Patent Grant
12157945
A PCT Request Form is filed concurrently with this specification as part of the present application. Each application that the present application claims benefit of or priority to as identified in the concurrently filed PCT Request Form is incorporated by reference herein in its entirety and for all purposes.
Semiconductor device fabrication includes fabrication of microprocessors, logic, and memory devices. Semiconductor device fabrication may involve deposition of oxide and/or nitride films. As device and features size continue to shrink in the semiconductor industry, and also as 3-D device structures become more prevalent in integrated circuit (IC) design, the capability of depositing conformal films will continue to gain importance. Semiconductor device fabrication may involve deposition of nitride films. Atomic layer deposition (ALD) is a film forming technique which is well-suited to the deposition of conformal films. ALD processes may include thermal ALD and plasma-enhanced ALD.
The background provided herein is for the purposes of generally presenting the context of the disclosure. Work of the presently named inventors, to the extent that it is described in this background, as well as aspects of the description that may not otherwise qualify as prior art at the time of filing, are neither expressly nor impliedly admitted as prior art against the present disclosure.
One aspect of the disclosure relates to a method of depositing a silicon oxide film. The method includes providing a substrate in a plasma processing chamber, depositing a first silicon oxide layer on a substrate via thermal atomic layer deposition (thermal ALD) in the plasma processing chamber, and depositing a second silicon oxide layer on the substrate via plasma-enhanced atomic layer deposition (PEALD) in the plasma processing chamber.
In some implementations, depositing the first silicon oxide layer by thermal ALD comprises heating the substrate to an elevated temperature, exposing the substrate to a silicon-containing precursor to adsorb onto a surface of the substrate, and posing the substrate to an oxygen-containing reactant while the substrate is heated to the elevated temperature to drive a reaction between the oxygen-containing reactant and the silicon-containing precursor to form the first silicon oxide layer. In some implementations, the elevated temperature is between about 500° C. and about 750° C. In some implementations, the oxygen-containing reactant includes oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), water (H2O), or combinations thereof. In some implementations, the silicon-containing precursor includes an aminosilane. In some implementations, a chamber pressure in the plasma processing chamber is equal to or greater than about 7 Torr. In some implementations, depositing the first silicon oxide layer by thermal ALD comprises heating the substrate to an elevated temperature, exposing the substrate to a silicon-containing precursor to adsorb onto a surface of the substrate, and flowing hydrogen (H2) and oxygen (O2) towards the substrate in the plasma processing chamber while the substrate is heated at the elevated temperature, where the hydrogen and oxygen react within the plasma processing chamber, where the first silicon oxide layer is formed on the substrate. In some implementations, depositing the second silicon oxide layer by PEALD comprises exposing the substrate to a second silicon-containing precursor to adsorb onto a surface of the substrate, and exposing the substrate to plasma generated from a second oxygen-containing reactant, where the plasma drives a reaction between reactive species of the second oxygen-containing reactant and the second silicon-containing precursor to form the second silicon oxide layer.
Another aspect of the disclosure relates to a method of depositing silicon oxide film. The method includes heating a substrate to an elevated temperature, exposing the substrate to a silicon-containing precursor to adsorb onto a surface of the substrate in a plasma processing chamber, and flowing hydrogen (H2) and an oxygen-containing reactant towards the substrate in the plasma processing chamber, where the hydrogen and the oxygen-containing reactant react within the plasma processing chamber, where a layer of a silicon oxide film is formed on the substrate.
In some implementations, the hydrogen and the oxygen-containing reactant react in situ with one another within the plasma processing chamber in an exothermic reaction and drive formation of the layer of the silicon oxide film. In some implementations, the elevated temperature is between about 500° C. and about 650° C. In some implementations, a chamber pressure of the plasma processing chamber is equal to or greater than about 7 Torr. In some implementations, the oxygen-containing reactant includes oxygen (O2) or ozone (O3). In some implementations, the method further includes applying plasma power to the plasma processing chamber to ignite plasma generated from the hydrogen and oxygen-containing reactant in the plasma processing chamber. In some implementations, flowing the hydrogen and the oxygen-containing reactant comprises flowing the oxygen-containing reactant continuously into the plasma processing chamber, and pulsing the hydrogen at regular intervals into the plasma processing chamber. In some implementations, (i) exposing the substrate to the silicon-containing precursor and (ii) flowing the hydrogen and oxygen-containing reactant are performed cyclically in a thermal atomic layer deposition (thermal ALD) process. In some implementations, (i) exposing the substrate to the silicon-containing precursor and (ii) flowing the hydrogen and oxygen-containing reactant are performed continuously in a thermal chemical vapor deposition (thermal CVD) process. In some implementations, the method further includes depositing one or more additional layers the silicon oxide film on the substrate via PEALD in the plasma processing chamber.
Another aspect of the disclosure relates to a plasma apparatus for depositing a silicon oxide film. The plasma apparatus includes a plasma processing chamber, a substrate support in the plasma processing chamber for supporting a substrate, where the substrate support is configured to be heated to an elevated temperature, a showerhead fluidly coupled to the plasma processing chamber for delivery of precursors and reactants into the plasma processing chamber, an RF power supply configured to power plasma in the plasma processing chamber, and a controller. The controller is configured with instructions for performing the following operations: heat the substrate to an elevated temperature, expose the substrate to a silicon-containing precursor to adsorb onto a surface of the substrate in the plasma processing chamber, and flow hydrogen (H2) and an oxygen-containing reactant towards the substrate in the plasma processing chamber, where the hydrogen and oxygen-containing reactant react within the plasma processing chamber, where a layer of a silicon oxide film is formed on the substrate.
In some implementations, the controller is further configured with instructions for performing the following operation: apply plasma power to the plasma processing chamber to ignite plasma generated from the hydrogen and oxygen-containing reactant in the plasma processing chamber. In some implementations, the controller is further configured with instructions for performing the following operations: deposit one or more additional layers of the silicon oxide film on the substrate via PEALD in the plasma processing chamber.
These and other aspects are described below with reference to the drawings.
In the present disclosure, the terms “semiconductor wafer,” “wafer,” “substrate,” “wafer substrate,” and “partially fabricated integrated circuit” are used interchangeably. One of ordinary skill in the art would understand that the term “partially fabricated integrated circuit” can refer to a silicon wafer during any of many stages of integrated circuit fabrication. A wafer or substrate used in the semiconductor device industry typically has a diameter of 200 mm, or 300 mm, or 450 mm. The following detailed description assumes the present disclosure is implemented on a wafer. However, the present disclosure is not so limited. The work piece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other work pieces that may take advantage of the present disclosure include various articles such as printed circuit boards and the like.
Introduction
Silicon-containing films have various physical, chemical, and mechanical properties and are often used in semiconductor fabrication processes. For example, silicon nitride, silicon oxide, or silicon oxynitride films may be used as diffusion barriers, gate insulators, sidewall spacers, etch stop layers, dielectric films, and encapsulation layers. For example, silicon oxide films may be used as a low-k dielectric film in a semiconductor device. In various applications, silicon-containing films are deposited by chemical vapor deposition (CVD) or atomic layer deposition (ALD). In various implementations, the silicon-containing films are deposited conformally onto features of a substrate.
ALD is a technique that deposits thin layers of material using sequential self-limiting reactions. Typically, an ALD cycle includes operations to deliver and adsorb at least one precursor to the substrate surface, and then react the adsorbed precursor with one or more reactants to form the partial layer of film. Purge steps are ordinarily carried out between delivery of the precursor and delivery of the one or more reactants.
Thermal ALD uses heat to cause a reaction between the adsorbed precursor and the one or more reactants. While thermal ALD may work well to deposit certain types of materials, thermal ALD often has a slow deposition rate due to long reaction completion times. Thermal ALD is often performed at very high temperatures, but many chemical precursors or reactants may decompose (e.g., pyrolysis) at such elevated temperatures.
PEALD uses plasma to promote reaction between the adsorbed precursor and reactant radicals within the plasma. Reactant plasma is pulsed into a deposition chamber to react with the adsorbed precursor and form deposited material. PEALD may have a higher deposition rate and may operate at lower temperatures than thermal ALD. While PEALD processes may overcome some of the shortcomings of thermal ALD, PEALD processes may have some limitations. For example, PEALD may cause plasma damage to a substrate (e.g., etching, oxidations), and such plasma damage may occur on sensitive substrate materials such as silicon, germanium, silicon-germanium, carbon, and metals like molybdenum, tungsten, copper, cobalt, ruthenium, rhodium, and iridium. Additionally, PEALD may be incompatible with certain chemical precursors.
Conventional methods for depositing films by thermal ALD are accomplished using furnace reactors or batch reactors. Some furnace reactors can be hot wall systems, which have the advantage of more uniform temperature distributions and reduced convection effects.
The thermal ALD furnace reactor 100 can include a plurality of wafers 106 stacked over one another. Each of the wafers 106 may be supported by a wafer support 104 and held by gravity. The wafer-to-wafer spacing along the vertical direction of the thermal ALD furnace reactor 100 can be uniform. This allows for tens or hundreds of wafers 106 to be batch processed in a single run through the thermal ALD furnace reactor 100. The thermal ALD furnace reactor 100 is shown holding wafers 106 in a vertically-separated manner, though it will be understood that the thermal ALD furnace reactor 100 can hold wafers 106 in a horizontally-separated manner.
Reactant gases 130 enter the thermal ALD furnace reactor 100 by flowing through a gas inlet 122. The reactant gases 130 can include precursors for adsorption followed by reactant species to react with the adsorbed precursors. The timing and rate of flow of the reactant gases 130 can be controlled by, e.g., valves and mass flow controllers, as known in the art. The reactant gases 130 circulate through the thermal ALD furnace reactor 100 by convection and flow towards the wafers 106 by diffusion. To deposit thin films on each of the wafers 106, the thermal ALD furnace reactor 100 can be reduced to a low pressure and heated to a desirable deposition temperature, such as a temperature greater than about 700° C., or between about 700° C. and about 850° C., or between about 700° C. and about 800° C. The high temperature drives a chemical reaction between the reactant gases 130 to form thin films on each of the wafers 106, where the reactant gases 130 may be delivered sequentially in pulses. The reactant gases 130 are delivered through the gas inlet 122 and diffuse towards each of the wafers 106. Excess reactant gases 130 may exit the thermal ALD furnace reactor 100 via gas outlet 124. The deposition temperature must remain high to achieve a sufficient deposition rate for sufficient throughput.
Various oxides and nitrides, such as silicon oxide, silicon nitride, aluminum nitride, aluminum oxide, and titanium oxide, may be deposited using a thermal ALD reactor like the thermal ALD furnace reactor 100 of
The plasma reactor 200 includes a power source 240 coupled to the plasma processing chamber 210 and configured to generate plasma 250 in the plasma processing chamber 210. For example, the power source 240 may be coupled to either the showerhead 254 or the substrate support 230. An RF voltage may be applied to an electrode of the showerhead 254, where the plasma 250 may be generated between two electrodes spaced apart. The plasma 250 may be generated at relatively low pressure. The use of the plasma 250 reduces the temperature for growth/formation of films on the substrate 232 due to the high reactivity of radicals in the plasma 250.
Various oxides and nitrides, such as silicon oxide, silicon nitride, aluminum nitride, aluminum oxide, and titanium oxide, may be deposited using a plasma reactor like the plasma reactor 200 of
Thermal ALD in Plasma Processing Chamber
The present disclosure relates to deposition of oxide and/or nitride films on a substrate using thermal ALD in a single wafer plasma reactor. The oxide and/or nitride films may be silicon-containing films, where the silicon-containing films may be silicon oxide (SiOx), silicon nitride (SixNy), or silicon oxynitride (SiOxNy). While such silicon-containing films may ordinarily be deposited by PEALD processes, such silicon-containing films may be deposited by thermal ALD within the same plasma reactor used for PEALD processes. In some implementations, the thermal ALD performed within the same plasma reactor as the PEALD processes may drive thermal oxidation/nitridation at an elevated temperature that is less than the high temperatures used in conventional thermal ALD furnace reactors. For example, the elevated temperature may be between about 500° C. and about 750° C. or between about 500° C. and about 650° C. Thermal ALD performed within the same plasma reactor as PEALD processes may enable deposition of silicon-containing films with high conformality, high deposition rate, limited surface oxidation, limited bending of substrate features (e.g., pillars, fins), and uniform wet etch rate along the depth of the structure, among other advantages. In other words, highly conformal films may be deposited by thermal ALD in a plasma processing chamber with little to no damage/oxidation to the substrate.
In some implementations of the present disclosure, thermal ALD of silicon-containing films in a plasma processing chamber may be achieved using a silicon-containing precursor and multiple gas reactants that react with one another in situ. For example, thermal ALD of a silicon oxide film in a plasma processing chamber may be achieved using a silicon-containing precursor and hydrogen (H2) and oxygen (O2) that react in situ over a substrate to cause an exothermic reaction. The exothermic reaction may provide energy to drive oxide formation for improved deposition rate. In some implementations of the present disclosure, low RF power may be applied to the plasma processing chamber to ignite plasma while flowing hydrogen and oxygen during thermal ALD. In some implementations of the present disclosure, silicon-containing films may be deposited in a plasma processing chamber using thermal CVD instead of thermal ALD. In some implementations of the present disclosure, silicon-containing films may be deposited in a plasma processing chamber using thermal ALD followed by PEALD. In some implementations of the present disclosure, silicon-containing films may be deposited in a plasma processing chamber using PEALD followed by thermal ALD.
