Deposition of organic materials

Abstract

In one aspect, methods, systems, and apparatus are disclosed for selectively depositing a layer of an organic material on a substrate comprising a first surface and a second surface by a cyclic deposition process, the process comprising providing the substrate in a reaction chamber, providing a first vapor phase precursor in the reaction chamber, and providing a second vapor phase precursor in the reaction chamber, wherein the first and second gas phase precursors selectively form an organic material on the first surface relative to the second surface, and wherein the first gas phase precursor comprises a diamine or triamine compound.

Description

Technical Field

[0001] The present disclosure relates to methods and apparatus for manufacturing semiconductor devices. More particularly, the present disclosure relates to methods and apparatus for selectively depositing an organic layer on a substrate including at least two different surfaces. Background Art

[0002] Semiconductor device manufacturing processes often use advanced deposition methods. Patterning is often used to deposit different materials on semiconductor substrates. Semiconductor manufacturers are increasingly interested in selective deposition, which can reduce the steps required for conventional patterning, thereby reducing processing costs. Selective deposition can also enhance scaling in narrow structures. Various alternatives to achieve selective deposition have been proposed, and additional improvements are needed to expand the use of selective deposition in industrial-scale device manufacturing.

[0003] Organic polymer layer can be used as the starting point of semiconductor application of amorphous carbon film or layer, for example.For example, the layer containing polyimide is valuable because of its thermal stability and resistance to mechanical stress and chemical substances, and they are described as passivation layer to allow the selective deposition of different materials.Vapor deposition process such as chemical vapor deposition (CVD), vapor deposition polymerization (VDP), molecular layer deposition (MLD) and sequential deposition process such as atomic layer deposition (ALD) and cyclic CVD can be used to deposit organic polymer layer.In this process, the precursor for depositing material plays an important role in the property of deposited layer.When different materials are selectively deposited on different surface combinations, this affects the availability of material again.Therefore, this area needs to widen the selection of precursor for depositing organic polymer layer.

[0004] Any discussion set forth in this section, including discussion of problems and solutions, has been included in the present disclosure merely to provide context for the present disclosure. Such discussion should not be construed as an admission that any or all information was known or constituted prior art when the present invention was made. Summary of the invention

[0005] This Summary may introduce some concepts in a simplified form that are further described below. This Summary is not intended to necessarily identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

[0006] In one aspect, a method for selectively depositing an organic material layer on a substrate comprising a first surface and a second surface by a cyclic deposition process, the process comprising providing a substrate in a reaction chamber, providing a first gaseous precursor in the reaction chamber, and providing a second gaseous precursor in the reaction chamber, wherein the first and second gaseous precursors selectively form an organic material on the first surface relative to the second surface, and wherein the first gaseous precursor comprises a triamine compound having three amine groups and at least three carbon atoms, wherein the amine groups are primary amines. The method may also include wherein the second gaseous precursor comprises a dianhydride. The method may also include wherein the organic material comprises a polyimide and / or a polyamic acid. The method may also include wherein the second surface comprises an inorganic dielectric surface and / or silicon. The method may also include wherein the organic material is deposited on the first surface with a selectivity greater than about 50% relative to the second surface.

[0007] The method may also include where the first surface comprises a metal oxide, a metal nitride, an elemental metal, or a metallic surface.

[0008] The method can also include wherein the first surface comprises a metal selected from the group consisting of aluminum, copper, tungsten, cobalt, nickel, niobium, iron, molybdenum, indium, gallium, manganese, zinc, ruthenium, and vanadium.

[0009] The method may also include wherein the triamine compound is a C3 to C11 compound.

[0010] The method may also include wherein the triamine is triaminopropane, triaminobutane, triaminopentane, triaminohexane, triaminoheptane, or triaminooctane, or a combination thereof.

[0011] The method may also include wherein the triamine compound is: tris(aminoethyl)phosphine; tris(aminoethyl)arsine; bis(aminoethyl)aminomethylamine; tris(aminoethyl)silane; tris(aminoethyl)stannane; tris(aminoethyl)methylsilane; 2-toluene-1,3,5-triamine; pentane-1,2,4-triamine; cyclohexane-1,3,5-triamine; pentane-1,3,5-triamine; tris(2-aminoethyl)amine; 2-aminomethyl-1,3-diaminopropane; 2-(Aminomethyl)propane-1,3-diamine; propane-1,2,3-triamine; 2-aminomethyl-1,4-diaminobutane; tris(2-aminoethyl)phosphine; 2-aminomethyl-1,5-diaminopentane; 3-aminomethyl-1,5-diaminopentane; 2-aminomethyl-1,6-diaminohexane; 3-aminomethyl-1,6-diaminohexane; 3-aminoethyl-1,6-diaminohexane; 1,3,5-triaminobenzene or a combination thereof.

[0012] The method may also include a pre-cleaning comprising reduction and oxidation steps prior to depositing the organic material on the first surface of the substrate. Other technical features will be apparent to those skilled in the art from the following drawings, description and claims.

[0013] In one aspect, a method for selectively depositing an organic material layer on a substrate comprising a first surface and a second surface by a cyclic deposition process, the process comprising contacting the substrate with a first vapor precursor, and contacting the substrate with a second vapor precursor, wherein the first and second vapor precursors selectively form an organic material on the first surface relative to the second surface; and wherein the first vapor precursor comprises a triamine compound containing at least three carbon atoms, wherein the amine group is a primary amine.

[0014] In one aspect, a method for selectively depositing an organic material layer on a substrate comprising a first surface and a second surface by a cyclic deposition process, the process comprising providing the substrate in a reaction chamber, providing a first vapor precursor in the reaction chamber, and providing a second vapor precursor in the reaction chamber, wherein the first and second vapor precursors selectively form an organic material on the first surface relative to the second surface, and wherein the first vapor precursor comprises a diamine compound having two amine groups bonded to a cyclic carbon backbone, or a backbone having one or more carbon-carbon double bonds or carbon-carbon triple bonds, or a combination thereof.

[0015] The method may also include wherein the diamine includes trans-1,4-diaminocyclohexane, 2,4-diamino-2,4-dimethylpentane, 1,5-diamino-2-methylpentane, 1,3-diamino-3-methylbutane, 2,5-diamino-2,5-dimethylhexane, 1,2-diaminocyclopropane, 1,3-diaminocyclobutane, 1,3-diaminocyclohexane, 1,3-diaminocyclopentane, 1,4-diaminocyclohexane; 1,3-diaminocycloheptane, 1,4-diaminocycloheptane, 2,7-diamino-2,7-dimethyloctane, diaminocyclohexane, 1,3-diaminobenzene and 1,4-diaminobenzene, or cis or trans stereoisomers thereof. Other technical features will be apparent to those skilled in the art based on the following drawings, descriptions and claims.

[0016] In one aspect, a method for selectively depositing an inorganic material on a second surface of a substrate relative to a first surface of the substrate by a cyclic deposition process, wherein the process includes depositing a layer of organic material on the first surface by: providing a substrate in a reaction chamber; providing a first vapor precursor in the reaction chamber; and providing a second vapor precursor in the reaction chamber, wherein the first and second vapor precursors selectively form an organic material on the first surface relative to the second surface, and wherein the first vapor precursor includes a triamine compound containing three primary amines and at least three carbon atoms; and depositing the inorganic material on the second surface.

[0017] In one aspect, a deposition assembly for selectively depositing an organic material layer on a substrate comprises: one or more reaction chambers constructed and arranged to hold a substrate; and a precursor injector system constructed and arranged to provide a first precursor and a second precursor in a vapor phase into the reaction chamber, wherein the deposition assembly comprises a precursor container constructed and arranged to hold the first precursor, and wherein the assembly is constructed and arranged to provide a first precursor comprising a triamine compound and a second precursor comprising a dianhydride to the reaction chamber via the precursor injector system to deposit an organic material layer on the substrate, and wherein the triamine compound comprises at least three carbon atoms, and wherein the amine group is a primary amine.

[0018] The method may also include wherein the second surface comprises SiO2.

[0019] The method may also include wherein the triamine compound comprises a cis or trans stereoisomer or a combination thereof. Other technical features will be apparent to those skilled in the art from the following drawings, descriptions and claims.

[0020] As used herein, the term "substrate" may refer to any one or more underlying materials that can be used to form or on which a device, circuit, material, or material layer can be formed. The substrate may include a bulk material, such as silicon (e.g., single crystal silicon), other IV group materials, such as germanium, or other semiconductor materials, such as II-VI or III-V semiconductor materials. The substrate may include one or more layers covering the bulk material. The substrate may include various topological structures, such as gaps, including recesses, lines, grooves, or spaces between raised portions (e.g., fins) formed in or on at least a portion of a layer of the substrate. The substrate may include nitrides, such as TiN, oxides, insulating materials, dielectric materials, conductive materials, metals, such as tungsten, ruthenium, molybdenum, cobalt, aluminum, or copper, or metallic materials, crystalline materials, epitaxial materials, heteroepitaxial materials, and / or single crystal materials. In some examples of the present disclosure, the substrate includes silicon. As described above, in addition to silicon, the substrate may include other materials. Other materials may form layers. The substrate according to the present disclosure includes two surfaces having different material properties.

