Gapfill of variable aspect ratio features with a composite PEALD and PECVD method

Information

  • Patent Grant
  • 11133180
  • Patent Number
    11,133,180
  • Date Filed
    Friday, May 31, 2019
    5 years ago
  • Date Issued
    Tuesday, September 28, 2021
    2 years ago
Abstract
Provided herein are methods and apparatus for filling one or more gaps on a semiconductor substrate. The disclosed embodiments are especially useful for forming seam-free, void-free fill in both narrow and wide features. The methods may be performed without any intervening etching operations to achieve a single step deposition. In various implementations, a first operation is performed using a novel PEALD fill mechanism to fill narrow gaps and line wide gaps. A second operation may be performed using PECVD methods to continue filling the wide gaps.
Description
INCORPORATION BY REFERENCE

An Application Data Sheet 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 Application Data Sheet is incorporated by reference herein in its entirety and for all purposes.


BACKGROUND

The fabrication of integrated circuits includes many diverse processing steps. One of the operations frequently employed is the deposition of a dielectric film into a gap between features patterned over or into silicon substrates. One of the goals in depositing such material is to form a void-free, seam-free fill in the gap. As device dimensions become smaller in the context of DRAM, flash memory and logic, for example, it has become increasingly difficult to achieve this type of ideal fill.


While deposition methods such as high density plasma (HDP), sub-atmospheric chemical vapor deposition (SACVD), and low pressure chemical vapor deposition (LPCVD) have been used for gap fill, these methods do not achieve the desired fill capability. Flowable chemical vapor deposition and spin-on dielectric (SOD) methods can achieve the desired fill, but tend to deposit highly porous films. Further, these methods are especially complex and costly to integrate, as they require many extra processing steps. Atomic layer deposition (ALD) processes have also been used for gap fill, but these processes suffer from long processing times and low throughput, especially for large gaps. In some cases, multi-step deposition processes are used, including deposition-etch-deposition processes which require distinct etching operations between subsequent deposition operations. The etching may be done to remedy or prevent void formation in the gap. While this method is useful, it would be preferable to use a process that involves only deposition, with no required etch operations.


A further challenge is simultaneously filling gaps of different sizes on a substrate. For example, a deposition method optimized for a wide gap with a small aspect ratio may not be suitable for filling a narrow gap with a large aspect ratio, and vice versa. Therefore, a method of achieving void-free, seam-free fill of dielectric material into a gap is needed, particularly one that may be used to simultaneously fill gaps of various sizes.


SUMMARY

Certain embodiments herein relate to methods and apparatus for filling a gap on a semiconductor substrate. In certain cases, the gap is filled through a plasma enhanced atomic layer deposition (PEALD) operation. In other cases, the gap is filled through a hybrid method including both PEALD and plasma enhanced chemical vapor deposition (PECVD) operations. In one aspect of the embodiments herein, a method is provided for filling a gap including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface; (b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface; (c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface to form a film layer that lines the bottom and sidewalls of the gap; (d) sweeping the reaction chamber without performing a pumpdown; and (e) repeating operations (a) through (d) to form additional film layers, where when opposing film layers on opposite sidewalls of the gap approach one another, surface groups present on the opposing film layers crosslink with one another to thereby fill the gap. The methods may be used to fill the gap without the formation of a void or seam.


In some embodiments, the first reactant is a silicon-containing reactant and the second reactant is an oxidizing reactant. For example, the first reactant may include bis(tertiary-butyl-amino)silane (BTBAS). In a further example, the second reactant may include oxygen and/or nitrous oxide. In various cases, the gap is reentrant. Further, in many embodiments, the gap is filled through a mechanism that may be characterized at least in part as a bottom-up fill mechanism. This bottom-up fill mechanism may achieve a seam-free, void-free fill, even where a gap is reentrant.


In another aspect of the disclosed embodiments, a method of filling a gap on a substrate surface is provided, including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface; (b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface; and (c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface to form a film layer that lines the bottom and sidewalls of the gap, where the film is denser and/or thinner near the field region and upper sidewalls of the gap compared to near the bottom and lower sidewalls of the gap. The method may include an operation of (d) sweeping the reaction chamber without performing a pumpdown after (c) is performed. In some embodiments, the method includes repeating operations (a) through (c) (or (a) through (d)) to form additional film layers to thereby fill the gap. In certain embodiments the gap may be filled through a bottom-up fill mechanism, without the formation of a void or seam.


In another aspect of the disclosed embodiments, a method of filling a gap on a substrate surface is provided, including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface; (b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface; (c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface to form a film layer that lines the bottom and sidewalls of the gap, (d) sweeping the reaction chamber without performing a pumpdown; and repeating operations (a) through (d) to form additional film layers where ligands of one or more reactants are preferentially buried in the film near the bottom and lower sidewalls of the gap compared to the field region and upper sidewalls of the gap. The method may include an operation of (d) sweeping the reaction chamber without performing a pumpdown after (c) is performed. In certain embodiments, the gap may be filled through a bottom-up fill mechanism without the formation of a void or seam.


In a further aspect of the disclosed embodiments, a method of filling a gap on a substrate surface is provided, including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface; (b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface; (c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface to form a film lining the gap; (d) sweeping or purging the reaction chamber; (e) introducing a third reactant in vapor phase and fourth reactant in vapor phase into the reaction chamber concurrently; and (f) generating a plasma from the vapor phase reactants to drive a gas phase reaction between the third and fourth reactants, where the gas phase reaction produces a gap-filling material, and where the gap-filling material partially or completely fills the gap on the substrate surface.


The first and second reactants may be the same as at least one of the third and fourth reactants. For example, the first and second reactants may each be the same as the third and fourth reactants. In other cases, there may be no overlap between the first and second reactants and the third and fourth reactants. In many cases, the film formed in (c) is the same material as the gap-filling material formed in (f). For example, the film formed in (c) and the gap-filling material formed in (f) may be silicon oxide. In these cases, the first reactant may be a silicon-containing reactant and the second reactant may be an oxidizing reactant. For example, the first reactant may include BTBAS. In a further example, the second reactant may include oxygen and/or nitrous oxide. In these or other cases, examples of the third reactant may be TEOS or silane, with examples of the fourth reactant being an oxidizing reactant.


In some implementations, operations (a) through (c) are repeated before operations (e) through (f), and no pumpdown occurs after each iteration of operation (c). In these or other cases, the method may be performed without any intervening etching operations. One advantage of the disclosed embodiments is that the method may be performed in a single reaction chamber. In many cases, the substrate is not removed from the reaction chamber during or between any of operations (a) through (f). In some implementations, operations (a) through (c) include forming a conformal film that is thicker at the bottom of the gap than on the upper sidewalls of the gap. This may be achieved in a variety of ways. In some embodiments, operation (c) may include preferentially densifying the film near the top of the gap compared to the film near the bottom of the gap. In these or other embodiments, operation (c) may include preferentially burying ligands of one or more reactants in the film near the bottom of the gap compared to near the upper sidewalls of the gap. Operation (c) may also include promoting crosslinking between the film formed on a first sidewall of the gap and the film formed on an opposing sidewall of the gap.


In yet another aspect of the disclosed embodiments, a method of filling gaps on a substrate surface is provided, including (a) introducing a first reactant in vapor phase into a reaction chamber having the substrate therein, and allowing the first reactant to adsorb onto the substrate surface, where the substrate has at least a narrow gap having a critical dimension less than about 50 nm and a wide gap having a critical dimension greater than or equal to about 50 nm; (b) introducing a second reactant in vapor phase into the reaction chamber and allowing the second reactant to adsorb onto the substrate surface; (c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface to form a film, where the film completely fills the narrow gap and lines the wide gap; (d) sweeping or purging the reaction chamber; (e) introducing a third reactant in vapor phase and fourth reactant in vapor phase into the reaction chamber concurrently; and (f) generating a plasma from the vapor phase reactants to drive a gas phase reaction between the third and fourth reactants, where the gas phase reaction produces a gap-filling material, and wherein the gap-filling material partially or completely fills the wide gap on the substrate surface.


In some cases, the narrow gap has an aspect ratio of greater than about 4:1 and the wide gap has an aspect ratio of less than or equal to about 4:1. The narrow gap may be reentrant in some embodiments. Even where the narrow gap is reentrant, it may be filled without forming seams or voids. In some implementations, operations (a) through (c) are repeated before operations (e) through (f), and no pumpdown occurs after each iteration of operation (c). In these or other cases, the film formed in (c) may be the same material as the gap-filling material formed in (f). In many embodiments, the method is performed without any intervening etching operations. The disclosed embodiments allow the narrow gap and wide gap to be filled without forming seams or voids.


In a further aspect of the disclosed embodiments, an apparatus for filling gaps on a semiconductor substrate is disclosed. The apparatus may include a reaction chamber, a substrate supporter, a plasma generation source, one or more process gas inlets, one or more outlets, and a controller. The controller may be configured to perform any of the methods disclosed herein.