Deposition of silicon-containing films by thermal ALD in a plasma processing chamber reduces damage that may otherwise be caused by deposition of silicon-containing films by PEALD. This can be due in part to the low presence of radicals and ionic species in thermal ALD. Moreover, thermal ALD in the plasma processing chamber of the present disclosure reduces damage on substrates that may otherwise be caused by deposition of silicon-containing films using conventional thermal ALD reactors operating at high thermal budgets. The silicon-containing films deposited by thermal ALD in the plasma processing chamber of the present disclosure may be deposited at a comparable deposition rate as PEALD and may provide as high quality film as films deposited by PEALD.
Though the present disclosure is largely described with reference to thermal ALD in the present disclosure, it will be understood that “thermal ALD” in the present disclosure can refer to reaction mechanisms for thermal ALD reactions occurring cyclically and reaction mechanisms for thermal CVD reactions occurring continuously. In addition, it will be understood that though the present disclosure is largely described with reference to deposition of silicon oxide films, the present disclosure can encompass deposition of any oxide or nitride films using thermal ALD.
At block 310 of the process 300a, a substrate is provided in a plasma processing chamber. The plasma processing chamber may be a single wafer plasma reactor configured to perform thermal ALD processes, PEALD processes, or combinations thereof. The substrate may be a silicon substrate, such as a 200-mm, 300-mm, or 450-mm substrate, including substrates having one or more layers of material, such as dielectric, conducting, or semiconducting material. In some implementations, the substrate on which silicon oxide films are deposited may include a material that is sensitive to plasma damage/oxidation by PEALD. For example, the material may include but is not limited to silicon (Si), germanium (Ge), silicon-germanium (Si—Ge), carbon (C), and metals, where example metals include molybdenum (Mo), tungsten (W), copper (Cu), cobalt (Co), ruthenium (Ru), rhodium (Rh), and iridium (Ir). The substrate on which the silicon oxide films are deposited may include one or more features, which may refer to non-planar structures of a substrate. For example, the one or more features may include vertical structures such as fins or pillars. In some implementations, the one or more features may include an under-layer such as a barrier layer, liner layer, or adhesion layer.
At block 320 of the process 300a, a first silicon oxide layer is deposited via thermal ALD in the plasma processing chamber. Any suitable number of thermal ALD cycles may be performed at block 320 prior to performing PEALD. Each thermal ALD cycle may be broken down into a series of phases, including a dose phase, a first purge phase, a thermal oxidation phase, and a second purge phase. It will be understood that one or both of the first purge phase and the second purge phase may be optionally performed in each thermal ALD cycle. Depositing a thin film via thermal ALD includes: heating the substrate to an elevated temperature, exposing the substrate to a precursor to adsorb onto a surface of the substrate, and exposing the substrate to one or more gas reactants to drive a surface reaction between the one or more gas reactants and the precursor, thereby forming the thin film via thermal ALD. Specifically, depositing the first silicon oxide layer via thermal ALD includes: heating the substrate to an elevated temperature, exposing the substrate to a silicon-containing precursor to adsorb onto a surface of the substrate, and exposing the substrate to an oxygen-containing reactant to drive a reaction between the oxygen-containing reactant and the silicon-containing precursor, thereby forming the first silicon oxide layer via thermal ALD.
In some implementations, the plasma processing chamber may be purged between operations of exposing the substrate to the silicon-containing precursor and exposing the substrate to the oxygen-containing reactant. In addition, the plasma processing chamber may be purged after exposing the substrate to the oxygen-containing reactant. Purging may involve a sweep gas, which may be a carrier gas used in other operations/phases or a different gas. Purging may remove excess species in the vapor phase that did not adsorb or react on the surface of the substrate. As shown in
As shown in
In some implementations, the oxygen-containing reactant can include an oxidant gas such as oxygen (O2), ozone (O3), hydrogen peroxide (H2O2), water (H2O), or combinations thereof. In some implementations, exposing the substrate to the oxygen-containing reactant includes flowing hydrogen and oxygen to the substrate to react in situ within the plasma processing chamber to cause an exothermic reaction. In some implementations, it is believed that water may be formed in situ by a reaction between the hydrogen and oxygen. Water vapor is not flowed into the plasma processing chamber as a starting reactant, but may or may not be formed in situ within the plasma processing chamber. As used herein, flowing “hydrogen” refers to flowing molecular hydrogen and flowing “oxygen” refers to flowing molecular oxygen. The hydrogen and oxygen may be flowed towards the substrate in the plasma processing chamber simultaneously. The exothermic reaction involving hydrogen and oxygen may release energy for driving a surface reaction with the adsorbed silicon-containing precursor to form the first silicon oxide layer. A flow rate of hydrogen during the thermal oxidation phase 461A may be between about 0 slm and about 20 slm, between about 1 slm and about 10 slm, between about 2 slm and about 6 slm, greater than about 3 slm, such as about 4 slm. A flow rate of oxygen during the thermal oxidation phase 461A may be between about 0.5 slm and about 20 slm, between about 1 slm and about 10 slm, or between about 2 slm and about 8 slm, such as about 5 slm. A flow rate ratio between hydrogen and oxygen may be equal to or less than about 1.2:1, such as between about 0.5:1 and about 1.2:1.
The substrate may be exposed to the oxygen-containing reactant and exposed to an elevated temperature for a suitable duration during the thermal oxidation phase 461A. Ordinarily, thermal oxidation in furnace or batch reactors in thermal ALD/CVD chambers may last at least 10 seconds to obtain an appreciable deposition rate, particularly for silicon oxide films. However, the duration of thermal oxidation in the plasma processing chamber of the present disclosure may be less than about 10 seconds. In some implementations, the duration of thermal oxidation in the thermal oxidation phase 361A may be between about 0.1 seconds and about 6 seconds, between about 0.2 seconds and about 4 seconds, or between about 0.5 seconds and about 3 seconds.
The substrate may be exposed to an elevated temperature during the thermal oxidation phase 461A and/or prior to the thermal oxidation phase 461A. The substrate may be operating at the elevated temperature simultaneously with exposing the substrate to the oxygen-containing reactant. In some implementations, the elevated temperature may be between about 500° C. and about 750° C., between about 500° C. and about 700° C., between about 500° C. and about 650° C., or between about 550° C. and about 650° C. Ordinarily, temperatures in furnace or batch reactors in thermal ALD/CVD chambers may be greater than 700° C. in driving surface reactions for deposition of silicon oxide films. However, temperatures may be equal to or less than about 700° C. in driving surface reactions for deposition of silicon oxide films by thermal ALD in a plasma processing chamber of the present disclosure. Furthermore, many conventional plasma processing chambers for PEALD do not operate at temperatures equal to or greater than about 400° C. Deposition by thermal ALD in the plasma processing chamber at the elevated temperature may be equal to or greater than about 0.2 Å/cycle.
The substrate may be exposed to increased chamber pressure during the thermal oxidation phase 461A. Increased chamber pressure may increase deposition rate and drive the surface reaction between the silicon-containing precursor and the oxygen-containing reactant. In some implementations, the chamber pressure of the plasma processing chamber may be equal to or greater than about 7 Torr, equal to or greater than about 10 Torr, equal to or greater than about 12 Torr, or between about 10 Torr and about 20 Torr. Ordinarily, a pressure in a furnace or batch reactor in thermal ALD/CVD chambers may be less than about 5 Torr. However, chamber pressure may be equal to or greater than about 5 Torr for deposition by thermal ALD in the plasma processing chamber of the present disclosure. In addition, some conventional plasma processing chambers for PEALD do not typically operate at pressures equal to or greater than 5 Torr.
The process conditions to achieve an appreciable deposition rate may be different during the thermal oxidation phase 461A depending on the selected gas reactants. In some implementations, where the gas reactant consists of oxygen, a deposition rate greater than about 0.2 Å/cycle may be achieved at temperatures between about 550° C. and about 700° C. and chamber pressures equal to or greater than about 12 Torr. Such implementations may be referred to as an oxygen-only flow. In some implementations, where the gas reactants consist of hydrogen and oxygen, a deposition rate equal to or greater than about 0.7 Å/cycle may be achieved at temperatures between about 500° C. and about 700° C. and chamber pressures equal to or greater than about 7 Torr. Such implementations may be referred to as a co-flow of hydrogen and oxygen (H2/O2). The co-flow of hydrogen and oxygen may enable higher deposition rates even at lower temperatures and pressures in the plasma processing chamber. Specifically, thermal oxidation may occur at a faster rate using the co-flow of hydrogen and oxygen compared to an oxygen-only flow.
A plurality of thermal ALD cycles 410A may be performed to form the first silicon oxide layer on the substrate. In some implementations, the first silicon oxide layer deposited by thermal ALD may serve as a liner layer prior to deposition by PEALD. The liner layer may protect underlying layers from substrate damage and/or provide a high quality liner in high aspect ratio structures. In some implementations, the first silicon oxide layer may be relatively thin and be between about 1 Å and about 100 Å, such as between about 10 Å and about 100 Å. For such thicknesses involving an oxygen-only flow, the number of thermal ALD cycles may be between about between about 5 cycles and about 50 cycles, between about 5 cycles and about 20 cycles, or between about 5 cycles and about 10 cycles.
The first silicon oxide layer deposited by the plurality of thermal ALD cycles 410A may cause little to no damage to the substrate and little to no oxidation to the substrate. For example, an amount of silicon substrate oxidation may be between about 1 Å and about 3 Å when using oxygen-only flow of thermal ALD process, whereas a typical PEALD process results in silicon substrate oxidation between about 15 Å and about 35 Å. Where the first silicon oxide layer is deposited on vertical structures of the substrate, little to no bending occur on the vertical structures. The wet etch rate of the first silicon oxide layer along the depth of the vertical structures is uniform. Furthermore, where the substrate includes one or more features, a step coverage of the first silicon oxide layer is highly conformal. For example, the step coverage of the first silicon oxide layer may be equal to or greater than about 85%, equal to or greater than about 90%, or equal to or greater than about 95%.
At block 330 of the process 300, a second silicon oxide layer is deposited on the substrate via PEALD in the plasma processing chamber. The thermal ALD operation at block 320 and the PEALD operation at block 330 are performed in the same plasma processing chamber. Any suitable number of PEALD cycles may be performed at block 330 after performing thermal ALD. Each PEALD cycle may be broken down into a series of phases, including a dose phase, a first purge phase, a plasma exposure phase, and a second purge phase. It will be understood that one or both of the first purge phase and the second purge phase may be optionally performed in each PEALD cycle. Depositing a thin film via PEALD includes: exposing the substrate to a precursor to adsorb onto a surface of the substrate, and exposing the substrate to plasma generated from one or more gas reactants, where the plasma drives a reaction between reactive species of the one or more gas reactants and the precursor, thereby forming the thin film via PEALD. Specifically, depositing the second silicon oxide layer by PEALD includes: exposing the substrate to a silicon-containing precursor to adsorb onto the surface of the substrate, and exposing the substrate to plasma generated from an oxygen-containing reactant, where the plasma drives a reaction between reactive species of the oxygen-containing reactant and the silicon-containing precursor, thereby forming the second silicon oxide layer via PEALD. The silicon-containing precursor in the PEALD cycles may or may not be the same as the silicon-containing precursor in the thermal ALD cycles. In addition, the oxygen-containing reactant in the PEALD cycles may or may not be the same as the oxygen-containing reactant in the thermal ALD cycles. For example, the oxygen-containing reactant may include oxygen, ozone, or combinations thereof.
As shown in
In some implementations, the plasma processing chamber may be purged between operations of exposing the substrate to the silicon-containing precursor and exposing the substrate to an oxygen-containing reactant. In addition, the plasma processing chamber may be purged after exposing the substrate to the oxygen-containing reactant. Purging may involve a sweep gas, which may be a carrier gas used in other operations/phases or a different gas. Purging may remove excess species in the vapor phase that did not adsorb or react onto the surface of the substrate. As shown in
As shown in
Process conditions in the plasma processing chamber may vary for the oxygen plasma during the plasma exposure phase 461B. In some implementations, the substrate temperature may be maintained between about 0° C. and about 750° C. or between about 20° and about 200° C. In some implementations, the chamber pressure in the plasma processing chamber may be relatively low and between about 10 mTorr and about 200 mTorr, or may be relatively high and between about 1 Torr and about 7 Torr. An RF field is applied to the plasma processing chamber to generate ions and radicals of the oxygen-containing reactant. In various implementations, the RF frequency used to generate the plasma may be at least about 13.56 MHz, at least about 27 MHz, at least about 40 MHz, or at least about 60 MHz, though other frequencies may also be used. In some implementations, the RF power may be a few hundred Watts, for example about 500 W or less, about 400 W or less, or about 300 W or less, though it will be understood that other RF powers may be applied depending on substrate area. In some implementations, the duration of the plasma exposure phase 461B may be between about 0.1 seconds and about 120 seconds or between about 1 second and about 60 seconds.
A plurality of PEALD cycles 410B may be performed to form the second silicon oxide layer on the first silicon oxide layer. The first silicon oxide layer deposited by thermal ALD cycles 410A may provide a liner layer of silicon oxide film to protect underlying layers. In some implementations, the liner layer may be relatively thin and between about 10 Å and about 100 Å thick. In some implementations, the liner layer may serve as a protective liner on soft layers to eliminate or otherwise reduce substrate damage. In some implementations, the liner layer may serve as a high quality liner on high aspect ratio structures. Such high aspect ratio structures may include fins and pillars. The high aspect ratio structures may be prone to bending/damage when exposed to only PEALD operations. However, having the first silicon oxide layer deposited by thermal ALD prior to the second silicon oxide layer provides high conformality, high deposition rate, limited surface oxidation, limited bending of substrate features (e.g., pillars, fins), and uniform wet etch rate on sidewalls. The second silicon oxide layer deposited by PEALD cycles 410B may follow as bulk deposition of silicon oxide film on the liner layer. Accordingly, in various implementations, nucleation of silicon oxide film may be performed by thermal ALD and bulk deposition may be performed by PEALD in the same plasma processing chamber.