[0021] As used herein, the terms "layer" and / or "film" may refer to any continuous or discontinuous structure and material, such as a material deposited by the methods disclosed herein. For example, a layer and / or film may include a two-dimensional material, a three-dimensional material, nanoparticles, or even a partial or complete molecular layer or a partial or complete atomic layer or atom and / or molecular cluster. A film or layer may include a material or layer having pinholes, which may be at least partially continuous. A seed layer may be a discontinuous layer used to increase the nucleation rate of another material. However, a seed layer may also be substantially or completely continuous.

[0022] In the present disclosure, "gas" may include materials that are gaseous at normal temperature and pressure (NTP), evaporated solids and / or evaporated liquids, and may be composed of a single gas or a gas mixture as appropriate. Precursors according to the present disclosure may be provided to a reaction chamber in a gas phase. The term "inert gas" may refer to a gas that does not participate in a chemical reaction and / or does not become part of a layer to a perceptible degree. Exemplary inert gases include He and Ar and any combination thereof. In some cases, molecular nitrogen and / or hydrogen may be inert gases. Gases other than process gases, i.e., gases that are not introduced by a precursor injector system, other gas distribution devices, etc., may be used, for example, to seal a reaction space and may include a sealing gas.

[0023] The terms "precursor" and "reactant" may refer to molecules (compounds or molecules containing a single element) that participate in a chemical reaction that produces another compound. A precursor typically contains a portion that is at least partially incorporated into the compound or element produced by the chemical reaction. The resulting compound or element may be deposited on a substrate. A reactant may be an element or compound that is not incorporated into the resulting compound or element to a significant extent. However, in some examples, a reactant may also contribute to the resulting compound or element.

[0024] In some examples, the precursor is provided as a mixture of two or more compounds. In the mixture, the other compounds besides the precursor may be inert compounds or elements. In some examples, the precursor is provided as a composition. Compositions suitable for use as a composition may include compositions that may be solutions or gases under standard conditions.

[0025] In the present disclosure, any two numbers of a variable may constitute a feasible range for the variable, and any range indicated may include or exclude endpoints. In addition, any values ​​of the variables indicated (regardless of whether they are expressed as "about") may refer to exact values ​​or approximate values, and include equivalents, and may refer to average values, median values, representative values, majority values, etc. In addition, in the present disclosure, the terms "including", "consisting of" and "having" independently refer to "generally or broadly including", "comprising", "essentially consisting of" or "consisting of" in some examples. In the present disclosure, the meaning of any definition does not necessarily exclude the common and customary meanings in some examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings, which are included to provide a further understanding of the present disclosure and constitute a part of this specification, illustrate exemplary embodiments and together with the description help to explain the principles of the present disclosure. In the drawings:

[0027] Figure 1 a) to c) in FIG. 5 show selective deposition according to the present disclosure.

[0028] Figure 2A and Figure 2B A block diagram of a process according to the present disclosure is shown.

[0029] Figure 3 a) to d) in FIG. 1 are schematic diagrams of depositing an organic layer on a metal surface opposite to a dielectric surface of a substrate according to the present disclosure.

[0030] Figure 4 is a schematic diagram of a vapor deposition assembly according to the present disclosure. DETAILED DESCRIPTION

[0031] The detailed description of various examples herein refers to the accompanying drawings, which illustrate exemplary examples by way of illustration. Although these exemplary examples are described in sufficient detail to enable those skilled in the art to practice the present disclosure, it should be understood that other examples may be implemented without departing from the spirit and scope of the present disclosure, and logical, chemical and / or mechanical changes may be made. Therefore, the detailed description here is only for the purpose of illustration, not for limitation. For example, the steps described in any method or process description may be performed in any combination and / or order, and are not limited to the presented combination and / or order. In addition, one or more steps from one of the disclosed methods or processes may be combined with one or more steps from another disclosed method or process in any suitable combination and / or order. In addition, any function or step may be outsourced to one or more third parties or performed by a third party. In addition, any reference to the singular includes plural examples, and any reference to more than one component may include a singular example.

[0032] Although certain examples and examples are disclosed below, those skilled in the art will appreciate that the disclosure extends beyond the specifically disclosed examples and / or uses of the disclosure and obvious modifications and equivalents thereof. Therefore, it is intended that the scope of the disclosure should not be limited by the specific examples described herein.

[0033] The illustrations presented herein are not meant to be actual views of any particular material, apparatus, structure, or device, but are merely representations of examples used to describe the present disclosure.

[0034] As used herein, the term "substrate" may refer to any underlying material or materials that may be used or upon which a device, circuit, or film / layer may be formed.

[0035] As used herein, the term "atomic layer deposition" (ALD) may refer to a vapor deposition process in which a deposition cycle, preferably a plurality of consecutive deposition cycles, is performed in a processing chamber. Typically, during each cycle, a precursor is chemically adsorbed to a deposition surface (e.g., a substrate surface or a previously deposited underlying surface, such as material from a previous ALD cycle) to form a monolayer or sub-monolayer that is not easily reacted with additional precursors (i.e., a self-limiting reaction). Thereafter, if desired, a reactant (e.g., another precursor or a reactive gas) may subsequently be introduced into the processing chamber for converting the chemically adsorbed precursor into the desired material on the deposition surface. Typically, the reactant is capable of further reacting with the precursor. In addition, a purge step may also be used during each cycle to remove excess precursor from the processing chamber and / or remove excess reactants and / or reaction byproducts from the processing chamber after the chemically adsorbed precursor is converted. In addition, the term "atomic layer deposition" as used herein is also meant to include processes designated by related terms, such as "chemical vapor atomic layer deposition", "atomic layer epitaxy" (ALE), molecular beam epitaxy (MBE), gas source MBE or organometallic MBE, and chemical beam epitaxy when performed with alternating pulses of a precursor composition, a reactive gas, and a purge gas (e.g., an inert carrier gas).

[0036] As used herein, the term "chemical vapor deposition" (CVD) may refer to any process in which a substrate is exposed to one or more volatile precursors that react and / or decompose on the substrate surface to produce the desired deposit.

[0037] As used herein, the terms "layer", "film" and / or "film" may refer to any continuous or discontinuous structure and material deposited by the methods disclosed herein. For example, a "layer", "film" and / or "film" may include 2D materials, nanorods, nanotubes or nanoparticles, or even part or all of a molecular layer or part or all of an atomic layer or atom and / or molecular clusters. A "layer", "film" and / or "film" may include a material or layer with pinholes, but still at least partially continuous. In addition, in the present disclosure, any two numbers of a variable may constitute a feasible range of the variable, and any range indicated may include or exclude endpoints. In addition, any value of the variable indicated (regardless of whether they are expressed as "about") may refer to an exact value or an approximate value, and include equivalents, and may refer to an average value, an intermediate value, a representative value, a majority value, etc. In addition, in the present disclosure, the terms "including", "consisting of" and "having" may independently refer to "generally or broadly including", "including", "essentially consisting of" or "consisting of" in some examples. In the present disclosure, the meaning of any definition does not necessarily exclude the common and customary meanings in some examples.

[0038] surface

[0039] According to some aspects of the present disclosure, selective deposition can be used to deposit organic materials on a first surface relative to a second surface. The two surfaces can have different material properties. In some examples, the organic material is selectively deposited on a first conductive (e.g., metal or metallic) surface of the substrate relative to the second dielectric surface of the substrate. In some examples, the second surface includes hydroxyl groups (-OH), such as a silicon oxide-based surface. In some examples, the second surface may additionally include a hydrogen (-H) terminal, such as a Si immersed in HF or a Ge immersed in HF. In such examples, the surface of interest will be considered to include the material below the -H terminal and the -H terminal. In some examples, organic materials such as polyamic acid or polyimide are selectively deposited on the first dielectric surface of the substrate relative to different second dielectric surfaces. In some such examples, the dielectric has different compositions (e.g., silicon, silicon nitride, carbon, silicon oxide, silicon oxynitride, germanium oxide). In other such examples, the dielectric may have the same basic composition (e.g., a silicon oxide-based layer), but has different material properties due to the formation method (e.g., thermal oxide, natural oxide, deposited oxide). In some examples, a vapor deposition method is used. In some examples, cyclic vapor deposition is used, such as using a cyclic CVD or atomic layer deposition (ALD) process. After the selective deposition of the organic material is completed, further processing can be performed to form the desired structure. Advantageously, selectivity can be obtained without a blocking agent on the surface to receive less organic layer; and / or without a catalyst on the surface to receive more organic layer. However, in some examples, a blocking agent is used to prevent or reduce the deposition of the organic layer on the second surface.

[0040] For example, a surface of a substrate contains metal, which is referred to as a metal surface. It can be a metal surface or a metallic surface. In some examples, the metal or metallic surface can include metal, metal oxide and / or a mixture thereof. In some examples, the metal or metallic surface can include surface oxidation. In some examples, the metal or metallic material of the metal or metallic surface is conductive with or without surface oxidation. In some examples, the metal or metallic surface contains one or more transition metals. In some examples, the metal or metallic surface contains one or more transition metals of the 4th row of the periodic table. In some examples, the metal or metallic surface contains one or more transition metals of the 4th to 11th groups of the periodic table. In some examples, the metal or metallic surface includes aluminum (Al). In some examples, the metal or metallic surface includes one or more of the following: copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), one or more noble metals, conductive metal oxides, conductive metal nitrides, conductive metal carbides, conductive metal borides, etc., or a combination thereof. In some examples, the metal or metallic surface includes a combination of conductive materials. For example, the metal or metallic surface may include one or more of RuOx, NbCx, NbBx, NiOx, CoOx, NbOx, WNCx, TaN, or TiN.

