Silicon oxide deposition method

Abstract

To provide methods of depositing silicon oxide on a substrate, methods of forming a semiconductor device, and a method of forming a structure.SOLUTION: The method comprises: providing a substrate into a reaction chamber; providing a silicon precursor into the reaction chamber, the silicon precursor comprising a silicon atom connected to at least one oxygen atom, the at least one oxygen atom being connected to a carbon atom; and providing a reactant comprising hydrogen atoms into the reaction chamber to form silicon oxide on the substrate.SELECTED DRAWING: Figure 1A

Description

[Technical Field]

[0001] The present disclosure relates generally to the field of semiconductor device manufacturing. More particularly, the present disclosure relates to a method and apparatus for thermally depositing silicon oxide on a substrate. [Background technology]

[0002] Silicon oxide (SiO2) layers are used in a wide range of applications in the manufacture of electronic devices, such as integrated circuits. They can be used, for example, as insulating layers and to form spacers. Silicon oxide layers are deposited on the surface of a substrate, and deposition typically requires a separate oxygen reactant, such as ozone or oxygen plasma, or relatively high deposition temperatures if a thermal process is used. To enable the fabrication of complex structures and devices, the deposition process must not harm materials already deposited on the substrate.

[0003] It may be desirable to deposit silicon oxide only on specific areas of a substrate. This type of selectivity can be achieved by first depositing a continuous layer on the substrate and then patterning the layer using lithography and etching. These methods have drawbacks in cost, efficiency, and accuracy, which is why selective deposition can offer an improved alternative in many situations. In a selective process, the target layer is deposited directly on the predetermined area of ​​the substrate, and no subsequent patterning is required.

[0004] Therefore, there is a need in the art for a low temperature, radical-free silicon oxide deposition process for selectively growing layers. Summary of the Invention

[0005] This Summary may introduce selected concepts in a simplified form that may be described in more detail below. This Summary is not necessarily intended to 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]

[0003] Embodiments of the present disclosure relate to a method for depositing silicon oxide on a substrate. In the method, the substrate is provided in a reaction chamber. Then, reactants including a silicon precursor and hydrogen atoms are provided in the reaction chamber to form silicon oxide on the substrate. The silicon precursor according to the present disclosure includes a silicon atom bonded to at least one oxygen atom, and at least one oxygen atom is bonded to a carbon atom. The carbon may be, for example, carbon in a carbonyl group.

[0007] Embodiments of the present disclosure also relate to a method of forming a structure, wherein silicon oxide is deposited by providing a substrate into a reaction chamber, providing reactants comprising a silicon precursor according to the present disclosure and hydrogen atoms into the reaction chamber to form silicon oxide on the substrate.

[0008] Embodiments of the present disclosure further relate to a method of forming a semiconductor device, the method comprising: depositing silicon oxide by providing a substrate into a reaction chamber; providing a reactant comprising a silicon precursor according to the present disclosure and hydrogen atoms into the reaction chamber, forming silicon oxide on the substrate;

[0009] Another embodiment of the present disclosure relates to a deposition assembly for depositing silicon oxide on a substrate. The deposition assembly includes a reaction chamber configured and arranged to hold the substrate and a precursor injector system configured and arranged to deliver precursors and / or reactants into the reaction chamber. The assembly further includes a precursor container configured and arranged to contain and vaporize a silicon precursor, the silicon precursor including a silicon atom bonded to at least one oxygen atom, and the at least one oxygen atom bonded to a carbon atom. The assembly is further configured and arranged to deliver the precursor to the reaction chamber via the precursor injector system to deposit silicon oxide on the substrate.

[0010] Silicon oxide has many uses in semiconductor applications, and silicon oxide deposited in accordance with the present disclosure can be used in the fabrication of electronic devices, such as memory and / or logic circuits.

[0011] Furthermore, in this disclosure, any two variables can constitute a workable range for that variable, and any stated range may include or exclude endpoints. Furthermore, any value of a stated variable (whether or not it is indicated as "about") refers to an exact or approximate value, including equivalents, and may refer to an average, median, representative value, or majority, etc. Furthermore, in this disclosure, the terms "comprise," "comprised of," and "having" independently refer, in some embodiments, to "typically or broadly include," "comprise," "consist essentially of," or "consist." In this disclosure, any defined meaning does not necessarily exclude, in some embodiments, the ordinary and customary meaning. [Brief explanation of the drawings]

[0012] 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, serve to explain the principles of the disclosure. [Figure 1A]FIG. 1A is an embodiment of a method according to the present disclosure. [Figure 1B] FIG. 1B is an embodiment of a method according to the present disclosure. [Figure 2] FIG. 2 is a schematic diagram of an alternative embodiment of the present disclosure. [Figure 3] FIG. 3 is one embodiment of an optional method according to the present disclosure. [Figure 4] FIG. 4 is a schematic diagram of an assembly according to the present disclosure.

[0013] Elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help to improve understanding of the illustrated embodiments of the present disclosure. DETAILED DESCRIPTION OF THE INVENTION

[0014] The descriptions of exemplary embodiments of methods, structures, devices, and apparatus provided below are merely exemplary and intended for illustrative purposes only. The following descriptions are not intended to limit the scope of the present disclosure or the claims. Moreover, the recitation of multiple embodiments having described features is not intended to exclude other embodiments having additional features or incorporating different combinations of the described features. For example, various embodiments may be described as exemplary embodiments and recited in the following claims.

[0015] It will be understood by those skilled in the art that the present invention extends beyond the specifically disclosed embodiments and / or applications of the present invention, as well as obvious modifications and equivalents thereof. Therefore, it is not intended that the scope of the disclosed invention should be limited by the specific disclosed embodiments described below. Unless otherwise specified, example embodiments or components thereof may be combined or applied separately from each other.

[0016] In this disclosure, any two variables can constitute a workable range for that variable, and any stated range may include or exclude the endpoints. Furthermore, any values ​​for stated variables (whether they are stated as "about" or not) refer to exact or approximate values, include equivalents, and may refer to the mean, median, representative value, or majority, etc.

[0017] Exemplary embodiments of the present disclosure can be used to fabricate electronic devices, such as memory and / or logic circuits. More specifically, embodiments of the present disclosure can be used to fabricate spacers, etch stop layers, and any layers where electrical isolation is beneficial. Embodiments of the present disclosure can be used to generate sacrificial layers and patterning layers.

[0018] In one aspect, a method for depositing silicon oxide on a substrate is disclosed. In some embodiments, the silicon oxide can form a layer. The term layer (or film) 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, partial or complete molecular layers, partial or complete atomic layers, or clusters of atoms and / or molecules. The film or layer can include materials or layers with pinholes, and can be at least partially continuous. In some embodiments, the silicon oxide layer is continuous. In some embodiments, the silicon oxide layer is discontinuous.

[0019] The method for depositing silicon oxide according to the present disclosure includes providing a substrate in a reaction chamber. In other words, the substrate is brought into a space where deposition conditions can be controlled. The substrate may comprise, consist essentially of, or consist of a dielectric, such as silicon oxide, SiN, SiOC, SiON, SiOCN, or any other material used in semiconductor device manufacturing technology. Examples of substrate materials include, but are not limited to, low-k materials, metal-containing silicon oxide compounds, such as SiGeOx, metals and their alloys, such as copper, ruthenium, cobalt, niobium, tungsten, titanium, tantalum, iridium, gold, aluminum, iron, nickel, molybdenum, rhenium, manganese, and vanadium. Another example of a substrate material is a metal oxide, such as copper oxide, ruthenium oxide, cobalt oxide, niobium oxide, tungsten oxide, titanium oxide, hafnium oxide, zirconium oxide, tantalum oxide, iridium oxide, gold oxide, zinc oxide, aluminum oxide, iron oxide, nickel oxide, molybdenum oxide, rhenium oxide, manganese oxide, and vanadium oxide. The metal oxides may be halogenated, e.g., fluorinated. Furthermore, in some embodiments, the substrate may comprise, consist essentially of, or consist of one or more metal nitrides, e.g., titanium nitride, tantalum nitride, or aluminum nitride, metal carbides, and / or metal borides. The substrate may comprise, consist essentially of, or consist of a carbon-based material, e.g., amorphous carbon, produced by spin coating, PECVD, or PEALD. The substrate may also comprise a photoresist material. In some embodiments, metal nitrides may be more suitable for silicon oxide deposition, and the reactant may include oxygen. For example, the reactant may include water. In some embodiments, the organic material-containing substrate surface may be more suitable for hydrogen- and nitrogen-containing reactants, in which case the reactant may be an oxygen-free reactant, such as ammonia.