In some implementations, the process 300a further includes exposing the substrate to plasma generated from a nitrogen-containing reactant in the plasma processing chamber, where the plasma drives a reaction between reactive species of the nitrogen-containing reactant and at least the second silicon oxide layer, thereby converting at least the second silicon oxide layer to a silicon oxynitride layer. In some implementations, the nitrogen-containing reactant may include nitrogen (N2), ammonia (NH3), or combinations thereof. A nitrogen plasma may cause nitridation of one or both of the first and second silicon oxide layer to form the silicon oxynitride layer.
In addition or in the alternative to the aforementioned nitridation of silicon oxide, the process 300a may include depositing a silicon nitride layer on the first and second silicon oxide layer by thermal ALD or PEALD in the plasma processing chamber. Thus, the combination of the first silicon oxide layer, the second silicon oxide layer, and the silicon nitride layer collectively form a silicon oxynitride film. In various implementations, silicon oxide and silicon nitride layers may be deposited in alternating fashion to form nanolaminates of silicon oxide/silicon nitride. In some implementations, the process 300a further includes annealing the substrate to form the silicon oxynitride film from the first silicon oxide layer, the second silicon oxide layer, and the silicon nitride layer.
At block 350 of the process 300b, a substrate is heated to an elevated temperature. The substrate may be heated to the elevated temperature before and during thermal ALD. This allows the substrate to be heated to the elevated temperature to drive surface reactions between precursors and reactants in thermal ALD. In some implementations, the elevated temperature applied to the substrate may be between about 500° C. and about 750° C., between about 500° C. and about 700° C., between about 500° C. and about 650° C., or between about 550° C. and about 650° C. In some implementations, a pressure of a plasma processing chamber may be equal to or greater than about 7 Torr, equal to or greater than about 10 Torr, or equal to or greater than about 12 Torr. Chamber pressure may provide a further knob to control the deposition rate of the layer of silicon oxide film.
In some implementations, prior to heating the substrate to the elevated temperature, the substrate may be provided into the plasma processing chamber. The plasma processing chamber may be a single wafer plasma reactor configured to perform thermal ALD processes, PEALD processes, or combinations thereof. The substrate may be a silicon substrate, such as a 200-mm, 300-mm, or 450-mm substrate, including substrates having one or more layers of material, such as dielectric, conducting, or semiconducting material. In some implementations, the substrate on which silicon oxide films are deposited may include a material that is sensitive to plasma damage by PEALD. For example, the material may include but is not limited to silicon, germanium, silicon-germanium, carbon, and metals, where example metals may include molybdenum, tungsten, copper, cobalt, ruthenium, rhodium, and iridium. The substrate on which the silicon oxide films are deposited may include one or more features such as fins or pillars. In some implementations, the one or more features may include an under-layer such as a barrier layer, liner layer, or adhesion layer.
At block 360 of the process 300b, the substrate is exposed to a silicon-containing precursor to adsorb onto a surface of the substrate in the plasma processing chamber. In some implementations, the silicon-containing precursor includes a silane, such as an aminosilane. An aminosilane includes at least one nitrogen atom bonded to a silicon atom, but may also contain hydrogens, oxygens, halogens and carbons. Examples of aminosilanes may include BTBAS, N-SAM-24, 3DMAS, and 4DMAS. In some implementations, the substrate is exposed to the silicon-containing precursor while the substrate is heated to the elevated temperature.
In some implementations, the plasma processing chamber may be purged between operations of exposing the substrate to the silicon-containing precursor and flowing hydrogen and an oxygen-containing reactant into the plasma processing chamber. In addition, the plasma processing chamber may be purged after the flow of hydrogen and oxygen-containing reactant has ceased. Purging may involve a sweep gas, which may be a carrier gas used in other operations/phases or a different gas. Purging may remove excess species in the vapor phase that did not adsorb or react on the surface of the substrate. As shown in
Returning to
During the flow of hydrogen and the oxygen-containing reactant, the substrate is maintained at the elevated temperature. The substrate is at the elevated temperature while the hydrogen and oxygen-containing reactant are flowing towards the substrate to drive a reaction with the adsorbed silicon-containing precursor in the plasma processing chamber, thereby forming the layer of the silicon oxide film. The elevated temperature may promote formation of the layer of the silicon oxide film at an appreciable deposition rate. Without being limited by any theory, the in situ exothermic reaction between hydrogen and the oxygen-containing reactant along with the heated substrate at the elevated temperature may provide sufficient energy to drive the formation of the layer of the silicon oxide film at an appreciable deposition rate. In some implementations, the deposition rate of the layer of the silicon oxide film using co-flowed hydrogen and oxygen-containing reactant may be equal to or greater than about 0.7 Å/cycle.
As shown in
Example process times and process conditions are shown in Table 1 for co-flowed hydrogen and oxygen in thermal ALD.
In some implementations, the process 300b further includes applying plasma power to the plasma processing chamber to ignite plasma generated from the hydrogen and oxygen-containing reactant in the plasma processing chamber. In some implementations, the plasma may include ions, radicals, and other reactive species of hydrogen and oxygen (e.g., H* and O*). In some implementations, the plasma may further include ions, radicals, and other reactive species of the carrier gas (e.g., Art). The plasma power applied to the plasma processing chamber may be relatively small. In some implementations, the plasma power applied to the plasma processing chamber is equal to or less than about 300 W, equal to or less than about 200 W, or between about 10 W and about 200 W. That way, the plasma may include more radicals and fewer ions. In various implementations, the RF frequency used to generate the plasma may be at least about 13.56 MHz, at least about 27 MHz, at least about 40 MHz, or at least about 60 MHz, though other frequencies may also be used.
Without being limited by any theory, low RF power may ignite low RF plasma with energy from the exothermic reaction between the hydrogen and the oxygen-containing reactant. Without an in situ exothermic reaction between hydrogen and the oxygen-containing reactant, plasma may not be ignited at relatively low RF powers. In other words, a combustion reaction of hydrogen and the oxygen-containing reactant may contribute to generating low RF plasma in the plasma processing chamber. A stable plasma may be maintained at relatively low RF powers. The low RF plasma may limit damage to the substrate and particularly limit damage to any sensitive substrate. The low RF plasma may enhance or at least modulate deposition and properties of the layer of silicon oxide film. In some implementations, the low RF plasma may modulate deposition rate and provide higher wet etch rates. In some implementations, the low RF plasma may provide more conformal films, lower operating temperatures, and/or higher deposition rates.
In the thermal oxidation phase 661A/661B, plasma is turned on rather than off. The plasma power can be a low RF plasma power that is equal to or less than about 300 W, equal to or less than about 200 W, or between about 10 W and about 200 W. Application of the low RF plasma power occurs while hydrogen and oxygen-containing reactant are being flowed toward the substrate and while the substrate is heated at the elevated temperature. Reactive species in the plasma such as radicals of oxygen may react with the adsorbed silicon-containing precursor to form silicon oxide.
In some implementations at block 370 of the process 300b, flowing hydrogen and oxygen-containing reactant towards the substrate may include flowing the oxygen-containing reactant continuously into the plasma processing chamber and pulsing hydrogen at regular intervals into the plasma processing chamber. The hydrogen may be pulsed at regular intervals while the oxygen-containing reactant is simultaneously and continuously flowed towards the substrate. For example, a constant oxygen flow may be combined with pulsed hydrogen flow into the plasma processing chamber. In some implementations, pulses of hydrogen may be introduced into the plasma processing chamber at regular intervals that last between about 0.1 seconds and about 1 second, between about 0.1 seconds and about 0.8 seconds, or between about 0.2 seconds and about 0.6 seconds. Pulsing hydrogen may facilitate combustion reactions of hydrogen and oxygen-containing reactant that occur in pulses rather than continuously. Pulsing hydrogen may affect the deposition and properties of the layer of silicon oxide film. When pulsing hydrogen, the duration of the thermal oxidation phase may be longer. Without being limited by any theory, this permits pulsed exothermic reaction(s) to proceed for as long as desired to drive film properties.
In the thermal oxidation phase 761A/761B, hydrogen flow is pulsed rather than continuous. Oxygen-containing reactant flow is continuous and simultaneous with the pulsed hydrogen flow. Typically, pulses in the pulsed hydrogen flow can be in the form of a square waveform. The pulses in the pulsed hydrogen flow can occur in regular intervals, where each of the regular intervals can last between about 0.1 seconds and about 1 second, between about 0.1 seconds and about 0.8 seconds, or between about 0.2 seconds and about 0.6 seconds. In some implementations, a total duration of the thermal oxidation phase 761A/761B may be equal to or greater than 0.5 seconds, equal to or greater than 1 second, or between about 1 second and about 30 seconds. It will be understood that the total duration of the thermal oxidation phase 761A/761B may be longer to permit pulsed exothermic reactions to drive film properties. A duty cycle can refer to the percentage of on time (Ton) that flow is turned on during the total of on and off time, where T=Ton+Toff during the thermal oxidation phase 761A/761B. In some implementations, the duty cycle of the pulsed hydrogen flow can be between about 1% and about 99%, between about 5% and about 95%, between about 15% and about 90%, or between about 25% and about 75%.
In some implementations at block 370 of the process 300b, flowing hydrogen and oxygen-containing reactant towards the substrate may include generating oxygen radicals from the oxygen-containing reactant in a remote plasma source, introducing the radicals of oxygen into the plasma processing chamber, and flowing the hydrogen into the plasma processing chamber. Instead of pure oxygen gas, the radicals of oxygen may provide more reactive species to react with the hydrogen and the adsorbed silicon-containing precursor. Without being limited by any theory, the radicals of oxygen may react with hydrogen to form hydroxyl radicals or water, where the hydroxyl radicals or water may promote oxidation of the adsorbed silicon-containing precursor. In some implementations, the oxygen radicals are generated from oxygen gas or ozone. In some implementations, remote plasma source is located upstream of the plasma processing chamber, where the remote plasma source can be any suitable plasma generator such as an inductively-coupled plasma generator or capacitively-coupled plasma generator.
In the thermal oxidation phase 861A/861B, oxygen radicals are introduced into the plasma processing chamber instead of pure oxygen gas. Hydrogen flow may be continuous and simultaneous with the flow of oxygen radicals into the plasma processing chamber. However, it will be understood that in some implementations, hydrogen flow may be pulsed. In the thermal oxidation phase 861A/861B, remote plasma power is turned on rather than off. RF power may be applied to a remote plasma source to generate the oxygen radicals upstream from the plasma processing chamber.
In some implementations, at block 380 of the process 300b, the process 300b further includes performing PEALD in the plasma processing chamber. For example, the process 300b can include depositing one or more additional layers of the silicon oxide film on the substrate via PEALD in the plasma processing chamber. In addition or in the alternative, the process 300b can include depositing one or more layers of a silicon nitride film on the layer of the silicon oxide film by thermal ALD or PEALD in the plasma processing chamber to ultimately form a silicon oxynitride film. In some implementations, at block 380 of the process 300b, a PEALD cycle can include exposing the substrate to plasma of a nitrogen-containing reactant to convert the layer of the silicon oxide film to a silicon oxynitride film during a plasma exposure phase. The layer of silicon oxide film deposited by thermal ALD may serve as a liner layer protecting underlying layers of the substrate, and subsequent layers of silicon oxide and/or silicon nitride may be deposited in bulk over the liner layer. The layer of silicon oxide film deposited by thermal ALD may exhibit high conformality, high deposition rate, limited surface oxidation, limited bending of substrate features (e.g., pillars, fins), and uniform wet etch rate on sidewalls. In some implementations, however, performing PEALD in the plasma processing chamber may occur before thermal ALD in the plasma processing chamber. In other words, layers of silicon oxide film may be deposited by PEALD and followed by additional layers of silicon oxide film deposited by thermal ALD.
In the plasma oxidation/nitridation phase 961B, the substrate may be exposed to an oxygen plasma or nitrogen plasma. If plasma nitridation takes place, one or more nitrogen-containing reactants may be flowed towards the substrate and plasma turned on. For example, the one or more nitrogen-containing reactants may include N2/NH3. The plasma nitridation may deposit a layer of silicon nitride film over the layer of silicon oxide film. In some implementations, the plasma nitridation may convert silicon oxide to silicon oxynitride. If plasma oxidation takes place, one or more oxygen-containing reactants may be flowed towards the substrate and plasma turned on. For example, the one or more oxygen-containing reactants may include O2. The plasma oxidation may deposit an additional layer of silicon oxide film over the layer of silicon oxide film.
In some implementations, at blocks 360 and 370 of the process 300b, exposing the substrate to the silicon-containing precursor and flowing the hydrogen and oxygen-containing reactant may occur in a continuous manner rather than in a cyclic manner Specifically, exposing the substrate to the silicon-containing precursor and flowing the hydrogen and oxygen-containing reactant occurs in a thermal CVD process instead of a thermal ALD process. Briefly, thermal ALD reactions involve cyclically performing (a) delivery of precursor to form an adsorbed precursor layer, (b) optional purge operation, (c) delivery of reactant(s) on a heated substrate, (d) optional purge operation, and (e) repeating operations (a)-(d) until the film reaches a desired thickness. However, thermal CVD reactions involve delivering the precursor and reactant(s) continuously while the substrate is heated. CVD reactions are gas phase reactions, which deposition reaction products on the substrate surface. Hence, the reaction mechanism of the present disclosure may involve thermal CVD using silicon-containing precursor, hydrogen, and oxygen-containing reactant being delivered continuously rather than cyclically in thermal ALD.