[0041] In some examples, the metal or metallic surface comprises a metal selected from the group consisting of Al, Mn, Fe, Co, Ni, Cu, Zn, Nb, Mo, Ru, and W. In some examples, the metal or metallic surface comprises a transition metal selected from the group consisting of Zn, Fe, Mn, and Mo. In some examples, the metallic surface comprises titanium nitride.

[0042] In some examples, the metal or metallic surface can be any surface capable of accepting or cooperating with the first or second precursors used in the selective deposition processes described herein.

[0043] In some examples, the organic material is selectively deposited on the metal oxide surface relative to another surface. The metal oxide surface may include, for example, CoOx, MoOx, RuOx, WOx, HfOx, TiOx, AlOx GaOx, InOx or ZrOx surfaces. In some examples, the metal oxide surface is an oxidized surface of a metallic material. In some examples, the metal oxide surface is produced by oxidizing at least the surface of a metallic material using an oxygen compound, such as a compound containing O3, H2O, H2O2, O2, oxygen atoms, plasma or free radicals or a mixture thereof. In some examples, the metal oxide surface is a natural oxide formed on a metallic material.

[0044] In some examples, the first surface can include a passivated metal surface, such as a passivated Cu surface. That is, in some examples, the first surface can include a metal surface including a passivation layer, such as an organic passivation layer, such as a benzotriazole (BTA) layer.

[0045] In some examples, the organic material is selectively deposited on the first dielectric surface relative to the second SiO2 surface. In some examples, the organic material is selectively deposited on the first dielectric surface relative to the second Si or Ge surface, such as the HF-immersed Si or HF-immersed Ge surface.

[0046] In some examples, the organic material is selectively deposited on the first metal or metallic surface of the substrate relative to the second dielectric surface of the substrate. In some examples, the first surface includes a metal oxide, an elemental metal or a metallic surface. In some examples, the first surface includes a metal selected from aluminum, copper, tungsten, cobalt, nickel, niobium, iron, molybdenum, indium, gallium, manganese, zinc, ruthenium and vanadium. In some examples, the selectively deposited organic material is polyamic acid, polyimide or other polymeric materials. The term dielectric is used in the description of this article to simplify the distinction from other surfaces (i.e., metal or metallic surfaces). Those skilled in the art will appreciate that not all non-conductive surfaces are dielectric surfaces. For example, a metal or metallic surface can include an oxidized metal surface that is non-conductive or has a very high resistivity. The selective deposition process taught herein is used to deposit on such non-conductive metal surfaces, while the deposition on adjacent dielectric surfaces is minimal.

[0047] In some examples, the organic material is selectively deposited on the first metal oxide surface of the substrate relative to the second SiO2 surface. In some examples, the first metal oxide surface can include, for example, CoOx, MoOx, RuOx, WOx, HfOx, TiOx, AlOx GaOx, InOx, or ZrOx surface. In some examples, the second SiO2 surface can be, for example, a natural oxide, a thermal oxide, or a chemical oxide. In some examples, the organic material is selectively deposited on the first metal oxide surface relative to a second Si or Ge surface, such as a HF-immersed Si or HF-immersed Ge surface.

[0048] In some examples, a substrate comprising a first metal or metallic surface and a second dielectric surface is provided. In some examples, a substrate comprising a first metal oxide surface is provided. In some examples, the second surface may include -OH groups. In some examples, the second surface may be a surface based on SiO2. In some examples, the second surface may include Si-O bonds. In some examples, the second surface may include a low-k material based on SiO2. In some examples, the second surface may contain greater than about 30%, preferably greater than about 50% SiO2. In some examples, the second surface may include GeO2. In some examples, the second surface may include Ge-O bonds. In some examples, an organic material is selectively deposited on a first metal or metallic surface relative to a second Si or Ge surface, such as a HF-immersed Si or HF-immersed Ge surface.

[0049] In some examples, the first surface may include a silicon dioxide surface and the second dielectric surface may include a different second silicon dioxide surface. For example, the first surface may include a naturally or chemically grown silicon dioxide surface. In some examples, the second surface may include a thermally grown silicon dioxide surface. In other examples, the first or second surface may be replaced with a deposited silicon oxide layer. Thus, in some examples, the organic material may be selectively deposited on the first silicon dioxide surface of the substrate relative to the second silicon dioxide surface formed by a different technique, and therefore has different material properties.

[0050] In some examples, the substrate may be pretreated or cleaned before or at the start of the selective deposition process. In some examples, the substrate may be subjected to a plasma cleaning process before or at the start of the selective deposition process. In some examples, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some examples, the substrate surface may be exposed to plasma, free radicals, excited species, and / or atomic species before or at the start of the selective deposition process. In some examples, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic species before or at the start of the selective deposition process. In some examples, the pretreatment or cleaning process may be performed in the same reaction chamber as the selective deposition process. However, in some examples, the pretreatment or cleaning process may be performed in a separate reaction chamber.

[0051] In some examples, a sealant such as a silylating agent is used to seal the second surface before depositing the organic material on the first surface. In some examples, a second surface on the substrate, such as an oxide surface, is sealed by silylation with a silylating agent, such as alkyltrimethylsilane (TMS-A), trimethylchlorosilane (TMS-Cl), N-(trimethylsilyl)imidazole (TMS-Im), octadecyltrichlorosilane (ODTCS), hexamethyldisilazane (HMDS) or N-(trimethylsilyl)dimethylamine (TMSDMA), and the organic material is selectively deposited on the first surface of the same substrate. The substrate can be contacted with a sufficient amount of the sealant for a sufficient period of time so that the second surface is selectively sealed by the silicon substance.

[0052] Deposition process

[0053] Selective deposition using the methods described herein can be advantageously achieved without having to treat the second dielectric surface to prevent deposition thereon and / or without having to treat the first surface (whether metallic or a different dielectric surface) to catalyze deposition. Thus, in some examples, the second dielectric surface does not include a passivation layer or barrier layer, such as a self-assembled monolayer (SAM), which would prevent the actual top surface of the second dielectric surface from being exposed to the chemicals of the deposition process described herein. Thus, in some examples, selectivity is achieved despite the lack of a capping agent or catalyst, and both the first and second surfaces are directly exposed to the deposition precursor. Even in material pairs where selectivity is not ideal, etch back or similar corrective treatments using, for example, a plasma can allow selective deposition of organic materials.

[0054] Vapor deposition techniques can be applied to organic layers and polymers, such as polyimide films, polyamide films, polyurea films, polyurethane films, polythiophene films, etc. CVD of polymer films can produce greater thickness control, mechanical flexibility, conformal coverage, and biocompatibility compared to the application of liquid precursors. Sequential deposition processing of polymers can produce high growth rates in small research-scale reactors. Similar to CVD, sequential deposition processes can produce greater thickness control, mechanical flexibility, and conformality.

[0055] In some examples, the cyclic deposition process according to the present disclosure includes a thermal deposition process. In thermal deposition, the temperature increase relative to the ambient temperature promotes the chemical reaction. Generally speaking, in the absence of other external energy sources (such as plasma, free radicals or other forms of radiation), the temperature increase provides the energy required to form the organic material.

[0056] In the present invention, the deposition process may include a cyclic deposition process, such as an atomic layer deposition (ALD) process, a cyclic chemical vapor deposition (VCD) process, a molecular layer deposition (MLD) or a hybrid process thereof, regardless of the reaction mechanism. The term "cyclic deposition process" (or sequential deposition) may refer to the sequential introduction of precursors and / or reactants into a reaction chamber to deposit materials, such as organic materials, such as polyimide or polyamic acid, on a substrate. Cyclic deposition includes processing techniques such as atomic layer deposition (ALD), cyclic chemical vapor deposition (cyclic CVD), and a mixed cyclic deposition process including an ALD component and a cyclic CVD component. The process may include a purge step between providing the precursors into the reaction chamber.

[0057] As used herein, the term "purge" may refer to a process of removing gaseous precursors and / or gaseous byproducts from a substrate surface, such as by evacuating a reaction chamber with a vacuum pump and / or by replacing the gas in the reaction chamber with an inert or substantially inert gas such as argon or nitrogen. Purge may be performed between two gas pulses that react with each other. However, purge may be performed between two gas pulses that do not react with each other. For example, purge may be provided between pulses of two precursors. Purge may avoid or at least reduce gas phase interactions between two gases that react with each other. It should be understood that purge may be performed in time or space, or both. For example, in the case of time purge, a purge step may be used, such as in a time sequence of providing a first precursor to a reactor chamber, providing a purge gas to the reactor chamber, and providing a second precursor to the reactor chamber, wherein the substrate on which the layer is deposited does not move. For example, in the case of space purge, a purge step may take the form of moving a substrate from a first position where a first precursor is continuously supplied to a second position where a second precursor is continuously supplied through a purge gas curtain.

