Method and system for catalytic vapor deposition of polymeric materials

Abstract

Gas phase methods and reactor systems for depositing a layer of polymeric material on a substrate surface are disclosed. An exemplary method includes providing a reactant to a reaction chamber, providing a precursor to the reaction chamber, and providing a catalyst to the reaction chamber, wherein the catalyst catalyzes a polymerization reaction involving the precursor and the reactant to form the layer of polymeric material.

Description

Technical Field

[0001] This disclosure generally relates to vapor phase deposition and systems. More specifically, this disclosure relates to vapor phase methods and systems for depositing polymer materials. Background Technology

[0002] Vapor deposition of polymer materials can be used in a variety of applications. For example, it can be used to form electronic devices, such as semiconductor devices.

[0003] In some semiconductor device manufacturing processes, it may be desirable to form material only on certain areas of a substrate. Typically, this is achieved by depositing a continuous film of material and subsequently patterning the continuous film using photolithography and etching steps. This photolithography and etching process can be time-consuming and expensive. Furthermore, this process may not provide the precision or resolution required for many applications.

[0004] Recently, techniques have been developed that allow for the selective deposition of material on a first surface of a substrate relative to a second surface of the substrate without the use of photolithography. Selective deposition processes can take many forms, including but not limited to selective dielectric deposition (DoD) on dielectric surfaces, selective dielectric deposition (DoM) on metallic surfaces, selective metal deposition (MoD) on dielectric surfaces, and selective metal deposition (MoM) on metallic surfaces.

[0005] Vapor deposition of polymer materials can be used to facilitate selective deposition of materials on a first surface relative to a second surface. While these techniques work well for some applications, the uniformity of deposition and / or polymerization may be lower than desired. Additionally, or alternatively, the deposited polymer film may not exhibit the required (e.g., thermal) stability. Furthermore, it is generally desirable for vapor-phase polymer material methods to be performed at lower temperatures and / or at higher deposition rates at a given temperature. Therefore, improved vapor deposition techniques are needed for depositing polymer materials.

[0006] Any discussion of the problems and solutions described in this section is included in this disclosure for the purpose of providing background information only. This should not be construed as an admission that any or all of the discussions are prior art or known at the time of making this invention. Summary of the Invention

[0007] This synopsis is provided to introduce some concepts in a simplified form. Exemplary concepts are further described in detail in the following description of exemplary embodiments of this disclosure. This synopsis is not intended to necessarily identify key or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.

[0008] According to exemplary embodiments of the present disclosure, methods are provided for forming structures comprising a layer of polymeric material. Exemplary methods include providing a substrate in a reaction chamber of a reactor system, providing reactants, providing a precursor to the reaction chamber, and providing a catalyst to the reaction chamber. According to examples of these embodiments, the precursor comprises at least one acid anhydride compound. According to another example, the reactant comprises an amine compound containing at least two amine groups. The catalyst is configured to catalyze a polymerization reaction involving the precursor and the reactants to form a layer of polymeric material. In some cases, two or more of the steps of providing the precursor, providing the reactants, and providing the catalyst overlap. In some cases, two or more of the steps of providing the precursor, providing the reactants, and providing the catalyst do not overlap. According to various examples, the method includes a cyclic deposition process comprising one or more cycles. The one or more cycles may suitably include: providing the precursor comprising pulsed the precursor to the reaction chamber during a precursor pulse cycle; providing the reactants comprising pulsed the reactants to the reaction chamber during a reactant pulse cycle; and / or providing the catalyst comprising pulsed the catalyst to the reaction chamber during a catalyst pulse cycle. In some cases, the catalyst may flow into the reaction chamber together with the precursor and / or reactants, for example, to increase yield. The reaction chamber can be purged between one or more pulse cycles and / or between one or more cycles.

[0009] According to another embodiment, a structure is provided. This structure may include a substrate and a polymer material, such as a polymer film formed using the methods and / or systems described herein.

[0010] According to another embodiment, a reactor system is provided. An exemplary reactor system includes a reaction chamber, a precursor source comprising a container and at least one anhydride compound therein, a reactant source comprising a container and at least one amine compound containing at least two amine groups therein, a catalyst source comprising a container and at least one catalyst therein, and a controller. The controller may be configured to provide a precursor to the reaction chamber, a reactant to the reaction chamber, and a catalyst to the reaction chamber to form a polymer material layer. The controller may be configured to perform one or more steps of the method in any combination.

[0011] For the purpose of summarizing the invention and its advantages relative to the prior art, certain objects and advantages of the invention may have been described above. It should be understood, of course, that not all of these objects or advantages may necessarily be achieved according to any particular embodiment. Therefore, for example, those skilled in the art will recognize that certain embodiments may embody or implement one or more advantages taught or suggested herein in a manner that achieves or optimizes them, without necessarily achieving other objects or advantages that may be taught or suggested herein.

[0012] All these embodiments are intended to fall within the scope of this disclosure. Those skilled in the art will readily appreciate these and other embodiments from the following detailed description of certain embodiments with reference to the accompanying drawings. This disclosure is not limited to any particular embodiment disclosed. Attached Figure Description

[0013] Embodiments of this disclosure can be more fully understood when considered in conjunction with the following illustrative drawings, and by referring to the detailed description and claims.

[0014] Figure 1 A method according to an exemplary embodiment of the present disclosure is shown.

[0015] Figure 2 The structure of an example according to this disclosure is shown.

[0016] Figure 3 Another structure based on an example of this disclosure is shown.

[0017] Figure 4 A reactor system according to an example of this disclosure is shown.

[0018] Figure 5 A reactor system with multiple reaction chambers according to an example of this disclosure is shown.