It will be understood that any of the foregoing techniques described in
Apparatus
The methods described herein may be performed by any suitable apparatus or combination of apparatus. A suitable apparatus includes hardware for accomplishing the process operations and a system controller having instructions for controlling process operations in accordance with the present disclosure. For example, in some implementations, the hardware may include one or more process stations included in a process tool. In the present disclosure, the thermal ALD/CVD and PEALD/PECVD may be performed in a single station/chamber.
The apparatus or process station 1100a fluidly communicates with reactant delivery system 1101a for delivering process gases to a distribution showerhead 1106. Reactant delivery system 1101a includes a mixing vessel 1104 for blending and/or conditioning process gases, such as a silicon-containing precursor in the vapor phase, for delivery to showerhead 1106. In some implementations, the reactant delivery system 1101a includes a mixing vessel 1104 for blending and/or conditioning an oxygen-containing reactant (e.g., oxygen) for delivery to the showerhead 1106. In some implementations, the reactant delivery system 1101a includes a mixing vessel 1104 for blending and/or conditioning hydrogen and an oxygen-containing reactant (e.g., oxygen) for delivery to the showerhead 1106. One or more mixing vessel inlet valves 1120 may control introduction of process gases to mixing vessel 1104. Plasma of the oxygen-containing reactant may also be delivered to the showerhead 1106 or may be generated in the plasma apparatus or process station 1100a. The showerhead 1106 may be fluidly coupled to the plasma processing chamber 1102 for delivery of silicon-containing precursors and reactants into the plasma processing chamber 1102.
As an example, the implementation of
In some implementations, a liquid flow controller (LFC) upstream of vaporization point 1103 may be provided for controlling a mass flow of liquid for vaporization and delivery to the plasma apparatus or process station 1100a. For example, the LFC may include a thermal mass flow meter (MFM) located downstream of the LFC. A plunger valve of the LFC may then be adjusted responsive to feedback control signals provided by a proportional-integral-derivative (PID) controller in electrical communication with the MFM. However, it may take one second or more to stabilize liquid flow using feedback control. This may extend a time for dosing a liquid reactant. Thus, in some implementations, the LFC may be dynamically switched between a feedback control mode and a direct control mode. In some implementations, this may be performed by disabling a sense tube of the LFC and the PID controller.
The showerhead 1106 distributes process gases toward a substrate 1112. In the implementation shown in
In some implementations, the substrate support 1108 may be raised or lowered to expose the substrate 1112 to a volume between the substrate 1112 and the showerhead 1106. It will be appreciated that, in some implementations, substrate support height may be adjusted programmatically by a suitable system controller 1150.
In another scenario, adjusting a height of the substrate support 1108 may allow a plasma density to be varied during plasma activation cycles included in the process. At the conclusion of a processing phase, the substrate support 1108 may be lowered during another substrate transfer phase to allow removal of the substrate 1112 from the substrate support 1108.
In some implementations, the substrate support 1108 may be configured to be heated to an elevated temperature via a heater 1110. In some implementations, the substrate support 1108 may be heated to a temperature less than about 700° C., such as about between about 500° C. and about 750° C. or between about 500° C. and about 650° C., during deposition of silicon oxide films as described in the disclosed implementations. Further, in some implementations, pressure control for the apparatus or process station 700a may be provided by a butterfly valve 1118. As shown in the implementation of
In some implementations, the pressure in the plasma processing chamber 1102 may be controlled to be equal to or greater than about 7 Torr, equal to or greater than about 10 Torr, or equal to or greater than about 12 Torr during deposition of silicon oxide films as described in the disclosed implementations.
In some implementations, a position of the showerhead 1106 may be adjusted relative to the substrate support 1108 to vary a volume between the substrate 1112 and the showerhead 1106. Further, it will be appreciated that a vertical position of substrate support 1108 and/or showerhead 1106 may be varied by any suitable mechanism within the scope of the present disclosure. In some implementations, the substrate support 1108 may include a rotational axis for rotating an orientation of the substrate 1112. It will be appreciated that, in some implementations, one or more of these example adjustments may be performed programmatically by one or more suitable system controllers 1150.
In some implementations where plasma may be used as discussed above, showerhead 1106 and substrate support 1108 electrically communicate with a radio frequency (RF) power supply 1114 and matching network 1116 for powering a plasma in the plasma processing chamber 1102. In some implementations, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 1114 and matching network 1116 may be operated at any suitable power to form a plasma having a desired composition of radical species. In some implementations, the RF power supply 1114 and matching network 1116 may be operated to apply plasma power to the plasma processing chamber 1102 to ignite plasma generated from hydrogen and oxygen-containing reactant in the plasma processing chamber 1102. Example plasma powers applied by the RF power supply 1114 may be equal to or less than about 300 W, equal to or less than about 200 W, or between about 10 W and about 200 W. Likewise, RF power supply 1114 may provide RF power of any suitable frequency. In some implementations, RF power supply 1114 may be configured to control high- and low-frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 0 kHz and 500 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz, or at least about 13.56 MHz, or at least about 27 MHz, or at least about 40 MHz, or at least about 60 MHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions.
In some implementations, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and/or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some implementations, one or more plasma parameters may be programmatically adjusted based on measurements from such in situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some implementations, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.
In some implementations, instructions for a controller 1150 may be provided via input/output control (IOC) sequencing instructions. In one example, the instructions for setting conditions for a process phase may be included in a corresponding recipe phase of a process recipe. In some cases, process recipe phases may be sequentially arranged, so that all instructions for a process phase are executed concurrently with that process phase. In some implementations, instructions for setting one or more reactor parameters may be included in a recipe phase. For example, a first recipe phase may include instructions for setting a flow rate of an inert and/or a precursor gas (e.g., the silicon-containing precursor), instructions for setting a flow rate of a carrier gas (such as argon), and time delay instructions for the first recipe phase. A second, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and/or a precursor gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the second recipe phase. A third recipe phase may include instructions for modulating a flow rate of an oxygen-containing reactant gas such as oxygen, instructions for modulating a flow rate of hydrogen gas, instructions for modulating the flow rate of a carrier or purge gas, and time delay instructions for the third recipe phase. A fourth, subsequent recipe phase may include instructions for modulating or stopping a flow rate of an inert and/or a reactant gas, and instructions for modulating a flow rate of a carrier or purge gas and time delay instructions for the fourth recipe phase. The fourth recipe, in some implementations, may include instructions for igniting plasma of the oxygen-containing reactant. It will be appreciated that these recipe phases may be further subdivided and/or iterated in any suitable way within the scope of the disclosed implementations.
In certain implementations, the controller 1150 has instructions to perform the operations described in the present disclosure. For example, the controller 1150 may be configured with instructions to perform the following operations: expose a substrate 1112 to a silicon-containing precursor to adsorb onto a surface of the substrate 1112 in the plasma processing chamber 1102, flow hydrogen and oxygen-containing reactant towards the substrate 1112 in the plasma processing chamber 1102, and heat the substrate 1112 to an elevated temperature, where the hydrogen and oxygen-containing reactant react with one another in the plasma processing chamber 1102, where a layer of silicon oxide film is formed on the substrate 1112. In some implementations, the elevated temperature is between about 500° C. and about 650° C. and the oxygen-containing reactant is oxygen. In some implementations, the controller 1150 is further configured with instructions to perform the following operation: deposit one or more additional layers of the silicon oxide film on the substrate 1112 via PEALD in the plasma processing chamber 1102. In some implementations, the controller 1150 configured with instructions for flowing the hydrogen and oxygen-containing reactant is configured with instructions for performing the following operations: flow the oxygen-containing reactant continuously into the plasma processing chamber 1102, and pulse hydrogen at regular intervals into the plasma processing chamber 1102. In some implementations, the controller 1150 may include any of the features described below with respect to system controller 1250 of
The multi-station processing tool 1200 also includes one or more substrate source modules 1201 where substrates are stored before and after processing. An atmospheric robot 1204 in the atmospheric transfer chamber 1219 first removes substrates from the one or more substrate source modules 1201 to load locks 1221. While the implementation depicted includes load locks 1221, it will be appreciated that, in some implementations, direct entry of a substrate into a process station may be provided. A substrate transfer device 1205, such as a robot arm unit, in the transfer module 1203 moves the substrates from the load locks 1221 to and among the reactors 1207, 1208, and 1209. This can be done in a pressurized (e.g., vacuum) environment. The multi-station processing tool 1200 may perform one or more of the processes described in the present disclosure as well as other operations such as soaking/cleaning, plasma treatment, annealing, etc. Such processes may be performed in the multi-station processing tool 1200 without introducing a vacuum break.
In some implementations, a controller is part of a system, which may be part of the above-described examples. Such systems can comprise semiconductor processing equipment, including a processing tool or tools, chamber or chambers, a platform or platforms for processing, and/or specific processing components (a wafer pedestal, a gas flow system, etc.). These systems may be integrated with electronics for controlling their operation before, during, and after processing of a semiconductor wafer or substrate. The electronics may be referred to as the “controller,” which may control various components or subparts of the system or systems. The controller, depending on the processing requirements and/or the type of system, may be programmed to control any of the processes disclosed herein, including the delivery of processing gases, temperature settings (e.g., heating and/or cooling), pressure settings, vacuum settings, power settings, radio frequency (RF) generator settings, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, positional and operation settings, wafer transfers into and out of a tool and other transfer tools and/or load locks connected to or interfaced with a specific system.
Broadly speaking, the controller may be defined as electronics having various integrated circuits, logic, memory, and/or software that receive instructions, issue instructions, control operation, enable cleaning operations, enable endpoint measurements, and the like. The integrated circuits may include chips in the form of firmware that store program instructions, digital signal processors (DSPs), chips defined as application specific integrated circuits (ASICs), and/or one or more microprocessors, or microcontrollers that execute program instructions (e.g., software). Program instructions may be instructions communicated to the controller in the form of various individual settings (or program files), defining operational parameters for carrying out a particular process on or for a semiconductor wafer or to a system. The operational parameters may, in some implementations, be part of a recipe defined by process engineers to accomplish one or more processing operations during the fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and/or dies of a wafer.
The controller, in some implementations, may be a part of or coupled to a computer that is integrated with, coupled to the system, otherwise networked to the system, or a combination thereof. For example, the controller may be in the “cloud” or all or a part of a fab host computer system, which can allow for remote access of the wafer processing. The computer may enable remote access to the system to monitor current progress of fabrication operations, examine a history of past fabrication operations, examine trends or performance metrics from a plurality of fabrication operations, to change parameters of current processing, to set processing operations to follow a current processing, or to start a new process. In some examples, a remote computer (e.g. a server) can provide process recipes to a system over a network, which may include a local network or the Internet. The remote computer may include a user interface that enables entry or programming of parameters and/or settings, which are then communicated to the system from the remote computer. In some examples, the controller receives instructions in the form of data, which specify parameters for each of the processing operations to be performed during one or more operations. It should be understood that the parameters may be specific to the type of process to be performed and the type of tool that the controller is configured to interface with or control. Thus as described above, the controller may be distributed, such as by comprising one or more discrete controllers that are networked together and working towards a common purpose, such as the processes and controls described herein. An example of a distributed controller for such purposes would be one or more integrated circuits on a chamber in communication with one or more integrated circuits located remotely (such as at the platform level or as part of a remote computer) that combine to control a process on the chamber.
Without limitation, example systems may include a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a clean chamber or module, a bevel edge etch chamber or module, a physical vapor deposition (PVD) chamber or module, a chemical vapor deposition (CVD) chamber or module, an atomic layer deposition (ALD) chamber or module, an atomic layer etch (ALE) chamber or module, an ion implantation chamber or module, a track chamber or module, and any other semiconductor processing systems that may be associated or used in the fabrication and/or manufacturing of semiconductor wafers.
As noted above, depending on the process operation or operations to be performed by the tool, the controller might communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located throughout a factory, a main computer, another controller, or tools used in material transport that bring containers of wafers to and from tool locations and/or load ports in a semiconductor manufacturing factory.
Returning to the implementation of
In some implementations, system control software may include input/output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of a thermal ALD cycle or each phase of a PEALD cycle may include one or more instructions for execution by system controller 1250. The instructions for setting process conditions for an ALD process phase may be included in a corresponding ALD recipe phase. In some implementations, the ALD recipe phases may be sequentially arranged, so that all instructions for an ALD process phase are executed concurrently with that process phase.
Other computer software and/or programs stored on mass storage device and/or memory device associated with system controller 1250 may be employed in some implementations. Examples of programs or sections of programs for this purpose include a substrate positioning program, a process gas control program, a pressure control program, a heater control program, and a plasma control program.
A substrate positioning program may include program code for process tool components that are used to load the substrate onto pedestal and to control the spacing between the substrate and other parts of multi-station processing tool 1200.
A process gas control program may include code for controlling gas composition and flow rates and optionally for flowing gas into one or more process stations prior to deposition in order to stabilize the pressure in the process station. In some implementations, the controller includes instructions for depositing a first silicon oxide layer by thermal ALD in a plasma processing chamber, and depositing a second silicon oxide layer by PEALD in the same plasma processing chamber. In some implementations, the controller includes instructions for depositing a layer of silicon oxide by delivering silicon-containing precursor to a substrate in a dose phase and co-flowing hydrogen and oxygen towards the substrate in a thermal oxidation phase.