[0058] The purge time can be, for example, from about 0.01 seconds to about 90 seconds, or from about 0.05 seconds to about 80 seconds, or from about 0.05 seconds to about 70 seconds, or from about 1 second to about 60 seconds, or from about 0.05 seconds to about 50 seconds, or from about 0.5 seconds to about 40 seconds, or from about 0.05 seconds to about 30 seconds, or from about 0.05 seconds to about 20 seconds, or from about 0.05 seconds to about 10 seconds, or between about 1 second and about 7 seconds, such as 4 seconds, 5 seconds, 6 seconds, or 8 seconds, or any other suitable time period ("about" in this case means ± 5 seconds). Other purge times can be used, such as where highly conformal step coverage is desired on very high aspect ratio structures or other structures with complex surface morphology, or in specific reactor types, such as batch reactors can be used.

[0059] The process may include one or more cyclic phases. For example, pulses of the first precursor and the second precursor may be repeated. In some examples, the process includes one or more non-cyclic phases. In some examples, the deposition process includes a continuous flow of at least one precursor. In some examples, the precursor may be provided continuously in the reaction chamber. In such examples, the process includes a continuous flow of precursors or reactants. In some examples, one or more precursors and / or reactants are provided continuously to the reaction chamber.

[0060] The term "atomic layer deposition" (ALD) may refer to a vapor deposition process in which a deposition cycle (e.g., multiple consecutive deposition cycles) is performed in a reaction chamber. As used herein, the term atomic layer deposition is also meant to include processes specified by related terms, such as chemical vapor atomic layer deposition, when performed with alternating pulses of precursor / reactant and optional purge gas. Typically, for an ALD process, during each cycle, a precursor is introduced into the reaction chamber and chemically adsorbed onto a deposition surface (e.g., a substrate surface that may include previously deposited materials or other materials from a previous ALD cycle), forming a monolayer or sub-monolayer of a material that is not easily reacted with an additional precursor (i.e., a self-limiting reaction). Thereafter, in some cases, another precursor or reactant may be subsequently introduced into the processing chamber for converting the chemically adsorbed precursor into a desired material on the deposition surface. The second precursor or reactant is capable of further reacting with the precursor. During one or more cycles, such as during each step of each cycle, a purge step may be utilized to remove any excess precursor from the processing chamber and / or remove any excess precursor and / or reaction byproducts from the reaction chamber. Thus, in some examples, the cyclic deposition process includes purging the reaction chamber after providing the first precursor into the reaction chamber. In some examples, the cyclic deposition process includes purging the reaction chamber after providing the second precursor into the reaction chamber.

[0061] CVD type processes generally involve gas phase reactions between two or more precursors and / or reactants. Precursors and reactants can be provided to the reaction space or substrate simultaneously, or provided in partially or completely separated pulses. The substrate and / or reaction space can be heated to promote the reaction between gaseous precursors and / or reactants. In some examples, precursors and reactants are provided until a layer with a desired thickness is deposited. In some examples, a cyclic CVD process can use multiple cycles to deposit a film with a desired thickness. In the cyclic CVD process, precursors and / or reactants can be provided to the reaction chamber with pulses that do not overlap or partially or completely overlap. In some examples, a first precursor is supplied in pulses, a second precursor is supplied in pulses, and the reaction chamber is purged between continuous pulses of the first and second precursors.

[0062] In some examples, the processes described herein can be batch processes, that is, these processes can be performed on two or more substrates at the same time. In some examples, the processes described herein can be performed on two or more, five or more, 10 or more, 25 or more, 50 or more, or 100 or more substrates at the same time. In some examples, the substrate can include a wafer, such as a semiconductor or silicon wafer. In some examples, the substrate can have a diameter of 100 mm or more, 200 mm or more, or 300 mm or more. In some cases, a substrate with a diameter of 450 mm or more may be ideal.

[0063] Selectivity

[0064] Selectivity can be given as a percentage calculated by [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). Deposition can be measured by any of a variety of methods. In some examples, deposition can be given as a measured thickness of deposited material. In some examples, deposition can be given as a measured amount of deposited material.

[0065] In some examples, the selectivity is greater than about 30%, greater than about 50%, greater than about 75%, greater than about 85%, greater than about 90%, greater than about 93%, greater than about 95%, greater than about 98%, greater than about 99%, or even greater than about 99.5%. In some examples, the organic material is deposited on the first surface with a selectivity greater than about 50% relative to the second surface. In the examples described herein, the selectivity can vary with the duration or thickness of the deposition. In some examples, for the vapor phase polymer deposition described herein, the selectivity increases with the duration of the deposition. In contrast, typical selective deposition based on differential nucleation on different surfaces tends to decrease in selectivity with increasing duration or thickness of the deposition.

[0066] In some examples, deposition occurs substantially only on the first surface and not on the second surface. In some examples, deposition on the first surface of the substrate has a selectivity of at least about 80% relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some examples, deposition on the first surface of the substrate has a selectivity of at least about 50% relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications. In some examples, deposition on the first surface of the substrate has a selectivity of at least about 10% relative to the second surface of the substrate, which may be sufficient selectivity for some specific applications.

[0067] In some examples, the thickness of the organic film deposited on the first surface of the substrate can be less than about 50 nm, less than about 20 nm, less than about 10 nm, less than about 5 nm, less than about 3 nm, less than about 2 nm, or less than about 1 nm. In some examples, the ratio of material deposited on the first surface of the substrate relative to the second surface of the substrate can be greater than or equal to about 2:1, greater than or equal to about 20:1, greater than or equal to about 15:1, greater than or equal to about 10:1, greater than or equal to about 5:1, or greater than or equal to about 3:1.

[0068] In some examples, the selectivity of the selective deposition processes described herein may depend on the materials constituting the first and / or second surfaces of the substrate. For example, in some examples, where the first surface comprises a Cu surface and the second surface comprises a low-k material, the selectivity may be greater than about 8:1 or greater than about 15:1. In some examples, when the first surface comprises a metal or metal oxide and the second surface comprises a natural or chemical silicon dioxide surface, the selectivity may be greater than about 5:1 or greater than about 10:1. In some examples, when the first surface comprises a chemical or natural silicon dioxide surface and the second surface comprises a thermal silicon dioxide surface, the selectivity may be greater than about 5:1 or greater than about 10:1. In some examples, when the first surface comprises natural or chemical silicon dioxide and the second surface comprises a Si-H termination, such as a Si surface dipped in HF, the selectivity may be greater than about 5:1 or greater than about 10:1. In some examples, when the first surface comprises a Si-H termination, such as a Si surface dipped in HF, and the second surface comprises thermal silicon dioxide, the selectivity may be greater than about 5:1 or greater than about 10:1.

[0069] Selective deposition

[0070] In some examples, a substrate including a first surface and a second surface is provided. The first and second surfaces may have different material properties. In some examples, the first surface may be a metallic surface and the second surface may be a dielectric surface. In some examples, a first organic precursor is evaporated to form a first precursor vapor. The evaporated precursor may be a liquid or a solid under standard temperature and pressure conditions (room temperature and atmospheric pressure). In some examples, the first precursor is a liquid precursor under standard conditions. In some examples, the evaporated precursor includes a diamine compound or a triamine compound (e.g., 1,3-diaminopentane (1,3-DAP) or cyclohexane-1,3,5-triamine). The substrate is then exposed to the first precursor vapor. The substrate is also exposed to a second gas phase precursor, such as an organic precursor, such as a dianhydride. For example, the dianhydride may be pyromellitic dianhydride (PMDA). The cyclic exposure of the substrate to the two precursors results in the deposition of an organic material. The method may include additional steps and may be repeated, but need not be performed in the order shown, nor in the same order in each repetition, and may be easily extended to more complex vapor deposition techniques.

[0071] In one example, the diamine according to the present disclosure may include at least three carbon atoms. However, in some examples, the diamine according to the present disclosure includes four carbons. For example, the diamine according to the present disclosure may be selected from 1,2-diaminobutane, 1,3-diaminobutane and 2,4-diaminobutane. Therefore, in the four-carbon example, at least one amino group is attached to a carbon atom that is bonded to two other carbon atoms. In other words, at least one amino group is not at the end of the carbon chain.

[0072] In some examples, the two amine groups of the diamine can be bonded to a cyclic carbon backbone, or a carbon backbone comprising a carbon-carbon double bond and / or a carbon-carbon triple bond. As used herein, the term "carbon backbone" refers to a main continuous chain or a ring structure containing three or more carbon atoms. Such diamines may include, for example, one or more of the following: trans-1,4-diaminocyclohexane; 2,4-diamino-2,4-dimethylpentane, 1,5-diamino-2-methylpentane, 1,3-diamino-3-methylbutane, 2,5-diamino-2,5-dimethylhexane, 1,2-diaminocyclopropane, 1,3-diaminocyclobutane, 1,3-diaminocyclohexane, 1,3-diaminocyclopentane, 1,4-diaminocyclohexane; 1,3-diaminocycloheptane, 1,4-diaminocycloheptane, 2,7-diamino-2,7-dimethyloctane, diaminocyclohexane, 1,3-diaminobenzene and 1,4-diaminobenzene, or cis or trans stereoisomers thereof.

[0073] In some examples, the carbon chain is branched. Therefore, there is at least one carbon atom bonded to three or four other carbon atoms. In some examples, there is one such branching position in the diamine compound. In some examples, there are two such branching positions in the diamine compound. In some examples, there are three or more branching points. In some examples, the side chain of the longer carbon chain is a methyl group. In some examples, the side chain of the longer carbon chain is an ethyl group. In some examples, the side chain from the longer carbon chain is a propyl group. In some examples, the side chain of the longer carbon chain is an isopropyl group. In some examples, the side chain from the longer carbon chain is a butyl group. In some examples, the side chain of the longer carbon chain is a tert-butyl group. In some examples, the side chain of the diamine compound is a linear alkyl chain. In some examples, the side chain of the diamine compound is a branched alkyl chain. In some examples, the side chain of the diamine compound is a cyclic alkyl chain.