[0020] The reaction chamber may be part of a cluster tool in which different processes are performed to form an integrated circuit. In some embodiments, the reaction chamber may be a flow-type reactor, such as a cross-flow reactor. In some embodiments, the reaction chamber may be a showerhead reactor. In some embodiments, the reaction chamber may be a spatially divided reactor. In some embodiments, the reaction chamber may be a single-wafer ALD reactor. In some embodiments, the reaction chamber may be a single-wafer ALD reactor capable of mass production. In some embodiments, the reaction chamber may be a batch reactor for simultaneously producing multiple substrates.

[0021] As used herein, the term substrate can refer to any underlying material or materials that can be used to form or on which a device, circuit, material, or material layer can be formed. The substrate can include bulk materials, such as silicon (e.g., monocrystalline silicon), or one or more layers overlying the bulk material. The substrate can include various topologies, such as recesses, lines, trenches, or gaps, including spaces between raised portions, such as fins, formed within or on at least a portion of a layer of the substrate. Substrates can include nitrides, such as TiN, oxides, insulating materials, dielectric materials, conductive materials, metals, such as tungsten, ruthenium, molybdenum, or copper, or metallic materials, crystalline materials, epitaxial, heteroepitaxial, and / or monocrystalline materials. In some embodiments of the present disclosure, the substrate includes silicon. In addition to silicon, the substrate may include other materials, as described above, from which layers can be formed.

[0022] The substrate may be patterned. The patterned substrate may include semiconductor device structures formed in or on the surface of the substrate. For example, the patterned substrate may comprise partially or fully fabricated semiconductor device structures, such as transistors and / or memory elements. The patterned features may be formed, for example, by depositing a layer of material and etching portions of the layer.

[0023] In a method according to the present disclosure, a silicon precursor is provided in a reaction chamber. A reactant containing hydrogen atoms is also provided in the reaction chamber to form silicon oxide on a substrate. Thus, silicon oxide is formed by the reaction of the silicon precursor with the reactant. The process of forming silicon oxide may be performed, for example, by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In some embodiments, the silicon oxide is deposited by a CVD process. In some embodiments, the method is a cyclic deposition method. In some embodiments, the silicon oxide is deposited by an ALD process. In some embodiments, the method is an ALD method. In some embodiments, the method is a CVD method.

[0024] In some embodiments, silicon oxide can be deposited using plasma-enhanced CVD (PECVD). In some embodiments, silicon oxide can be deposited using plasma-enhanced ALD (PEALD). Using a plasma-enhanced variant of the deposition process can further reduce the deposition temperature. Alternatively, or additionally, using a plasma-enhanced process can positively impact the quality of the deposited silicon oxide. The plasma can be hydrogen (H2) plasma, nitrogen (N2) plasma, argon (Ar) plasma, helium (He) plasma, neon (Ne) plasma, N2 / H2 plasma, oxygen (O2) plasma, NH3 plasma, or a combination thereof. The plasma can be generated remotely (remote plasma) or in situ (direct plasma). In some embodiments, the plasma is generated by ionization of the gas phase of a gas with radio frequency (RF) power. The RF power can be between 100 W and 2,000 W.

[0025] CVD processes typically involve a gas-phase reaction between two or more reactants. The reactants can be supplied to a reaction chamber or substrate simultaneously or in partially or completely separated pulses (cyclic CVD). The substrate and / or reaction chamber can be heated to promote the reaction between the gaseous reactants. In some embodiments, the reactants, and possible plasma, are supplied until a thin film having a desired thickness is deposited.

[0026] As used herein, ALD refers to a vapor deposition process in which deposition cycles occur in a reaction chamber. ALD is based on the controlled, usually self-limiting, surface reaction of precursor chemicals. Gas-phase reactions are avoided by alternately supplying precursors into the reaction chamber. Typically, during each cycle, a first precursor (e.g., a silicon precursor) chemisorbs onto the deposition surface (e.g., a substrate surface, which may contain previously deposited material or other materials from previous ALD cycles) to form a monolayer or submonolayer of material that does not readily react with additional first precursor. A second precursor, reactant, or reaction gas (e.g., a hydrogen-containing reactant) can then, optionally, be subsequently introduced into the reaction chamber for use in converting the chemisorbed precursor to the desired material on the deposition surface. In some embodiments, the process may begin with the introduction of a second precursor, reactant, or reaction gas (e.g., a hydrogen-containing reactant), followed by the introduction of the first precursor (e.g., a silicon precursor).

[0027] In ALD, gas-phase precursors and reactants can be separated from one another within the reaction chamber, for example, by removing excess reactants and / or reactant by-products from the reaction chamber between reactant pulses. This can be achieved using an evacuation step and / or an inert gas pulse (purging). In some embodiments, the substrate is contacted with a purge gas, such as an inert gas. For example, the substrate can be contacted with a purge gas between reactant pulses to remove excess reactants and reaction by-products. In some embodiments, prior to supplying reactants into the reaction chamber, excess silicon precursor is purged from the reaction chamber and / or substrate with an inert gas. In some embodiments, prior to supplying silicon precursor into the reaction chamber, excess reactants are purged from the reaction chamber and / or substrate with an inert gas.

[0028] Purge gas pulses and / or the vacuum generated by the evacuation system can be used to remove excess precursors and reaction by-products from the reaction chamber and / or substrate surface. The purge gas can be any inert gas. The flow rate of the purge gas during purging of the reaction chamber and / or substrate surface can range from about 500 sccm to about 4500 sccm, or from about 2000 sccm to about 4000 sccm. In some embodiments, the purge gas flow rate is set to less than 500 sccm. In some embodiments, the purge gas flow rate is about 300 sccm. In some embodiments, the purge gas flow rate is about 100 sccm. In some embodiments, the method includes supplying a purge gas into the reaction chamber after supplying precursors and / or reactants into the reaction chamber. In some embodiments, the method includes evacuating the reaction chamber after supplying precursors and / or reactants into the reaction chamber. The carrier gas can have a flow rate similar to that of the purge gas. In some embodiments, the flow rates of the carrier gas and the purge gas are the same. In some embodiments, the flow rate of the purge gas is greater than the flow rate of the carrier gas. In some embodiments, the flow rate of the carrier gas is greater than the flow rate of the purge gas.

[0029] In some embodiments, the method includes supplying an inert gas to the reaction chamber. The inert gas may be used to provide a protective atmosphere for the substrate before and after depositing silicon oxide on the substrate. The inert gas may be used to purge precursors and / or reaction by-products from the reaction chamber. The inert gas may be used to adjust the flow rate of the precursor. Thus, the precursor concentration and residence time in the reaction chamber can be adjusted by using the inert gas. Such a gas may be referred to as a carrier gas. In some embodiments, the method includes supplying a carrier gas into the reaction chamber. The term inert gas (including carrier gas and purge gas) may refer to a gas that does not participate in a chemical reaction and / or does not become part of the deposited material to any significant extent. Exemplary inert gases include helium (He), argon (Ar), nitrogen (N), hydrogen (H), and any combination thereof.

[0030] In some embodiments, deposition of silicon oxide is carried out at a pressure of less than about 0.001 Torr, less than 0.01 Torr, less than 0.1 Torr, less than 10 Torr, or less than 50 Torr. In some embodiments, the pressure in the reaction chamber during at least a portion of a method according to the present disclosure is less than about 0.001 Torr, less than 0.01 Torr, less than 0.1 Torr, less than 10 Torr, or less than 50 Torr.