A pressure control program may include code for controlling the pressure in the process station by regulating, for example, a throttle valve in the exhaust system of the process station, a gas flow into the process station, etc. In some implementations, the controller includes instructions for providing a chamber pressure in the plasma processing chamber to be at least about 7 Torr prior to performing thermal ALD of silicon oxide layer.
A heater control program may include code for controlling the current to a heating unit that is used to heat the substrate. Alternatively, the heater control program may control delivery of a heat transfer gas (such as helium) to the substrate. In certain implementations, the controller includes instructions for heating the substrate to an elevated temperature during a thermal oxidation phase of a thermal ALD cycle, where the elevated temperature is between about 500° C. and about 650° C.
A plasma control program may include code for setting RF power levels and exposure times in one or more process stations in accordance with the implementations herein. In some implementations, the controller includes instructions for igniting plasma at an RF power level between about 10 W and about 200 W during a thermal oxidation phase of a thermal ALD cycle when hydrogen and oxygen are being co-flowed.
In some implementations, there may be a user interface associated with system controller 1250. The user interface may include a display screen, graphical software displays of the apparatus and/or process conditions, and user input devices such as pointing devices, keyboards, touch screens, microphones, etc.
In some implementations, parameters adjusted by system controller 1250 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF power levels and exposure times), etc. These parameters may be provided to the user in the form of a recipe, which may be entered utilizing the user interface.
Signals for monitoring the process may be provided by analog and/or digital input connections of system controller 1250 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of multi-station processing tool 1200. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, etc. Appropriately programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.
System controller 1250 may provide program instructions for implementing the above-described deposition processes. The program instructions may control a variety of process parameters, such as DC power level, RF bias power level, pressure, temperature, gas flow composition, flow rates, etc. The instructions may control the parameters to operate thermal ALD or thermal CVD of silicon oxide film according to various implementations described herein.
The system controller 1250 will typically include one or more memory devices and one or more processors configured to execute the instructions so that the apparatus will perform a method in accordance with the disclosed implementations. Machine-readable, non-transitory media containing instructions for controlling process operations in accordance with the disclosed implementations may be coupled to the system controller.
The various hardware and method implementations described above may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels and the like. Typically, though not necessarily, such tools/processes will be used or conducted together in a common fabrication facility.
In the foregoing description, numerous specific details are set forth to provide a thorough understanding of the presented embodiments. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail to not unnecessarily obscure the disclosed embodiments. While the disclosed embodiments are described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments.
Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, it will be apparent that certain changes and modifications may be practiced within the scope of the appended claims. It should be noted that there are many alternative ways of implementing the processes, systems, and apparatus of the present embodiments. Accordingly, the present embodiments are to be considered as illustrative and not restrictive, and the embodiments are not to be limited to the details given herein.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2020/043459 | 7/24/2020 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2021/025874 | 2/11/2021 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4158717 | Nelson | Jun 1979 | A |
| 4419809 | Riseman et al. | Dec 1983 | A |
| 4500563 | Ellenberger et al. | Feb 1985 | A |
| 4575921 | Bhagat | Mar 1986 | A |
| 4869781 | Euen et al. | Sep 1989 | A |
| 5091332 | Bohr et al. | Feb 1992 | A |
| 5202272 | Hsieh et al. | Apr 1993 | A |
| 5230929 | Caporiccio et al. | Jul 1993 | A |
| 5314724 | Tsukune et al. | May 1994 | A |
| 5459099 | Hsu | Oct 1995 | A |
| 5496608 | Matsuda et al. | Mar 1996 | A |
| 5528719 | Yamada | Jun 1996 | A |
| 5670432 | Tsai | Sep 1997 | A |
| 5731235 | Srinivasan et al. | Mar 1998 | A |
| 5854105 | Tseng | Dec 1998 | A |
| 5856003 | Chiu | Jan 1999 | A |
| 5891805 | Cheng et al. | Apr 1999 | A |
| 5976990 | Mercaldi et al. | Nov 1999 | A |
| 6039834 | Tanaka et al. | Mar 2000 | A |
| 6080676 | Nguyen et al. | Jun 2000 | A |
| 6153519 | Jain et al. | Nov 2000 | A |
| 6197701 | Shue et al. | Mar 2001 | B1 |
| 6225175 | Houston | May 2001 | B1 |
| 6228779 | Bloom et al. | May 2001 | B1 |
| 6326322 | Kim et al. | Dec 2001 | B1 |
| 6380056 | Shue et al. | Apr 2002 | B1 |
| 6395652 | Kim et al. | May 2002 | B2 |
| 6403416 | Huang et al. | Jun 2002 | B1 |
| 6416822 | Chiang et al. | Jul 2002 | B1 |
| 6428859 | Chiang et al. | Aug 2002 | B1 |
| 6448192 | Kaushik | Sep 2002 | B1 |
| 6518167 | You et al. | Feb 2003 | B1 |
| 6534395 | Werkhoven et al. | Mar 2003 | B2 |
| 6548368 | Narwankar et al. | Apr 2003 | B1 |
| 6632478 | Gaillard et al. | Oct 2003 | B2 |
| 6632741 | Clevenger et al. | Oct 2003 | B1 |
| 6638879 | Hsieh et al. | Oct 2003 | B2 |
| 6645574 | Lee et al. | Nov 2003 | B1 |
| 6709928 | Jenne et al. | Mar 2004 | B1 |
| 6730614 | Lim et al. | May 2004 | B1 |
| 6794284 | Vaartstra | Sep 2004 | B2 |
| 6926798 | Biberger et al. | Aug 2005 | B2 |
| 6933245 | Lee et al. | Aug 2005 | B2 |
| 6967159 | Vaartstra | Nov 2005 | B2 |
| 7019159 | Dussarrat et al. | Mar 2006 | B2 |
| 7041335 | Chung | May 2006 | B2 |
| 7169704 | Koo et al. | Jan 2007 | B2 |
| 7172792 | Wang et al. | Feb 2007 | B2 |
| 7211525 | Shanker et al. | May 2007 | B1 |
| 7297641 | Todd et al. | Nov 2007 | B2 |
| 7300885 | Hasebe et al. | Nov 2007 | B2 |
| 7301210 | Abadeer et al. | Nov 2007 | B2 |
| 7351668 | Chou et al. | Apr 2008 | B2 |
| 7462571 | Hasebe et al. | Dec 2008 | B2 |
| 7465669 | Iyer et al. | Dec 2008 | B2 |
| 7482247 | Papasouliotis et al. | Jan 2009 | B1 |
| 7507676 | Chou et al. | Mar 2009 | B2 |
| 7510984 | Saito et al. | Mar 2009 | B2 |
| 7514366 | Trivedi et al. | Apr 2009 | B2 |
| 7611980 | Wells et al. | Nov 2009 | B2 |
| 7622369 | Lee et al. | Nov 2009 | B1 |
| 7625820 | Papasouliotis et al. | Dec 2009 | B1 |
| 7629267 | Wan et al. | Dec 2009 | B2 |
| 7651730 | Hasebe | Jan 2010 | B2 |
| 7651953 | Todd et al. | Jan 2010 | B2 |
| 7651959 | Fukazawa et al. | Jan 2010 | B2 |
| 7682657 | Sherman | Mar 2010 | B2 |
| 7700492 | Kikuchi | Apr 2010 | B2 |
| 7713592 | Nguyen et al. | May 2010 | B2 |
| 7732343 | Niroomand et al. | Jun 2010 | B2 |
| 7758920 | Hasebe et al. | Jul 2010 | B2 |
| 7790633 | Tarafdar et al. | Sep 2010 | B1 |
| 7807578 | Bencher et al. | Oct 2010 | B2 |
| 7825039 | Takahashi et al. | Nov 2010 | B2 |
| 7910288 | Abatchev et al. | Mar 2011 | B2 |
| 7910497 | Olsen et al. | Mar 2011 | B2 |
| 7919416 | Lee et al. | Apr 2011 | B2 |
| 7939455 | Clark | May 2011 | B2 |
| 7964241 | Hasebe et al. | Jun 2011 | B2 |
| 7964513 | Todd et al. | Jun 2011 | B2 |
| 7989365 | Park et al. | Aug 2011 | B2 |
| 8034673 | Kadonaga et al. | Oct 2011 | B2 |
| 8080290 | Hasebe et al. | Dec 2011 | B2 |
| 8084088 | Huy et al. | Dec 2011 | B2 |
| 8105901 | Cheng et al. | Jan 2012 | B2 |
| 8119544 | Hasebe et al. | Feb 2012 | B2 |
| 8129555 | Cheng et al. | Mar 2012 | B2 |
| 8178448 | Nodera et al. | May 2012 | B2 |
| 8227032 | Dussarrat et al. | Jul 2012 | B2 |
| 8257789 | Matsunaga et al. | Sep 2012 | B2 |
| 8298628 | Yang et al. | Oct 2012 | B2 |
| 8298954 | Arnold et al. | Oct 2012 | B1 |
| 8366953 | Kohno et al. | Feb 2013 | B2 |
| 8383525 | Raisanen et al. | Feb 2013 | B2 |
| 8394466 | Hong et al. | Mar 2013 | B2 |
| 8580699 | Mallick | Nov 2013 | B2 |
| 8592328 | Hausmann et al. | Nov 2013 | B2 |
| 8623770 | Gao et al. | Jan 2014 | B1 |
| 8669185 | Onizawa et al. | Mar 2014 | B2 |
| 8703578 | Hoentschel et al. | Apr 2014 | B2 |
| 8728955 | Lavoie et al. | May 2014 | B2 |
| 8728956 | Lavoie et al. | May 2014 | B2 |
| 8753984 | Murakami et al. | Jun 2014 | B2 |
| 8791034 | Shealy et al. | Jul 2014 | B2 |
| 8802882 | Wang et al. | Aug 2014 | B2 |
| 8846484 | Lee et al. | Sep 2014 | B2 |
| 8936977 | Hoentschel et al. | Jan 2015 | B2 |
| 8975704 | Hoentschel et al. | Mar 2015 | B2 |
| 9023693 | Lin et al. | May 2015 | B1 |
| 9023737 | Beynet et al. | May 2015 | B2 |
| 9070555 | Hausmann et al. | Jun 2015 | B2 |
| 9095869 | Kilpi et al. | Aug 2015 | B2 |
| 9214333 | Sims et al. | Dec 2015 | B1 |
| 9355839 | Swaminathan et al. | May 2016 | B2 |
| 9379210 | Mountsier et al. | Jun 2016 | B2 |
| 9390909 | Pasquale et al. | Jul 2016 | B2 |
| 9406693 | Pang et al. | Aug 2016 | B1 |
| 9443731 | O'Meara et al. | Sep 2016 | B1 |
| 9472506 | Conklin et al. | Oct 2016 | B2 |
| 9502234 | Xiao et al. | Nov 2016 | B2 |
| 9502238 | Danek et al. | Nov 2016 | B2 |
| 9508604 | Sung et al. | Nov 2016 | B1 |
| 9530663 | Shih et al. | Dec 2016 | B1 |
| 9564312 | Henri et al. | Feb 2017 | B2 |
| 9576817 | Cheng et al. | Feb 2017 | B1 |
| 9589790 | Henri et al. | Mar 2017 | B2 |
| 9601693 | Henri et al. | Mar 2017 | B1 |
| 9611544 | Lavoie et al. | Apr 2017 | B2 |
| 9670579 | Hausmann et al. | Jun 2017 | B2 |
| 9721784 | Behera et al. | Aug 2017 | B2 |
| 9865815 | Hausmann | Jan 2018 | B2 |
| 9875891 | Henri et al. | Jan 2018 | B2 |
| 9892933 | Peng et al. | Feb 2018 | B2 |
| 9905415 | Chandra et al. | Feb 2018 | B2 |
| 10074543 | Mahorowala et al. | Sep 2018 | B2 |
| 10134579 | Baldasseroni et al. | Nov 2018 | B2 |
| 10141505 | Hausmann | Nov 2018 | B2 |
| 10269559 | Abel et al. | Apr 2019 | B2 |
| 10410872 | Cheng et al. | Sep 2019 | B2 |
| 10454029 | McKerrow et al. | Oct 2019 | B2 |
| 10559465 | Cheng et al. | Feb 2020 | B2 |
| 10629435 | Swaminathan et al. | Apr 2020 | B2 |
| 10658172 | Abel et al. | May 2020 | B2 |
| 10804099 | Henri et al. | Oct 2020 | B2 |