[0074] In some examples, the diamine compound is a C3 to C11 compound. The number of carbon atoms in the diamine compound generally affects the volatility of the compound, so higher molecular weight compounds may not be as volatile as smaller compounds.

[0075] In some examples of the present disclosure, the amine group is attached to non-adjacent carbon atoms. This may be beneficial to the availability of the amine group to react with the second precursor. In some examples, there is one carbon atom between the carbon atoms bonded to the amino group. In some examples, there is at least one carbon atom between the carbon atoms bonded to the amino group. In some examples, there are two carbon atoms between the carbon atoms bonded to the amino group. In some examples, there are at least two carbon atoms between the carbon atoms bonded to the amino group. In some examples, there are three carbon atoms between the carbon atoms bonded to the amino group. In some examples, there are at least three carbon atoms between the carbon atoms bonded to the amino group. In some examples, there are four carbon atoms between the carbon atoms bonded to the amino group. In some examples, there are at least four carbon atoms between the carbon atoms bonded to the amino group.

[0076] In some examples, the first precursor includes 1,5-diamino-2-methylpentane. Although 1,5-diamino-2-methylpentane has a lower vapor pressure than 1,3-diaminopentane, it is also a liquid at ambient temperature, requiring a moderate temperature of about 40°C to reach a vapor pressure of 1 Torr.

[0077] In some examples, the carbon atom bonded to the amine nitrogen in the diamine compound is bonded to at least two carbon atoms. Thus, in some examples where the diamine contains three or more carbons, at least one amino group is not located at the end of the carbon chain. The structure of the diamine compound affects its properties during vapor deposition. The branches of the diamine compound, including the number of branches and the relative position of the amino group to the branches, may result in deposited organic materials having different properties. Without limiting the invention to any particular theory, for example, steric factors may result in certain reactions being preferred. This may provide the possibility of designing a deposition process for a given purpose by using different diamine compounds, taking into account, for example, thermal budgets, organic material growth rate requirements, and the necessary degree of selectivity.

[0078] In some examples, the diamine is an aromatic diamine. In some examples, the aromatic diamine is a diaminobenzene, such as 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, or a cis or trans stereoisomer thereof. In some examples, the aromatic diamine comprises an alkylamino group at at least one position. For example, the alkylamino group can be a C1-C3 alkylamino group, such as -CH2NH2, -(CH2)2NH2, -(CH2)3NH2, -CH(CH3)NH2, or -CH2CH(CH3)NH2.

[0079] In some examples, the diamine is selected from 1,3-diaminopentane, 1,4-diaminopentane, 2,4-diaminopentane, 2,4-diamino-2,4-dimethylpentane, 1,5-diamino-2-methylpentane, 1,3-diaminobutane, 1,3-diamino-3-methylbutane, 2,5-diamino-2,5-dimethylhexane, 1,4-diamino-4-methylpentane, 1,3-diaminobutane, 1,5-diaminohexane, 1,3-diaminohexane, 2,5-diamino In some embodiments, the diamine compound comprises halogen.

[0080] In some examples, the first precursor includes a triamine compound (eg, any branched aliphatic or aromatic compound containing three primary amine functional groups).

[0081] In one example, the triamine may include the following structure:

[0082]

[0083] wherein X is CR, Si-R, Sn-R, N, P or As, and n1, n2 and n3 are positive integers.

[0084] Providing such a molecule can advantageously affect the availability of polymerization sites for the second gas phase reactant. The availability of three amine groups in a single molecule can result in a denser polymer network, which in turn can reduce metal migration through the organic material. In examples utilizing organic materials according to the present disclosure as passivation layers, this property can be advantageous.

[0085] Examples of suitable triamines include 1,2,3-triaminopropane, triaminobutane (with amines on carbons 1, 2 and 3 or carbons 1, 2 and 4), triaminopentane (particularly with amines on carbons 1 and 5, plus an amine on either carbon 2 or 3). Similarly, triaminohexane can contain amine groups on carbons 1 and 6 and at either position 2 or 3; triaminoheptane can contain amine groups on carbons 1 and 7 and at either position 2, 3 or 4; and triaminooctane can contain amine groups on carbons 1 and 8 and at either position 2, 3 or 4. Furthermore, branched carbon chains, in particular tris(aminoethyl)phosphine; tris(aminoethyl)arsine; bis(aminoethyl)aminomethylamine; tris(aminoethyl)silane; tris(aminoethyl)stannane; tris(aminoethyl)methylsilane; 2-toluene-1,3,5-triamine; pentane-1,2,4-triamine; cyclohexane-1,3,5-triamine; pentane-1,3,5-triamine; tris(2-aminoethyl)amine; 2-aminomethyl-1,3-diaminopropane; 2-(aminomethyl)propane-1,3-diamine; propane-1,2,3-triamine; 2-(aminomethyl)butane-1,4-diamine; 2-aminomethyl-1,4-diaminobutane (or an alternative having two amino groups elsewhere in the butane chain); Tris(2-aminoethyl)phosphine; 2-aminomethyl-1,5-diaminopentane (or an alternative with two amino groups elsewhere in the pentane chain); 3-aminomethyl-1,5-diaminopentane (or an alternative with two amino groups elsewhere in the pentane chain); 2-aminomethyl-1,6-diaminohexane (or an alternative with two amino groups elsewhere in the hexane chain); 3-aminomethyl-1,6-diaminohexane (or an alternative with two amino groups elsewhere in the hexane chain); 3-aminoethyl-1,6-diaminohexane (or an alternative with two amino groups elsewhere in the hexane chain), or its cis or trans stereoisomers, may be alternatives for some examples. In addition, aromatic triamines such as 2-methylbenzene-1,3,5-triamine and / or 1,3,5-triaminobenzene or its cis or trans stereoisomers may be alternatives for some examples.

[0086] In some examples, the organic film includes a polymer. In some examples, the deposited polymer is a polyimide. In some examples, the deposited polymer is a polyamic acid. Therefore, in some examples, the organic material includes a polyimide. In some examples, the organic material is substantially composed only of polyimide. In some examples, the organic material includes polyamic acid. In some examples, the organic material is substantially composed only of amide and polyimide. In some examples, the organic material is deposited at a temperature below 190°C and then heat treated at a temperature of about 190°C or higher (e.g., 200°C or 210°C) to increase the ratio of the organic material from polyamic acid to polyimide. Other examples of deposited polymers include dimers, trimers, polyurethanes, polythioureas, polyesters, polyimines, other polymeric forms, or mixtures of the above materials.

[0087] In some examples, the second vapor-phase precursor includes pyromellitic dianhydride (PMDA).

[0088] In some examples, the substrate is thermally annealed for a period of about 1 to about 15 minutes. In some examples, the substrate is thermally annealed at a temperature of about 200° C. to about 500° C. In some examples, the thermal annealing step includes two or more steps, wherein the substrate is thermally annealed at a first temperature for a first period of time and then thermally annealed at a second temperature for a second period of time.

[0089] Before, after or between the processing steps described herein, additional treatments, such as thermal or chemical treatments, may be performed. For example, the treatment may modify the surface or remove portions of the material on the substrate surface exposed at various stages of the process. In some examples, the substrate may be pretreated or cleaned before or at the beginning of the selective deposition of organic materials. In some examples, the substrate may be subjected to a plasma cleaning process before or at the beginning of the selective deposition of organic materials. In some examples, the plasma cleaning process may not include ion bombardment, or may include a relatively small amount of ion bombardment. For example, in some examples, the substrate surface may be exposed to plasma, free radicals, excited species, and / or atomic species before or at the beginning of the selective deposition of organic materials. In some examples, the substrate surface may be exposed to hydrogen plasma, free radicals, or atomic species before or at the beginning of the selective deposition of organic materials. In some examples, the pretreatment or cleaning process may be performed in the same reaction chamber as the selective deposition of organic materials, whereas in some examples, the pretreatment or cleaning process may be performed in a separate reaction chamber.

[0090] The present disclosure is further explained by the following illustrative examples depicted in the accompanying drawings. The illustrations presented herein are not meant to be actual views of any particular material, structure, device, or apparatus, but are merely schematic representations of examples describing the present disclosure. It should be understood that the elements in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the sizes of some elements in the drawings may be exaggerated relative to other elements to help improve the understanding of the illustrated examples of the present disclosure. The structures and devices depicted in the drawings may include additional elements and details, which may be omitted for clarity.

[0091] Figure 1 Schematic diagram of selective deposition of organic materials according to the present disclosure. Substrate 100 includes a first surface 102 including a first material and a second surface 104 including a second material. Figure 1 In an exemplary embodiment of the present invention, a substrate 100 is depicted that includes a first surface 102 having a first material and a second surface 104 including a second material. The substrate 100 may include additional layers below the surface. In Figure a), the surface of the substrate is formed by the first surface 102 and the second surface 104. The first surface 102 includes, consists of, or consists essentially of the first material. The second surface 104 includes, consists of, or consists essentially of the second material. The first material and the second material are different materials. In Figure 1 In the illustration of FIG. 1 , the first surface 102 and the second surface 104 are at the same vertical level. However, in reality, the first and second surfaces 102, 104 may be at different levels.

