one type of metal centers M. Such an embodiment can be provided by flowing more than one type of metal precursor into the vacuum chamber simultaneously or in alternating pulses.

[0096] It should be understood that various embodiments are not limited to a substantially uniform metal oxide photoresist layer. For example, the composition of the metal oxide photoresist layer can be adjusted throughout the thickness of the metal oxide photoresist layer. For example, the metal center can be changed, the percentage of metal can be changed, or the carbon concentration can be changed, among many other variations.

[0097] The vacuum deposition process used to form the metal oxide photoresist enables the composition of the metal oxide photoresist layer to be varied through the thickness. For example, the metal precursor vapor or oxidant vapor can be varied at different points in the metal oxide photoresist deposition (e.g., different molecules can be used, different vapor flow rates can be used, etc.). This is a significant improvement over existing wet-based spin-coating processes, which are limited to having a substantially uniform material composition throughout the thickness of the photoresist layer.

[0098] Thus, the various embodiments disclosed herein enable enhanced tunability to optimize metal oxide photoresist layers for various applications. For example, the first few nanometers (e.g., the first 10 nm or less) of a metal oxide photoresist layer above a substrate may have a different composition than the rest of the film. This may allow the rest of the metal oxide photoresist to be optimized for dose while the bottom portion is tuned to have improved adhesion, sensitivity to EUV photons, or sensitivity to development chemicals to improve post-lithography pattern control (e.g., scum), as well as to improve defects and prevent collapse / peeling. In other embodiments, a composition gradient may be provided throughout the thickness of the metal oxide photoresist. Grading the material composition may be used to control the exposure latitude curve of the photoresist. This allows control of the development profile of the photoresist and / or can be used to provide OPC. The gradient may also be optimized for pattern type. For example, a pillar may require improved adhesion, while a line / space pattern may allow for lower adhesion while being tuned to improve dose.

[0099] Now refer to Figure 5 According to another embodiment of the present disclosure, a flow chart is provided showing a process 550 for depositing a metal oxide photoresist on a substrate surface. In process 550, the material composition of the metal oxide photoresist is non-uniform throughout the thickness of the metal oxide photoresist. Process 550 may begin with operation 551, which includes forming a first metal oxide film on the substrate using a first vapor phase process. In one embodiment, the first vapor phase process may include a first metal precursor vapor and a first oxidant vapor. In one embodiment, the first vapor phase process may include a CVD or PE-CVD process similar to the above-described process 220. In another embodiment, the first vapor phase process may include an ALD or PE-ALD process similar to the above-described process 340. The first metal precursor vapor may include any of the metal precursor vapors described in more detail above.

[0100] In one embodiment, process 550 may continue with operation 552, which includes forming a second metal oxide film over the first metal oxide film using a second vapor phase process including a second metal precursor vapor and a second oxidant vapor. In one embodiment, the second vapor phase process may include a CVD or PE-CVD process similar to process 220 described above. In another embodiment, the second vapor phase process may 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 oxidant vapor may be different from the first metal precursor vapor and the first oxidant vapor. Thus, the second metal oxide film may have a different composition than the first metal oxide film.

[0101] In some embodiments, only two different metal oxide film layers are provided. Figure 6A An example of such an embodiment is shown in FIG. As shown, a photoresist layer including a first metal oxide film 671 and a second metal oxide film 672 is disposed on a substrate 601. In one embodiment, the first metal oxide film 671 is an interface layer that provides improved adhesion to the substrate 601. The first metal oxide film 671 may have a thickness of approximately 10 nm or less.

[0102] In other embodiments, the photoresist layer may include multiple different metal oxide film layers. Figure 6B An example of such an embodiment is shown in FIG. As shown, the photoresist layer includes multiple different metal oxide film layers 671 to 678 having different compositions. This embodiment can be formed using process 550, which includes additional vapor phase processes for each layer. In the embodiment shown, each of layers 671 to 678 is substantially uniform in thickness. However, it should be understood that various embodiments may include metal oxide film layers having non-uniform thicknesses.

[0103] In one embodiment, process 550 may further include optional plasma treatment of the metal oxide film (or multiple metal oxide films). In one embodiment, the plasma treatment may be performed after the deposition of the first metal oxide film and the second metal oxide film. Alternatively, the plasma treatment may be performed after the deposition of each metal oxide film. That is, the first metal oxide film may be deposited first, and then the plasma treatment may be performed before the second metal oxide film is deposited. In one embodiment, the plasma treatment may include plasma generated from one or more inert gases (such as Ar, N2, He, etc.). In one embodiment, the one or more inert gases may also be mixed with one or more oxygen-containing gases (such as O2, CO2, CO, NO, NO2, H2O, etc.).