| 10832908 | LaVoie | Nov 2020 | B2 |
| 20010028922 | Sandhu | Oct 2001 | A1 |
| 20020001889 | Kim et al. | Jan 2002 | A1 |
| 20020001929 | Biberger et al. | Jan 2002 | A1 |
| 20020068466 | Lee et al. | Jun 2002 | A1 |
| 20030034244 | Yasar et al. | Feb 2003 | A1 |
| 20030092280 | Lee et al. | May 2003 | A1 |
| 20030116421 | Xu et al. | Jun 2003 | A1 |
| 20030143841 | Yang et al. | Jul 2003 | A1 |
| 20040043570 | Fujisaki et al. | Mar 2004 | A1 |
| 20040077184 | Anderson et al. | Apr 2004 | A1 |
| 20040096582 | Wang et al. | May 2004 | A1 |
| 20050025885 | McSwiney et al. | Feb 2005 | A1 |
| 20050042865 | Cabral, Jr. et al. | Feb 2005 | A1 |
| 20050100670 | Dussarrat et al. | May 2005 | A1 |
| 20050109276 | Iyer et al. | May 2005 | A1 |
| 20050118837 | Todd et al. | Jun 2005 | A1 |
| 20050123690 | Derderian et al. | Jun 2005 | A1 |
| 20050142878 | Jung | Jun 2005 | A1 |
| 20050158983 | Hoshi et al. | Jul 2005 | A1 |
| 20050159017 | Kim et al. | Jul 2005 | A1 |
| 20050170104 | Jung et al. | Aug 2005 | A1 |
| 20050196977 | Saito et al. | Sep 2005 | A1 |
| 20050227017 | Senzaki et al. | Oct 2005 | A1 |
| 20050287309 | Veerasamy | Dec 2005 | A1 |
| 20050287775 | Hasebe et al. | Dec 2005 | A1 |
| 20060003557 | Cabral et al. | Jan 2006 | A1 |
| 20060008656 | Veerasamy | Jan 2006 | A1 |
| 20060032442 | Hasebe | Feb 2006 | A1 |
| 20060032443 | Hasebe et al. | Feb 2006 | A1 |
| 20060084283 | Paranjpe et al. | Apr 2006 | A1 |
| 20060088985 | Haverkort et al. | Apr 2006 | A1 |
| 20060119248 | Howard et al. | Jun 2006 | A1 |
| 20060199357 | Wan et al. | Sep 2006 | A1 |
| 20060263699 | Abatchev et al. | Nov 2006 | A1 |
| 20060273456 | Sant et al. | Dec 2006 | A1 |
| 20060286776 | Ranish et al. | Dec 2006 | A1 |
| 20060289385 | Kikuchi | Dec 2006 | A1 |
| 20070032047 | Hasebe et al. | Feb 2007 | A1 |
| 20070099431 | Li | May 2007 | A1 |
| 20070137572 | Matsuura et al. | Jun 2007 | A1 |
| 20070148350 | Rahtu et al. | Jun 2007 | A1 |
| 20070148968 | Kwon et al. | Jun 2007 | A1 |
| 20070167028 | Chou et al. | Jul 2007 | A1 |
| 20070190782 | Park | Aug 2007 | A1 |
| 20070212850 | Ingle et al. | Sep 2007 | A1 |
| 20070218661 | Shroff et al. | Sep 2007 | A1 |
| 20070238299 | Niroomand et al. | Oct 2007 | A1 |
| 20070238301 | Cabral et al. | Oct 2007 | A1 |
| 20070238316 | Ohashi | Oct 2007 | A1 |
| 20070251444 | Gros-Jean et al. | Nov 2007 | A1 |
| 20070298585 | Lubomirsky et al. | Dec 2007 | A1 |
| 20080038936 | Todd et al. | Feb 2008 | A1 |
| 20080063791 | Hasebe et al. | Mar 2008 | A1 |
| 20080081470 | Clark | Apr 2008 | A1 |
| 20080119057 | Chua et al. | May 2008 | A1 |
| 20080124946 | Xiao et al. | May 2008 | A1 |
| 20080138996 | Nishizuka | Jun 2008 | A1 |
| 20080139003 | Pirzada et al. | Jun 2008 | A1 |
| 20080142483 | Hua et al. | Jun 2008 | A1 |
| 20080213479 | Chou et al. | Sep 2008 | A1 |
| 20080237726 | Dyer | Oct 2008 | A1 |
| 20080242116 | Clark | Oct 2008 | A1 |
| 20080260969 | Dussarrat et al. | Oct 2008 | A1 |
| 20080274302 | Hasebe et al. | Nov 2008 | A1 |
| 20080311760 | Nodera et al. | Dec 2008 | A1 |
| 20080318443 | Kim et al. | Dec 2008 | A1 |
| 20090018668 | Galbraith | Jan 2009 | A1 |
| 20090035665 | Tran | Feb 2009 | A1 |
| 20090075490 | Dussarrat | Mar 2009 | A1 |
| 20090146322 | Weling et al. | Jun 2009 | A1 |
| 20090148625 | Yeom et al. | Jun 2009 | A1 |
| 20090155606 | Yoon et al. | Jun 2009 | A1 |
| 20090163041 | Mungekar et al. | Jun 2009 | A1 |
| 20090191722 | Hasebe et al. | Jul 2009 | A1 |
| 20090286381 | Van Schravendijk et al. | Nov 2009 | A1 |
| 20100003797 | Smith | Jan 2010 | A1 |
| 20100038727 | Chakravarthi et al. | Feb 2010 | A1 |
| 20100099271 | Hausmann et al. | Apr 2010 | A1 |
| 20100102407 | Kajiyama et al. | Apr 2010 | A1 |
| 20100124618 | Kobayashi et al. | May 2010 | A1 |
| 20100124621 | Kobayashi et al. | May 2010 | A1 |
| 20100136260 | Matsunaga et al. | Jun 2010 | A1 |
| 20100136313 | Shimizu et al. | Jun 2010 | A1 |
| 20100151681 | Knapp et al. | Jun 2010 | A1 |
| 20100221925 | Lee et al. | Sep 2010 | A1 |
| 20100267238 | Johnson et al. | Oct 2010 | A1 |
| 20100304047 | Yang et al. | Dec 2010 | A1 |
| 20100304574 | Nodera et al. | Dec 2010 | A1 |
| 20100310791 | Shimazu et al. | Dec 2010 | A1 |
| 20110003477 | Park et al. | Jan 2011 | A1 |
| 20110014795 | Lee et al. | Jan 2011 | A1 |
| 20110021010 | Cheng et al. | Jan 2011 | A1 |
| 20110086516 | Lee et al. | Apr 2011 | A1 |
| 20110127582 | Cheng et al. | Jun 2011 | A1 |
| 20110129978 | Cheng et al. | Jun 2011 | A1 |
| 20110151142 | Seamons et al. | Jun 2011 | A1 |
| 20110159673 | Hanawa et al. | Jun 2011 | A1 |
| 20110176967 | Okuda et al. | Jul 2011 | A1 |
| 20110183528 | Wang et al. | Jul 2011 | A1 |
| 20110223769 | Ko et al. | Sep 2011 | A1 |
| 20110244142 | Cheng et al. | Oct 2011 | A1 |
| 20110256734 | Hausmann et al. | Oct 2011 | A1 |
| 20110262642 | Xiao et al. | Oct 2011 | A1 |
| 20120009802 | Lavoie et al. | Jan 2012 | A1 |
| 20120009803 | Jung et al. | Jan 2012 | A1 |
| 20120011889 | Bogdahn et al. | Jan 2012 | A1 |
| 20120028469 | Onizawa et al. | Feb 2012 | A1 |
| 20120058282 | Hong et al. | Mar 2012 | A1 |
| 20120068347 | Isobayashi et al. | Mar 2012 | A1 |
| 20120088369 | Weidman et al. | Apr 2012 | A1 |
| 20120104347 | Quick | May 2012 | A1 |
| 20120108079 | Mahajani | May 2012 | A1 |
| 20120115074 | Zhang et al. | May 2012 | A1 |
| 20120142194 | Hwang | Jun 2012 | A1 |
| 20120156882 | Lee et al. | Jun 2012 | A1 |
| 20120156888 | Sato et al. | Jun 2012 | A1 |
| 20120164846 | Ha et al. | Jun 2012 | A1 |
| 20120171846 | Hwang | Jul 2012 | A1 |
| 20120177841 | Thompson | Jul 2012 | A1 |
| 20120213940 | Mallick | Aug 2012 | A1 |
| 20120244711 | Yin et al. | Sep 2012 | A1 |
| 20120264305 | Nakano | Oct 2012 | A1 |
| 20120282418 | Chou et al. | Nov 2012 | A1 |
| 20120315394 | Ito | Dec 2012 | A1 |
| 20130065404 | Weidman et al. | Mar 2013 | A1 |
| 20130071580 | Weidman et al. | Mar 2013 | A1 |
| 20130084688 | O'Meara et al. | Apr 2013 | A1 |
| 20130113073 | Liu et al. | May 2013 | A1 |
| 20130115783 | Kim et al. | May 2013 | A1 |
| 20130129940 | Xiao et al. | May 2013 | A1 |
| 20130189845 | Kim et al. | Jul 2013 | A1 |
| 20130189854 | Hausmann et al. | Jul 2013 | A1 |
| 20130196082 | Spence et al. | Aug 2013 | A1 |
| 20130200384 | Mieno | Aug 2013 | A1 |
| 20130210236 | Ogihara et al. | Aug 2013 | A1 |
| 20130252437 | Sano et al. | Sep 2013 | A1 |
| 20130273704 | Jee et al. | Oct 2013 | A1 |
| 20130302980 | Chandrashekar et al. | Nov 2013 | A1 |
| 20130327636 | Majetich et al. | Dec 2013 | A1 |
| 20130344248 | Clark | Dec 2013 | A1 |
| 20140023794 | Mahajani et al. | Jan 2014 | A1 |
| 20140113455 | Reimer et al. | Apr 2014 | A1 |
| 20140113457 | Sims et al. | Apr 2014 | A1 |
| 20140120737 | Swaminathan et al. | May 2014 | A1 |
| 20140134812 | Kim et al. | May 2014 | A1 |
| 20140141625 | Fukazawa et al. | May 2014 | A1 |
| 20140141626 | Hausmann et al. | May 2014 | A1 |
| 20140158580 | Xiao et al. | Jun 2014 | A1 |
| 20140170853 | Shamma et al. | Jun 2014 | A1 |
| 20140193983 | LaVoie | Jul 2014 | A1 |
| 20140216337 | Swaminathan et al. | Aug 2014 | A1 |
| 20140262038 | Wang et al. | Sep 2014 | A1 |
| 20140273477 | Niskanen et al. | Sep 2014 | A1 |
| 20140273528 | Niskanen et al. | Sep 2014 | A1 |
| 20140273529 | Nguyen et al. | Sep 2014 | A1 |
| 20140273530 | Nguyen et al. | Sep 2014 | A1 |
| 20140273531 | Niskanen et al. | Sep 2014 | A1 |
| 20140302686 | Pan et al. | Oct 2014 | A1 |
| 20150021712 | Zschaetzsch et al. | Jan 2015 | A1 |
| 20150031218 | Karakawa | Jan 2015 | A1 |
| 20150056540 | Fukuda | Feb 2015 | A1 |
| 20150126042 | Pasquale et al. | May 2015 | A1 |
| 20150132965 | Devilliers et al. | May 2015 | A1 |
| 20150137061 | Donghi et al. | May 2015 | A1 |
| 20150155198 | Tsai et al. | Jun 2015 | A1 |
| 20150162416 | Chang et al. | Jun 2015 | A1 |
| 20150167163 | Kubota et al. | Jun 2015 | A1 |
| 20150200110 | Li et al. | Jul 2015 | A1 |
| 20150243708 | Ravasio | Aug 2015 | A1 |
| 20150249153 | Morin et al. | Sep 2015 | A1 |
| 20150251917 | Hong et al. | Sep 2015 | A1 |
| 20150259791 | Hausmann et al. | Sep 2015 | A1 |
| 20160020092 | Kang et al. | Jan 2016 | A1 |
| 20160042950 | Dai et al. | Feb 2016 | A1 |
| 20160046501 | Kverel et al. | Feb 2016 | A1 |
| 20160049307 | Chen | Feb 2016 | A1 |
| 20160064224 | Hung et al. | Mar 2016 | A1 |
| 20160079054 | Chen et al. | Mar 2016 | A1 |
| 20160093484 | Marsh | Mar 2016 | A1 |
| 20160099143 | Yan et al. | Apr 2016 | A1 |
| 20160109804 | Huli | Apr 2016 | A1 |
| 20160111297 | Chen et al. | Apr 2016 | A1 |
| 20160148800 | Henri et al. | May 2016 | A1 |
| 20160148806 | Henri et al. | May 2016 | A1 |
| 20160155739 | Ting et al. | Jun 2016 | A1 |
| 20160172194 | Kunnen et al. | Jun 2016 | A1 |
| 20160190008 | Chandrashekar et al. | Jun 2016 | A1 |
| 20160225640 | Raley et al. | Aug 2016 | A1 |
| 20160247678 | Feng et al. | Aug 2016 | A1 |
| 20160247680 | O'Meara et al. | Aug 2016 | A1 |
| 20160254171 | Shamma et al. | Sep 2016 | A1 |
| 20160284567 | Reilly et al. | Sep 2016 | A1 |
| 20160293398 | Danek et al. | Oct 2016 | A1 |
| 20160293418 | Pasquale et al. | Oct 2016 | A1 |
| 20160300718 | Raley et al. | Oct 2016 | A1 |
| 20160329238 | Tang et al. | Nov 2016 | A1 |
| 20160336178 | Swaminathan et al. | Nov 2016 | A1 |
| 20160336187 | Liou et al. | Nov 2016 | A1 |
| 20160343580 | Hudson | Nov 2016 | A1 |
| 20160365425 | Chen et al. | Dec 2016 | A1 |
| 20160372334 | Mignot et al. | Dec 2016 | A1 |
| 20170069510 | Kal et al. | Mar 2017 | A1 |
| 20170092496 | Devilliers | Mar 2017 | A1 |
| 20170092857 | Hausmann | Mar 2017 | A1 |
| 20170110550 | Tsai et al. | Apr 2017 | A1 |
| 20170117134 | Henri et al. | Apr 2017 | A1 |
| 20170148637 | Devilliers | May 2017 | A1 |
| 20170170015 | Kim et al. | Jun 2017 | A1 |
| 20170170026 | Hudson et al. | Jun 2017 | A1 |
| 20170207082 | Wang et al. | Jul 2017 | A1 |
| 20170323785 | Singhal et al. | Nov 2017 | A1 |
| 20170323803 | Van Schravendijk et al. | Nov 2017 | A1 |
| 20170358450 | Ko et al. | Dec 2017 | A1 |
| 20180005814 | Kumar et al. | Jan 2018 | A1 |
| 20180033622 | Swaminathan et al. | Feb 2018 | A1 |
| 20180061628 | Ou et al. | Mar 2018 | A1 |
| 20180061650 | Mahorowala et al. | Mar 2018 | A1 |
| 20180076023 | Yan et al. | Mar 2018 | A1 |
| 20180114903 | Hausmann | Apr 2018 | A1 |
| 20180138028 | Henri et al. | May 2018 | A1 |
| 20180138036 | Baldasseroni et al. | May 2018 | A1 |
| 20180138040 | LaVoie | May 2018 | A1 |
| 20180138405 | McKerrow et al. | May 2018 | A1 |
| 20180223429 | Fukazawa | Aug 2018 | A1 |
| 20180308695 | LaVoie et al. | Oct 2018 | A1 |
| 20190027362 | Cheng et al. | Jan 2019 | A1 |
| 20190041756 | Hasebe et al. | Feb 2019 | A1 |
| 20190055645 | Li et al. | Feb 2019 | A1 |