[0092] In stage b), an organic material (e.g., a polyimide-containing material) is deposited on the first surface 102 of the substrate 100. The deposition process for depositing an organic material layer on the first surface 102 of the substrate 100 includes providing a first gaseous precursor in a reaction chamber, and providing a second gaseous precursor in a reaction chamber. The first and second gaseous precursors selectively form an organic material on the first surface 102 relative to the second surface 104, wherein the first gaseous precursor includes a diamine compound having a structural feature that prevents rotation around one or more carbon-carbon bonds (e.g., a diamine molecule having an amine group that is all bonded to a cyclic carbon backbone or a backbone having a carbon-carbon double bond or triple bond, or a combination thereof), and wherein the first precursor is liquid or solid at room temperature. Next, in stage c), an inorganic material 108 is deposited on the second surface 104. In some embodiments, the deposition of the inorganic material can be performed by a cyclic deposition process, such as ALD or cyclic CVD. In some embodiments, the deposited inorganic material is a metallic material, a metallic material, a dielectric material, or a combination thereof. In some embodiments, the deposited inorganic material is aluminum oxide. In some embodiments, the deposited inorganic material is a silicon-containing material. In some embodiments, the silicon-containing material is SiO2, SiOC, SiN, a material containing a metal silicate, or a combination thereof. For example, the deposited inorganic material can be yttrium-doped silicon oxide. In some embodiments, the deposited inorganic material is an oxide material. In some embodiments, the deposited material can be a material containing yttrium oxide, a material containing zirconium oxide, a material containing hafnium oxide, or a combination thereof. In some embodiments, the deposited inorganic material forms an etch stop layer.

[0093] In some embodiments, especially when the substrate is exposed to air for a long period of time, the substrate may be pre-cleaned to prepare a metal, such as a Cu surface, for deposition of organic materials according to the present disclosure. Pre-cleaning may also remove any migrated metal particles from the dielectric surface to prevent or reduce parasitic deposition of organic materials on the dielectric surface. Pre-cleaning may include reduction and controlled oxidation. In some embodiments, pre-cleaning includes reducing the metal surface before selective deposition and re-oxidizing it. For example, alcohols such as ethanol or plasmas such as H2 plasma may be used to reduce metals such as Cu surfaces. The intensity of the treatment may be adjusted according to the initial degree of oxidation. The deeper the oxidation, the more stringent the reduction treatment needs to be. The reduced metal surface is oxidized to a predetermined depth in a controlled manner to allow the metal surface for deposition of organic materials according to the present disclosure to be prepared by etching the newly formed oxide layer.

[0094] In some embodiments, if the organic layer according to the present disclosure is deposited immediately after preparation of the substrate surface, typically after a CMP process, the need for a pre-cleaning process can be avoided. The deposited organic material can be heated to at least 150°C, for example from about 150°C to about 800°C, or from about 150°C to about 700°C, or about 600°C, or between about 150°C and 500°C, or about 400°C, or between about 150°C and 300°C, or about 250°C, or between about 150°C and 250°C, or about 200°C (where "about" in this context means ±50°C), or any sufficient temperature. This can increase its resistance to migration of underlying metals such as Cu layers through the material. This solution can allow storage of prepared substrates, providing greater flexibility in designing deposition process flows.

[0095] Figure 2A and 2B An aspect of the present invention is described in which an organic material layer is selectively deposited on a substrate comprising a first surface and a second surface by a cyclic deposition process. Figure 2A , process 200 includes providing a substrate in a reaction chamber at block 202. The substrate according to the present disclosure includes a first surface and a second surface, and the first and second surfaces have different material properties. In some examples, the first surface may or may not be a conductive surface, such as a metal or metallic surface (e.g., Cu, Co, W, Mo), and the second surface may be a dielectric surface (e.g., SiO2, SiOC, SiN, HfO2), or may be a semiconductor surface, or may or may not be conductive, and the claimed subject matter is not limited thereto.

[0096] In some examples, the second surface includes an inorganic dielectric surface. In some examples, the second surface includes silicon. In some examples, the second surface includes SiO2. In some examples, the second surface includes a silicon oxide-based material, such as a metal silicate. In some examples, the second surface is a high-k surface, such as a hafnium oxide surface, a lanthanum oxide surface. In some examples, the second surface is an etch stop layer. The etch stop layer can include, for example, a nitride.

[0097] In some examples, the first surface can be a dielectric surface and the second surface can be a different second dielectric surface. In some examples, the first and second surfaces can have the same basic composition, but can have different material properties due to different formation methods (e.g., thermal oxide, deposited oxide, native oxide). In some examples, the first surface is a silicon-containing surface and the second surface is a silicon-containing surface of a different composition. For example, the first or second surface can be a silicon oxide-based surface, such as a surface containing silicon oxide or a metal silicate, while the other surface is a silicon nitride-based surface.

[0098] At block 204, a first gas phase precursor is provided to a reaction chamber. A first precursor according to the present disclosure may include a triamine compound including at least three carbon atoms and three primary amine functional groups. Providing the precursor to the reaction chamber results in contacting the substrate with the precursor. Thus, in one aspect, the method includes contacting the substrate with the first gas phase precursor, and contacting the substrate with the second gas phase precursor.

[0099] In some examples, the first precursor evaporates at a first temperature to form a first gaseous precursor. In some examples, the first precursor vapor is transported to the substrate through a gas line at a second temperature. In some examples, the second temperature is higher than the first temperature. In some examples, the substrate can contact the first gaseous precursor at a third temperature. Therefore, the reaction chamber temperature and / or the susceptor temperature can be different from the evaporation temperature and the gas line. In some examples, the third temperature is higher than the first temperature. In some examples, the third temperature is higher than the second temperature. In some examples, the third temperature is higher than the first temperature and the second temperature. In some examples, the third temperature is the susceptor temperature. In some examples, the third temperature is the susceptor temperature, and it is between about 125°C and 300°C, such as about 160°C, about 190°C, about 230°C (in this context, "about" means ±50°C) or any sufficient temperature. In some examples, during the deposition process of depositing the organic material, the substrate is maintained at a temperature higher than about 100°C, such as higher than about 150°C.

[0100] When the first precursor is provided to the reaction chamber in frame 204, it will contact the substrate. Without limiting the present disclosure to any particular theory, the first precursor can be selectively chemically adsorbed on the first surface of the substrate relative to the second surface of the substrate. In some examples, the first gas phase precursor is provided to the reaction chamber in frame 204 for a first exposure time period (first precursor pulse time). In some examples, the first precursor pulse time is from about 0.01 seconds to about 60 seconds, about 0.05 seconds to about 30 seconds, about 0.1 seconds to about 10 seconds, or about 0.2 seconds to about 5 seconds. The optimal exposure time period can be determined experimentally based on a specific environment, such as substrate characteristics and the composition of the first surface and the second surface. In some examples, such as examples using a batch reactor, an exposure time period greater than 60 seconds can be used.

[0101] In block 205, the first gaseous precursor and / or any reaction byproducts are purged from the reaction chamber. In some examples, this stage of the process can be omitted. However, purging is used in many examples. In some examples, purging is performed by providing an inert gas (e.g., a carrier gas) to the reaction chamber over a period of time (purge time). In some examples, an inert gas (e.g., Ar and / or N2) is used for purging. In some examples, the purge time can be, for example, from about 0.01 seconds to about 90 seconds, or from about 0.05 seconds to about 80 seconds, or from about 0.05 seconds to about 70 seconds, or from about 0.05 seconds to about 60 seconds, or from about 0.05 seconds to about 50 seconds, or from about 0.5 seconds to about 40 seconds, or from about 0.05 seconds to about 30 seconds, or from about 0.05 seconds to about 20 seconds, or from about 0.05 seconds to about 10 seconds, or between about 1 second and 7 seconds, such as 5 seconds, 6 seconds, or 7 seconds, or any other suitable time period ("about" herein means ±5 seconds).

[0102] At block 206, a second vapor phase precursor is provided to the reaction chamber. In some examples, the second precursor is also an organic reactant capable of reacting with the adsorbed species of the first precursor under deposition conditions. For example, the second precursor can be an anhydride, such as furan-2,5-dione (maleic anhydride), or more specifically a dianhydride, such as pyromellitic dianhydride (PMDA), or any other monomer having two reactive groups that will react with the first precursor. In some examples, the second vapor phase precursor includes a dianhydride. In some examples, the second vapor phase precursor includes PMDA.

[0103] In some examples, at block 206, a second vapor precursor is provided to the reaction chamber for a second exposure period (second precursor pulse time). In some examples, the second precursor may be evaporated at a fourth temperature to form a second vapor precursor. In some examples, the second precursor vapor is delivered to the substrate via a gas line at a fifth temperature. In some examples, the fifth temperature is higher than the first temperature. In some examples, the second vapor precursor is provided to the reaction chamber at a sixth temperature higher than the fourth temperature. In some examples, the sixth temperature is substantially the same as the third temperature.