[0019] It should be understood that the elements in the accompanying drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, the dimensions of some elements may be exaggerated relative to other elements to aid in understanding the embodiments shown in this disclosure. The illustrations presented herein are not necessarily intended to be actual views of any particular material, structure, or system, but are merely representations for describing embodiments of this disclosure. Detailed Implementation

[0020] Although certain embodiments and examples are disclosed below, those skilled in the art will understand that the invention extends beyond the specific embodiments and / or uses disclosed herein, as well as their obvious modifications and equivalents. Therefore, it is intended that the scope of the disclosed invention should not be limited to the specific embodiments described below.

[0021] As described in more detail below, various embodiments of this disclosure provide methods for forming structures comprising layers of polymeric material. The methods described herein can be used to form structures that can be used, for example, to form electronic devices, such as semiconductor devices, microelectromechanical systems (MEMS), photonic devices, etc. For example, exemplary methods can be used to (e.g., selectively) form a polymeric material on a surface of a substrate. The polymeric material can then be used to facilitate the selective deposition of another material on another surface of the substrate. Thus, patterns of materials can be formed without photolithography and / or etching processes.

[0022] As used herein, the term substrate can refer to any one or more underlying materials that can be used to form or on which devices, circuits, or films are formed. A substrate may comprise a bulk material, such as silicon (e.g., single-crystal silicon), other group IV materials (e.g., germanium), or other semiconductor materials (e.g., group II-VI or III-V semiconductor materials), and may comprise one or more layers overlying or underlying the bulk material. Furthermore, a substrate may include various features formed within or on at least a portion of the substrate layers, such as recesses, protrusions, etc. For example, a substrate may comprise a semiconductor material. An exemplary substrate includes a first surface of a first material and a second surface of a second material, wherein the first material and the second material are different.

[0023] As used herein, a structure may be or include a substrate as described herein. A structure may include a substrate and one or more layers covering the substrate, such as one or more layers formed by the methods according to this disclosure.

[0024] As used herein, the terms film and / or layer can refer to any continuous or discontinuous structure and material, such as materials deposited by the methods disclosed herein. For example, films and / or layers can include two-dimensional materials, three-dimensional materials, nanoparticles, partially or entirely molecular layers, or partially or entirely atomic layers or atomic and / or molecular clusters. A film or layer can consist partially or entirely of a plurality of dispersed atoms on a substrate surface and / or embedded in the substrate and / or embedded in a device fabricated on the substrate. A film or layer can include a material or layer having pinholes and / or isolation islands.

[0025] As used herein, the term metallic surface can refer to a surface that includes metallic components, including but not limited to metal surfaces (e.g., elemental metals or metal alloys), metal oxide surfaces, metal silicide surfaces, metal nitride surfaces, metal carbide surfaces, mixtures thereof, etc. The term metallic surface can also include the surface of a natural oxide of a metallic material.

[0026] As used herein, the term silicon surface or silicon-containing surface may refer to a surface that includes silicon and may include additional elements. Exemplary silicon-containing materials include, for example, silicon, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, silicon carbonitride, and mixtures thereof.

[0027] The term cyclic deposition process or cyclic deposition process can refer to the sequential introduction of precursors (and / or reactants) into a reaction chamber to deposit a layer on a substrate, and includes processing techniques such as atomic layer deposition (ALD), molecular layer deposition, cyclic chemical vapor deposition (CCVD), and mixed cyclic deposition processes including ALD and CCVD components. In some cases, a cyclic deposition process may include continuously flowing one or more precursors, reactants, or inert gases and pulsed other precursors or reactants. The term molecular layer deposition (MLD) can refer to a vapor deposition process in which one or more deposition cycles are performed in a processing chamber. Typically, during each cycle, an organic precursor is adsorbed (e.g., chemisorbed) onto a surface (e.g., a substrate surface or a previously deposited underlying layer, such as material from a previous MLD cycle), typically forming a monolayer that does not readily react with another organic precursor (i.e., a self-limiting reaction). Subsequently, if desired, another precursor (e.g., another organic precursor or reactant) can be subsequently introduced into the processing chamber to form the desired organic material on the surface. A purging step may also be used during each cycle to remove excess organic precursors and / or reactants and / or reaction byproducts from the processing chamber after the desired organic material has been formed.

[0028] As used herein, the term "purge" can refer to the process of supplying an inert or substantially inert gas to a reaction chamber between two potentially interacting gas pulses. For example, a purging process using, for instance, an inert gas (e.g., a rare gas) can be provided between a precursor pulse and a reactant pulse to reduce gas-phase interactions between the precursor and reactant that might otherwise occur. It should be understood that purging can be performed temporally, spatially, or both. For example, in the case of temporal purging, purging steps can be used, for instance, in a temporal sequence of supplying a precursor to the reaction chamber, supplying a purge gas to the reaction chamber, and supplying a reactant or another precursor to the reaction chamber, wherein the substrate on which the deposited layer is located remains stationary. In the case of spatial purging, the purging step can take the form of moving the substrate from (e.g., continuously) a first position supplying the precursor through a purge gas curtain to (e.g., continuously) a second position supplying the reactant or other precursor.

[0029] In this disclosure, "continuous" or "sequential" can refer to a step that does not break the vacuum, is not interrupted as a timeline, does not involve any material intervention, does not change the processing conditions, immediately follows as the next step, or, in some embodiments and depending on the situation, a discrete physical or chemical structure that, apart from the two structures, has no intervention between them.