Another aspect of the disclosed embodiments is a method of filling one or more gaps on a semiconductor substrate with a dielectric material, including: (a) depositing a silicon-containing film in the one or more gaps on the substrate through a plasma enhanced atomic layer deposition surface reaction to partially fill the one or more gaps with the silicon-containing film; and (b) depositing additional silicon-containing film on the film deposited in (a) through a plasma enhanced chemical vapor deposition gas-phase reaction to complete fill of the one or more gaps with the silicon-containing film.


These and other features will be described below with reference to the associated drawings.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 shows a flowchart of a method of depositing a film through a plasma enhanced atomic layer deposition (PEALD) process.



FIG. 2 shows a substrate having gaps of different aspect ratios that may be filled according to the disclosed embodiments.



FIG. 3 shows the substrate of FIG. 2 after a PEALD deposition process is performed.



FIG. 4 shows a close-up view of a narrow gap of FIGS. 2 and 3 as the PEALD process is performed to fill the gap.



FIG. 5 shows a flowchart of a method of depositing a film through a plasma enhanced chemical vapor deposition (PECVD) process.



FIG. 6 shows a block diagram of an apparatus that may be used to carry out the disclosed methods.



FIG. 7 depicts a multi-station apparatus that may be used to carry out the disclosed methods.



FIG. 8 shows a partially filled high aspect ratio gap that was filled according to the disclosed PEALD methods.



FIGS. 9-11 show additional pictures of high aspect ratio gaps filled according to the disclosed PEALD methods.



FIG. 12 shows a wide gap filled with silicon oxide deposited according to a disclosed PECVD method.





DETAILED DESCRIPTION

In this application, 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 thereon. A wafer or substrate used in the semiconductor device industry may have a diameter of 200 mm, or 300 mm, or 450 mm. The following detailed description assumes the invention is implemented on a wafer. However, the invention 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 this invention include various articles such as printed circuit boards, glass panels, and the like.


In the following description, numerous specific details are set forth in order 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 will be described in conjunction with the specific embodiments, it will be understood that it is not intended to limit the disclosed embodiments.


Conventional gap fill techniques have been unsuccessful in achieving void-free, seam-free fill for high density films in high aspect ratio gaps. HDP, SACVD and LPCVD have only limited fill capability, and typically result in the formation of voids and seams. These voids and seams can open up after a chemical mechanical polishing (CMP) operation, or after an etch-back is performed. These opened seams and voids can then trap materials, such as polysilicon and tungsten, that are subsequently deposited. These materials are often incompletely removed in subsequent CMP or etch-back operations, and can remain in the device to cause shorts and/or loss of yield. Flowable CVD (e.g., flowable oxide) and SOD techniques have complex integration schemes that may result in high costs associated with the various additional steps involved.


Certain embodiments herein relate to a hybrid method of filling differently sized gaps on a semiconductor substrate. The first portion of the method relates to an ALD operation, for example a plasma enhanced ALD (PEALD) operation. The ALD operation may be performed in a novel way to promote a bottom-up type fill in narrow gaps. This bottom-up fill mechanism helps achieve the void-free, seam-free fill, particularly in narrow gaps (e.g., gaps having a critical dimension (CD) of about 50 nm or less) and/or gaps having high aspect ratios (e.g., depth to width aspect ratio of about 4:1 or higher). The ALD operation also acts to form a layer on, but not completely fill, wider gaps present on the substrate (e.g., gaps having a CD larger than about 50 nm) having lower aspect ratios (e.g., aspect ratios of about 4:1 or lower).


The second portion of the method relates to a plasma enhanced chemical vapor deposition (PECVD) method that is used to fill the remainder of the wider gaps. In certain embodiments, this method may be performed using a direct (in situ) capacitively coupled plasma. In many embodiments, a radio frequency (RF) plasma source is employed, though any type of plasma source capable of generating a direct plasma may be employed, including microwave and DC sources. Further, in some embodiments, a remotely-generated plasma may be employed. The remote plasma may be capacitively-coupled or inductively-coupled according to various embodiments.


The plasmas used in the PECVD methods described herein may have lower plasma density than high density plasmas generated by in-situ inductively coupled plasma generators such as those used in HDP processes. For example, in HDP processes plasma densities may be on the order of about 1011-1013 ions/cm3, as opposed to about 108-1010 ions/cm3 for PECVD processes in certain embodiments. HDP methods generally do not produce the required fill results, as described above, and typically require the use of etch operations between subsequent deposition steps. In HDP methods, charged dielectric precursor species are directed downwards to fill the gap. This results in some sputtering of material, which can then redeposit on the sidewalls of the gap, especially near the top of the gap, as well as in the field region. Further, uncharged particles present in the chamber may deposit in the upper sidewall region, as well. This unwanted deposition can build up to form sidewall deposits and top-hats, which prevent the gap from being uniformly filled. Etch steps may be used to combat the undesired upper sidewall deposition that occurs with HDP, though this increases the complexity of the deposition method. If no etch steps are performed, the gap will generally not be able to fill without formation of a void. The HDP methods are also much more expensive to implement, with a lower throughput than PECVD methods.


According to various embodiments, the PEALD and PECVD methods may be implemented in the same chamber. Both of these types of processes run in similar pressure and flow regimes, and can use the same RF power sources. Further, the PECVD methods may be performed in a single step, meaning that no intervening etching operations (or other processes such as deposition processes) are required. By contrast, it is not practical to run PEALD and HDP processes in the same chamber. First, the two processes operate in substantially different pressure regimes. PEALD processes generally run in the range of a few Torr, and benefit from high gas flows for purging. HDP processes operate in the mTorr range, which requires relatively low gas flows compared to what is used with PEALD. Next, HDP processes are typically practiced in large volume chambers, while ALD processes benefit from substantially smaller volumes. Furthermore, HDP processes generally require a different power source than PEALD, which would further complicate reactor design.


Although HDP processes have shown good gap fill, HDP processes suffer from engineering problems related to “forbidden gap” sizes. Where a hybrid ALD/HDP deposition approach is used, a forbidden gap may exist where the CD of the gap is slightly larger than 2× the thickness of the ALD layer deposited. In these cases, the HDP processes are unable to fill the remaining gap. The PECVD methods described herein can fill gaps including those previously lined with PEALD. After any challenging structures are lined/filled with PEALD, the PECVD process may be used to fill remaining structures in a less conformal manner.


The PECVD operation is advantageous in achieving a high deposition rate to fill larger gaps that would take a long time to fill through ALD alone. In some embodiments, however, the methods include only the first operation of performing PEALD.


In various embodiments, the PEALD and PECVD operations are performed in the same chamber. This setup is beneficial, as there is no need to transfer the substrate from a PEALD reaction chamber to a PECVD reaction chamber. Thus, there is no need to worry about moisture getting on or into the film, and there is no corresponding need to perform a de-gassing operation or high temperature anneal to remove the moisture before performing the PECVD operation. Another benefit to the single chamber approach is that it reduces capital costs, cycle times and process flow complexity.


Variations may be made to the basic method described above to achieve different hybrid filling scenarios. In one example, a first portion of the method includes a PEALD operation performed under optimum conditions for filling a high aspect ratio gap, and a second portion of the method includes a more relaxed PEALD operation such as one having reduced dose and purge times. These relaxed PEALD operations may also promote PECVD or partial PECVD deposition. In another example, an etch step is used to taper the gap profile. The etch step may be performed between a first portion of the method and a second portion of the method (e.g., between a PEALD operation and a PECVD operation), or within a single portion of the method (e.g., between two PEALD operations or between two PECVD operations). Of course, the methods may be combined as appropriate. The optimum solution will depend on the actual distribution of aspect ratios and gap dimensions present on the substrate.


Combined PEALD and PECVD methods for filling gaps on substrates are discussed in U.S. patent application Ser. No. 13/084,399, which was incorporated by reference above. In certain cases, as discussed in Ser. No. 13/084,399, there may be a transition phase between an PEALD operation and a PECVD operation in which both PEALD surface reactions and PECVD gas phase reactions occur simultaneously.


In such embodiments, the completed film is generated in part by ALD/CFD and in part by a CVD process such as PECVD. Typically, the ALD/CFD portion of the deposition process is performed first and the PECVD portion is performed second, although this need not be the case. Mixed ALD/CFD with CVD processes can improve the step coverage over that seen with CVD alone and additionally improve the deposition rate over that seen with ALD/CFD alone. In some cases, plasma or other activation is applied while one ALD/CFD reactant is flowing in order to produce parasitic CVD operations and thereby achieve higher deposition rates, a different class of films, etc.


In certain embodiments, two or more ALD/CFD phases may be employed and/or two or more CVD phases may be employed. For example, an initial portion of the film may be deposited by ALD/CFD, followed by an intermediate portion of the film being deposited by CVD, and a final portion of the film deposited by ALD/CFD. In such embodiments, it may be desirable to modify the CVD portion of the film, as by plasma treatment or etching, prior to depositing the later portion of the film by ALD/CFD.