[0104] Metal oxide photoresist films provided using vapor phase processes such as those described in the various embodiments above provide significant advantages over wet chemical methods. One advantage is the elimination of wet process byproducts. Utilizing vapor phase processes, waste liquids are eliminated and byproduct removal is simplified. Additionally, vapor phase processes provide a more uniform photoresist layer. Uniformity in this sense can refer to thickness uniformity across the wafer and / or uniformity of distribution of the metal component of the metal oxide film. In particular, CVD, PE-CVD, ALD, and PE-ALD processes have been demonstrated to provide excellent thickness uniformity and composition uniformity.

[0105] In addition, the use of a vapor phase process provides the ability to fine-tune the percentage of metal in the photoresist and the composition of the metal in the photoresist. The percentage of metal can be modified by increasing / decreasing the flow of the metal precursor entering the vacuum chamber and / or by modifying the pulse length of the metal precursor / oxidant. The use of a vapor phase process also allows a variety of different metals to be included in the metal oxide film. For example, a single pulse flowing two different metal precursors can be used, or alternating pulses of two different metal precursors can be used. The use of a vapor phase process also allows the formation of metal oxide films with different material compositions so that the photoresist can be adjusted for the desired application.

[0106] Furthermore, metal oxide photoresists formed using vapor phase processes have been shown to be more resistant to thickness reduction after exposure. It is believed that, independent of a specific mechanism, the resistance to thickness reduction is at least partially due to reduced carbon loss during exposure.

[0107] In addition to the composition variation throughout the thickness of the photoresist, a plurality of embodiments can also provide spatial composition variation. Spatial composition variation can refer to the variation at different points throughout the substrate. For example, the composition of the photoresist at the center of the substrate can be different from the composition of the photoresist at the edge of the substrate. In particular, the concentration of the photosensitive component in the surface modification photoresist can be throughout the surface. Such spatial composition variation can also be achieved by dry deposition process. That is, using traditional wet process (e.g., spin coating, etc.) does not take into account spatial composition variation.

[0108] Now refer to 7A to 7C , a series of cross-sectional views are shown that depict a process for forming a photoresist having spatial composition variation, according to an embodiment. Referring now to Figure 7A , a cross-sectional view of a substrate 701 is shown according to an embodiment. In one embodiment, a first layer 702 is provided over the substrate. The first layer 702 is a layer that will be patterned using a photoresist layer 780. In one embodiment, the photoresist layer 780 can be deposited over the first layer 702 using the vacuum deposition process of the embodiment described above.

[0109] To provide spatial composition variation, the process tool's showerhead 790 can distribute process gas at a non-uniform flow rate. For example, the outer edge of the showerhead 790 can be customized 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 an inverse bias in the lithography step. For example, the center of the photoresist 780 can have a photosensitive component concentration Δ0 and the edge of the photoresist 780 can have a photosensitive component concentration Δ0+Δ.

[0110] Now refer to Figure 7B , according to an embodiment, shows a cross-sectional view of a photoresist 780 after exposure and patterning. As shown, the center of the photoresist 780 has a dimension CD and the edge of the photoresist 780 has a dimension CD+ΔCD. The difference in the resulting dimensions of the patterned photoresist 780 can be attributed to different sensitivities due to variations in spatial composition.

[0111] Now refer to Figure 7C , according to an embodiment, shows a cross-sectional view of a substrate after transferring a photoresist pattern into a first layer 702. As shown, the resulting structure in the first layer 702 has the same CD at the center and edge of the substrate 701. Figure 7B , resulting in plasma non-uniformity, still achieve uniform dimensions in the first layer 702. Thus, various embodiments allow for improved CD uniformity by using a photoresist with a gradient across the substrate (eg, center to edge).

[0112] In the above-described embodiment, the substrate may be a wafer, such as a silicon wafer or similar wafer. However, it should be understood that this dry photoresist deposition and development process is also applicable to other substrates. For example, when the substrate is a master mask (reticle), the above-described process may also be used. Typically, the photoresist deposited on the master mask substrate is completed by spin coating. The square plate of the master mask makes uniform photoresist deposition particularly difficult. This is because the surface tension effect from the mask corners makes it difficult to systematically and consistently control the photoresist thickness. Similar problems occur during the wet development process. There is also a significant pattern collapse problem because the liquid does not roll off as easily as for a circular wafer. The mask requires a "top-coat" (i.e., a charge dissipation layer (CDL)) on the photoresist layer. This top coating is also deposited by a spin coating process, which adds another level of complexity due to the convoluted thickness non-uniformity effect.