[0030] Furthermore, in this disclosure, any two numbers of a variable may constitute a feasible range of the variable, and any indicated range may include or exclude endpoints. Additionally, any value of the indicated variable (whether or not it is indicated by the term "approx.") may refer to an exact value or an approximation and include equivalents, and may refer to an average, median, representative value, multi-value, etc. For example, the term "approx." may refer to + / - 20%, 10%, 5%, 2%, or 1% of a value. In some embodiments, the terms "comprising," "including," "consisting of," and "having" independently mean generally or broadly comprising, including, substantially consisting of, or consisting of in some embodiments. In this disclosure, the meaning of any definition does not necessarily exclude the common and customary meanings in some embodiments.

[0031] Although numerous exemplary materials are given throughout the embodiments of this disclosure, it should be noted that the chemical formulas given for each exemplary material should not be construed as limiting, and the non-limiting exemplary materials given should not be limited by the given exemplary stoichiometry.

[0032] Various examples of this disclosure relate to the selective formation of material on one surface relative to another surface. The selectivity of forming or depositing material can refer to a relatively high amount of material formed or deposited on a surface relative to another surface. For example, the selectivity of deposition on surface A relative to surface B can be given as a percentage calculated as [(deposition on surface A) - (deposition on surface B)] / (deposition on surface A). Deposition can be measured in any of a variety of ways. For example, deposition can be given as a measured thickness of the deposited material, or it can be given as a measured amount of the deposited material (e.g., weight).

[0033] As described in more detail below, in the embodiments described herein, selective deposition of a polymer material layer can be performed on a first surface (A) relative to a second surface (B). Subsequently, another material can be selectively deposited on the second surface (A) relative to the passivation film (B). In some embodiments, the selectivity is greater than about 10%, or greater than about 50%, or greater than about 75%, or greater than about 85%, or greater than about 90%, or greater than about 93%, or greater than about 95%, or greater than about 98%, or greater than about 99%, or even greater than about 99.5%. In some embodiments, selective deposition occurs only on one surface and not on the other. It should be understood that a partially selective process can produce a fully selective structure, for example, through post-deposition treatment.

[0034] Now turn to the attached diagram. Figure 1A method 100 for forming a structure comprising a layer of polymer material according to an embodiment of the present disclosure is illustrated. Method 100 includes the steps of providing a substrate 102, providing reactants 104, providing a precursor 106, and providing a catalyst 108 in a reaction chamber of a reactor. Method 100 may optionally include a processing step 110. Although shown separately, two or more steps of method 100 may overlap in time, as described in more detail below.

[0035] During step 102, a substrate is provided in the reaction chamber. The reaction chamber may be a stand-alone reaction chamber or part of a cluster tool, such as the cluster tool described in more detail below. The reaction chamber may include a substrate heater to heat the substrate to the temperatures described herein. Alternatively or additionally, the reaction chamber may include rapid thermal processing equipment (such as a lamp) to heat the substrate.

[0036] The reaction chamber may be configured to perform all or some of the steps of method 100. In some embodiments of this disclosure, the first reaction chamber may be configured to perform one or more steps of method 100, and additional reaction chambers may be used for other steps of method 100. However, in other embodiments of this disclosure, the first reaction chamber may be configured to perform all steps of method 100.

[0037] Reactors and associated reaction chambers capable of performing one or more steps of method 100 include atomic / molecular layer deposition (ALD / MLD) reaction chambers, plasma-enhanced atomic layer deposition (PEALD) reaction chambers, and chemical vapor deposition (CVD) reaction chambers, equipped with suitable devices and means for providing precursors. According to some embodiments, a spray-head reaction chamber may be used. According to some embodiments, a plasma reaction chamber, such as a PEALD reaction chamber, may be used. In such embodiments, the plasma may be direct, remote, or near the substrate. In some embodiments, the reactor is a spatial ALD or MLD reactor, wherein the substrate moves or rotates during processing. In some cases, the reactor is a thermal reactor.

[0038] In some embodiments, a batch reactor may be used. In some embodiments, a vertical batch reactor is utilized, wherein the boats rotate during processing. For example, a vertical batch reactor may include a reaction chamber and a lift configured and arranged to move boats configured to support a batch of 10 to 200 substrates into or out of the reaction chamber.

[0039] In other embodiments, the batch reactor comprises a small batch reactor configured to accommodate 10 or fewer wafers, 8 or fewer wafers, 6 or fewer wafers, 4 or fewer wafers, or 2 wafers. In some embodiments where a batch reactor is used, the inter-wafer non-uniformity is less than 3% (1 sigma), less than 2%, less than 1%, or even less than 0.5%.

[0040] Method 100 can optionally be carried out in a reactor and associated reaction chambers forming a cluster tool. In a cluster tool, each reaction chamber can be dedicated to a single type of process, such that the temperature of the reaction chamber in each module can be kept constant, which can increase throughput compared to reaction chambers where the substrate is heated to the processing temperature before each run. Additionally, in a cluster tool, the time required to pump the reaction space to the desired processing pressure level between substrates can be reduced. In some embodiments of this disclosure, the stand-alone reactor can be equipped with a loading lock. In this case, cooling the reaction space between runs may not be necessary.

[0041] Figure 2 A substrate 200 that can be supplied during step 102 is shown. The substrate 200 supplied during step 102 may include a first surface 202 and a second surface 204, as well as an optional bulk layer or material 206. The first surface 202 may include a first material 208, and the second surface 204 may include a second material 210 different from the first material 208.