| 20190080903 | Abel et al. | Mar 2019 | A1 |
| 20190206677 | Abel et al. | Jul 2019 | A1 |
| 20190279866 | Pore | Sep 2019 | A1 |
| 20190284694 | Knisley et al. | Sep 2019 | A1 |
| 20190333753 | Ueda et al. | Oct 2019 | A1 |
| 20200105509 | Drewery et al. | Apr 2020 | A1 |
| 20200227314 | Kim et al. | Jul 2020 | A1 |
| 20210301400 | Lee et al. | Sep 2021 | A1 |
| 20230220544 | Gupta et al. | Jul 2023 | A1 |
| 20230317449 | Gupta et al. | Oct 2023 | A1 |
| Number | Date | Country |
|---|---|---|
| 1732288 | Feb 2006 | CN |
| 1841676 | Oct 2006 | CN |
| 101006195 | Jul 2007 | CN |
| 101255548 | Sep 2008 | CN |
| 101328578 | Dec 2008 | CN |
| 101378007 | Mar 2009 | CN |
| 101506955 | Aug 2009 | CN |
| 101981225 | Feb 2011 | CN |
| 102224573 | Oct 2011 | CN |
| 102471885 | May 2012 | CN |
| 102479672 | May 2012 | CN |
| 102906305 | Jan 2013 | CN |
| 103168344 | Jun 2013 | CN |
| 103225071 | Jul 2013 | CN |
| 103403847 | Nov 2013 | CN |
| 103515197 | Jan 2014 | CN |
| 103632955 | Mar 2014 | CN |
| 103635605 | Mar 2014 | CN |
| 103918068 | Jul 2014 | CN |
| 104046955 | Sep 2014 | CN |
| 104272441 | Jan 2015 | CN |
| 104517892 | Apr 2015 | CN |
| 104576506 | Apr 2015 | CN |
| 104752199 | Jul 2015 | CN |
| 105448701 | Mar 2016 | CN |
| 205164805 | Apr 2016 | CN |
| 105609471 | May 2016 | CN |
| 105789027 | Jul 2016 | CN |
| 105917445 | Aug 2016 | CN |
| 105977141 | Sep 2016 | CN |
| 106057637 | Oct 2016 | CN |
| 106449360 | Feb 2017 | CN |
| 108411281 | Aug 2018 | CN |
| 109791875 | May 2019 | CN |
| 0277766 | Aug 1988 | EP |
| 2278046 | Jan 2011 | EP |
| 1181559 | Feb 1970 | GB |
| 2005011904 | Jan 2005 | JP |
| 2005136300 | May 2005 | JP |
| 2005163084 | Jun 2005 | JP |
| 2005210076 | Aug 2005 | JP |
| 2006060091 | Mar 2006 | JP |
| 2006080359 | Mar 2006 | JP |
| 2007281181 | Oct 2007 | JP |
| 2008517479 | May 2008 | JP |
| 2008306093 | Dec 2008 | JP |
| 2009010318 | Jan 2009 | JP |
| 2009170823 | Jul 2009 | JP |
| 2010010497 | Jan 2010 | JP |
| 2010087187 | Apr 2010 | JP |
| 2010527138 | Aug 2010 | JP |
| 2010232214 | Oct 2010 | JP |
| 2010239103 | Oct 2010 | JP |
| 2010283388 | Dec 2010 | JP |
| 2011192776 | Sep 2011 | JP |
| 2012084707 | Apr 2012 | JP |
| 2012142574 | Jul 2012 | JP |
| 2012169408 | Sep 2012 | JP |
| 5225081 | Jul 2013 | JP |
| 2013153164 | Aug 2013 | JP |
| 2013182951 | Sep 2013 | JP |
| 2013225655 | Oct 2013 | JP |
| 2014038968 | Feb 2014 | JP |
| 2014179607 | Sep 2014 | JP |
| 2014532304 | Dec 2014 | JP |
| 2015029097 | Feb 2015 | JP |
| 2015512568 | Apr 2015 | JP |
| 2015159335 | Sep 2015 | JP |
| 20010075177 | Aug 2001 | KR |
| 20060023137 | Mar 2006 | KR |
| 100861851 | Oct 2008 | KR |
| 20090080019 | Jul 2009 | KR |
| 20090131821 | Dec 2009 | KR |
| 20100027062 | Mar 2010 | KR |
| 20100128863 | Dec 2010 | KR |
| 20120098448 | Sep 2012 | KR |
| 20130062256 | Jun 2013 | KR |
| 20130135087 | Dec 2013 | KR |
| 20140069326 | Jun 2014 | KR |
| 20140079431 | Jun 2014 | KR |
| 20140126241 | Oct 2014 | KR |
| 20140141686 | Dec 2014 | KR |
| 20150025224 | Mar 2015 | KR |
| 20150053253 | May 2015 | KR |
| 20150103642 | Sep 2015 | KR |
| 20160033057 | Mar 2016 | KR |
| 20160045527 | Apr 2016 | KR |
| 101884555 | Aug 2018 | KR |
| 20210014483 | Feb 2021 | KR |
| 102407031 | Jun 2022 | KR |
| 483103 | Apr 2002 | TW |
| 201033739 | Sep 2010 | TW |
| 201430951 | Aug 2014 | TW |
| 201439105 | Oct 2014 | TW |
| 201606855 | Feb 2016 | TW |
| WO-2006018441 | Feb 2006 | WO |
| WO-2006026350 | Mar 2006 | WO |
| WO-2011130397 | Oct 2011 | WO |
| WO-2012061593 | May 2012 | WO |
| WO-2013043330 | Mar 2013 | WO |
| WO-2013066667 | May 2013 | WO |
| WO-2013137115 | Sep 2013 | WO |
| WO-2013148880 | Oct 2013 | WO |
| WO-2014030393 | Feb 2014 | WO |
| WO-2020131635 | Jun 2020 | WO |
| WO-2021025874 | Feb 2021 | WO |
| Entry |
|---|
| Aboaf, J.A. (1969) “Some Properties of Vapor Deposited Silicon Nitride Films Obtained by the Reaction of SiBr4 and NH 3,” Journal of the Electrochemical Society, 116(12):1736-1740. |
| Becker, F.S. and Rohl, S. (Nov. 1987) “Low Pressure Deposition of Doped SiO2 by Pyrolysis of Tetraethylorthosilicate (TEOS),” J. Electrochem. Soc.: Solid-State Science and Technology, 134(11):2923-2931. |
| Cecchi et al., (2007) “Ultra-thin conformal pore-sealing of low-k materials by plasma-assisted ALD,” University of New Mexico, Albuquerque, NM, Sandia National Labs, Albuquerque, NM, 1 page. |
| Chinese First Office Action dated Apr. 12, 2021 issued in Application No. CN 201711112653.9. |
| Chinese First Office Action dated Jul. 31, 2020 issued in Application No. CN 201710636255.0. |
| Chinese First Office Action dated Jun. 23, 2020 issued in Application No. CN 201811075877.1. |
| Chinese First Office Action dated Mar. 30, 2018 issued in Application No. CN 201610206201.6. |
| Chinese First Office Action dated May 19, 2016 issued in Application No. CN 201310021460.8. |
| Chinese First Office Action dated Nov. 13, 2020 issued in Application No. CN 201710772400.8. |
| Chinese First Office Action dated Nov. 8, 2017 issued in Application No. CN 201510615853.0. |
| Chinese Fourt Office Action dated May 16, 2018 issued in Application No. CN 201310021460.8. |
| Chinese Notification of Reexamination dated Apr. 17, 2020 issued in Application No. CN 201310021460.8. |
| Chinese Second Office Action dated Apr. 13, 2017 issued in Application No. CN 201310021460.8. |
| Chinese Second Office Action dated Jan. 24, 2019 issued in Application No. CN 201610206201.6. |
| Chinese Second Office Action dated Mar. 15, 2021 issued in Application No. CN 201811075877.1. |
| Chinese Third Office Action dated Oct. 17, 2017 issued in Application No. CN 201310021460.8. |
| CN Office Action dated Mar. 7, 2022, in Application No. CN201711112653.9 with English translation. |
| CN Office Action dated Mar. 15, 2023 in Application No. CN201780070122.X with English Translation. |
| CN Office Action dated Mar. 30, 2023, in Application No. CN201880073124.9 with English translation. |
| CN Office Action dated Nov. 19, 2021, in application No. CN201711112653 with English translation. |
| CN Office Action dated Oct. 8, 2022 in Application No. CN201780070122.X with English Translation. |
| CN Office Action dated Sep. 16, 2022, in Application No. CN201780070305.1 with English translation. |
| CN Office Action dated Sep. 2, 2021, in application No. CN201811075877.1 with English translation. |
| European Examination Report dated Dec. 11, 2017 issued in Application No. EP 13 15 2046. |
| European Extended Search Report dated Apr. 14, 2014 issued in Application No. EP13152046.2. |
| Huang et al. (2017) “Design of efficient mono-aminosilane precursors for atomic layer deposition of SiO2 thin films,” Royal Society of Chemistry Adv. 2017, 7:22672-22678. |
| International Preliminary Report on Patentability dated Dec. 15, 2022 from PCT/US2021/035269. |
| International Preliminary Report on Patentability dated Feb. 9, 2023 in PCT Application No. PCT/US2021/070988. |
| International Preliminary Report on Patentability dated Feb. 17, 2022 in PCT Application No. PCT/US2020/043459. |
| International Preliminary Report on Patentability dated Mar. 26, 2020 issued in Application No. PCT/US2018/050049. |
| International Preliminary Report on Patentability dated May 23, 2019 issued in Application No. PCT/US17/60692. |
| International Preliminary Report on Patentability dated May 23, 2019 issued in Application No. PCT/US2017/060240. |
| International Search Report and Written Opinion dated Apr. 14, 2023 in PCT Application No. PCT/US2022/080683. |
| International Search Report and Written Opinion dated Dec. 2, 2022 in PCT Application No. PCT/US2022/075296. |
| International Search Report and Written Opinion dated Feb. 13, 2018 issued in Application No. PCT/US2017/060692. |
| International Search Report and Written Opinion dated Feb. 21, 2018 issued in Application No. PCT/US2017/060240. |
| International Search Report and Written Opinion dated Feb. 25, 2019 issued in Application No. PCT/US2018/050049. |
| International Search Report and Written Opinion dated Nov. 11, 2020 issued in Application No. PCT/US2020/043459. |
| International Search Report and Written Opinion dated Nov. 17, 2021, in PCT Application No. PCT/US2021/070988. |
| International Search Report and Written Opinion dated Sep. 23, 2021 in PCT Application No. PCT/US2021/035269. |
| Japanese Decision of Rejection dated Jan. 9, 2018 issued in Application No. JP 2013-007612. |
| Japanese First Office Action dated Dec. 1, 2020 issued in Application No. JP 2016-185454. |
| Japanese First Office Action dated May 28, 2019 issued in Application No. JP 2017-143195. |
| Japanese First Office Action dated May 29, 2019 issued in Application No. JP 2018-090402. |
| Japanese First Office Action dated Oct. 8, 2019 issued in Application No. JP 2015-184688. |
| Japanese Notice of Allowance Apr. 28, 2020 issued in Application No. JP 2015-184688. |
| Japanese Office Action dated Jan. 10, 2017 issued in Application No. JP 2013-007612. |
| Japanese Reason for Refusal dated Apr. 2, 2019 issued in Application No. JP 2013-007612. |
| Japanese Second Office Action dated Dec. 24, 2019 issued in Application No. JP 2017-143195. |
| Japanese Second Office Action [Decision of Rejection] dated Jan. 14, 2020 issued in Application No. JP 2018-090402. |
| Japanese Third Office Action dated Aug. 25, 2020 issued in Application No. JP 2017-143195. |
| JP Office Action dated Oct. 18, 2022, in Application No. JP2020-514992 with English translation. |
| King, Sean W., (Jul./Aug. 2011) “Plasma enhanced atomic layer deposition of SiNx:H and SiO2,” J. Vac. Sci. Technol. A29(4):041501-1 through 041501-9 (9 pages). |
| Korean Decision from the Patent Tribunal of the KIPO (description) dated May 26, 2015 issued in Application No. KR 10-2012-0043797. |
| Korean Final Office Action dated Aug. 18, 2014 issued in Application No. KR 10-2012-0043797. |
| Korean First Office Action dated Nov. 27, 2019 issued in Application No. KR 10-2017-0093932. |
| Korean Notice of Provisional Rejection dated Dec. 6, 2013 issued in Application No. KR 10-2012-0043797. |
| Korean Second Office Action dated Oct. 27, 2020 issued in Application No. KR 10-2017-0093932. |
| KR Office Action dated Jul. 5, 2022 in Application No. KR10-2015-0163065 with English translation. |
| KR Office action dated Aug. 8, 2022 in KR Application No. KR10-2015-0162556 with English translation. |
| KR Office action dated Feb. 24, 2023 in KR Application No. KR10-2015-0162556 with English translation. |
| KR Office Action dated Jan. 5, 2023 in Application No. KR10-2016-0039946 with English translation. |