[0031] In some embodiments, each reaction is self-limiting, achieving monolayer growth. These can be referred to as "true ALD" reactions. In some such embodiments, the silicon precursor can be self-limitingly adsorbed onto the substrate surface. Reactants react sequentially with the adsorbed silicon precursor to form up to a monolayer of silicon oxide on the substrate.

[0032] Furthermore, as used herein, the term atomic layer deposition is also meant to include processes denoted by related terms, such as chemical vapor deposition atomic layer deposition, atomic layer epitaxy (ALE), molecular beam epitaxy (MBE), gas source MBE, or metalorganic MBE, as well as chemical beam epitaxy, when performed with alternating pulses of precursor / reactive gases and purge (e.g., inert gas) gases.

[0033] In some embodiments, the silicon oxide deposition process has one or more stages that are not self-limiting. For example, in some embodiments, at least one of the silicon precursor and the reactants is at least partially decomposed on the substrate surface. Thus, in some embodiments, the process can operate at process conditions that are close to, or even entirely at, CVD conditions.

[0034] In some embodiments, silicon oxide deposition according to the present disclosure may be conformal, for example, silicon oxide deposited using ALD-type reactions may form a conformal layer.

[0035] In some embodiments, the method according to the present disclosure is a thermal deposition method. In thermal deposition, a chemical reaction is driven by an increase in temperature relative to the ambient temperature. Generally, the increase in temperature provides the energy necessary for the formation of silicon oxide in the absence of other external energy sources, such as plasma, radicals, or other forms of radiation. In some embodiments, the method according to the present disclosure is a plasma-enhanced deposition method, such as PEALD or PECVD.

[0036] Silicon precursors according to the present disclosure include a silicon atom bonded to at least one oxygen atom, and at least one oxygen atom bonded to a carbon atom, hi some embodiments, the silicon atom is bonded to one oxygen atom, and the oxygen atom is bonded to a carbon atom.

[0037] In some embodiments, the silicon atom in the silicon precursor is bonded to multiple oxygen atoms. In other words, the silicon atom may be bonded to two, three, or four oxygen atoms. In embodiments in which the silicon atom is bonded to two oxygen atoms, one or both of the two oxygen atoms may be bonded to a carbon atom. In embodiments in which the silicon atom is bonded to three oxygen atoms, one, two, or three of the three oxygen atoms may be bonded to a carbon atom. In embodiments in which the silicon atom is bonded to four oxygen atoms, one, two, three, or four of the four oxygen atoms may be bonded to a carbon atom. Thus, in some embodiments, the silicon atom is bonded to at least three oxygen atoms, and one, two, or three of the oxygen atoms are further bonded to a carbon atom.

[0038] In some embodiments, at least one of the carbon atoms in the silicon precursor is bonded to a second oxygen atom. The second oxygen atom can be bonded to the carbon atom by a double bond. Thus, the oxygen atom bonded to the silicon atom can be bonded to a carbonyl carbon atom. In other words, the carbon atom is bonded to two oxygen atoms, one of which is bonded to the silicon atom and the other of which forms a carbonyl group with the carbon atom. In some embodiments, the silicon atom is bonded to multiple oxygen atoms, with one, two, three, or four oxygen atoms further bonded to the carbonyl carbon atom.

[0039] In some embodiments of the method according to the present disclosure, each of the carbon atoms (i.e., the carbon atom bonded to the silicon atom through an oxygen atom) in the silicon precursor belongs to an independently selected unsubstituted, substituted, and / or functionalized C1-C5 hydrocarbon. Thus, there can be one, two, three, or four hydrocarbon groups in the silicon precursor. SiR a (OOCR') 4-a Formula I

[0040] In some embodiments, the silicon precursor comprises a compound according to Formula I, where each R and R′ is independently selected from hydrogen or unsubstituted, substituted, saturated, unsaturated, and / or functionalized hydrocarbons, and 4>a≧0. Each R and R′ may be a linear hydrocarbon, a branched hydrocarbon, or a cyclic or aromatic hydrocarbon. The hydrocarbon may be a C1-C10 hydrocarbon, e.g., a C2, C3, C4, C5, C6, C7, C8, or C9 hydrocarbon. By way of example, each R and R′ may independently comprise a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl group, including any of their isomers, e.g., n-, iso-, sec-, and tert-isomers. The alkyl group may be linear, branched, or cyclic and may comprise any structural isomer of the alkyl group. The alkyl group may be substituted. The substituent of the alkyl group may be a single atom, e.g., a halogen, or a functional group, e.g., a hydroxyl group. In some embodiments, R can be a halogen. In some embodiments, R can be Cl, Br, I, or F. In some embodiments, R and / or R' can comprise a halogen. When multiple halogens are present in the silicon precursor, the halogen atoms can be the same or different.

[0041] Exemplary embodiments of silicon precursors according to Formula I may be, for example, molecules generally represented by structures (1)-(4). As explained above, in the structures, each R and R' may be independently selected from hydrogen or unsubstituted, substituted, saturated, unsaturated, and / or functionalized hydrocarbons. [ka]

[0042] Examples of silicon precursors are silicon tetraacetate (triacetyloxysilyl acetate), triacetoxyvinylsilane, silicon tetrapropionate, triacetoxysilane, triacetoxy(methyl)silane, triacetoxy(methoxy)silane, and diacetoxydimethylsilane. Other examples of silicon precursors are silicon(vinyl) tripropionate, silicon(vinyl) triacetate, SiCl(OAc)3, SiCl2(OAc)2, and SiCl3(OAc).

[0043] Reactants according to the present disclosure include hydrogen atoms. This means that there are at least two hydrogen atoms in the reactant molecule. In some embodiments, the reactants include at least one other atom, which is other than hydrogen. The other atom may be, for example, nitrogen. The other atom may be oxygen. In some embodiments, the other atom may be other than oxygen. In some embodiments, the reactants include hydrogen and nitrogen. In some embodiments, the reactants include hydrogen and oxygen.

[0044] In some embodiments, the reactants include ammonia (NH). In some embodiments, the reactants include ammonia mixed with an inert gas. In some embodiments, the reactants include ammoniacal nitrogen (NH-N) or ammonia-hydrogen (NH-H) mixtures. In some embodiments, the reactants include either a primary or secondary amine, such as dimethylamine, methylamine, or ethanediamine. In some embodiments, the reactants are diamines, such as ethanediamine or hexanediamine. In some embodiments, the reactants may include a mixture of at least two compounds.

[0045] In some embodiments, the reactants may include water (H2O). In some embodiments, the reactants may include hydrogen peroxide (H2O2). In some embodiments, the reactants include an amine. The amine may be a primary amine, a secondary amine, or a tertiary amine. In embodiments where the reactants include oxygen, the reactants may include an alcohol. The reactants may include formic acid (HCOOH). The reactants may consist essentially of or consist of one compound.

[0046] In some embodiments, the reactant is selected from hydrazine (N2H4) or a methyl-substituted hydrazine, such as N,N-dimethylhydrazine or N,N'-dimethylhydrazine.

[0047] Silicon oxide can be formed at a temperature of about 65°C to about 500°C. For example, silicon oxide can be formed at a temperature of about 100°C to about 450°C, or about 150°C to about 400°C. In some embodiments of the present disclosure, silicon oxide can be formed at a temperature of about 200°C to about 400°C, or about 300°C to about 350°C. For example, silicon oxide can be formed at a temperature of 75°C, or 125°C, or 175°C, or 225°C, 275°C, or 325°C, or 375°C.

[0048] Silicon oxide deposited according to the present disclosure can form a layer or part of a layer. Silicon oxide or silicon oxide-containing layers according to the present disclosure can comprise at least 50% silicon oxide, or at least 70% silicon oxide, or at least 85% silicon oxide. Silicon oxide or silicon oxide-containing layers according to the present disclosure can comprise at least 90% silicon oxide, or at least 95% silicon oxide, or at least 98% silicon oxide. In some embodiments, silicon oxide or silicon oxide-containing layers according to the present disclosure can comprise at least 99.5% silicon oxide. In some embodiments, silicon oxide-containing layers can consist essentially of silicon oxide or can consist of silicon oxide.