[0042] In various examples, the first surface 202 is or includes a metal carbide, metal oxide, metal nitride, metal boride, elemental metal, metal surface, amorphous carbon, alloy of two or more metals, or a combination thereof. In some examples, the first surface comprises a metal including aluminum (Al), copper (Cu), tungsten (W), cobalt (Co), nickel (Ni), niobium (Nb), iron (Fe), molybdenum (Mo), indium (In), gallium (Ga), manganese (Mn), zinc (Zn), ruthenium (Ru), titanium (Ti), tantalum (Ta), chromium (Cr), or vanadium (V), or a combination thereof. In some cases, the first surface does not contain silicon. In some cases, the first surface may include a variety of metallic materials. For example, the first surface may include a liner or barrier layer material and a filler material, such as a metal or metal alloy.

[0043] In various examples, the second surface is a dielectric surface containing SiCO. x SiO x Silicon, SiO2, zirconium oxide (ZrO2), hafnium oxide (HfO2), aluminum oxide (Al2O3), titanium nitride (TiN), and titanium oxide (TiO2) or aluminum nitride (AlN), or combinations thereof. In some examples, the second surface contains RuO. x NiO x CoO x NbO x MoO x WO x NbB x 、NbC x WNC xThe second surface may contain silicon, such as TaN or TiN, or combinations thereof. In some cases, the second surface may contain silicon. In some cases, the second surface may include a passivation barrier layer formed thereon. When the second surface includes a barrier layer, the first surface may include a dielectric or insulating or other material layer.

[0044] In some examples, the passivation barrier layer comprises a self-assembled monolayer (SAM) or an alkylsilane having at least one alkoxy group bonded to a silicon atom. Example SAMs used as passivation barrier layers (“inhibitors”) are disclosed in U.S. Patent Application No. 17 / 388,773, filed July 29, 2021, the entire disclosure of which is incorporated herein by reference for all purposes, provided that such disclosure does not conflict with this disclosure. Example alkylsilane passivation barrier layers (“inhibitors”) are disclosed in U.S. Provisional Patent Application No. 63 / 583,732, filed September 19, 2023, the entire disclosure of which is incorporated herein by reference for all purposes. Examples of selectively deposited alkylsilanes that can be used as passivation barrier layers include alkylsilanes such as bis(tert-pentoxy)methylsilanol, tri(tert-pentoxy)silanol, tri(tert-butoxy)silanol (TBS), tri(isopropoxy)silanol (TIS) or tri(tert-pentoxy)silanol (TPS), bis(tert-pentoxy)methylsilanol, bis(tert-butoxy)methylsilanol or bis(tert-pentoxy)ethylsilanol.

[0045] In another example, the inhibitor can be represented by the following formula:

[0046] Si a R x (OH) y (OR') z

[0047] Where: a is 1, 2 or 3, x is 1, 2 or 3, y is 0, 1 or 2, z is 1, 2 or 3, but x+y+z=a+2, and each R and R' is independently selected from straight-chain and branched C1 to C8 alkyl groups.

[0048] In one example, R' in Formula 1 is selected from isopropyl, sec-butyl, tert-butyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-methylbutyl, 3-methylbutyl, 3-pentyl, 1,2-dimethylpropyl, and 2-methylbutyl. In one example, R is methyl or ethyl.

[0049] Once the substrate is loaded into the appropriate reaction chamber, it can be heated to a suitable temperature—for example, for degassing or for subsequent step 104. For instance, the substrate can be heated to a temperature of about 150°C to about 250°C or about 250°C to about 400°C. During step 102, the pressure within the reaction chamber can be between about 1 and about 5 Torr, or between about 5 and about 10 Torr.

[0050] During steps 104-108, a polymer material layer is deposited on the surface of the substrate. In some cases, the polymer material may be selectively deposited on the first surface relative to the second surface. Figure 3 The structure 300 is shown, which includes a polymer material layer 302 selectively deposited on a first surface 202.

[0051] According to examples of this disclosure, the polymer material layer is or includes an organic material. According to a particular example, the polymer material layer includes one or more of polyimide, polyamide, dimer, trimer, polyurethane, polythiourea, polyester, polyimide, or another polymer layer that can be (e.g., selectively) formed on the first surface 202.

[0052] Various precursors and reactants can be used to deposit the first material. Exemplary polymeric material precursors and / or reactants include polyimide precursors, SAM precursors, etc.

[0053] In some embodiments, the polymeric material precursor / reactant for selectively depositing organic polymers may be an aliphatic compound containing 1-6 carbon atoms, 2-5 carbon atoms, 2-4 carbon atoms, 5 or fewer carbon atoms, 4 or fewer carbon atoms, 3 or fewer carbon atoms, or 2 carbon atoms. In some embodiments, the bonds between carbon atoms in the reactant or precursor may be single bonds, double bonds, triple bonds, or some combination thereof.

[0054] Refer again Figure 1 During step 104, reactants are provided to the reaction chamber. According to examples of this disclosure, the reactants comprise amine compounds. In various examples, the reactants include diamines, triamines, tetraamines, cyclic compounds comprising at least two primary amines, or combinations thereof. Therefore, according to examples of this disclosure, step 104 includes providing the reaction chamber with reactants comprising amine compounds comprising at least two amine groups.

[0055] In some embodiments, the reactant comprises two amino groups. In some embodiments, the amino groups of the reactant may occupy one or both terminal positions on an aliphatic carbon chain. However, in some embodiments, the amino groups of the reactant may not occupy either terminal position on an aliphatic carbon chain. In some embodiments, the reactant may comprise a diamine. In some embodiments, the reactant may comprise one or more of 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,2-diaminopropane, 2,3-butanediamine, and 2,2-dimethyl-1,3-propanediamine.