A transition phase may be employed between the ALD/CFD and CVD phases. The conditions employed during such transition phase different from those employed in either the ALD/CFD or the CVD phases. Typically, though not necessarily, the conditions permit simultaneous ALD/CFD surface reactions and CVD type gas phase reactions. The transition phase typically involves exposure to a plasma, which may be pulsed for example. Further, the transition phase may involve delivery of one or more reactants at a low flow rate, i.e., a rate that is significantly lower than that employed in the corresponding ALD/CFD phase of the process.


Methods


Plasma Enhanced Atomic Layer Deposition


The disclosed PEALD processes are useful in achieving void-free, seam-free fill of relatively narrow/high aspect ratio features. Unexpectedly, certain embodiments of the processes appear to result in a bottom-up fill mechanism where material is preferentially deposited near the bottom of the gap as opposed to the top of the gap as the gap is being filled. Although deposition happens on the sidewalls and field region as well, the film deposits thicker at/near the bottom of the gap and in many cases achieves a tapered profile as the gap is filled. The tapered profile is defined to mean that the film deposits thicker near the bottom and thinner near the top of the gap, as shown in the Experimental section, below. This tapered profile is especially useful in achieving a high quality fill without voids or seams in high aspect ratio features. This fill mechanism was unexpected, as atomic layer deposition methods typically result in the formation of a seam as the sidewalls close in towards one another. By promoting bottom-up fill, this seam can be avoided and a more robust device results.


Without wishing to be bound by any theory or mechanism of action, it is believed that the bottom-up fill mechanism may be caused by preferential film densification near the top of the gap. As the film is exposed to plasma, species present in the plasma (especially ions) bombard the film surface, thereby compacting and densifying the film. Under appropriate conditions, this densification may happen preferentially near the top of the gap. Due to the shape of the gap, it is much easier for ions to bombard the film in the field region and near the top of the gap, as opposed to near the bottom of the gap, which is much more protected. Thus, the film near the top becomes denser and thinner than the material near the bottom of the trench, which remains thicker and less dense.


Another factor that may promote seam-free, void-free, bottom-up filling is that crosslinking may occur between groups present on opposing sidewalls of the gap. As deposition proceeds and the sidewalls close in towards one another, the terminal groups may crosslink with one another, thus avoiding any seam. In the case of a gap-filling silicon oxide film, for example, surface hydroxyls/silanols on one sidewall may crosslink with surface hydroxyls/silanols on the opposing wall, thereby liberating water and forming a silicon-oxide matrix. These terminal cross-linking groups may preferentially be found on the sidewalls of a gap.


A further factor that may promote seam-free, void-free, bottom-up filling is that ligand byproducts may be liberated from the film in a non-uniform manner, such that the byproducts become preferentially trapped at or near the bottom of the gap as opposed to near the top of the gap. This entrapment may lead to a higher deposition rate within the feature, especially near the bottom of the gap. For example, where bis(tertiary-butyl-amino)silane (BTBAS) is used as a precursor, one type of ligand byproduct that may become entrapped is tert-butylamine (TBA). It is understood, however, that where ligands become trapped in a growing film, the properties of the film may be affected to some degree.



FIG. 1 presents a flowchart for a method of performing a plasma enhanced atomic layer deposition process 100. The process 100 begins at operation 101, where a dose of a first reactant is provided to a reaction chamber containing a substrate. The substrate will typically have gaps therein that are to be filled, partially or completely, through the PEALD process. In one embodiment, the PEALD process 100 completely fills gaps of a first type, and partially fills (e.g., lines) gaps of a second type, as discussed further below. In various cases, the first reactant may be a silicon-containing reactant. Next, at operation 103 the reaction chamber is purged, for example with an inert gas or a nitrogen carrier gas. This helps remove any remaining first reactant from the reaction chamber.


At operation 105, the second reactant is provided to the reaction chamber. In certain cases, the second reactant is an oxidizing reactant. The second reactant may also be a mix of reactants. In a particular embodiment, the second reactant is a roughly equal volume flow of oxygen and nitrous oxide. As used herein, the phrase “roughly equal volume flow” means that the flow of a first species and the flow of a second species do not differ by more than about 20%, as measured in SLM. The second reactant is provided in operation 105, which may include pre-flowing the reactant before flowing the reactant coincident with plasma activation in operation 107. When the plasma is activated, it drives a reaction between the first and second reactants on the surface of the substrate. Next, the plasma is extinguished, and then the reaction chamber is purged, for example with inert gas or a nitrogen carrier gas. This operation 109 is referred to as the post-RF purge.


The method 100 is typically repeated a number of times to build up the desired film thickness. By using the conditions and methods disclosed herein, the method 100 can result in a fill having a tapered profile and bottom-up fill characteristics. These factors promote void-free, seam-free fill. Advantageously, the film deposited through the disclosed methods are fairly dense.


In a particular example, operation 101 includes providing BTBAS (or other primary reactant) at a flow rate of about 0.5-2.5 mL/min, or about 1.5-2.5 L/min, for example 2 mL/min, for a time period of between about 0.1-1 second, or about 0.2-0.5 seconds, for example about 0.3 seconds. Operation 103 includes purging the reaction chamber with inert gas for between about 0.1-1 seconds, or between about 0.2-0.5 seconds, for example about 0.3 seconds. Operation 105 includes co-flowing O2 and N2O at a flow rate between about 2-20 SLM each, or between about 8-12 SLM each, for example about 10 SLM each. Coincident with this reactant delivery, a plasma is generated at operation 107 using between about 300 W-10 kW, or between about 4-6 kW, for example about 5 kW RF power. These values represent the total RF power delivered, which is divided among four stations/pedestals. The plasma exposure lasts for a duration between about 10 milliseconds and 3 seconds, or between about 0.25-1 second, for example about 0.5 seconds. The RF frequency applied to generate the plasma may be about 13.56 or 27 MHz. Next, the reaction chamber is purged with inert gas at operation 109 for a time period between about 10 milliseconds and 5 seconds, or between about 50-150 milliseconds, for example about 90 milliseconds. It should be understood that the above conditions are examples, with other reactants, flow rates, pulse times, and power used as appropriate for the particular implementation.


The PEALD methods described herein may be conformal film deposition (CFD) methods. Plasma enhanced conformal film deposition techniques and apparatus are further discussed and described in U.S. patent application Ser. No. 13/084,399, filed Apr. 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION,” which is incorporated by reference in its entirety above.


PEALD Reactants


The disclosed methods and apparatus are not limited to use with particular precursors. While the methods have already proven to be effective with certain precursors (as shown in the Experimental section) it is believed that the methods may also be used with a variety of other precursors to gain similar benefits.


At least one of the reactants will generally contain an element that is solid at room temperature, the element being incorporated into the film formed by the PEALD/PECVD method. This reactant may be referred to as a principal reactant. The principal reactant typically includes, for example, a metal (e.g., aluminum, titanium, etc.), a semiconductor (e.g., silicon, germanium, etc.), and/or a non-metal or metalloid (e.g., boron). The other reactant is sometimes referred to as an auxiliary reactant or a co-reactant. Non-limiting examples of co-reactants include oxygen, ozone, hydrogen, hydrazine, water, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like. The co-reactant may also be a mix of reactants, as mentioned above.


The PEALD/PECVD process may be used to deposit a wide variety of film types and in particular implementations to fill gaps with these film types. While much of the discussion herein focuses on the formation of undoped silicon oxides, other film types such as nitrides, carbides, oxynitrides, carbon-doped oxides, nitrogen-doped oxides, borides, etc. may also be formed. Oxides include a wide range of materials including undoped silicate glass (USG), doped silicate glass. Examples of doped glasses included boron doped silicate glass (BSG), phosphorus doped silicate glass (PSG), and boron phosphorus doped silicate glass (BPSG). Still further, the PEALD/PECVD process may be used for metal deposition and feature fill.


While the disclosed embodiments are not limited to particular reactants, an exemplary list of reactants is provided below.