[0049] In some embodiments, silicon oxide or silicon oxide-containing layers deposited according to the present disclosure may contain less than 5 atomic percent carbon, or less than 2 atomic percent carbon, or less than 1 atomic percent carbon. When the reactant contains nitrogen, some nitrogen may be included in the silicon oxide or silicon oxide-containing layer. In some embodiments, the silicon oxide or silicon oxide-containing layer may contain less than 8 atomic percent nitrogen, or less than 5 atomic percent nitrogen, or less than 2 atomic percent nitrogen.

[0050] In some embodiments, silicon oxide deposited according to the disclosed methods can have a wet etch rate similar to or the same as that of thermal oxide. In some embodiments, silicon oxide deposited according to the disclosed methods can have a wet etch rate that is two or five times that of thermal oxide. In some embodiments, silicon oxide deposited according to the disclosed methods can have a wet etch rate that is more than five times, more than ten times, or more than thirty times that of thermal oxide. In some embodiments, silicon oxide deposited according to the disclosed methods can have a wet etch rate that is not more than 50 times that of thermal oxide. In some embodiments, silicon oxide deposited according to the disclosed methods can have a wet etch rate in the range of 10 to 80 nm / min in a 0.5% (v / v) HF solution.

[0051] In some embodiments, silicon oxide deposited according to the methods of the present disclosure can have a dielectric constant of about 4, or less than about 5, or less than about 6. In some embodiments, silicon oxide deposited according to the methods of the present disclosure can have a dielectric constant of about 7. In some embodiments, the dielectric breakdown of the silicon oxide is about 8 to about 15 MV×cm. -1 In some embodiments, the thermal conductivity of silicon oxide deposited according to the methods of the present disclosure is similar to that of thermal oxide. In some embodiments, the silicon oxide has a thermal conductivity of 0.2 to 2 watts x meters. -1 Kelvin -1 It has a thermal conductivity in the range of

[0052] The method according to the present invention may be selective. Selective deposition can provide advantages in different applications. Selective deposition can be used in several areas of application, for example, in the fabrication of perfectly aligned vias, dielectric on back-end dielectric deposition, gate stacks, and conductive line isolation. In some embodiments, the reactants used to selectively deposit silicon oxide do not contain oxygen. In some embodiments, the reactants used to selectively deposit silicon oxide include nitrogen. In some embodiments, the reactants used to selectively deposit silicon oxide include, consist essentially of, or consist of two or more of the elements oxygen, nitrogen, and hydrogen. In some embodiments, the reactants used to selectively deposit silicon oxide include, consist essentially of, or consist of oxygen and nitrogen. In some embodiments, the reactants used to selectively deposit silicon oxide include, consist essentially of, or consist of hydrogen and nitrogen. In some embodiments, the reactants used to selectively deposit silicon oxide include, consist essentially of, or consist of ammonia, amines, or hydrazine, or oxygen-containing reactants, such as water, ozone, or oxygen.

[0053] In some embodiments of the present disclosure, a substrate comprises a surface. The surface may comprise a first portion comprising a first material and a second portion comprising a second material. In some embodiments, the first portion comprises 20 atomic % or more of the first material, or the first portion comprises 30 atomic % or more of the first material, or the first portion comprises 50 atomic % or more of the first material, or the first portion comprises 70 atomic % or more of the first material, or the first portion comprises 85 atomic % or more of the first material. The first portion may comprise 90 atomic % or more of the first material, or 95 atomic % or more of the first material. In some embodiments, the first portion can consist essentially of the first material or can consist of the first material. Similarly, in some embodiments, the second portion comprises 20 atomic % or more of the second material, or the second portion comprises 30 atomic % or more of the second material, or the second portion comprises 50 atomic % or more of the second material, or the second portion comprises 70 atomic % or more of the second material, or the second portion comprises 85 atomic % or more of the second material. The second portion can comprise 90 atomic % or more of the second material, or 95 atomic % or more of the second material, hi some embodiments, the second portion can consist essentially of or consist of the second material.

[0054] The first and second portions may be arranged in any suitable pattern. For example, the first and second portions may be alternating lines, or one portion may surround the other portion in a plan view or a 3D view. The first and second portions may be coplanar, the first portion may be raised relative to the second portion, or the second portion may be raised relative to the first portion. The first and second portions may be formed using one or more reaction chambers. The patterned structure may be provided on any suitable substrate.

[0055] The first material or the second material may be selectively deposited on the first portion and / or the second portion, and the first material and / or the second material may be processed after they are deposited (post-processed).

[0056] The first material may comprise a dielectric. The dielectric may comprise silicon oxide (SiO), silicon nitride (SiN), silicon oxycarbide (SiOC), silicon oxynitride (SiON), silicon oxycarbonitride (SiOCN), or a low-k material, such as SiOC, SiOCH, or SiOH, or a carbon-based layer. In some embodiments, the dielectric consists essentially of or consists of silicon oxide, silicon nitride, silicon oxycarbide (SiOC), silicon oxycarbonitride (SiOCN), or a low-k material. In some embodiments, the first material is silicon carbide. The first material may comprise, consist essentially of, or consist of a metal-containing silicon oxide compound or metal silicate, including, but not limited to, SiGeOx, GeOx, AlSiOx, HfSiOx, LaSiOx, LaHfSiOx, etc.

[0057] The first material may comprise, consist essentially of, or consist of a metal nitride, including, but not limited to, titanium nitride, tantalum nitride, aluminum nitride, titanium aluminum nitride, gallium nitride, and nitride alloys containing indium, aluminum, or gallium. The first material may comprise, consist essentially of, or consist of a metal carbide, including, but not limited to, titanium carbide, tungsten carbide, tantalum carbide, and niobium carbide. The first material may comprise, consist essentially of, or consist of a metal boride, including, but not limited to, niobium boride, boron-doped silicon boride, titanium boride, vanadium boride, lanthanum boride, and cobalt boride.

[0058] The first material may comprise a metal or metal alloy, including, but not limited to, copper, ruthenium, cobalt, niobium, tungsten, titanium, tantalum, iridium, gold, aluminum, iron, nickel, molybdenum, rhenium, manganese, and vanadium. Additionally, the first material may comprise a metal oxide, such as copper oxide, ruthenium oxide, cobalt oxide, niobium oxide, tungsten oxide, titanium oxide, hafnium oxide, zirconium oxide, tantalum oxide, iridium oxide, gold oxide, zinc oxide, aluminum oxide, iron oxide, nickel oxide, molybdenum oxide, rhenium oxide, manganese oxide, or vanadium oxide.

[0059] The second material may include an organic material. For example, the organic material may be an organic polymer. In some embodiments, the organic material consists essentially of, or consists of, carbon and hydrogen, while in some embodiments, the organic material comprises substantially only carbon, oxygen, and hydrogen. In some embodiments, the organic material consists essentially of, or consists of, carbon, nitrogen, and hydrogen. In yet other embodiments, the organic material consists essentially of, or consists of, carbon, oxygen, nitrogen, and hydrogen. In some embodiments, the organic material consists essentially of, or consists of, carbon, nitrogen, sulfur, and hydrogen, or carbon, oxygen, sulfur, and hydrogen, while in some embodiments, the organic material consists essentially of, or consists of, carbon, oxygen, nitrogen, sulfur, and hydrogen.

[0060] In some embodiments, the second material may include one or more SAMs (self-aligned monolayers). The one or more SAMs may be gas-phase SAMs. The one or more SAMs may be liquid-phase SAMs.

[0061] In some embodiments, silicon oxide is selectively deposited on a dielectric material relative to a metal or metal alloy or metal oxide with an organic passivation. In some embodiments, silicon oxide is selectively deposited on an oxygen-containing silicon layer compared to silicon with some organic passivation. In some embodiments, silicon oxide is selectively deposited on a metal or metal alloy or metal oxide with a dielectric film with an organic passivation. In some embodiments, the passivation is present as a passivation layer.