[0056] The reactant may contain at least two carbon atoms, such as 1,2-diaminoethane. In some embodiments, the reactant contains three carbon atoms. In some embodiments, the reactant contains four carbon atoms. For example, the reactant may be selected from 1,2-diaminobutane, 1,3-diaminobutane, 1,4-diaminobutane, and 2,4-diaminobutane. Thus, in some embodiments, at least one amino group is attached to a carbon atom bonded to two other carbon atoms. In other words, at least one amino group may be located at the end of the carbon chain. In some embodiments, the diamine according to the invention contains five carbon atoms. In some embodiments, the diamine according to the invention contains six carbon atoms.

[0057] In some embodiments, the carbon chain of the reactant is branched. In this case, at least one carbon atom may be bonded to three or four other carbon atoms. In some embodiments, there is one such branching position in the reactant. In some embodiments, there are two such branching positions in the reactant. In some embodiments, there are three or more branching points. In some embodiments, the side chain from the longer carbon chain is methyl. In some embodiments, the side chain from the longer carbon chain is ethyl. In some embodiments, the side chain from the longer carbon chain is propyl. In some embodiments, the side chain from the longer carbon chain is isopropyl. In some embodiments, the side chain from the longer carbon chain is butyl. In some embodiments, the side chain from the longer carbon chain is tert-butyl. In some embodiments, the side chain of the reactant is a straight-chain alkyl chain. In some embodiments, the side chain of the reactant is a branched alkyl chain. In some embodiments, the side chain of the reactant is a cyclic alkyl chain.

[0058] In some embodiments, the reactants are C2 to C11 compounds. The number of carbon atoms in the reactants generally affects the volatility of the compounds, making larger compounds less volatile than smaller ones. However, it has been found that medium-sized first organic polymer precursors containing, for example, four, five, or six carbon atoms can have suitable properties for use as reactants in the deposition process according to this disclosure. For example, 1,3-diaminopentane is a liquid at room temperature, has a boiling point of 164°C at atmospheric pressure, a vapor pressure of about 2.22 Torr at 25°C, and reaches a vapor pressure of 1 Torr at temperatures below 20°C. Therefore, when 1,3-diaminopentane is used as a reactant for the deposition of polymer materials according to this disclosure, heating of the precursor container is not required. This can be advantageous for the tool life of the precursor, as it may be less prone to degradation during continuous use. Furthermore, liquid precursors have the advantage of being less expensive to load into precursor containers than solid precursors. In some embodiments, the reactants comprise 1,3-diaminopentane.

[0059] In some embodiments of this disclosure, the amine group of the reactant is attached to a non-adjacent carbon atom. This may be advantageous for the availability of the amine group reacting with the precursor. In some embodiments, there is one carbon atom between the amino-bonded carbon atoms. In some embodiments, there is at least one carbon atom between the amino-bonded carbon atoms. In some embodiments, there are two carbon atoms between the amino-bonded carbon atoms. In some embodiments, there are at least two carbon atoms between the amino-bonded carbon atoms. In some embodiments, there are three carbon atoms between the amino-bonded carbon atoms. In some embodiments, there are at least three carbon atoms between the amino-bonded carbon atoms. In some embodiments, there are four carbon atoms between the amino-bonded carbon atoms. In some embodiments, there are at least four carbon atoms between the amino-bonded carbon atoms.

[0060] In some embodiments, the reactants comprise 1,5-diamino-2-methylpentane. Although the vapor pressure of 1,5-diamino-2-methylpentane is lower than that of 1,3-diaminopentane, it is also a liquid at ambient temperature and requires a moderate temperature of about 40°C to reach a vapor pressure of 1 Torr.

[0061] In some embodiments, the carbon atoms bonded to the nitrogen of the amine in the reactant are bonded to at least two carbon atoms. Therefore, in some embodiments where the reactant contains five or more carbons, at least one amino group may be located away from the carbon chain end. The structure of the reactant affects its properties during the vapor deposition process. Branching of the first organic polymer precursor, including the number of branches and the relative positions of the amino groups to the branches, can result in different properties of the deposited organic polymer. Without limiting this disclosure to any particular theory, for example, spatial factors may lead to certain reactions being preferred. Taking into account, for example, thermal budget, organic polymer growth rate requirements, and selectivity, this can provide the possibility of designing a deposition process for a given purpose by using different reactants.

[0062] In some embodiments, the reactant is a cyclic diamine. In some embodiments, the reactant comprises cyclopentanedialkylamine, cyclohexanedialkylamine, cyclopentadienedialkylamine, phenyldialkylamine, cyclopentanetrialkylamine, cyclohexanetrialkylamine, cyclopentadienetrialkylamine, and phenyltrialkylamine.

[0063] In some embodiments, the reactant is an aromatic diamine. In some embodiments, the aromatic diamine is a diaminobenzene, such as 1,2-diaminobenzene, 1,3-diaminobenzene, or 1,4-diaminobenzene. In some embodiments, the aromatic diamine contains an alkylamino group at at least one position. For example, the alkylamino group can be a C1 to C3 alkylamino group, such as -CH2NH2, -(CH2)2NH2, -(CH2)3NH2, -CH(CH3)NH2, or -CH2CH(CH3)NH2.

[0064] In some embodiments, the reactants are 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-Diaminohexane, 1,3-Diamino-5-methylhexane, 4,4,4-trifluoro-1,3-diamino-3-methylbutane, 2,4-diamino-2-methylpentane, 4-(1-methylethyl)-1,5-diaminohexane, 3-aminobutyramide, 1,3-diamino-2-ethylhexane, 2,7-diamino-2,7-dimethyloctane, 1,3-diaminobenzene, and 1,4-diaminobenzene. In some embodiments, the reactants contain halogens.