In certain embodiments, the deposited film is a silicon-containing film. In these cases, the silicon-containing reactant may be for example, a silane, a halosilane or an aminosilane. A silane contains hydrogen and/or carbon groups, but does not contain a halogen. Examples of silanes are silane (SiH4), disilane (Si2H6), and organo silanes such as methylsilane, ethylsilane, isopropylsilane, t-butylsilane, dimethylsilane, diethylsilane, di-t-butyl silane, allylsilane, sec-butyl silane, thexylsilane, isoamylsilane, t-butyldisilane, di-t-butyldisilane, tetra-ethyl-ortho-silicate (also known as tetra-ethoxy-silane or TEOS) and the like. A halosilane contains at least one halogen group and may or may not contain hydrogens and/or carbon groups. Examples of halosilanes are iodosilanes, bromosilanes, chlorosilanes and fluorosilanes. Although halosilanes, particularly fluorosilanes, may form reactive halide species that can etch silicon materials, in certain embodiments described herein, the silicon-containing reactant is not present when a plasma is struck. Specific chlorosilanes are tetrachlorosilane (SiCl4), trichlorosilane (HSiCl3), dichlorosilane (H2SiCl2), monochlorosilane (ClSiH3), chloroallylsilane, chloromethylsilane, dichloromethylsilane, chlorodimethylsilane, chloroethylsilane, t-butylchlorosilane, di-t-butylchlorosilane, chloroisopropylsilane, chloro-sec-butylsilane, t-butyldimethylchlorosilane, thexyldimethylchlorosilane, and the like. 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 are mono-, di-, tri- and tetra-aminosilane (H3Si(NH2)4, H2Si(NH2)2, HSi(NH2)3 and Si(NH2)4, respectively), as well as substituted mono-, di-, tri- and tetra-aminosilanes, for example, t-butylaminosilane, methylaminosilane, tert-butylsilanamine, bis(tertiarybutylamino)silane (SiH2(NHC(CH3)3)2 (BTBAS), tert-butyl silylcarbamate, SiH(CH3)—(N(CH3)2)2, SiHCl—(N(CH3)2)2, (Si(CH3)2NH)3 and the like. A further example of an aminosilane is trisilylamine (N(SiH3)).


In other cases, the deposited film contains metal. Examples of metal-containing films that may be formed include oxides and nitrides of aluminum, titanium, hafnium, tantalum, tungsten, manganese, magnesium, strontium, etc., as well as elemental metal films. Example precursors may include metal alkylamines, metal alkoxides, metal alkylamides, metal halides, metal β-diketonates, metal carbonyls, organometallics, etc. Appropriate metal-containing precursors will include the metal that is desired to be incorporated into the film. For example, a tantalum-containing layer may be deposited by reacting pentakis(dimethylamido)tantalum with ammonia or another reducing agent. Further examples of metal-containing precursors that may be employed include trimethylaluminum, tetraethoxytitanium, tetrakis-dimethyl-amido titanium, hafnium tetrakis(ethylmethylamide), bis(cyclopentadienyl)manganese, bis(n-propylcyclopentadienyl)magnesium, etc.


In certain implementations, an oxygen-containing oxidizing reactant is used. Examples of oxygen-containing oxidizing reactants include oxygen, ozone, nitrous oxide, carbon monoxide, etc.


In some embodiments, the deposited film contains nitrogen, and a nitrogen-containing reactant is used. A nitrogen-containing reactant contains at least one nitrogen, for example, ammonia, hydrazine, amines (e.g., amines bearing carbon) such as methylamine, dimethylamine, ethylamine, isopropylamine, t-butylamine, di-t-butylamine, cyclopropylamine, sec-butylamine, cyclobutylamine, isoamylamine, 2-methylbutan-2-amine, trimethylamine, diisopropylamine, diethylisopropylamine, di-t-butylhydrazine, as well as aromatic containing amines such as anilines, pyridines, and benzylamines. Amines may be primary, secondary, tertiary or quaternary (for example, tetraalkylammonium compounds). A nitrogen-containing reactant can contain heteroatoms other than nitrogen, for example, hydroxylamine, t-butyloxycarbonyl amine and N-t-butyl hydroxylamine are nitrogen-containing reactants.


Other precursors, such as will be apparent to or readily discernible by those skilled in the art given the teachings provided herein, may also be used.


Gap Conditions


The disclosed PEALD process is especially useful for filling relatively narrow gaps (CD<about 50 nm) having a relatively high aspect ratio (AR>about 4:1). However, the process may also be performed on larger gaps and gaps having smaller ARs, as well.


In various embodiments, the PEALD process is performed on a substrate having at least two different types of gaps. A first type may include gaps having a CD less than about 50 nm, and/or an AR greater than about 4:1. This first type is referred to as a narrow gap. A second type may include gaps having a CD greater than about 50 nm, and/or an AR less than about 4:1. This second type is referred to as a wide gap. For the reasons discussed above, it can be difficult to simultaneously fill both narrow and wide gaps. Another way to characterize the different types of gaps is by comparing their sizes relative to one another. In some cases, a wide gap is at least about 2 times, or at least about 5 times, or at least about 10 times wider than a narrow gap. In these or other cases, the AR of the narrow gap may be at least about 2 times, or at least about 5 times, or at least about 10 times greater than the AR of the wide gap.


In many implementations where the PEALD process is performed on a substrate having both narrow and wide gaps, the PEALD process will act to completely fill the narrow gap, and line the surface of the wide gap. FIG. 2 presents a substrate 200 having two different types of gaps 202 and 204. The aspect ratio of the gaps is calculated as the height of the gap divided by the width of the gap. These dimensions are labeled in FIG. 2. Gaps 202 are narrow gaps having an aspect ratio slightly larger than 4:1. Gaps 204 are wide gaps having an aspect ratio of about 1:2.



FIG. 3 shows the same substrate 200 after a PEALD deposition process is performed to deposit an oxide layer 210. The narrow gaps 202 are completely filled, while the wide gap 204 is lined with oxide material 210. The film 210 deposited on the bottom of the wide gap 204 may be slightly thicker than the film 210 deposited on the sidewalls of gap 204. However, this thickness difference is much more pronounced in the narrow gap 202 as it fills with material.



FIG. 4 shows a portion of substrate 200 at a time during the PEALD deposition process. In particular, narrow gap 202 is shown mid-deposition. The deposited oxide layer 210 has a tapered profile, such that the film is thinner near the top of the gap and thicker near the bottom of the gap. This results in a diminishing gap that is smaller at the bottom than at the top. This shape is ideal for promoting void-free, seam-free fill. As material fills into the bottom of the gap, the mechanisms described above (e.g., preferential film densification, preferential ligand trapping, and/or crosslinking) may act to fill the feature without any voids or seams. Experimental results demonstrating such a fill mechanism are included below in the Experimental section.


This fill mechanism has not been previously observed with PEALD type processes. Instead, conventional PEALD processes form films that have no such tapered profile, where more vertical sidewalls grow towards one another and meet in the center. In these conventional methods, chemicals may get trapped in the extremely narrow void/seam formed in the center of the gap. This trapping is likely to occur, in part because the entire height of the gap closes in at substantially the same time. Conversely, with the disclosed methods, the sidewalls close in towards each other to a greater degree towards the bottom of the gap as opposed to the top of the gap. Thus, as the sidewalls grow towards one another, the bottom of the deposited film grows upwards, and chemicals present in the gap are pushed out. This results in a process where seam and void formation is avoided, producing an excellent quality filled gap.


In some embodiments, a gap filled by a PEALD operation has a reentrant profile. In other words, the gap is smaller at an upper portion and wider at a lower portion. It has been observed that bottom-up fill can be achieved with the disclosed PEALD process, even with gaps that have a somewhat reentrant profile. These results are shown below in the Experimental section.


Chamber Conditions


The PEALD process has been shown to be fairly resilient to changes in temperature. In particular, the process has been shown to be effective at 200° C. and 400° C. In some embodiments, therefore, the process is conducted at a temperature between about 200-400° C. In other cases, however, the temperature may fall outside this range.


The pressure inside the reaction chamber during the PEALD process may be between about 1-10 Torr, or between about 3-7 Torr, for example about 6 Torr.


Plasma Generation Conditions


In the PEALD operation, the substrate is exposed to plasma to drive the reaction between the first and second reactants. Various types of plasma may be used to drive this reaction including capacitively coupled plasmas and inductively coupled plasmas. Various types of plasma generators may be used including RF, DC, and microwave plasma generators. Moreover, according to various embodiments, the plasma may be direct or remote.


The gas used to generate the plasma may include an inert gas such as argon or helium. The gas will also typically include one of the reactants, for example an oxidizing reactant where an oxide film is being formed.


In many cases, an RF signal is used to drive plasma formation. In some embodiments, the RF applied is high frequency RF only, for example at a frequency of about 13.56 or 27 MHz. In other embodiments, the RF has a low frequency component as well. The RF power delivered to drive plasma formation may be between about 300 W and about 10 kW. In some cases, the RF power delivered is between about 4-6 kW, for example about 5 kW. These values represent the total power delivered, which is divided among four stations/pedestals.


Additional plasma generation conditions are discussed in U.S. patent application Ser. No. 13/084,399, filed Apr. 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION,” which is incorporated by reference above.


The duration of plasma exposure may vary between different embodiments. In some cases, RF power is applied for between about 10 milliseconds and 3 seconds, or between about 0.25 seconds and about 1 second. In a particular example, RF power is applied for about 0.5 seconds. The RF power and RF time determine the RF flux delivered to the chamber. It has been found that by increasing the RF flux (either by increasing RF time or power), the wet etch rate (WER) of the film may be reduced. Because the PEALD process has shown a fair resilience to different RF conditions, these variables may be used to achieve a tunable WER.