[0113] Thus, various embodiments disclosed herein include a dry deposition process for photoresist and CDL deposition on a master mask substrate. Dry deposition allows for finer control of thickness uniformity and avoids the aforementioned issues. Additionally, the tools required for the dry deposition process already exist in many facilities. This can lead to the removal of spin coating tools dedicated to master mask manufacturing, which are often outdated platforms with poor design, resulting in defects and a large footprint in the facility.

[0114] Figure 8 Schematic diagram of a vacuum chamber configured to perform vapor deposition of metal oxide 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.

[0115] Process gases are supplied from gas sources 844 to the interior of chamber 805 via corresponding mass flow controllers 849. In certain embodiments, a gas distribution plate 835 provides distribution of process gases 844 (such as metal precursors, oxidants, and inert gases). Chamber 805 is evacuated via exhaust pump 855.

[0116] When RF power is applied during processing of substrate 810, a plasma is formed in the chamber processing region above substrate 810. A bias power RF generator 825 is coupled to temperature-controlled chuck 820. If necessary, bias power RF generator 825 provides bias power to ignite the plasma. Bias power RF generator 825 may have a low frequency, for example, between approximately 2 MHz and 60 MHz, and in a particular embodiment, in the 13.56 MHz frequency band. In certain embodiments, vacuum chamber 800 includes a third bias power RF generator 826 having a frequency in the approximately 2 MHz frequency band, which is connected to the same RF matcher 827 as bias power RF generator 825. A source power RF generator 830 is coupled to plasma generating elements (e.g., gas distribution plate 835) via a matcher (not depicted) to provide source power to ignite the plasma. Source RF generator 830 may have a frequency, for example, between 100 MHz and 180 MHz, and in a particular embodiment, in the 162 MHz frequency band. As substrate diameters have evolved over time from 150 mm, 200 mm, 300 mm, etc., it is common in the art to normalize the source and bias power of a plasma etch system to the substrate area.

[0117] The vacuum chamber 800 is controlled by a controller 870. The controller 870 may include a CPU 872, a memory 873, and an I / O interface 874. The CPU 872 may execute processing operations within the vacuum chamber 800 according to instructions stored in the memory 873. For example, one or more processes, such as processes 220, 340, and 550 described above, may be executed in the vacuum chamber by the controller 870.

[0118] Figure 9 Shown is a diagrammatic representation of a machine in the exemplary form of a computer system 900, within which a group of instructions for causing the machine to perform any one or more methods described herein can be executed. In an alternative embodiment, the machine can be connected (e.g., networked) to other machines in a local area network (LAN), an intranet, an extranet, or the Internet. The machine can operate as a server or client machine in a client-server network environment, or as a peer machine (peer machine) in a peer-to-peer (or distributed) network environment. The machine can be a personal computer (PC), a tablet PC, a set-top box (STB), a personal digital assistant (PDA), a cellular phone, a network appliance, a server, a network router, a switch or a bridge, or any machine that can perform a group of instructions (sequential or otherwise) specifying the action to be taken by the machine. In addition, although only a single machine is shown, the term "machine" should also be considered to include any set of machines (e.g., computers) that individually or jointly perform a group (or multiple groups) of instructions to perform any one or more methods in the methods described herein.

[0119] 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 memory 918 (e.g., a data storage device), which communicate with each other via a bus 930.

[0120] The processor 902 represents one or more general-purpose processors, such as a microprocessor, a central processing unit, or the like. More particularly, the processor 902 can 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. The processor 902 can 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, or the like. The processor 902 is configured to execute processing logic 926 to perform the operations described herein.

[0121] The computer system 900 may further include a network interface device 908. The computer system 900 may also include a video display unit 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).

[0122] 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) embodying any one or more of the methodologies or functionality described herein. The software 922 may also reside, completely or at least partially, within the main memory 904 and / or within the processor 902 during execution of the software 922 by the computer system 900, with the main memory 904 and the processor 902 also constituting machine-readable storage media. The software 922 may also be further transmitted or received over the network 920 via the network interface device e.

[0123] Although the machine-accessible storage medium 932 is shown as a single medium in the exemplary embodiment, the term "machine-readable storage medium" should also be considered to include a single medium or multiple media (e.g., a centralized or 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 considered to include any medium that can store or encode a set of instructions for execution by a machine and cause the machine to perform any one or more of the methods of the present disclosure. The term "machine-readable storage medium" should accordingly be considered to include, but not be limited to, solid-state memories, and optical and magnetic media.

[0124] According to an embodiment of the present disclosure, a machine-accessible storage medium has instructions stored on the machine-accessible storage medium, and these instructions cause a data processing system to execute a method for depositing a metal oxide photoresist on a substrate. The method includes evaporating a metal precursor into a vacuum chamber and evaporating an oxidant into the vacuum chamber. The metal precursor and the oxidant can be provided in sequence or can be supplied to the vacuum chamber simultaneously. The reaction between the metal precursor and the oxidant causes the formation of the metal oxide photoresist on the substrate. In some embodiments, the metal oxide photoresist can be processed by plasma treatment. Therefore, a method for forming a metal oxide photoresist using a vapor phase process has been disclosed.