[0065] In some embodiments, triamines can be used as reactants in the deposition of polymer materials. Providing such molecules can advantageously influence the availability of polymerization sites in the precursor, as described below. The availability of three amine groups in a single molecule can result in a denser polymer network, which in turn can reduce the migration of metals through the organic polymer. Such properties may be advantageous in embodiments utilizing an organic polymer according to this disclosure as a passivation layer. Examples of suitable triamines include 1,2,3-triaminopropane, triaminobutane (having an amine in carbons 1, 2, and 3 or in carbons 1, 2, and 4), and triaminopentane (particularly in carbons 1 and 5, plus having an amine in any of carbons 2, 3, or 4). Similarly, triaminohexane may contain an amine group in carbons 1 and 6 and in any of positions 2, 3, 4, or 5; triaminoheptane may contain an amine group in carbons 1 and 7 and in any of positions 2, 3, 4, 5, or 6; and triaminooctane may contain an amine group in carbons 1 and 8 and in any of positions 2, 3, 4, 5, 6, or 7. Furthermore, branched carbon chains, particularly 2-aminomethyl-1,3-diaminopropane, 2-aminomethyl-1,4-diaminobutane (or alternatives having two amino groups elsewhere in the butane chain), 2-aminomethyl-1,5-diaminopentane (or alternatives having two amino groups elsewhere in the pentane chain), 3-aminomethyl-1,5-diaminopentane (or alternatives having two amino groups elsewhere in the pentane chain), 2-aminomethyl-1,6-diaminohexane (or alternatives having two amino groups elsewhere in the hexane chain), 3-aminomethyl-1,6-diaminohexane (or alternatives having two amino groups elsewhere in the hexane chain), and 3-aminoethyl-1,6-diaminohexane (or alternatives having two amino groups elsewhere in the hexane chain). Additionally, aromatic triamines, such as 1,3,5-triaminobenzene, may be alternatives in some embodiments.

[0066] In some embodiments, the reactants used in the selective cyclic deposition process described herein may have the general formula:

[0067] R 1 (NH2)2

[0068] Among them, R 1 It can be an aliphatic carbon chain containing 1-5 carbon atoms, 2-5 carbon atoms, 2-4 carbon atoms, 5 or fewer carbon atoms, 4 or fewer carbon atoms, 3 or fewer carbon atoms, or 2 carbon atoms.

[0069] As a specific example, the reactants may be selected from 1,2-diaminoethane (I), 1,3-diaminopropane (I), 1,4-diaminobutane (I), 1,5-diaminopentane (I), 1,2-diaminopropane (I), 2,3-butanediamine, 2,2-dimethyl-1,3-propanediamine (I), 1,6-diaminohexane, 1,4-diaminocyclohexane, or any other monomer having two reactive groups, tris(2-aminoethyl)amine, or a cyclic compound containing at least two primary amine groups, such as 1,4-diaminocyclohexane (as described above) or p-phenylenediamine.

[0070] During step 106, a precursor is provided to the reaction chamber. In some embodiments, the precursor is an organic reactant capable of reacting with the adsorbate of the reactant under deposition conditions. In some cases, the terms reactant and precursor may be used interchangeably.

[0071] In some embodiments, the precursor is an anhydride compound, such as furan-2,5-dione (maleic anhydride). The anhydride can be a dianhydride, such as pyromellitic dianhydride. In some embodiments, the precursor can be any other monomer having two reactive groups that will react with the reactants to form a polymer material. In some cases, the precursor comprises one or more of an anhydride or dianhydride compound or dianhydrides containing a thioanhydride group.

[0072] In some embodiments, the precursor and / or reactant does not contain metal atoms. In some embodiments, the precursor and / or reactant does not contain half-metal atoms. In some embodiments, one of the precursor and / or reactant contains metal or half-metal atoms. In some embodiments, the precursor and / or reactant contains carbon and hydrogen, and one or more of the following elements: N, O, S, P, or halides, such as Cl or F.

[0073] In some embodiments, the precursor comprises an organic compound selected from 1,4-diisocyanate butane or 1,4-diisocyanate phenylene. In some embodiments, the precursor comprises an organic precursor selected from terephthaloyl chloride, alkyl diacyl chlorides, such as adipoyl chloride, octanoyl chloride, azeloyl chloride, sebacyl chloride, or terephthaloyl chloride. In some embodiments, the precursor comprises an organic precursor selected from 1,4-diisothiocyanate phenylene or terephthalaldehyde. In some embodiments, the evaporated precursor may also be a diamine, such as 1,4-diaminobenzene, decane-1,10-diamine, 4-nitrobenzene-1,3-diamine, 4,4'-diaminodiphenyl ether, or ethylenediamine. In some embodiments, the precursor may be bis(2-hydroxyethyl) terephthalate. In some embodiments, the precursor may be a carboxylic acid, such as an alkyl-, alkenyl-, dienyl-dicarboxylic acid, or a tricarboxylic acid, such as oxalic acid, malonic acid, succinic acid, glutaric acid, or propane-1,2,3-tricarboxylic acid. In some embodiments, the precursor may be an aromatic carboxylic acid or a dicarboxylic acid, such as benzoic acid, benzene-1,2-dicarboxylic acid, benzene-1,4-dicarboxylic acid, or benzene-1,3-dicarboxylic acid. In some embodiments, the precursor may contain one or more OH- groups bonded to a hydrocarbon. In some embodiments, the precursor may be selected from diols, triols, and aminophenols, such as 4-aminophenol, benzene-1,4-diol, or benzene-1,3,5-triol. In some embodiments, the precursor may be 8-hydroxyquinoline. In some embodiments, the precursor may contain an alkenylchlorosilane, such as an alkenyltrichlorosilane, for example, 7-octenyltrichlorosilane.