| KR Office Action dated Jan. 12, 2022 in Application No. KR1020150163065 with English translation. |
| KR Office Action dated Jan. 26, 2022, in Application No. 10-2019-7016749 with English translation. |
| KR Office Action dated Jul. 12, 2022 in Application No. KR20197016749 With English translation. |
| KR Office Action dated Jul. 20, 2022, in Application No. KR10-2017-0147904 with English translation. |
| KR Office Action dated Jun. 7, 2022 in Application No. KR20210086044 with English translation. |
| KR Office Action dated Jun. 10, 2022, in Application No. KR1020170109223 with English translation. |
| KR Office Action dated Mar. 4, 2022, in Application No. KR10-2019-7017087 with English Translation. |
| KR Office Action dated Nov. 4, 2022 in Application No. KR10-2022-7018901 with English translation. |
| KR Office Action dated Nov. 30, 2021 in Application No. KR10-2019-7017087 with English Translation. |
| KR Office Action dated Oct. 6, 2022, in Application No. KR10-2015-0133942 with English Translation. |
| KR Office Action dated Sep. 6, 2022, in Application No. KR10-2017-0109223 with English translation. |
| KR Office Action dated Sep. 27, 2021, in application No. KR20210086044 with English translation. |
| KR Office Action dated Sep. 29, 2021, in application No. KR1020170109223 with English translation. |
| Kunnen, E. et al., “A way to integrate multiple block layers for middle of line contact patterning”, in Advanced Etch Technology for Nanopatterning IV, Edited by Qinghuam Lin and Sebastian Engelmann, Mar. 17, 2015, Proc. of SPIE, vol. 9428, 94280W1-8, 8 pages. [Downloaded on Jun. 27, 2017 from http://proceedings.spiedigitallibrary.org ]. |
| Lin et al., (1998) “Silicon Nitride Films Deposited by Atmospheric Pressure Chemical Vapor Deposition,” Materials Research Society Symposium Proceedings vol. 495, Chemical Aspects of Electronic Ceramics Processing, Symposium held Nov. 30-Dec. 4, 1997, Boston, Massachusetts, U.S.A., 8 pages. |
| PCT International Preliminary Report on Patentability and Written Opinion, dated Oct. 26, 2012, issued in PCT/US2011/032303. |
| PCT International Search Report and Written Opinion, dated Feb. 20, 2012, issued in PCT/US2011/032303. |
| PCT Invitation to Pay Additional Fees; Communication Re Partial International Search, dated Dec. 16, 2011, issued in Application No. PCT/US2011/032303. |
| Plasma Enhanced Atomic Layer Deposition (PEALD), Website: http://www.asm.com/index.php?option=com_content&task=view&id=19&Itemid=161 (2010), 1 page. |
| “PlasmaProTM NGP®80 Range,” Oxford Instruments (2010), 8 pages. |
| Singapore Notice of Eligibility for Grant and Supplemental Examination Report dated Jan. 20, 2020 issued in Application No. SG 10201507848X. |
| Taiwan Examination Report dated Mar. 29, 2017 issued in Application No. TW 102102054. |
| Taiwan First Office Action dated Feb. 27, 2019, issued in Application No. TW 106124691. |
| Taiwan First Office Action dated Oct. 16, 2019 issued in Application No. TW 105109955. |
| Taiwanese First Decision of Refusal dated Dec. 22, 2020 issued in Application No. TW 1051305401. |
| Taiwanese First Office Action dated Apr. 25, 2019 issued in Application No. TW 104131344. |
| Taiwanese First Office Action dated Jun. 13, 2019 issued in Application No. TW 104138370. |
| Taiwanese First Office Action dated Mar. 25, 2020 issued in Application No. TW 105130541. |
| Taiwanese Notice of Allowance dated Feb. 17, 2019 issued in Application No. TW 104138370. |
| TW Office Action dated Jun. 17, 2022 in Application No. TW107131673 With English Translation. |
| U.S. Advisory Action dated May 20, 2019 issued in U.S. Appl. No. 15/349,746. |
| U.S. Appl. No. 16/852,261, inventors Abel et al., filed on Apr. 17, 2020. |
| U.S. Final Office Action dated Apr. 20, 2018 issued in U.S. Appl. No. 15/349,753. |
| U.S. Final Office Action dated Apr. 25, 2013 issued in U.S. Appl. No. 13/084,305. |
| U.S. Final Office Action dated Apr. 9, 2018 issued in U.S. Appl. No. 15/279,312. |
| U.S. Final Office Action dated Dec. 21, 2018 issued in U.S. Appl. No. 15/349,746. |
| U.S. Final Office Action dated Feb. 5, 2020 issued in U.S. Appl. No. 15/349,746. |
| U.S. Final Office Action dated Jan. 2, 2018 issued in U.S. Appl. No. 15/351,221. |
| U.S. Final Office Action dated Jan. 18, 2018 issued in U.S. Appl. No. 15/349,746. |
| U.S. Final Office Action dated Jan. 21, 2020 issued in U.S. Appl. No. 15/847,744. |
| U.S. Final Office Action dated Nov. 14, 2014 issued in U.S. Appl. No. 14/065,334. |
| U.S. Final Office Action dated Oct. 19, 2017 issued in U.S. Appl. No. 15/279,314. |
| U.S. Non-Final Office Action dated Jul. 5, 2017 issued in U.S. Appl. No. 15/351,221. |
| U.S. Notice of Allowance dated Apr. 25, 2018 issued in U.S. Appl. No. 15/253,546. |
| U.S. Notice of Allowance dated Aug. 18, 2015 issued in U.S. Appl. No. 14/494,914. |
| U.S. Notice of Allowance dated Dec. 11, 2019 issued in U.S. Appl. No. 15/279,312. |
| U.S. Notice of Allowance dated Dec. 5, 2018 issued in U.S. Appl. No. 15/703,917. |
| U.S. Notice of Allowance dated Feb. 1, 2016 issued in U.S. Appl. No. 14/552,245. |
| U.S. Notice of Allowance dated Feb. 17, 2015 issued in U.S. Appl. No. 14/065,334. |
| U.S. Notice of Allowance dated Feb. 8, 2017 issued in U.S. Appl. No. 14/713,639. |
| U.S. Notice of Allowance dated Jan. 15, 2020 issued in U.S. Appl. No. 16/294,783. |
| U.S. Notice of Allowance dated Jul. 1, 2020 issued in U.S. Appl. No. 15/349,746. |
| U.S. Notice of Allowance dated Jul. 15, 2016 issued in U.S. Appl. No. 14/678,736. |
| U.S. Notice of Allowance dated Jul. 16, 2018 issued in U.S. Appl. No. 15/351,221. |
| U.S. Notice of Allowance dated Jul. 26, 2013, issued U.S. Appl. No. 13/414,619. |
| U.S. Notice of Allowance dated Jul. 26, 2018 issued in U.S. Appl. No. 15/829,702. |
| U.S. Notice of Allowance dated Jun. 17, 2019 issued in U.S. Appl. No. 15/349,753. |
| U.S. Notice of Allowance dated May 28, 2020 issued in U.S. Appl. No. 15/847,744. |
| U.S. Notice of Allowance dated Oct. 26, 2016 issued in U.S. Appl. No. 14/552,245. |
| U.S. Notice of Allowance dated Sep. 1, 2017 issued in U.S. Appl. No. 15/272,222. |
| U.S. Notice of Allowance dated Sep. 19, 2016 issued in U.S. Appl. No. 14/935,317. |
| U.S. Notice of Allowance dated Sep. 26, 2016 issued in U.S. Appl. No. 14/552,011. |
| U.S. Notice of Allowance dated Sep. 28, 2017 issued in U.S. Appl. No. 15/399,637. |
| U.S. Office Action dated Apr. 11, 2014 issued in U.S. Appl. No. 14/065,334. |
| U.S. Office Action dated Apr. 18, 2016 issued in U.S. Appl. No. 14/935,317. |
| U.S. Office Action dated Apr. 18, 2019 issued in U.S. Appl. No. 15/279,312. |
| U.S. Office Action dated Apr. 7, 2017 issued in U.S. Appl. No. 15/279,314. |
| U.S. Office Action dated Jul. 14, 2017 issued in U.S. Appl. No. 15/349,746. |
| U.S. Office Action dated Jul. 18, 2018 issued in U.S. Appl. No. 15/703,917. |
| U.S. Office Action dated Jul. 30, 2019 issued in U.S. Appl. No. 15/847,744. |
| U.S. Office Action dated Jun. 14, 2019 issued in U.S. Appl. No. 15/349,746. |
| U.S. Office Action dated Jun. 29, 2017 issued in U.S. Appl. No. 15/279,312. |
| U.S. Office Action dated Jun. 29, 2018 issued in U.S. Appl. No. 15/349,746. |
| U.S. Office Action dated Jun. 7, 2013 issued U.S. Appl. No. 13/414,619. |
| U.S. Office Action dated May 19, 2017 issued in U.S. Appl. No. 15/272,222. |
| U.S. Office Action dated May 24, 2016 issued in U.S. Appl. No. 14/552,245. |
| U.S. Office Action dated May 25, 2016 issued in U.S. Appl. No. 14/552,011. |
| U.S. Office Action dated Oct. 1, 2015 issued in U.S. Appl. No. 14/552,245. |
| U.S. Office Action dated Oct. 23, 2017 issued in U.S. Appl. No. 15/349,753. |
| U.S. Office Action dated Oct. 6, 2017 issued in U.S. Appl. No. 15/253,546. |
| U.S. Office Action dated Sep. 14, 2012 issued in U.S. Appl. No. 13/084,305. |
| U.S. Office Action dated Sep. 28, 2018 issued in U.S. Appl. No. 15/349,753. |
| U.S. Appl. No. 18/000,562, inventors Gupta et al., filed on Dec. 2, 2022. |
| U.S. Appl. No. 18/003,133, inventors Gupta et al., filed on Dec. 22, 2022. |
| Wikipedia, The Free Encyclopedia, Definition of “Silicon Nitride,” Archived from Apr. 9, 2015, 1 page [Downloaded on Oct. 12, 2017 from https://web.archive.org/web/20150409055521/https://en.wikipedia.org/wiki/Silicon_nitride]. |
| CN Office Action dated Jun. 29, 2023 in Application No. CN201780070122.X with English Translation. |
| CN Office Action dated Sep. 21, 2023, in Application No. CN201880073124.9 with English translation. |
| International Search Report and Written Opinion dated Apr. 28, 2023, in Application No. PCT/US2022/081972. |
| KR Office Action dated Aug. 17, 2023, in application No. KR10-2016-0039946 with English translation. |
| KR Office Action dated Jul. 14, 2023, in application No. KR10-2022-7018901 with English translation. |
| CN Office Action dated Dec. 6, 2023, in CN Application No. 202080055912.2, with English translation. |
| International Search Report and Written Opinion dated Oct. 28, 2022 in PCT Application No. PCT/US2022/036026. |
| International Preliminary Report on Patentability and Written Opinion dated Jan. 18, 2024 in PCT Application No. PCT/US2022/036026. |
| International Preliminary Report on Patentability and Written Opinion dated Mar. 7, 2024 in PCT Application No. PCT/US2022/075296. |
| International Search Report and Written Opinion dated Dec. 26, 2023 in PCT Application No. PCT/US2023/031873. |
| KR office action dated Apr. 24, 2022 in Application No. KR10-2015-0133942 with English Translation. |
| KR Office Action dated Aug. 30, 2023, in Application No. KR10-2020-7010492 with English Translation. |
| KR Office Action dated Feb. 5, 2024 in KR Application No. 10-2023-0184996, with English Translation. |
| KR Office Action dated Mar. 31, 2023, in Application No. KR10-2016-0122046 with English translation. |
| SG Written Opinion dated Jan. 17, 2024 in SG Application No. 11202201069Y. |
| U.S. Appl. No. 18/577,681, inventors Kumar; Ravi, et al., filed on Jan. 8, 2024. |
| U.S. Appl. No. 18/684,591, inventors Yang N, et al., filed on Feb. 16, 2024. |
| CN Office Action dated Sep. 11, 2024 in CN Application No. 202080055912.2 with English translation. |
| International Preliminary Report on Patentability and Written Opinion dated Jul. 4, 2024 in PCT Application No. PCT/US2022/081972. |
| International Preliminary Report on Patentability and Written Opinion dated Jul. 18, 2024 in PCT Application No. PCT/US2022/082624. |
| U.S. Appl. No. 18/727,030, inventors Gupta A, et al., filed on Jul. 5, 2024. |
| Number | Date | Country | |
|---|---|---|---|
| 20220275510 A1 | Sep 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62883556 | Aug 2019 | US |