[0104] In some examples, the first precursor is provided to the reaction chamber before the second precursor is provided to the reaction chamber. Therefore, in some examples, a triamine comprising at least three carbon atoms and three primary amines is provided to the reaction chamber before another precursor is provided to the reaction chamber. However, in some examples, the second precursor, such as a dianhydride, is provided to the reaction chamber before the first precursor is provided to the reaction chamber. Therefore, in some examples, before contacting with another precursor, the substrate is contacted with an anhydride, such as furan-2,5-dione (maleic anhydride), or more specifically with a dianhydride, such as pyromellitic dianhydride (PMDA).

[0105] In the method, first and second vapor precursors selectively form an organic material on a first surface relative to a second surface, and the first vapor precursor comprises a triamine compound. Without limiting the present disclosure to any particular theory, the selectivity may be at least partially due to preferential chemical adsorption of the first precursor on the first surface.

[0106] In one aspect, an organic material according to the present disclosure forms an organic material layer. The organic material may include polyimide, polyamic acid, or both. The deposition methods disclosed herein may produce advantageous organic material compositions.

[0107] In block 207, the second gaseous precursor and / or any reaction byproducts are purged from the reaction chamber. In some examples, this stage of the process can be omitted. However, purging is used in many examples. In some examples, purging is performed by providing an inert gas (e.g., Ar and / or N2), such as a carrier gas, into the reaction chamber for a period of time (the purge time). In some examples, the purge time can be, for example, from about 0.01 seconds to about 90 seconds, or from about 0.05 seconds to about 80 seconds, or from about 0.05 seconds to about 70 seconds, or from about 0.05 seconds to about 60 seconds, or from about 0.05 seconds to about 50 seconds, or from about 0.5 seconds to about 40 seconds, or from about 0.05 seconds to about 30 seconds, or from about 0.05 seconds to about 20 seconds, or from about 0.05 seconds to about 10 seconds, or between about 1 second and about 7 seconds, such as 5 seconds, 6 seconds, or 7 seconds, or any other suitable time period ("about" in this document means ±5 seconds).

[0108] The use of purge stages 205 and 207 is independently optional. Thus, both or either of stages 205 and 207 may be performed, and parameters such as the duration and composition of the purge gas may be independently selected. In some examples, each deposition cycle includes removing excess first gas-phase precursors and reaction byproducts after providing the first gas-phase precursor to the reaction chamber. In some examples, each deposition cycle includes removing excess second gas-phase precursors and reaction byproducts after providing the second gas-phase precursor to the reaction chamber. However, the deposition process may include one or more cycles in which the purge stage is omitted. Thus, for simplicity, in the case of purge, each deposition cycle may mean "substantially each deposition cycle".

[0109] The selective deposition process according to the present disclosure is a cyclic process. In addition to the conditions during the provision of the first precursor and the second precursor into the reaction chamber, the thickness of the deposited organic material layer is also determined by the number of deposition cycles 208 performed. In some examples, the deposition cycle includes stages 204 and 206. In some examples, the deposition cycle includes stages 204 and 206, and one or two of stages 205 and 207. In some examples, the deposition cycle includes stages 204, 205, 206, and 207. In some examples, the first precursor and the second precursor are alternately and sequentially provided to the reaction chamber.

[0110] In some examples, the deposition cycle can be repeated until an organic layer of desired thickness is selectively deposited. The selective deposition cycle can include additional actions that do not need to be performed in the same order or identically in each repetition, and can be easily extended to more complex vapor deposition techniques. For example, the selective deposition cycle can include additional reactant supply processes, such as supplying and removing (relative to the substrate) additional reactants in each cycle or selected cycles. Although not shown, the process can also include treating the deposited film to form a polymer (e.g., UV treatment, annealing, etc.).

[0111] In some examples, the organic material includes polyimide. In some examples, the organic material includes polyamic acid.

[0112] Figure 2B An example is depicted in which the method further comprises performing an etching process 209 on the substrate after a plurality of consecutive deposition cycles. Figure 2A The process is performed as in the example of , including repeating the deposition cycle according to block 208. The etching process may be performed once at the end of the deposition process, or may be performed intermittently after a predetermined number of deposition cycles, as shown in block 210. After the etching process, the selective deposition of organic material may continue.

[0113] In some examples, the etching process removes substantially all of any deposited organic material from the second surface of the substrate and does not remove substantially all of the deposited organic material from the first surface of the substrate. In some examples, the etching process includes exposing the substrate to hydrogen atoms, hydrogen radicals, hydrogen plasma, or a combination thereof. In some examples, the etching process includes exposing the substrate to oxygen atoms, oxygen radicals, oxygen plasma, or a combination thereof.

[0114] In some examples, the substrate can be etched to remove at least a portion of the deposited organic film. In some examples, the etching process after selectively depositing the organic film can remove the deposited organic material from the first surface and the second surface of the substrate. In some examples, the etching process can be isotropic.

[0115] In some examples, the etching process can remove the same amount or thickness of organic material from the first and second surfaces. That is, in some examples, the etching rate of the organic material deposited on the first surface can be substantially similar to the etching rate of the organic material deposited on the second surface. Due to the selectivity of the deposition process described herein, the amount of organic material deposited on the second surface of the substrate can be significantly less than the amount of material deposited on the first surface of the substrate. Therefore, the etching process can completely remove the deposited organic material from the second surface of the substrate, while the deposited organic material can remain on the first surface of the substrate.

[0116] In some examples, the etching process may include an etching process known in the art, such as a dry etching process, such as a plasma etching process. In some examples, the etching process may include exposing the substrate to hydrogen atoms, hydrogen radicals, hydrogen plasma, or a combination thereof. For example, the etching process may include exposing the substrate to a plasma generated by H2 using a power of about 10 W to about 5000 W, about 25 W to about 2500 W, about 50 W to about 500 W, or preferably about 100 W to about 400 W.

[0117] In some examples, triamine compounds according to the present disclosure can be used to deposit organic materials that are more resistant to etching processes (e.g., etching processes performed with hydrogen plasma as an etchant). This can be advantageous because it can allow for easier tuning of the etching process, which in turn can achieve a wider selectivity window.

[0118] In some examples, the etching process may include exposing the substrate to a plasma. In some examples, the plasma may include oxygen atoms, oxygen radicals, oxygen plasma, or a combination thereof. In some examples, the plasma may include hydrogen atoms, hydrogen radicals, hydrogen plasma, or a combination thereof. In some examples, the plasma may also include a rare gas species, such as an Ar or He species. In some examples, the plasma may be mainly composed of a rare gas species. In some examples, the plasma may include other substances, such as nitrogen atoms, nitrogen radicals, nitrogen plasma, or a combination thereof. In some examples, the etching process may include exposing the substrate to an etchant containing oxygen (e.g., O3). In some examples, the substrate may be exposed to an etchant having a temperature between about 30°C and about 500°C, such as between about 100°C and about 400°C. In some examples, the etchant may be provided in one continuous pulse, or may be provided in multiple shorter pulses. A purge phase may be performed between etching pulses.

[0119] Figure 3An aspect of the present disclosure is depicted, wherein an inorganic material is selectively deposited on a second surface 304 of a substrate 300 relative to a first surface 302 of the substrate 300. In stage a), a substrate 300 is provided. The substrate may be provided in a reaction chamber. In stage b), an organic material such as a polyimide-containing material is deposited on the first surface 302 of the substrate 300. The deposition process for depositing an organic material layer on the first surface 302 of the substrate 300 includes providing a first gaseous precursor in the reaction chamber, and providing a second gaseous precursor in the reaction chamber. The first and second gaseous precursors selectively form an organic material on the first surface 302 relative to the second surface 304, wherein the first gaseous precursor includes a triamine compound containing at least three carbon atoms, and wherein the amine group is a primary amine. Next, in stage c), an inorganic material is deposited on the second surface 304. In some examples, the deposition of the inorganic material may be performed by a cyclic deposition process, such as ALD or cyclic CVD. In some examples, the deposited inorganic material is a metallic material, a metallic material, a dielectric material, or a combination thereof. In some examples, the deposited inorganic material is aluminum oxide. In some examples, the deposited inorganic material is a silicon-containing material. In some examples, the silicon-containing material is SiO2, SiOC, SiN, a material containing a metal silicate, or a combination thereof. For example, the deposited inorganic material may be yttrium-doped silicon oxide. In some examples, the deposited inorganic material is an oxide material. In some examples, the deposited material may be a material containing yttrium oxide, a material containing zirconium oxide, a material containing hafnium oxide, or a combination thereof. In some examples, the deposited inorganic material forms an etch stop layer.

[0120] exist Figure 3 In stage d), the organic material deposited on the first surface 302 is removed, leaving the inorganic material deposited on the second surface 304 and the original material of the first surface 302 as the uppermost surface of the substrate. The above stage may be followed by additional processing steps known in the art.

[0121] Figure 4 A deposition assembly 400 according to the present disclosure is shown in schematic form. The deposition assembly 400 can be used to perform the methods described herein and / or selectively deposit the organic materials described herein.

[0122] In the illustrated example, the deposition assembly 400 includes one or more reaction chambers 402, a precursor injector system 401, a first precursor container 404, a second precursor container 406, an exhaust source 44, and a controller 45. The deposition assembly 400 may include one or more additional gas sources (not shown), such as an inert gas source, a carrier gas source, and / or a purge gas source. The reaction chamber 402 may include any suitable reaction chamber, such as an ALD or CVD reaction chamber described herein.