[0062] Examples of organic materials according to the present disclosure include, but are not limited to, polyimides, polyamides, and poly(methyl methacrylate) (PMMA). Other examples of organic materials include polyureas, polyurethanes, polythioureas, polyesters, polyimines, polyamic acids, and other polymeric forms or mixtures of the above materials. In some embodiments, the organic material may comprise, consist essentially of, or consist of precursor materials for polymeric films that can be converted or polymerized by treatment processes. For example, the as-deposited organic material may comprise a polyimide or polyamide. In some embodiments, the deposited organic material may comprise, consist essentially of, or consist of a polyimide film resulting from an incomplete reaction. In some embodiments, the deposited organic film may comprise, consist essentially of, or consist of a polyimide, including some polyamic acids. In some embodiments, polyamic acids are converted to polyimides. Conversion processes known in the art include annealing, plasma (e.g., using inert gases), chemical treatment (e.g., using anhydrides), UV treatment, and other post-deposition treatments.

[0063] In some embodiments of the present disclosure, the second material may include, consist essentially of, or consist of a passivation agent. In other words, the second portion may include a passivation agent. A passivation agent is a substance, compound, or mixture of compounds that can inhibit the deposition or growth of a depositable material on a substrate. Various passivation agents are known in the art. Some passivation agents include an organic material. In some embodiments, the passivation agent is an organic material according to the present disclosure. In other words, the organic material can function as an organic passivation agent.

[0064] In methods according to the present disclosure, silicon oxide is selectively deposited on the first portion relative to the second portion. Selectivity can be expressed as a ratio calculated as [(deposition on the first surface) - (deposition on the second surface)] / (deposition on the first surface). Deposition can be measured in different ways. In some embodiments, deposition may be given as a measured thickness of deposited material. In some embodiments, deposition may be given as a measured amount of deposited material.

[0065] In some embodiments, the selectivity is greater than about 10%, greater than about 35%, or greater than about 50%. In some embodiments, the selectivity is greater than about 75%, greater than about 85%, greater than about 90%, or greater than about 93%. In some embodiments, the selectivity is greater than about 95%, greater than about 98%, greater than about 99%, or greater than about 99.5%. In some embodiments described herein, the selectivity can vary with the duration or thickness of the deposition.

[0066] In some embodiments, silicon oxide deposition occurs only on the first portion and not on the second portion. In some embodiments, deposition on the first portion relative to the second portion is at least about 80% selective, which may be sufficiently selective for some applications. In some embodiments, deposition on the first portion relative to the second portion is at least about 50% selective, which may be sufficiently selective for some applications. In some embodiments, deposition on the first portion relative to the second portion is at least about 10% selective, which may be sufficiently selective for some applications.

[0067] In some embodiments, the passivation agent, which may be an organic passivation agent, is selectively deposited on the second portion relative to the first portion prior to delivering the silicon precursor into the reaction chamber. In some embodiments, the passivation agent, which may be an organic passivation agent, is selectively deposited on the second portion relative to the first portion prior to delivering the reactants into the reaction chamber.

[0068] In some embodiments, the method further includes selectively removing the passivation agent, which may be an organic passivation agent, after depositing silicon oxide on the first portion. Removal of the passivation agent may result in removal of some silicon oxide from the first portion. Methods according to the present disclosure may include deposition of more than one passivation agent. For example, in situations where selectivity is less than 100%, it may be beneficial to deposit the passivation agent twice and / or more times. In such embodiments, there may be partial deposition of silicon oxide on the second portion containing the passivation agent. Intermittent removal and redeposition of the passivation agent can improve selectivity by removing silicon oxide deposited in undesired areas of the substrate. Removal of the passivation agent may be selective; simply depositing more passivation agent may be sufficient.

[0069] In some embodiments of the method, one or more unit deposition cycles are performed. A unit deposition cycle includes supplying a silicon precursor into the reaction chamber and supplying reactants into the reaction chamber. A unit deposition cycle may include additional steps, such as purging or depositing a passivation agent.

[0070] In some embodiments, metal oxides and / or metal silicates may be deposited. Metal oxide or metal silicate-containing materials according to the present disclosure may be utilized, for example, as UV primer layers in patterning, adhesion layers, or sacrificial layers for various purposes. The metal oxide and / or metal silicate-containing materials may form a layer. In some embodiments, the metal oxide is aluminum oxide (e.g., Al2O3), titanium oxide (e.g., TiO2), tantalum oxide (e.g., Ta2O5), niobium oxide (e.g., NbO2, Nb2O5), tungsten oxide (e.g., Al2O3, WO2, W2O5), hafnium oxide (e.g., HfO2), or zirconium oxide (e.g., ZrO2). The metal oxide and / or metal silicate-containing materials may be selectively deposited as described above. In embodiments in which the silicon oxide or silicon oxide-containing layer includes a metal oxide and / or metal silicate, the silicon oxide content of the layer may be reduced compared to a layer that does not include a metal oxide and / or metal silicate.

[0071] In some embodiments, the metal precursor may be selected from alkylamides, amidinates, alkoxides, alkyls, halides, cyclopentadiene, and β-diketonate compounds. In some embodiments, the metal precursor may be tetrakis(dimethylamido)titanium, titanium(IV) isopropoxide, dimethylaluminum isopropoxide, trimethylaluminum (TMA), diethylzinc, tetrakis(ethylmethylamido)hafnium(IV), tetrakis(ethylmethylamido)zirconium(IV), tetrakis(dimethylamido)hafnium(IV), dimethylbis(cyclopentadienyl)hafnium(IV), or the like. In some embodiments, the alkylamido metal precursor is selected for metals such as titanium, gallium, germanium, and tantalum. In some embodiments, the method includes supplying a metal precursor into a reaction chamber. In some embodiments, the silicon precursor, reactants, and metal precursor are supplied alternately and sequentially into the reaction chamber. The ratio between supplying the metal precursor into the reaction chamber and supplying the silicon precursor into the reaction chamber may be adjusted depending on the desired metal oxide content of the silicon oxide. For example, the ratio of providing a metal precursor into the reaction chamber to providing a silicon precursor into the reaction chamber may be, for example, 1:1, 1:2, 1:5, 1:8, 1:10, 1:15, 1:20, 1:30, 1:50, 1:100, 2:1, or 5:1, or 10:1, or 20:1.

[0072] In some embodiments, the silicon precursor according to the present disclosure includes triacetoxyvinylsilane (CAS nr 4130-08-9) and the reactant includes TMA. In such embodiments, the deposition temperature may be, for example, about 200°C to about 450°C, e.g., 250°C, 300°C, or 350°C. The amount of silicon in the deposited aluminum silicate-containing material may be, for example, about 2 to about 20 atomic %, e.g., 5 atomic %, 10 atomic %, or 15 atomic %. The amount of carbon in the deposited aluminum silicate-containing material may be, for example, about 0.5 to about 15 atomic %, e.g., 1 atomic %, 3 atomic %, or 8 atomic %.

[0073] In another embodiment, a three-step deposition process, such as an ALD process, may be used to deposit materials with tunable compositions. Silicon precursors and reactants according to the present disclosure can be combined with organometallic precursors to deposit metal silicate materials. For example, a deposition cycle may include sequentially supplying a silicon precursor (e.g., silicon tetraacetate), a metal precursor (e.g., TMA), and a reactant (e.g., water) into a reaction chamber. In one embodiment, each deposition cycle includes two subcycles, one for a metal oxide and one for a silicon oxide. For example, the metal precursor (e.g., TMA) and the reactant (e.g., water) may be alternately supplied into the reaction chamber a predetermined number of times, after which the silicon precursor (e.g., silicon tetraacetate) and the reactant (e.g., water) are supplied into the reaction chamber a predetermined number of times. The number of times each subcycle is repeated may be independently selected. For example, each subcycle may be performed from about 5 to about 50 times, e.g., 10, 20, or 30 times. By adjusting the relative amounts of the subcycles, a material of a desired composition can be obtained. In some embodiments, the deposited material comprises 5-50 atomic % silicon. In some embodiments, the deposited material comprises 2-20 atomic % carbon. In some embodiments, the deposited material comprises 10-40 atomic % aluminum. In some embodiments, the deposited material comprises 45-65 atomic % oxygen. However, the amount of each element in the deposited material depends on the selected cycling regime and deposition conditions.