Purge Conditions


Generally, two sweep/purge operations occur during a single cycle of a PEALD reaction. The first purge occurs after the dose of the first reactant is delivered to the processing chamber, and may be referred to as a reactant purge. This purge is conducted to sweep out any remaining, non-adsorbed first reactant. The second purge occurs after the substrate is exposed to plasma, and may be referred to as the post-RF purge. This purge is conducted to sweep out any remaining reactants, as well as any film formation byproducts.


There are various ways to purge a reaction chamber. One method involves supplying the chamber with a flow of non-reactant gas (e.g., argon, helium, nitrogen, etc.) to sweep out any undesired species. With a sweep, the pressure in the reaction chamber stays substantially constant. Another method of purging a reaction chamber is to perform a pump down. Where this is the case, a vacuum is applied and the reaction chamber is evacuated. During the evacuation, the pressure in the reaction chamber is significantly reduced, for example to less than about 1 Torr.


It has been found that gapfill results are better where the post-RF purge includes a sweep, as compared to a pump down. Without wishing to be bound by a particular theory or mechanism of action, it is believed that the post-RF conditions, including the presence or absence of a pump down, may affect the surface functionality present on the surface of the deposited film. This surface functionality may determine whether or not crosslinking occurs between opposing sidewalls as the gap is filled. One way to encourage the desired bottom-up deposition pattern is to sweep the reaction chamber instead of performing a pump down. Thus, in certain embodiments, no pump down is performed after plasma exposure during the PEALD deposition. In some cases, however, a pump down may be performed between a PEALD operation and a PECVD operation.


The reactant purge may be performed for a duration between about 0.1-1 seconds, for example between about 0.2-0.5 seconds. In a particular example, the reactant purge has a duration of about 0.3 seconds.


The post-RF purge may be performed for a duration between about 0.01-5 seconds, for example between about 0.05-0.15 seconds. In one case the post-RF purge has a duration of about 0.09 seconds.


Plasma Enhanced Chemical Vapor Deposition


The PECVD methods disclosed herein may be practiced after a PEALD process to finish filling gaps that were only partially filled/lined. This method is advantageous compared to a PEALD process alone because it offers a much higher deposition rate, resulting in decreased processing times and increased throughput. Thus, the PEALD process may be used to fill small gaps and line large gaps, and then the PECVD process may be used to complete the filling of the large gaps. This offers a convenient way to fill features of varying sizes and aspect ratios. In many cases, the gaps can be filled without any intervening etching operations.


In a PECVD reaction, a substrate is exposed to one or more volatile precursors, which react and/or decompose to produce the desired deposit on the substrate surface. FIG. 5 shows a flow chart for a method 500 of filling a gap with PECVD. In various embodiments, the method 500 may be performed after the method 100 of FIG. 1. The PECVD method generally begins by flowing one or more reactants into the reaction chamber at operation 501. The reactant delivery may continue as plasma is generated in operation 503. The substrate surface is exposed to plasma, which causes deposition to occur on the substrate surface in operation 505. This process continues until a desired film thickness is reached. At operation 507, the plasma is extinguished and the reactant flow is terminated. Next, the reaction chamber is purged at operation 509.


In one example process, operation 501 includes flowing TEOS at a rate of about 1-20 mL/min and O2 at a rate of about 2,000-30,000 sccm. RF power is applied with an HF component between about 200-3,000 W, and an LF component between about 200-2,500 W (divided among four stations). The HF frequency is about 13.56 or 27 MHz, while the LF frequency is between about 300-400 kHz. The pressure in the reaction chamber is between about 1-10 Torr, and the temperature is between about 100-450° C. Of course, it is understood that in other embodiments, the reactants, chamber conditions, timing, etc. may vary depending on the desired film and application. The values provided in this section are not intended to be limiting.


PECVD methods and apparatus are further discussed and described in the following patent documents, which are each herein incorporated by reference in their entireties: U.S. Pat. No. 7,381,644, titled “PULSED PECVD METHOD FOR MODULATING HYDROGEN CONTENT IN HARD MASK”; U.S. Pat. No. 8,110,493, titled “PULSED PECVD METHOD FOR MODULATING HYDROGEN CONTENT IN HARD MASK”; U.S. Pat. No. 7,923,376, titled “METHODS OF REDUCING DEFECTS IN PECVD TEOS FILMS”; and U.S. patent application Ser. No. 13/478,999, titled “PECVD DEPOSITION OF SMOOTH SILICON FILMS,” filed May 23, 2012.


In many cases, there will be no downtime between a PEALD process and a PECVD process. For example, the PEALD process may end by extinguishing the plasma, performing the post-RF purge (with or without a pump down), and then immediately flowing the PECVD reactant(s).


In some embodiments, hybrid PEALD/PECVD methods as discussed and described in U.S. patent application Ser. No. 13/084,399, filed Apr. 11, 2011, and titled “PLASMA ACTIVATED CONFORMAL FILM DEPOSITION,” which is incorporated by reference above, may be used.


PECVD Reactants


The PECVD reaction may be performed with either the same reactants as the ALD reaction, or with different reactants. In one embodiment, the PEALD reaction is performed with BTBAS and a mixture of O2/N2O, and the PECVD reaction is performed with TEOS and/or silane. The TEOS and silane reactants have been found to be especially useful in practicing the PECVD reaction. Generally, the reactants listed above in the PEALD Reactants section may be used in the PECVD reaction.


The flow rate of reactants may vary depending on the desired process. In one embodiment related to PECVD undoped silicate glass (USG), SiH4 is used as a reactant and has a flow rate between about 100-1,500 sccm, with a flow of N2O between about 2,000-20,000 sccm. In another embodiment related to PECVD using TEOS, the flow of TEOS is between about 1-20 mL/min, and the flow of O2 is between about 2,000-30,000 sccm.


Chamber Conditions


The temperature in the reaction chamber during the PECVD reaction may be between about 50-450° C., in certain embodiments. This range may be especially appropriate for reactions using silane. Where other reactants are used, the temperature range may be more limited or more broad, for example between about 100-450° C. where TEOS is used.


The pressure in the reaction chamber during the PECVD reaction may be between about 1-10 Torr, for example about 5 Torr.


Because the chamber conditions are very similar between the PEALD operation and the PECVD operation, it is feasible to implement both types of reactions in a single reaction chamber. As discussed above, this is advantageous because it reduces or eliminates the risk of moisture entering the film as the substrate is moved between processing chambers, and reduces the need to perform a degassing operation between the two processes.


Plasma Generation Conditions


The PECVD reactions are driven by exposure to plasma. The plasma may be a capacitively coupled plasma or a remotely generated inductively coupled plasma. For the reasons discussed above, it may be preferable to avoid using an in situ inductively coupled plasma.


The gas used to generate the plasma will include at least one reactant. The plasma generation gas may also include other species, as well. For example, in certain embodiments the plasma generation gas includes an inert gas.


The frequency used to drive plasma formation may contain both LF and HF components. In some embodiments the HF frequency may be about 13.56 MHz or about 27 MHz. The LF frequency may be between about 300-400 kHz. The HF RF power used to drive plasma formation may be between about 200-3,000 W. The LF RF power used to drive plasma formation may be between about 200-2,500 W. These power levels represent the total power delivered, which is divided among four stations. The duration of plasma exposure depends on the desired thickness of the deposited film.


In some embodiments, pulsed PECVD methods may be used. These methods may involve pulsing precursor and/or RF power levels.


Purge Conditions


A purge is typically conducted after the PECVD deposition is complete. This purge operates to remove reactants and any byproducts from the reaction chamber. Because the film is already deposited at this point, the purge conditions are less important than with the PEALD reactions, which require many iterations of reactant purge and post-RF purge as the PEALD film is formed.


Apparatus


A suitable apparatus for performing the disclosed methods typically includes hardware for accomplishing the process operations and a system controller having instructions for controlling process operations in accordance with the present invention. For example, in some embodiments, the hardware may include one or more PEALD, PECVD or joint PEALD/PECVD process stations included in a process tool.



FIG. 6 provides a block diagram of an example apparatus that may be used to practice the disclosed embodiments. As shown, a reactor 600 includes a process chamber 624, which encloses other components of the reactor and serves to contain the plasma generated by, e.g., a capacitor type system including a showerhead 614 working in conjunction with a grounded heater block 620. A high-frequency RF generator 602, connected to a matching network 606, and a low-frequency RF generator 604 are connected to showerhead 614. The power and frequency supplied by matching network 606 is sufficient to generate a plasma from the process gas, for example 400-700 W total energy. In one implementation of the present invention both the HFRF generator and the LFRF generator are used. In a typical process, the high frequency RF component is generally between about 2-60 MHz; in a preferred embodiment, the HF component is about 13.56 MHz or 27 MHz. The low frequency LF component is generally between about 250-400 kHz; in a particular embodiment, the LF component is about 350 kHz.


Within the reactor, a wafer pedestal 618 supports a substrate 616. The pedestal typically includes a chuck, a fork, or lift pins to hold and transfer the substrate during and between the deposition and/or plasma treatment reactions. The chuck may be an electrostatic chuck, a mechanical chuck or various other types of chuck as are available for use in the industry and/or research.