[0123] The first precursor container 404 may include a container and one or more first precursors as described herein - alone or mixed with one or more carrier gases (e.g., inert gases). The second precursor container 406 may include a container and one or more second precursors as described herein - alone or mixed with one or more carrier gases. Although two source containers 404, 406 are shown, the deposition assembly 400 may include any suitable number of source containers. The source containers 404, 406 may be coupled to the reaction chamber 402 via lines 414 and 416, which may each include a flow controller, a valve, a heater, etc. In some examples, the first precursor in the first precursor container 404 and the second precursor in the second precursor container 406 may be heated.

[0124] The exhaust source 44 may include one or more vacuum pumps. The controller 45 includes electronic circuits and software to selectively operate valves, manifolds, heaters, pumps and other components included in the deposition assembly 400. Such circuits and components are used to introduce precursors, reactants and purge gases from corresponding sources. The controller 312 can control the timing of the gas pulse sequence, the temperature of the substrate and / or the reaction chamber 402, the pressure in the reaction chamber 402, and various other operations to provide the correct operation of the deposition assembly 400. The controller 45 may include control software to control the flow of precursors, reactants and purge gases into and out of the reaction chamber 402 by electrically or pneumatically controlling the valve. The controller 45 may include modules that perform specific tasks, such as software or hardware components. The module may be configured to reside on an addressable storage medium of the control system and configured to perform one or more processes.

[0125] Other configurations of the deposition assembly 400 are also possible, including different numbers and types of precursor and reactant sources. In addition, it should be understood that there are many arrangements of valves, conduits, precursor sources, and auxiliary reactant sources that can be used to achieve the goal of selectively and in a coordinated manner supplying gases to the reaction chamber 402. In addition, as a schematic representation of the deposition assembly, many components have been omitted for simplicity of illustration, and these components may include, for example, various valves, manifolds, purifiers, heaters, containers, vents, and / or bypasses.

[0126] During operation of the deposition assembly 400, a substrate, such as a semiconductor wafer (not shown), is transferred from, for example, a substrate handling system to the reaction chamber 402. Once the substrate is transferred to the reaction chamber 402, one or more gases, such as precursors, reactants, carrier gases, and / or purge gases, are introduced into the reaction chamber 402 from a gas source.

[0127] On the other hand, a deposition assembly for selectively depositing an organic material layer on a substrate is disclosed. The deposition assembly includes one or more reaction chambers, which are constructed and arranged to hold a substrate, and a precursor injector system, which is constructed and arranged to provide a first precursor and a second precursor to the reaction chamber in a gas phase. The deposition assembly also includes a precursor container, which is constructed and arranged to accommodate a first precursor, and the assembly is constructed and arranged to provide the first precursor and the second precursor to the reaction chamber through the precursor injector system to deposit an organic material layer on the substrate. In one example, the first precursor may include a diamine bonded to a cyclic carbon backbone, or a carbon backbone including one or more carbon-carbon double bonds and / or carbon-carbon triple bonds. In another example, the first precursor may include a triamine compound containing at least three carbon atoms, wherein the amine group is a primary amine.

[0128] Although exemplary examples of the present disclosure are described herein, it should be understood that the present disclosure is not limited thereto. Various modifications, changes and enhancements may be made to the systems and methods described herein without departing from the spirit and scope of the present disclosure.

[0129] The subject matter of the present disclosure includes all novel and nonobvious combinations and subcombinations of the various systems, components and configurations, and other features, functions, acts, and / or properties disclosed herein, as well as any and all equivalents thereof.

Claims

1. A method for selectively depositing an organic material layer on a substrate comprising a first surface and a second surface by a cyclic deposition process, the process comprising: providing a substrate in a reaction chamber; providing a first gaseous precursor in a reaction chamber; as well as providing a second gaseous precursor in the reaction chamber, wherein the first and second vapor precursors selectively form an organic material on the first surface relative to the second surface; and wherein the first vapor precursor comprises a triamine compound comprising three amine groups and at least three carbon atoms, wherein the amine groups are primary amines.

2. The method according to claim 1, wherein: The second gas-phase precursor includes a dianhydride.

3. The method according to claim 1, wherein: The organic material includes polyimide.

4. The method according to claim 1, wherein: The organic material includes polyamic acid.

5. The method according to claim 1, wherein: The second surface includes an inorganic dielectric surface.

6. The method according to claim 1, wherein: The second surface includes silicon.

7. The method according to claim 6, wherein: The second surface includes SiO2.

8. The method according to claim 1, wherein: The organic material is deposited on the first surface with a selectivity greater than about 50% relative to the second surface.

9. The method according to claim 1, wherein: The first surface comprises a metal oxide, a metal nitride, an elemental metal, or a metallic surface.

10. The method according to claim 1, wherein: The first surface comprises a metal selected from the group consisting of aluminum, copper, tungsten, cobalt, nickel, niobium, iron, molybdenum, indium, gallium, manganese, zinc, ruthenium, and vanadium.

11. The method according to claim 1, wherein: The triamine compound is a C3 to C11 compound.

12. The method according to claim 1, wherein: The triamine is triaminopropane, triaminobutane, triaminopentane, triaminohexane, triaminoheptane or triaminooctane, or a combination thereof.

13. The method according to claim 1, wherein: The triamine compound is: tris(aminoethyl)phosphine; tris(aminoethyl)arsine; bis(aminoethyl)aminomethylamine; tris(aminoethyl)silane; tris(aminoethyl)stannane; tris(aminoethyl)methylsilane; 2-toluene-1,3,5-triamine; pentane-1,2,4-triamine; cyclohexane-1,3,5-triamine; pentane-1,3,5-triamine; tris(2-aminoethyl)amine; 2-aminomethyl-1,3-diaminopropane; 2-(amino)-1,3-diaminopropane; methyl)propane-1,3-diamine; propane-1,2,3-triamine; 2-aminomethyl-1,4-diaminobutane; tris(2-aminoethyl)phosphine; 2-aminomethyl-1,5-diaminopentane; 3-aminomethyl-1,5-diaminopentane; 2-aminomethyl-1,6-diaminohexane; 3-aminomethyl-1,6-diaminohexane; 3-aminoethyl-1,6-diaminohexane; 1,3,5-triaminobenzene or a combination thereof.

14. The method according to claim 13, wherein: The triamine compound includes cis or trans stereoisomers, or a combination thereof.

15. The method according to claim 1, wherein: The method includes a pre-clean including reduction and oxidation steps prior to depositing the organic material on the first surface of the substrate.

16. A method for selectively depositing an organic material layer on a substrate comprising a first surface and a second surface by a cyclic deposition process, the process comprising: contacting a substrate with a first vapor precursor; as well as contacting the substrate with a second vapor precursor, wherein The first and second vapor precursors selectively form an organic material on the first surface relative to the second surface, wherein the first vapor precursor comprises a triamine compound containing at least three carbon atoms, wherein the amine groups are primary amines.

17. A method for selectively depositing an organic material layer on a substrate comprising a first surface and a second surface by a cyclic deposition process, the process comprising: providing a substrate in a reaction chamber; providing a first gaseous precursor in a reaction chamber; as well as providing a second vapor precursor in the reaction chamber, wherein the first and second vapor precursors selectively form an organic material on the first surface relative to the second surface; And wherein the first gas phase precursor comprises a diamine compound having two amine groups bonded to a cyclic carbon backbone, or a backbone having one or more carbon-carbon double bonds or carbon-carbon triple bonds, or a combination thereof.

18. The method according to claim 17, wherein: The diamines include trans-1,4-diaminocyclohexane, 2,4-diamino-2,4-dimethylpentane, 1,5-diamino-2-methylpentane, 1,3-diamino-3-methylbutane, 2,5-diamino-2,5-dimethylhexane, 1,2-diaminocyclopropane, 1,3-diaminocyclobutane, 1,3-diaminocyclohexane, 1,3-diaminocyclopentane, 1,4-diaminocyclohexane; 1,3-diaminocycloheptane, 1,4-diaminocycloheptane, 2,7-diamino-2,7-dimethyloctane, diaminocyclohexane, 1,3-diaminobenzene and 1,4-diaminobenzene, or cis or trans stereoisomers thereof.

19. A method of selectively depositing an inorganic material on a second surface of a substrate relative to a first surface of the substrate by a cyclic deposition process, wherein the process comprises depositing a layer of organic material on the first surface by: providing a substrate in a reaction chamber; providing a first gaseous precursor in a reaction chamber; providing a second vapor precursor in the reaction chamber, wherein the first and second vapor precursors selectively form an organic material on the first surface relative to the second surface, wherein the first vapor precursor comprises a triamine compound comprising three primary amines and at least three carbon atoms; and An inorganic material is deposited on the second surface.

20. A deposition assembly for selectively depositing an organic material layer on a substrate, comprising: one or more reaction chambers constructed and arranged to hold a substrate; as well as A precursor injector system constructed and arranged to provide a first precursor and a second precursor in a vapor phase into a reaction chamber, wherein a deposition assembly includes a precursor container constructed and arranged to contain the first precursor, wherein the assembly is arranged to provide a first precursor comprising a triamine compound and a second precursor comprising a dianhydride to the reaction chamber via the precursor injector system to deposit an organic material layer on a substrate, and wherein the triamine compound comprises at least three carbon atoms and wherein the amine group is a primary amine.

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