[0074] In some embodiments, metal alkoxides may be used to increase the deposition rate of silicon oxide-containing materials. Metal alkoxide treatment may be used in combination with the three-step process described above. In some embodiments, metal alkoxides, such as dimethylaluminum isopropoxide, are used intermittently to improve deposition rates. For example, the metal alkoxide reactant may be supplied into the reaction chamber in a single pulse without supplying another reactant. The silicon precursor and reactant may then be supplied in subcycles that are repeated a predetermined number of times before the metal alkoxide reactant is supplied again. Without limiting the present disclosure to any particular theory, the metal alkoxide may improve the availability of hydroxyl groups on the substrate surface and enhance the chemisorption of the silicon precursor to the substrate. In some embodiments, the metal alkoxide reactant, such as dimethylaluminum isopropoxide, is supplied (i.e., pulsed) into the reaction chamber for 1 to 20 seconds, e.g., 2, 3, 5, or 10 seconds. In some embodiments, a subcycle comprising supplying a silicon precursor and reactants into the reaction chamber before a metal alkoxide reactant (including, for example, dimethylaluminum isopropoxide) is again supplied into the reaction chamber is performed 1 to 50 times, e.g., 5, 6, 8, 10, 15, or 20 times.

[0075] The metal alkoxide pulse may leave some metal in the deposit. In embodiments involving the use of dimethylaluminum isopropoxide, the deposit may contain aluminum. In some embodiments, the silicon oxide-containing material contains about 1 atomic % to about 10 atomic % aluminum. The silicon content of such materials may be about 20 atomic % to about 40 atomic %, e.g., about 25 atomic %, about 30 atomic %, or about 35 atomic %. However, the amount of each element in the deposit will depend on the selected cycle regime and deposition conditions.

[0076] The use of metal alkoxides may shorten the reactant pulse time to achieve a given material deposition rate. In one embodiment in which dimethylaluminum isopropoxide is used as the metal alkoxide, such that after each dimethylaluminum isopropoxide pulse, the silicon precursor (silicon tetraacetate) and reactant (water) are pulsed 3 to 9 times, the deposition rate per silicon pulse is at least doubled compared to a process without metal alkoxide pulses, despite the deposition temperature being 20°C lower and the reactant pulse duration being less than 10% shorter. Therefore, it may be possible to lower the deposition temperature when using metal alkoxide reactants. In some embodiments, the deposition temperature may be about 50°C to about 200°C, e.g., about 60°C, or about 80°C, or about 100°C. The use of metal alkoxide reactants may improve the selectivity of the deposition process, such that nucleation on the passivation layer is reduced.

[0077] In another aspect, a deposition assembly for depositing silicon oxide on a substrate is disclosed. The deposition assembly includes a reaction chamber configured and arranged to hold the substrate and a precursor injector system configured and arranged to deliver precursors and / or reactants into the reaction chamber. The deposition assembly includes a precursor container configured and arranged to contain and vaporize a silicon precursor including a silicon atom bonded to at least one oxygen atom, wherein the at least one oxygen atom is bonded to a carbon atom. The assembly is configured and arranged to deliver the silicon precursor to the reaction chamber via the precursor injector system to deposit silicon oxide on the substrate.

[0078] In some embodiments of the deposition assembly, the vessel includes a vaporizer configured and arranged to vaporize a silicon precursor. In some embodiments, the vaporizer is configured and arranged to vaporize the silicon precursor at a temperature between 65°C and 250°C. In some embodiments, a vaporizer according to the present disclosure is one in which the vaporizer surface is not in direct contact with a thermal heater. Such a vaporizer can improve heating uniformity in embodiments in which radiation-based heating is used. In some embodiments, the vaporizer can be a suspended vaporizer. In such a vaporizer, for example, there is no direct thermal contact between two metal surfaces.

[0079] In some embodiments, a separate jacket may be placed around the vessel to stabilize the vessel temperature. This can reduce surface temperature fluctuations. In some embodiments, the interior surfaces of the vaporizer may be made of a material other than metal. At least one of the interior surfaces of the vaporizer may comprise a polymer coating or a high performance thermoplastic (HTP).

[0080] In some embodiments, the deposition apparatus includes a pump configured and arranged to evacuate the pressure in the reaction chamber to less than 50 Torr. In some embodiments, the deposition apparatus includes a heater configured and arranged to control the temperature in the reaction chamber to between 65°C and 500°C.

[0081] Detailed Description of the Drawings 1A illustrates a method 100 for depositing silicon oxide in accordance with at least one embodiment of the present disclosure. The method 100 includes providing a substrate into a reaction chamber (102), providing a silicon precursor according to the present disclosure into the reaction chamber (104), and providing a reactant including hydrogen atoms into the reaction chamber (106).

[0082] During step 102, a substrate is fed into a reaction chamber of a reactor. The reaction chamber can form part of an atomic layer deposition (ALD) reactor. The reactor can be a single-wafer reactor. Alternatively, the reactor can be a batch reactor. The various steps of method 100 can be performed in a single reaction chamber, or they can be performed in multiple reaction chambers, such as reaction chambers of a cluster tool. In some embodiments, method 100 is performed in a single reaction chamber of a cluster tool, while other, previous, or subsequent, structure or device fabrication steps are performed in separate reaction chambers of the same cluster tool. Optionally, a reactor including a reaction chamber can include a heater to activate a reaction by increasing the temperature of one or more substrates and / or reactants and / or precursors.

[0083] During step 102, the substrate can be brought to a desired temperature and pressure to provide 104 a silicon precursor into the reaction chamber and / or 106 a reactant into the reaction chamber. The temperature in the reaction chamber (e.g., of the substrate or substrate support) can be, for example, from about 100°C to about 450°C, or from about 150°C to about 400°C. As another example, the temperature in the reaction chamber can be from about 200°C to about 400°C, or from about 300°C to about 350°C. Exemplary temperatures in the reaction chamber are 75°C, 125°C, 175°C, 225°C, 275°C, 325°C, and 375°C.

[0084] The pressure in the reaction chamber can be about 0.001 Torr, or less than 0.01 Torr, less than 0.1 Torr, less than 10 Torr, or less than 50 Torr.

[0085] A silicon precursor is supplied into a reaction chamber (104) containing a substrate. Without limiting the disclosure to any particular theory, the silicon precursor may chemisorb onto the substrate during supply of the silicon precursor into the reaction chamber (104). The duration of supply of the silicon precursor into the reaction chamber (silicon precursor pulse time) may be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 2.5 seconds, 3 seconds, 3.5 seconds, 4 seconds, 4.5 seconds, or 5 seconds. In some embodiments, the duration of supply of the silicon precursor into the reaction chamber (silicon precursor pulse time) may be greater than 5 seconds, greater than 10 seconds, or about 20 seconds.

[0086] When a reactant is supplied (106) into the reaction chamber, it can react with the chemisorbed silicon precursor or its derivative species to form silicon oxide. The duration of supplying the reactant into the reaction chamber (reactant pulse time) can be, for example, 0.5 seconds, 1 second, 1.5 seconds, 2 seconds, 2.5 seconds, 3 seconds, 3.5 seconds, 4 seconds, 4.5 seconds, 5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 11 seconds, or 12 seconds. In some embodiments, the duration of supplying the reactant into the reaction chamber is greater than 15 seconds, greater than 20 seconds, or about 30 seconds. Without limiting the disclosure to any particular theory, the reactant pulse may be shorter than the silicon precursor pulse.

[0087] Steps 104 and 106 can be performed in any order to form a deposition cycle, resulting in the deposition of silicon oxide. In some embodiments, the two steps of silicon oxide deposition, i.e., supplying a silicon precursor and reactants into the reaction chamber (104 and 106), may be repeated (loop 108). Such embodiments include several deposition cycles. The thickness of the deposited silicon oxide may be adjusted by adjusting the number of deposition cycles. The deposition cycle (loop 108) may be repeated until the desired silicon oxide thickness is achieved. For example, 50, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, or 900 deposition cycles may be performed.