The process gases are introduced via inlet 612. Multiple source gas lines 610 are connected to manifold 608. The gases may be premixed or not. Appropriate valving and mass flow control mechanisms are employed to ensure that the correct gases are delivered during the deposition and plasma treatment phases of the process. In the case that the chemical precursor(s) are delivered in liquid form, liquid flow control mechanisms are employed. The liquid is then vaporized and mixed with other process gases during its transportation in a manifold heated above its vaporization point before reaching the deposition chamber.


Process gases exit chamber 600 via an outlet 622. A vacuum pump 626 (e.g., a one or two stage mechanical dry pump and/or a turbomolecular pump) typically draws process gases out and maintains a suitably low pressure within the reactor by a close loop controlled flow restriction device, such as a throttle valve or a pendulum valve.


The invention may be implemented on a multi-station or single station tool. In specific embodiments, the 300 mm Novellus Vector™ tool having a 4-station deposition scheme or the 200 mm Sequel™ tool having a 6-station deposition scheme are used. It is possible to index the wafers after every deposition and/or post-deposition plasma anneal treatment until all the required depositions and treatments are completed, or multiple depositions and treatments can be conducted at a single station before indexing the wafer. It has been shown that film stress is the same in either case. However, conducting multiple depositions/treatments on one station is substantially faster than indexing following each deposition and/or treatment.



FIG. 7 shows a schematic view of an embodiment of a multi-station processing tool 2400 with an inbound load lock 2402 and an outbound load lock 2404, either or both of which may comprise a remote plasma source. A robot 2406, at atmospheric pressure, is configured to move wafers from a cassette loaded through a pod 2408 into inbound load lock 2402 via an atmospheric port 2410. A wafer is placed by the robot 2406 on a pedestal 2412 in the inbound load lock 2402, the atmospheric port 2410 is closed, and the load lock is pumped down. Where the inbound load lock 2402 comprises a remote plasma source, the wafer may be exposed to a remote plasma treatment in the load lock prior to being introduced into a processing chamber 2414. Further, the wafer also may be heated in the inbound load lock 2402 as well, for example, to remove moisture and adsorbed gases. Next, a chamber transport port 2416 to processing chamber 2414 is opened, and another robot (not shown) places the wafer into the reactor on a pedestal of a first station shown in the reactor for processing. While the embodiment depicted in FIG. 4 includes load locks, it will be appreciated that, in some embodiments, direct entry of a wafer into a process station may be provided.


The depicted processing chamber 2414 comprises four process stations, numbered from 1 to 4 in the embodiment shown in FIG. 4. Each station has a heated pedestal (shown at 2418 for station 1), and gas line inlets. It will be appreciated that in some embodiments, each process station may have different or multiple purposes. For example, in some embodiments, a process station may be switchable between a PEALD and PECVD process mode. Additionally or alternatively, in some embodiments, processing chamber 2414 may include one or more matched pairs of PEALD and PECVD process stations. While the depicted processing chamber 2414 comprises four stations, it will be understood that a processing chamber according to the present disclosure may have any suitable number of stations. For example, in some embodiments, a processing chamber may have five or more stations, while in other embodiments a processing chamber may have three or fewer stations.



FIG. 7 also depicts an embodiment of a wafer handling system 2490 for transferring wafers within processing chamber 2414. In some embodiments, wafer handling system 2490 may transfer wafers between various process stations and/or between a process station and a load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots. FIG. 7 also depicts an embodiment of a system controller 2450 employed to control process conditions and hardware states of process tool 2400. System controller 2450 may include one or more memory devices 2456, one or more mass storage devices 2454, and one or more processors 2452. Processor 2452 may include a CPU or computer, analog and/or digital input/output connections, stepper motor controller boards, etc.


In some embodiments, system controller 2450 controls all of the activities of process tool 2400. System controller 2450 executes system control software 2458 stored in mass storage device 2454, loaded into memory device 2456, and executed on processor 2452. System control software 2458 may include instructions for controlling the timing, mixture of gases, chamber and/or station pressure, chamber and/or station temperature, purge conditions and timing, wafer temperature, RF power levels, RF frequencies, substrate, pedestal, chuck and/or susceptor position, and other parameters of a particular process performed by process tool 2400. System control software 2458 may be configured in any suitable way. For example, various process tool component subroutines or control objects may be written to control operation of the process tool components necessary to carry out various process tool processes in accordance with the disclosed methods. System control software 2458 may be coded in any suitable computer readable programming language.


In some embodiments, system control software 2458 may include input/output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each phase of a PEALD process may include one or more instructions for execution by system controller 2450. The instructions for setting process conditions for a PEALD process phase may be included in a corresponding PEALD recipe phase. In some embodiments, the PEALD recipe phases may be sequentially arranged, so that all instructions for a PEALD process phase are executed concurrently with that process phase. The same can be said for PECVD processes and hybrid PEALD/PECVD processes.


Other computer software and/or programs stored on mass storage device 2454 and/or memory device 2456 associated with system controller 2450 may be employed in some embodiments. 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 2418 and to control the spacing between the substrate and other parts of process tool 2400.


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. 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.


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.


A plasma control program may include code for setting RF power levels applied to the process electrodes in one or more process stations.


In some embodiments, there may be a user interface associated with system controller 2450. 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 embodiments, parameters adjusted by system controller 2450 may relate to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels), pressure, temperature, 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 2450 from various process tool sensors. The signals for controlling the process may be output on the analog and digital output connections of process tool 2400. 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 2450 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 power level, RF bias power level, pressure, temperature, etc. The instructions may control the parameters to operate in-situ deposition of film stacks according to various embodiments described herein.


Lithographic patterning of a film typically comprises some or all of the following steps, each step enabled with a number of possible tools: (1) application of photoresist on a workpiece, e.g., a substrate having a silicon nitride film formed thereon, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or other suitable curing tool; (3) exposing the photoresist to visible or UV or x-ray light with a tool such as a wafer stepper; (4) developing the resist so as to selectively remove resist and thereby pattern it using a tool such as a wet bench or a spray developer; (5) transferring the resist pattern into an underlying film or workpiece by using a dry or plasma-assisted etching tool; and (6) removing the resist using a tool such as an RF or microwave plasma resist stripper. In some embodiments, an ashable hard mask layer (such as an amorphous carbon layer) and another suitable hard mask (such as an antireflective layer) may be deposited prior to applying the photoresist.


It is to be understood that the configurations and/or approaches described herein are exemplary in nature, and that these specific embodiments or examples are not to be considered in a limiting sense, because numerous variations are possible. The specific routines or methods described herein may represent one or more of any number of processing strategies. As such, various acts illustrated may be performed in the sequence illustrated, in other sequences, in parallel, or in some cases omitted. Likewise, the order of the above described processes may be changed.


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


EXPERIMENTAL


FIG. 8 presents a gap 802 partially filled with silicon oxide film 804 in a PEALD process according to the disclosed methods. Markers 806 are provided in order to evaluate the conformality of the oxide film 804. For the sake of clarity, only one marker is labeled in FIG. 8. Each of the markers 806 has an identical height. Thus, it is apparent that the deposited film is thicker at the bottom than at the top. Further, the lower sidewalls are thicker than the upper sidewalls, which are both thicker than the top region. The film thickness near the top is about the same as the film thickness in the top corner. The silicon oxide film 804 was deposited at about 400° C., with a 2 mL/min flow of BTBAS for a duration of about 0.3 seconds, followed by a reactant purge with a sweep duration of about 0.3 seconds, followed by delivery of a mixture of O2/N2O at 10 SLM each, coincident with a 0.5 second exposure to RF plasma, followed by a post-RF purge having a duration of 0.09 seconds. The plasma was a high frequency plasma, with a power of about 5 kW split among four pedestals. The film 804 shows a tapered profile, which is ideal for filling gaps, especially those having large aspect ratios. Although the PEALD process used to create the film 804 was terminated before the gap 802 was completely filled (in order to view the fill behavior), the PEALD process can be continued to completely fill the gap 802 without formation of any seams or voids.



FIG. 9 shows a substrate with a number of gaps filled with silicon-oxide according to the disclosed PEALD methods. The gaps in this case have an aspect ratio of about 7:1, and a CD on the order of about 30 nm. The deposited film was dense, and did not show any seams or voids.



FIG. 10 shows a close-up view of a gap filled according to the disclosed PEALD methods. No seams or voids are detected in the fill.



FIG. 11 shows a substrate having high aspect ratio gaps (AR about 8:1) filled according to the disclosed PEALD methods. Notably, the gap on the right shows some degree of reentrancy. The markers A and B are the same length. It can be seen that the gap is wider at marker B than at marker A. While the width difference is fairly slight, even small degrees of reentrancy will result in the formation of voids under many conventional methods.


It should be noted that the gaps shown in FIGS. 8-11 were filled with no etching operations performed.



FIG. 12 shows a wide gap filled with silicon oxide according to a disclosed PECVD method with TEOS performed at about 200° C. The film deposited was about 2,000 Å thick, and showed good gap fill properties, with no voids or seams. No etching operations were performed.