[0074] During step 106, the temperature inside the reaction chamber may be between about 100°C and about 200°C, or between about 200°C and about 400°C. The pressure inside the reaction chamber may be between about 0 Torr and about 5 Torr, or between about 5 Torr and about 20 Torr.

[0075] During step 108, a catalyst is supplied to the reaction chamber. The catalyst is configured to catalyze a polymerization reaction involving precursors and reactants to form a layer of polymer material.

[0076] According to examples of this disclosure, the catalyst comprises a nitrogen-containing compound. According to examples of this disclosure, the nitrogen-containing compound comprises a base. According to further examples, the nitrogen-containing compound may be represented by the following chemical formula:

[0077] N-R3

[0078] Each R is independently selected from C1-C6 alkyl groups or H. According to another example, a lone pair of electrons exists on the nitrogen in the above formula. In some cases, each R can be the same. For example, the catalyst can be or includes triethylamine.

[0079] According to another example, the nitrogen-containing compound comprises a cyclic structure. In some cases, the nitrogen-containing compound comprises a heterocyclic structure. In some cases, the nitrogen-containing compound comprises a cyclic structure in which N is contained in a portion of the cyclic structure. In some cases, the nitrogen-containing compound comprises pyridine substituted with an alkyl (e.g., branched or straight-chain C1-C4) or aromatic or tertiary amine (e.g., tertiary substituted amine). As a specific example, the nitrogen-containing compound may include one or more of the following: triethylamine, quinoline, isoquinoline, 2-methylpyridine, 2,6,-dimethylpyridine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethylaniline, tri-trimethylsilylamine, pyrrolidine, piperidine, pyridine, aminopyridine, other methylpyridine, piperazine, other dimethylpyridine, or methylamine.

[0080] Steps 104-108 can be performed using a cyclic deposition process. The cyclic deposition process may include one or more cycles, wherein one or more cycles of the cyclic deposition process include: providing a precursor including pulsed to the reaction chamber during a precursor pulse cycle; providing a reactant including pulsed to the reaction chamber during a reactant pulse cycle; and / or providing a catalyst including pulsed to the reaction chamber during a catalyst pulse cycle. For example, one or more cycles may include pulsed to the reaction chamber during a precursor pulse cycle, pulsed to the reaction chamber during a reactant pulse cycle, and pulsed to the reaction chamber during a catalyst pulse cycle. In some cases, one or more cycles may include pulsed to the reaction chamber during a precursor pulse cycle, pulsed to the reaction chamber during a first catalyst pulse cycle, pulsed to the reaction chamber during a reactant pulse cycle, and pulsed to the reaction chamber during a second catalyst pulse cycle.

[0081] The duration of the reactant pulse cycle can be between approximately 50 milliseconds and approximately 100 seconds, or between approximately 100 milliseconds and approximately 5 seconds. The duration of the precursor pulse cycle can be between approximately 50 milliseconds and approximately 100 seconds, or between approximately 50 milliseconds and approximately 100 seconds. The duration of the catalyst pulse cycle can be between approximately 50 milliseconds and approximately 100 seconds, or between approximately 100 milliseconds and approximately 5 seconds.

[0082] The cyclic deposition process may further include purging between one or more steps and / or cycles. For example, a purging step may be performed between pulsed precursors and pulsed reactants or any other steps.

[0083] The steps 104-108 may overlap. For example, the steps of providing the precursor and providing the catalyst may overlap in time. Alternatively, the steps of providing the reactants and providing the catalyst may overlap in time. In some cases, the catalyst may flow into the reaction chamber together with the precursor and / or reactants.

[0084] The thickness of the polymer material layer (e.g., layer 302) can be between about 0.1 nm and about 2.5 nm, or between about 2.5 nm and about 7.5 nm. The selectivity of the first material deposited on the second surface relative to the first surface can be as described above.

[0085] like Figure 1 As shown, method 100 may include an optional processing step 110. In some cases, step 110 includes one or more of direct plasma processing, remote plasma processing, UV processing, electron beam processing, or using other energy beams. In some cases, step 110 includes supplying one or more gases to the reaction chamber. One or more gases may be used to form excited material using one or more of the excitation techniques mentioned herein. Such gases may include one or more of Ar, N2, He, Ne, O2, H2, and any mixtures thereof.

[0086] Now for reference Figure 4 In various examples, reactor system 400 includes a reaction chamber 404, a base 406 for holding substrate 430 during processing, a gas distribution system 408 (e.g., a spray head) for distributing one or more precursors and / or reactants to the surface of substrate 430, one or more precursor or reactant sources 410, 412, and / or 413, and / or carrier gas and / or purge gas source 414, fluidly coupled to reaction chamber 404 via corresponding lines 416, 418, 419, and 420 and corresponding valves or controllers 422, 423, 425, and 427. Substrate 430 may include a substrate or structure as described herein. Purge gas / carrier gas 424 from gas source 414 may flow to and through reaction chamber 404 to act as a carrier gas, and / or purge or remove any excess reactants or other unwanted materials from reaction chamber 404. Sources 410, 412, and 413 may include containers and precursors or reactants as described herein. For example, source 410 may include a container and reactant 415; source 412 may include a container and precursor 417; source 413 may include a container and catalyst 421. Reactor system 400 may include additional sources. System 400 may also include a vacuum source 428 fluidly coupled to reaction chamber 404. Vacuum source 428 may be configured to expel reactants, purge gases, or other materials from reaction chamber 404.