[0088] The amount of silicon oxide deposited in one cycle (growth per cycle) varies depending on the process conditions and may be, for example, 0.03 Å / cycle, 0.05 Å / cycle, 0.1 Å / cycle, 0.15 Å / cycle, 0.2 Å / cycle, 0.25 Å / cycle, or 0.3 Å / cycle, 1 Å / cycle, 3 Å / cycle, or 5 Å / cycle. Depending on the deposition conditions, the number of deposition cycles, etc., a silicon oxide or silicon oxide-containing layer of variable thickness can be deposited. For example, the silicon oxide layer or silicon oxide-containing layer can have a thickness of about 0.3 nm to 30 nm, e.g., about 0.5 nm, 1 nm, 1.5 nm, 2 nm, 2.5 nm, 3 nm, 3.5 nm, 4 nm, 4.5 nm, 5 nm, 6 nm, 7 nm, 8 nm, 10 nm, 15 nm, 20 nm, or 25 nm. The desired thickness can be selected according to the application at hand.

[0089] The silicon precursor and reactants may be delivered into the reaction chamber in separate steps (104 and 106). FIG. 1B illustrates one embodiment according to the present disclosure, in which steps 104 and 106 are separated by purge steps 105 and 107. In such an embodiment, the deposition cycle includes one or more purge steps (103, 105). During the purge steps, the precursors and / or reactants can be separated in time from each other by an inert gas, such as argon (Ar), nitrogen (N), or helium (He), and / or vacuum pressure.

[0090] Purging the reaction chamber (103, 105) can prevent or mitigate gas-phase reactions between the silicon precursor and the reactants, allowing for self-saturating surface reactions. Any excess chemicals and reaction by-products are removed from the substrate surface before contacting the substrate with the next reactive chemical, for example, by purging the reaction chamber or by moving the substrate. However, in some embodiments, the substrate can be moved and contacted with the silicon precursor and the reactants separately. Because the reaction is self-saturating, strict substrate temperature control and precise precursor dose control may not be necessary. However, the substrate temperature is preferably such that the incident gas species do not condense into a monolayer or multilayer and do not thermally decompose at the surface.

[0091] FIG. 2 is a schematic diagram of an alternative embodiment of the present disclosure. As described above, the substrate provided during step 102 can have a surface comprising a first portion and a second portion. In the exemplary embodiment of FIG. 2, a substrate 200 is shown having a surface with a first portion 202 and a second portion 204. The substrate 200 may also have another subsurface layer. In panel a), the surface of the substrate is formed by the first portion 202 and the second portion 204. The first portion 202 comprises, consists essentially of, or consists of a first material. The second portion 204 comprises, consists essentially of, or consists of a second material. The first and second materials are different materials. Each of the first and second materials may be, for example, SiO2, SiN, SiOC, SiON, SiOCN, or a low-k material. The first and second materials may be a metal-containing silicon oxide, a metal nitride, a metal boride or carbide, a metal or metal alloy, or a metal oxide. 2, the first portion 202 and the second portion 204 are at the same vertical height, but in practice the first and second portions 202, 204 may be at different heights.

[0092] In panel b) of Figure 2, the second portion 204 comprises a passivation agent 206. The passivation agent 206 may include an organic material. The passivation agent 206 may be an organic passivation agent. In panel b), the surface of the substrate is formed by the first portion 202 and the second portion 204 covered by the passivation agent 206.

[0093] In panel c) of FIG. 2 , silicon oxide 208 according to the present disclosure is selectively deposited on first portion 202. Deposition of silicon oxide 208 may occur in one or more deposition cycles. The relative thicknesses of the passivation agent and silicon oxide layer may differ from those shown in the figure. In the exemplary embodiment of FIG. 2 , passivation agent 206 is deposited on the substrate before silicon oxide 208 is deposited on substrate 200. Although not shown in the schematic diagram of FIG. 2 , in some embodiments, there may be some deposition of silicon oxide 208 on passivation agent 206. However, in most embodiments, growth of silicon oxide 208 on passivation agent 206 is significantly slower than on first portion 202.

[0094] Panel d) of Figure 2 shows substrate 200 after passivation agent 206 has been removed from second portion 204. In embodiments in which some silicon oxide has deposited on passivation agent 206, removal of passivation agent 206 also removes any silicon oxide deposited thereon. After removal of passivation agent 206, second portion 204, along with silicon oxide 208 deposited on first surface 202, forms a surface of substrate 200 without passivation agent 206. The method shown in Figure 2 may be followed by another deposition method and / or treatment. Additionally, although not shown in Figure 2, passivation and deposition of silicon oxide may be repeated.

[0095] FIG. 3 is a diagram of a method 300 for depositing silicon oxide, in which a second portion of the substrate may be repeatedly passivated with a passivation agent. Initially, a substrate is provided in a reaction chamber (302). The substrate comprises a first portion and a second portion as described above. In the embodiment of FIG. 3, a second surface of the substrate is passivated with a passivation agent (303). The passivation agent may be deposited on the surface. In some other embodiments, the passivation agent is introduced onto the surface at a stage prior to providing the substrate in the reaction chamber (302). In other words, the substrate may be passivated in another reaction chamber of the cluster tool. Passivation may also be performed in a separate tool.

[0096] In some embodiments, the passivation agent is an organic passivation agent. However, any suitable passivation agent or passivation method known in the art may be used. The choice of passivation method may depend on the characteristics of the first and second portions, as will be apparent to those skilled in the art. After the second surface is passivated (303), silicon oxide is selectively deposited on the first surface (304-307). As described above, deposition of the silicon oxide may include alternately sequentially supplying a silicon precursor and a reactant into the reaction chamber (304, 306). The reaction chamber may be purged after supplying the silicon precursor and / or after supplying the reactant into the reaction chamber (305, 307). The deposition cycle may be repeated (loop 308) until the desired thickness and / or layer coverage of silicon oxide is achieved.

[0097] After one or more silicon oxide deposition cycles, the passivation agent may be removed (309) from the second portion of the substrate surface. In some embodiments, silicon oxide deposition is completed before the passivation agent is removed (309) from the second portion. In some embodiments, another passivation agent removal (309) is not required, and substrate processing can continue without it. In some embodiments, passivation agent removal (309) may occur before silicon oxide deposition is completed. In such embodiments, the second portion of the substrate surface may be passivated again (loop 310). The frequency of passivation agent removal varies depending on the details of the process and can be determined by one skilled in the art. However, in certain embodiments, the configuration of the second surface and the first surface may allow silicon oxide deposition to continue without repeated passivation.

[0098] FIG. 4 is a schematic illustration of an exemplary embodiment of a deposition assembly 400 for depositing silicon oxide on a substrate. The deposition assembly 400 can be used to perform methods according to the present disclosure and / or to form structures or device portions according to the present disclosure. In the illustrated embodiment, the deposition assembly 400 includes one or more reaction chambers 402 configured and arranged to hold a substrate and a precursor injector system 401 configured and arranged to deliver precursors and / or reactants into the reaction chambers 402. The reaction chambers 402 can include any suitable reaction chamber, such as an ALD or CVD reaction chamber. The deposition assembly 400 can also include a heater configured and arranged to control the temperature within the reaction chambers between 65° C. and 500° C.

[0099] The deposition assembly further comprises a precursor container 404 configured and arranged to contain and vaporize a silicon precursor comprising a silicon atom bonded to at least one oxygen atom, wherein the at least one oxygen atom is bonded to a carbon atom. The deposition assembly 400 is configured and arranged to deliver the precursor to a reaction chamber 402 via a precursor injector system 401 to deposit silicon oxide on a substrate in accordance with the present disclosure.