Claims

1. A method for forming a photoresist layer on a substrate, comprising: forming a first metal oxide film on the substrate using a first vapor phase process comprising a first metal precursor vapor and a first oxidant vapor, wherein flow rates of the first metal precursor vapor and the first oxidant vapor are non-uniform across the surface of the substrate; forming a second metal oxide film over the first metal oxide film using a second vapor phase process including a second metal precursor vapor and a second oxidant vapor, wherein flow rates of the second metal precursor vapor and the second oxidant vapor are non-uniform across the surface of the substrate; and During one or both of the first gas phase process and the second gas phase process, striking a plasma in a vacuum chamber and flowing a hydrocarbon into the vacuum chamber to incorporate carbon into the photoresist layer in the form of MC, where M is a metal, wherein the photoresist layer is compositionally non-uniform across the surface of the substrate. 2 . The method of claim 1 , wherein a material composition of the first metal oxide film is different from a material composition of the second metal oxide film.

3. The method of claim 1, wherein a thickness of the first metal oxide film is 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. The method of claim 1, wherein the first gas phase process and the second gas phase process are plasma enhanced CVD (PE-CVD) processes or plasma enhanced ALD (PE-ALD) processes. The method of claim 1 , wherein the temperature of the substrate is between 0° C. and 100° C. 7 . The method of claim 1 , wherein the adhesion strength of the first metal oxide film is greater than the adhesion strength of the second metal oxide film.

8. The method of claim 1, further comprising: A plurality of additional metal oxide films are formed over the second metal oxide film, wherein the first metal oxide film, the second metal oxide film, and the plurality of additional metal oxide films provide a composition gradient.

9. A method for forming a photoresist layer on a substrate in a vacuum chamber, comprising: A metal precursor vapor is provided into the vacuum chamber, wherein the metal precursor has 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; and providing an oxidant vapor into the vacuum chamber, wherein a reaction between the metal precursor vapor and the oxidant vapor results in formation of the photoresist layer on the surface of the substrate, wherein the photoresist layer is a metal-oxygen-containing material, and wherein flow rates of the metal precursor vapor and the oxidant vapor over the center of the substrate are different than flow rates of the metal precursor vapor and the oxidant vapor near an edge of the substrate, striking a plasma in the vacuum chamber and flowing hydrocarbons into the vacuum chamber during one or both of providing a metal precursor vapor into the vacuum chamber and providing an oxidant vapor into the vacuum chamber to incorporate carbon into the photoresist layer in the form of MC, wherein the photoresist layer is compositionally non-uniform across the surface of the substrate.

10. The method of claim 9, further comprising: The photoresist layer is treated with plasma.

11. The method of claim 9, wherein the ligand comprises a pseudohalide, a monodentate ligand comprising a nitrogen donor atom, a bidentate ligand comprising 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 that donates to more than one metal center, or a hydrogen ligand.

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

13. A method for forming a photoresist layer on a substrate in a vacuum chamber, comprising: Initiating a deposition cycle, wherein the deposition cycle comprises: A metal precursor vapor is provided into the vacuum chamber, wherein the metal precursor has 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 adsorbed to a surface above the substrate, and wherein 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 near an edge of the substrate; purifying the vacuum chamber; providing an oxidant vapor into the vacuum chamber, wherein a reaction between the metal precursor adsorbed to the surface above the substrate and the oxidant vapor results in formation of the photoresist layer above the surface of the substrate, wherein the photoresist layer is a metal-oxygen-containing material, and wherein a flow rate of the oxidant vapor over the center of the substrate is different than a flow rate of the oxidant vapor near an edge of the substrate; and purifying the vacuum chamber, striking a plasma in the vacuum chamber and flowing hydrocarbons into the vacuum chamber during the deposition cycle to incorporate carbon into the photoresist layer in the form of MC, wherein the photoresist layer is compositionally non-uniform across the surface of the substrate.

14. The method of claim 13, further comprising: The deposition cycle was repeated multiple times.

15. The method of claim 13, wherein the ligand comprises a pseudohalide, a monodentate ligand comprising a nitrogen donor atom, a bidentate ligand comprising 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 that donates to more than one metal center, or a hydrogen ligand.

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

17. The method of claim 13, wherein the deposition cycle further comprises: The photoresist layer is treated with plasma.

18. The method of claim 17, further comprising: After repeating the deposition cycle multiple times, the photoresist layer is treated with plasma.

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