Claims
  • 1. A method comprising: (a) introducing a first reactant in vapor phase into a reaction chamber having a substrate therein, the substrate comprising a gap to be filled and allowing the first reactant to adsorb onto a substrate surface;(b) introducing a second reactant in vapor phase into the reaction chamber;(c) exposing the substrate surface to plasma to drive a surface reaction between the first and second reactants on the substrate surface;(d) sweeping or purging the reaction chamber;(e) repeating (a)-(d) one or more times to deposit a first dielectric film in the gap;(f) introducing at least a third reactant in vapor phase into the reaction chamber; and(g) generating a plasma from at least the third reactant to drive a gas phase reaction, wherein the gas phase reaction produces a second dielectric film, and wherein the second dielectric film is deposited on the first dielectric film.
  • 2. The method of claim 1, wherein the plasma in operation (g) is a capacitively coupled plasma.
  • 3. The method of claim 1, wherein operation (f) further comprises introducing a fourth reactant in vapor phase into the reaction chamber while introducing the third reactant into the reaction chamber.
  • 4. The method of claim 1, wherein the first dielectric film deposited in (e) comprises the same material as the second dielectric film deposited in (g).
  • 5. The method of claim 1, wherein the first dielectric film completely fills the gap.
  • 6. The method of claim 1, wherein the first dielectric film forms an indentation over the gap.
  • 7. The method of claim 1, wherein the first dielectric film and the second dielectric film are silicon oxide.
  • 8. The method of claim 1, wherein the reaction chamber is a multi-station chamber.
  • 9. The method of claim 1, wherein a gas used to generate the plasma in (c) comprises the second reactant.
  • 10. The method of claim 1, wherein the third reactant is the same as one of the first reactant and the second reactant.
  • 11. The method of claim 1, wherein the first reactant is a first silicon-containing reactant and the third reactant is a second silicon-containing reactant.
  • 12. The method of claim 10, wherein the first reactant and the third reactant are different.
  • 13. The method of claim 12, wherein the first reactant is an aminosilane.
  • 14. The method of claim 13, wherein the third reactant is tetra-ethoxy-silane (TEOS) or silane (SiH4).
US Referenced Citations (498)
Number Name Date Kind
4500563 Ellenberger et al. Feb 1985 A
5094984 Liu et al. Mar 1992 A
5223443 Chinn et al. Jun 1993 A
5230929 Caporiccio et al. Jul 1993 A
5318928 Gegenwart et al. Jun 1994 A
5496608 Matsuda et al. Mar 1996 A
5593914 Evans, Jr. et al. Jan 1997 A
5670432 Tsai Sep 1997 A
5856003 Chiu Jan 1999 A
5874368 Laxman et al. Feb 1999 A
5916365 Sherman Jun 1999 A
5932286 Beinglass et al. Aug 1999 A
6069058 Hong May 2000 A
6100202 Lin et al. Aug 2000 A
6156149 Cheung et al. Dec 2000 A
6218293 Kraus et al. Apr 2001 B1
6270572 Kim et al. Aug 2001 B1
6346741 Van Buskirk et al. Feb 2002 B1
6391803 Kim et al. May 2002 B1
6399221 Marks et al. Jun 2002 B1
6416822 Chiang et al. Jul 2002 B1
6428859 Chiang et al. Aug 2002 B1
6465272 Davis, Jr. et al. Oct 2002 B1
6468924 Lee et al. Oct 2002 B2
6482726 Aminpur et al. Nov 2002 B1
6509601 Lee et al. Jan 2003 B1
6528430 Kwan et al. Mar 2003 B2
6551893 Zheng et al. Apr 2003 B1
6569501 Chiang et al. May 2003 B2
6576053 Kim et al. Jun 2003 B1
6602784 Sneh Aug 2003 B2
6632478 Gaillard et al. Oct 2003 B2
6645574 Lee et al. Nov 2003 B1
6689220 Nguyen Feb 2004 B1
6723595 Park Apr 2004 B2
6730614 Lim et al. May 2004 B1
6743738 Todd Jun 2004 B2
6756318 Nguyen et al. Jun 2004 B2
6765303 Krivokapic et al. Jul 2004 B1
6809421 Hayasaka et al. Oct 2004 B1
6828218 Kim et al. Dec 2004 B2
6835417 Saenger et al. Dec 2004 B2
6861356 Matsuse et al. Mar 2005 B2
6884466 Kaloyeros et al. Apr 2005 B2
6930058 Hill et al. Aug 2005 B2
6930060 Chou et al. Aug 2005 B2
6943092 Kim et al. Sep 2005 B2
6962876 Ahn et al. Nov 2005 B2
6987240 Jennings et al. Jan 2006 B2
7001844 Chakravarti et al. Feb 2006 B2
7041335 Chung May 2006 B2
7077904 Cho et al. Jul 2006 B2
7081271 Chung et al. Jul 2006 B2
7097886 Moghadam et al. Aug 2006 B2
7109129 Papasouliotis Sep 2006 B1
7115166 Vaartstra et al. Oct 2006 B2
7115528 Vaartstra et al. Oct 2006 B2
7122222 Xiao et al. Oct 2006 B2
7122464 Vaarstra Oct 2006 B2
7125815 Vaartstra Oct 2006 B2
7132353 Xia et al. Nov 2006 B1
7141278 Koh et al. Nov 2006 B2
7148155 Tarafdar et al. Dec 2006 B1
7151039 Lee et al. Dec 2006 B2
7172792 Wang et al. Feb 2007 B2
7176084 Lee et al. Feb 2007 B2
7205187 Leith et al. Apr 2007 B2
7223649 Oh et al. May 2007 B2
7235484 Nguyen et al. Jun 2007 B2
7241686 Marcadal et al. Jul 2007 B2
7244668 Kim Jul 2007 B2
7250083 Sneh Jul 2007 B2
7259050 Chen et al. Aug 2007 B2
7261919 Mehregany et al. Aug 2007 B2
7294582 Haverkort et al. Nov 2007 B2
7297641 Todd et al. Nov 2007 B2
7300885 Hasebe et al. Nov 2007 B2
7314835 Ishizaka et al. Jan 2008 B2
7341959 Brcka Mar 2008 B2
7351668 Chou et al. Apr 2008 B2
7361538 Luan et al. Apr 2008 B2
7361611 Chakravarti et al. Apr 2008 B2
7390743 Shin Jun 2008 B2
7393561 Paranjpe Jul 2008 B2
7399388 Moghadam et al. Jul 2008 B2
7419888 Yang et al. Sep 2008 B2
7435454 Brcka Oct 2008 B2
7435684 Lang et al. Oct 2008 B1
7462571 Hasebe et al. Dec 2008 B2
7482247 Papasouliotis et al. Jan 2009 B1
7488694 Kim et al. Feb 2009 B2
7507676 Chou et al. Mar 2009 B2
7510984 Saito et al. Mar 2009 B2
7521331 Park et al. Apr 2009 B2
7524762 Marcadal et al. Apr 2009 B2
7544615 Vaartstra Jun 2009 B2
7572052 Ravi et al. Aug 2009 B2
7592231 Cheng et al. Sep 2009 B2
7595010 Chakravarti et al. Sep 2009 B2
7601648 Chua et al. Oct 2009 B2
7615438 Ahn et al. Nov 2009 B2
7615449 Chung et al. Nov 2009 B2
7622369 Lee et al. Nov 2009 B1
7622383 Kim et al. Nov 2009 B2
7629267 Wan et al. Dec 2009 B2
7632757 Matsuura Dec 2009 B2
7633125 Lu et al. Dec 2009 B2
7638170 Li Dec 2009 B2
7645484 Ishizaka Jan 2010 B2
7651729 Kim et al. Jan 2010 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
7687409 Ahn et al. Mar 2010 B2
7713592 Nguyen et al. May 2010 B2
7745346 Hausmann et al. Jun 2010 B2
7758920 Hasebe et al. Jul 2010 B2
7776733 Hasegawa Aug 2010 B2
7790633 Tarafdar et al. Sep 2010 B1
7825039 Takahashi et al. Nov 2010 B2
7863190 Papasouliotis et al. Jan 2011 B1
7906168 Hasebe et al. Mar 2011 B2
7919416 Lee et al. Apr 2011 B2
7923068 Dickey et al. Apr 2011 B2
7923378 Hasebe et al. Apr 2011 B2
7959985 Ishizaka et al. Jun 2011 B2