[0100] The precursor injector system 401 of the deposition assembly 400 further comprises a reactant source 406, an optional purge gas source 408, an exhaust source 410, and a controller 412. The silicon precursor source 404 can include a container and one or more silicon precursors described herein, alone or mixed with one or more carrier (e.g., inert) gases. The reactant source 406 can include a container and one or more reactants according to the present disclosure, alone or mixed with one or more carrier gases. One or both containers can include a vaporizer configured and arranged to vaporize the silicon precursor or reactant, respectively, according to the present disclosure. The vaporizer can be configured and arranged to vaporize the silicon precursor or reactant, respectively, at a suitable temperature. A suitable temperature for the silicon precursor can be, for example, 60°C to 500°C. The purge gas source 408 can include one or more inert gases described herein. Although illustrated with three gas sources 404-408, the deposition assembly 400 can include any suitable number of gas sources. The gas sources 404-408 may be connected to the reaction chamber 402 via lines 414-418, each of which may include a flow controller, a valve, a heater, etc. The deposition apparatus 400 may include a pump configured and arranged to evacuate the pressure in the reaction chamber to less than 50 Torr. The pump may be included in an exhaust source 410, which may include one or more vacuum pumps.

[0101] The controller 412 includes electronic circuitry and software that operate the valves, manifolds, heaters, pumps, and other components included in the deposition assembly 400. Such circuitry and components operate to introduce one or more precursor, reactant, and purge gases from their respective sources 404-408. The controller 412 controls the timing of gas pulse sequences, the temperature of the substrate and / or reaction chamber, the pressure within the reaction chamber, and various other operations to properly operate the deposition assembly 400. The controller 412 can include control software that electrically or pneumatically controls valves to control the flow of precursor, reactant, and purge gases into and out of the reaction chamber 402. The controller 412 can include modules, e.g., software or hardware components that perform specific tasks. Modules are advantageously configured to reside on addressable storage media in the control system and can be configured to perform one or more processes.

[0102] Other configurations of the deposition assembly 400 are possible, including different numbers and types of precursor and reactant sources and purge gas sources. It will be appreciated that there are numerous arrangements of valves, conduits, precursor sources, and purge gas sources that can be used to achieve the goal of delivering suitable gases into the reaction chamber 402. Furthermore, as a schematic representation of the assembly, many components have been omitted for ease of illustration. Such components may include, for example, various valves, manifolds, purifiers, heaters, reservoirs, vents, and / or bypasses, as well as safety devices.

[0103] During operation of the deposition assembly 400, a substrate, e.g., a semiconductor wafer (not shown), is transferred, e.g., from a substrate handling system, to the reaction chamber 402. Once the substrate is transferred to the reaction chamber 402, one or more gases, e.g., precursor, reactant, carrier gas, and / or purge gas, from gas sources 404-408 are introduced into the reaction chamber 402. [Explanation of symbols]

[0104] 200 Base material 202 First Part 204 Second Part 206 Passivation Agent 208 Silicon oxide 400 Deposition Assembly 401 Precursor Injector System 402 Reaction Chamber 404 Silicon precursor source, precursor container 406 Reactant Source 408 Purge Gas Source 410 Exhaust Source 412 Controller 414, 416, 418 lines

Claims

1. 1. A method for depositing silicon oxide on a substrate, the method comprising: providing a substrate into a reaction chamber; delivering a silicon precursor into the reaction chamber, the silicon precursor comprising silicon atoms bonded to at least one oxygen atom, the at least one oxygen atom being bonded to a carbon atom; providing a reactant containing hydrogen atoms into the reaction chamber to form silicon oxide on the substrate; The silicon oxide is formed at a temperature of 65°C or higher and lower than 500°C, the substrate includes a surface, the surface includes a first portion including a first material and a second portion including a second material, the second material including an organic material; The method wherein the silicon oxide is selectively deposited on the first portion relative to the second portion.

2. The silicon precursor comprises a compound according to Formula I: SiR ａ (OOCR’) ４－ａ Formula I 2. The method of claim 1, wherein each R and R′ is independently selected from hydrogen or an unsubstituted, substituted, saturated, unsaturated, and / or functionalized hydrocarbon, and 4>a≧0.

3. 3. The method of claim 1, wherein the silicon precursor is selected from the group consisting of silicon tetraacetate (triacetyloxysilylacetate), triacetoxyvinylsilane, silicon tetrapropionate, triacetoxysilane, triacetoxy(methyl)silane, triacetoxy(methoxy)silane, and diacetoxydimethylsilane.

4. The method according to any one of claims 1 to 3, wherein the reactant contains at least one other atom which is not hydrogen.

5. The method of claim 4 wherein the other atom is nitrogen.

6. The reactants are ammonia (NH ３ ) or ammoniacal nitrogen (NH ３－ N ２ ) or ammonia-hydrogen (NH ３－ H ２ 6. The method of claim 5, comprising a mixture of

7. The method of claim 5 or 6, wherein the reactant comprises an amine.

8. The reactants are hydrazine (N ２ H ４ 8. The method according to claim 5, wherein the hydrazine is selected from the group consisting of methyl-substituted hydrazines and methyl-substituted hydrazines.

9. The method according to any one of claims 1 to 4, wherein the other atom is oxygen.

10. The method of claim 9 , wherein the reactant comprises an alcohol.

11. The method according to any one of claims 1 to 10, wherein the method is atomic layer deposition or cyclic chemical vapor deposition.

12. The method according to any one of claims 1 to 11, wherein the method is a thermal deposition method.

13. 13. The method of any of claims 1 to 12, wherein the method further comprises removing excess silicon precursor from the reaction chamber with an inert gas before supplying the reactants into the reaction chamber.

14. The method of any preceding claim, wherein the method comprises providing a metal alkoxide reactant into the reaction chamber.

15. 15. The method of claim 14, wherein the metal alkoxide is dimethylaluminum isopropoxide.

16. 16. The method of claim 14 or 15, wherein the method is a cyclic deposition method, and the silicon precursor and the reactants are fed into the reaction chamber at least twice each time the metal alkoxide is fed into the reaction chamber.

17. The method of claim 1 , wherein the first material comprises a dielectric.

18. The method of claim 1 , wherein the first material comprises a metal or a metal oxide.

19. The method of claim 1 , wherein the first material comprises a metal nitride, a metal carbide, or a metal boride.

20. The method of any preceding claim, wherein the second material comprises a passivation agent.

21. The method of claim 20 , wherein the passivation agent is an organic passivation agent.

22. One or more unit deposition cycles are performed, the unit deposition cycles comprising: delivering the silicon precursor into the reaction chamber; and providing the reactants in the reaction chamber.

23. 23. The method of any of claims 1 to 22, wherein the method comprises the step of supplying a purge gas and / or evacuating the reaction chamber after supplying precursors and / or reactants into the reaction chamber.

24. 24. The method of claim 23, wherein the pressure in the reaction chamber is between about 0.001 Torr and 50 Torr.

25. A method for forming a structure, wherein silicon oxide is deposited according to a method according to any of claims 1 to 24.

26. A method for forming a semiconductor device, said method comprising depositing silicon oxide according to the method of any of claims 1 to 25.

27. 1. A deposition assembly for depositing silicon oxide on a substrate, comprising: a reaction chamber constructed and arranged to hold the substrate; a precursor injector system constructed and arranged to supply a precursor and a reactant comprising hydrogen atoms into the reaction chamber; a heater constructed and arranged to control a temperature within the reaction chamber between 65°C and less than 500°C; The assembly comprises: a precursor vessel constructed and arranged to contain and vaporize a silicon precursor comprising a silicon atom bonded to at least one oxygen atom, the at least one oxygen atom being bonded to a carbon atom, the assembly constructed and arranged to deliver the precursor to the reaction chamber via the precursor injector system and to deposit the silicon oxide on the substrate; the substrate includes a surface, the surface includes a first portion including a first material and a second portion including a second material, the second material including an organic material; The silicon oxide is selectively deposited on the first portion relative to the second portion.

28. 28. The deposition assembly of claim 27, wherein the vessel comprises a vaporizer constructed and arranged to vaporize the silicon precursor.

29. 30. The deposition assembly of claim 28, wherein the vaporizer is constructed and arranged to vaporize the silicon precursor at a temperature between 65°C and 250°C.

30. 30. The deposition assembly of any of claims 27 to 29, wherein the deposition assembly comprises a pump constructed and arranged to evacuate the pressure in the reaction chamber to less than 50 Torr.

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