[0087] Reactor system 400 also includes a controller 452. Controller 452 can be configured to perform various functions and / or steps as described herein. Controller 452 may include one or more microprocessors, memory elements, and / or switching elements to perform various functions. Although shown as a single unit, controller 452 may alternatively include multiple devices. Controller 452 can be used to control airflow (e.g., by monitoring flow and controlling valves 422, 423, 425, and / or 427), motors, heaters, cooling devices, and / or vacuum source 428 to perform various processes (e.g., one or more (e.g., all) steps of method 100). Furthermore, when the system includes two or more reaction chambers, as described in more detail below, two or more reaction chambers may be coupled to the same / shared controller. For example, controller 452 may be configured to supply reactants to reaction chambers, supply precursors to reaction chambers, and supply catalysts to reaction chambers to form a layer of polymer material.

[0088] Figure 5 A reactor system 500 is shown comprising multiple reaction chambers 502-508, each reaction chamber being... Figure 4 An example of reaction chamber 404 is shown. Reaction chambers 502-508 may be disposed around and / or coupled to transfer chamber 510, which includes transfer tools 512 for transferring a substrate between reaction chambers 502-508 and load locking chamber 514, and between reaction chambers 502-508 (e.g., through transfer chamber 510). For example, substrate 430 may be disposed in different chambers for different steps of the method described herein. For example, one of reaction chambers 502-508 may be used to form a structure comprising a layer of polymer material, while another reaction chamber may be used to process that polymer material layer. Other configurations are also possible, such that one or more steps of method 100 are performed within a single reaction chamber.

[0089] The exemplary embodiments described above do not limit the scope of the invention, as these embodiments are merely examples of embodiments of the invention, the scope of which is defined by the appended claims and their legal equivalents. Any equivalent embodiments are intended to fall within the scope of the invention. In fact, various modifications to this disclosure, such as alternative useful combinations of the described elements, in addition to those shown and described herein, will become apparent to those skilled in the art from the description. These modifications and embodiments are also intended to fall within the scope of the appended claims.

Claims

1. A method for forming a structure comprising a layer of polymer material, the method comprising: Provide a substrate in the reaction chamber of the reactor in the reactor system; The reactants are supplied to the reaction chamber, and the reactants include amine compounds containing at least two amine groups; A precursor is provided to the reaction chamber, the precursor comprising at least one acid anhydride compound; as well as Provide catalyst to the reaction chamber, In this context, catalyst catalysis involves the polymerization reaction of precursors and reactants to form a polymer material layer.

2. The method according to claim 1, wherein, The polymer material includes a polyimide layer.

3. The method according to claim 1, wherein, The method includes a cyclic deposition process, which comprises one or more cycles, wherein, for one or more cycles: Providing the precursor includes pulsating the precursor into the reaction chamber during the precursor pulse cycle; Providing reactants includes pulsed reactants into the reaction chamber during the reactant pulse cycle; and / or Providing the catalyst involves pulsating the catalyst into the reaction chamber during the catalyst pulse cycle.

4. The method according to claim 3, wherein, The one or more loops include: The precursor pulse is delivered to the reaction chamber during the precursor pulse cycle; The reactants are pulsed into the reaction chamber during the reactant pulse cycle; and The catalyst is pulsed into the reaction chamber during the catalyst pulse cycle.

5. The method of claim 4, further comprising a purge step between the pulse precursor and the pulse reactant.

6. The method according to claim 3, wherein, The one or more loops include: The precursor pulse is delivered to the reaction chamber during the precursor pulse cycle; The catalyst is pulsed into the reaction chamber during the first catalyst pulse cycle; Pulsing reactants into the reaction chamber during the reactant pulse cycle; and The catalyst is pulsed into the reaction chamber during the second catalyst pulse cycle.

7. The method according to claim 1, wherein, The steps of providing the precursor and providing the catalyst overlap in time.

8. The method according to claim 1, wherein, The steps of providing reactants and providing catalysts overlap in time.

9. The method according to claim 1, wherein, The precursor comprises one or more of an anhydride or dianhydride compounds.

10. The method according to claim 9, wherein, The dianhydride compounds include pyromellitic dianhydride or dianhydrides containing thioanhydride groups.

11. The method according to claim 1, wherein, The reactants comprise one or more of diamines, triamines, tetraamines, or cyclic compounds containing two primary amine groups.

12. The method according to claim 1, wherein, The catalyst includes nitrogen-containing compounds.

13. The method according to claim 12, wherein, The nitrogen-containing compounds include bases.

14. The method according to claim 12, wherein, The nitrogen-containing compound contains a cyclic structure.

15. The method according to claim 12, wherein, The nitrogen-containing compound contains a heterocyclic structure.

16. The method according to claim 12, wherein, The nitrogen-containing compounds include pyridines substituted with alkyl, aromatic or tertiary amine groups.

17. The method according to claim 12, wherein, The nitrogen-containing compound includes one or more of the following: triethylamine, quinoline, isoquinoline, 2-methylpyridine, 2,6,-dimethylpyridine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0]undec-7-ene, NN-dimethylaniline or tri-trimethylsilylamine.

18. The method according to claim 1, wherein, The substrate includes a first surface and a second surface, wherein the polymer material layer is selectively formed on the first surface relative to the second surface.

19. The method according to claim 18, wherein, The first surface includes metal carbides, metal oxides, metal nitrides, metal borides, elemental metals, metal surfaces, amorphous carbon, or combinations thereof.

20. A reactor system comprising: Reaction chamber; A precursor source, comprising a container and at least one acid anhydride compound therein; A reactant source, comprising a container and therein at least one amine compound containing at least two amine groups; A catalyst source, comprising a container and at least one catalyst therein; as well as The controller is configured as follows: Provide precursors to the reaction chamber; Provide reactants to the reaction chamber; as well as A catalyst is supplied to the reaction chamber to form a layer of polymer material.

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