7964241 Hasebe et al. Jun 2011 B2
7964513 Todd et al. Jun 2011 B2
7972980 Lee et al. Jul 2011 B2
7981473 Kim et al. Jul 2011 B2
7989365 Park et al. Aug 2011 B2
8034673 Kadonaga et al. Oct 2011 B2
8080290 Hasebe et al. Dec 2011 B2
8101531 Li et al. Jan 2012 B1
8119424 Mather et al. Feb 2012 B2
8119544 Hasebe et al. Feb 2012 B2
8133797 van Schravendijk 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
8278224 Mui et al. Oct 2012 B1
8334218 Van Nooten et al. Dec 2012 B2
8338312 Sato et al. Dec 2012 B2
8357619 Hasebe et al. Jan 2013 B2
8366953 Kohno et al. Feb 2013 B2
8383525 Raisanen et al. Feb 2013 B2
8394466 Hong et al. Mar 2013 B2
8524612 Li et al. Sep 2013 B2
8592328 Hausmann et al. Nov 2013 B2
8633050 Pierreux Jan 2014 B2
8637411 Swaminathan et al. Jan 2014 B2
8647993 Lavoie et al. Feb 2014 B2
8669185 Onizawa et al. Mar 2014 B2
8728955 LaVoie et al. May 2014 B2
8728956 LaVoie et al. May 2014 B2
8829636 Ohchi et al. Sep 2014 B2
8846484 Lee et al. Sep 2014 B2
8956983 Swaminathan et al. Feb 2015 B2
8999859 Swaminathan et al. Apr 2015 B2
9023693 Lin et al. May 2015 B1
9076646 Sims et al. Jul 2015 B2
9214334 Swaminathan et al. Dec 2015 B2
9230800 Lavoie et al. Jan 2016 B2
9257274 Kang et al. Feb 2016 B2
9287113 Kang Mar 2016 B2
9355839 Swaminathan et al. May 2016 B2
9355886 Swaminathan et al. May 2016 B2
9373500 Swaminathan et al. Jun 2016 B2
9406693 Pang et al. Aug 2016 B1
9502238 Danek et al. Nov 2016 B2
9564312 Henri et al. Feb 2017 B2
9570274 Swaminathan et al. Feb 2017 B2
9570290 Swaminathan et al. Feb 2017 B2
9611544 Lavoie et al. Apr 2017 B2
9627221 Zaitsu et al. Apr 2017 B1
9673041 Swaminathan et al. Jun 2017 B2
9685320 Kang et al. Jun 2017 B2
9773643 Singhal et al. Sep 2017 B1
9786570 Kang et al. Oct 2017 B2
9793110 Kang et al. Oct 2017 B2
9875891 Henri et al. Jan 2018 B2
9892917 Swaminathan et al. Feb 2018 B2
9997357 Arghavani et al. Jun 2018 B2
10008428 Kang et al. Jun 2018 B2
10037884 Ou et al. Jul 2018 B2
10043655 Swaminathan et al. Aug 2018 B2
10043657 Swaminathan et al. Aug 2018 B2
10062563 Kumar et al. Aug 2018 B2
10269559 Abel et al. Apr 2019 B2
10361076 Kang et al. Jul 2019 B2
10373806 Singhal et al. Aug 2019 B2
10559468 Arghavani et al. Feb 2020 B2
10679848 Kumar et al. Jun 2020 B2
10741458 Kang et al. Aug 2020 B2
10763108 Hausmann et al. Sep 2020 B2
10804099 Henri et al. Oct 2020 B2
20020066411 Chiang et al. Jun 2002 A1
20020076507 Chiang et al. Jun 2002 A1
20020153101 Nguyen et al. Oct 2002 A1
20020175393 Baum et al. Nov 2002 A1
20030008070 Seutter et al. Jan 2003 A1
20030024477 Okuda et al. Feb 2003 A1
20030108674 Chung et al. Jun 2003 A1
20030134038 Paranjpe Jul 2003 A1
20030143839 Raaijmakers et al. Jul 2003 A1
20030200917 Vaartstra Oct 2003 A1
20030216006 Li et al. Nov 2003 A1
20040033698 Lee et al. Feb 2004 A1
20040043633 Vaartstra Mar 2004 A1
20040053515 Comita et al. Mar 2004 A1
20040121164 Iacovangelo et al. Jun 2004 A1
20040129212 Gadgil et al. Jul 2004 A1
20040146644 Xiao et al. Jul 2004 A1
20040151845 Nguyen et al. Aug 2004 A1
20040157472 Sugino et al. Aug 2004 A1
20040171280 Conley, Jr. et al. Sep 2004 A1
20040219746 Vaartstra et al. Nov 2004 A1
20040219784 Kang et al. Nov 2004 A1
20040231799 Lee et al. Nov 2004 A1
20050005851 Keshner et al. Jan 2005 A1
20050009368 Vaartstra Jan 2005 A1
20050042865 Cabral et al. Feb 2005 A1
20050079661 Cho et al. Apr 2005 A1
20050100670 Dussarrat et al. May 2005 A1
20050109276 Iyer et al. May 2005 A1
20050118837 Todd et al. Jun 2005 A1
20050142795 Ahn et al. Jun 2005 A1
20050158983 Hoshi et al. Jul 2005 A1
20050159017 Kim et al. Jul 2005 A1
20050181535 Yun et al. Aug 2005 A1
20050184397 Gates et al. Aug 2005 A1
20050196977 Saito et al. Sep 2005 A1
20050208718 Lim et al. Sep 2005 A1
20050230047 Collins et al. Oct 2005 A1
20050233553 Kountz et al. Oct 2005 A1
20050260347 Narwankar et al. Nov 2005 A1
20050276099 Horng et al. Dec 2005 A1
20050276930 Gates et al. Dec 2005 A1
20050282346 Barth et al. Dec 2005 A1
20050287775 Hasebe et al. Dec 2005 A1
20060003557 Cabral et al. Jan 2006 A1
20060009041 Iyer et al. Jan 2006 A1
20060030148 Seutter et al. Feb 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
20060105106 Balseanu et al. May 2006 A1
20060165890 Kaushal et al. Jul 2006 A1
20060183055 O'Neill et al. Aug 2006 A1
20060199357 Wan et al. Sep 2006 A1
20060216418 Matsuura Sep 2006 A1
20060228868 Ahn et al. Oct 2006 A1
20060281254 Lee et al. Dec 2006 A1
20060286774 Singh et al. Dec 2006 A1
20060286776 Ranish et al. Dec 2006 A1
20060286818 Wang et al. Dec 2006 A1
20070010071 Matsuura Jan 2007 A1
20070026540 Nooten et al. Feb 2007 A1
20070032047 Hasebe et al. Feb 2007 A1
20070048455 Koh et al. Mar 2007 A1
20070065576 Singh et al. Mar 2007 A1
20070087574 Gupta et al. Apr 2007 A1
20070087581 Singh et al. Apr 2007 A1
20070116887 Faguet May 2007 A1
20070119370 Ma et al. May 2007 A1
20070134942 Ahn et al. Jun 2007 A1
20070137572 Matsuura et al. Jun 2007 A1
20070145483 Ono Jun 2007 A1
20070167028 Chou et al. Jul 2007 A1
20070215036 Park et al. Sep 2007 A1
20070218701 Shimizu et al. Sep 2007 A1
20070231487 Ishizaka Oct 2007 A1
20070232082 Balseanu et al. Oct 2007 A1
20070243693 Nemani et al. Oct 2007 A1
20070245959 Paterson et al. Oct 2007 A1
20070251444 Gros-Jean et al. Nov 2007 A1
20070259110 Mahajani et al. Nov 2007 A1
20070281495 Mallick et al. Dec 2007 A1
20070298585 Lubomirsky et al. Dec 2007 A1
20080014759 Chua et al. Jan 2008 A1
20080038936 Todd et al. Feb 2008 A1
20080063791 Hasebe et al. Mar 2008 A1
20080075881 Won et al. Mar 2008 A1
20080081470 Clark Apr 2008 A1
20080085610 Wang et al. Apr 2008 A1
20080087890 Ahn et al. Apr 2008 A1
20080123394 Lee et al. May 2008 A1
20080131601 Kim et al. Jun 2008 A1
20080138996 Nishizuka Jun 2008 A1
20080139003 Pirzada et al. Jun 2008 A1
20080142483 Hua et al. Jun 2008 A1
20080207007 Thridandam et al. Aug 2008 A1
20080213479 Chou et al. Sep 2008 A1
20080233762 Hong Sep 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
20080317972 Hendriks et al. Dec 2008 A1
20090018668 Galbraith Jan 2009 A1
20090039349 Honda Feb 2009 A1
20090041952 Yoon et al. Feb 2009 A1
20090065896 Hwang et al. Mar 2009 A1
20090075490 Dussarrat Mar 2009 A1
20090148625 Yeom et al. Jun 2009 A1
20090155606 Yoon et al. Jun 2009 A1
20090155968 Min et al. Jun 2009 A1
20090163012 Clark et al. Jun 2009 A1
20090191687 Hong et al. Jul 2009 A1
20090191722 Hasebe et al. Jul 2009 A1
20090203197 Hanawa et al. Aug 2009 A1
20090208880 Nemani et al. Aug 2009 A1
20090278224 Kim et al. Nov 2009 A1
20090286381 van Schravendijk et al. Nov 2009 A1
20090286402 Xia et al. Nov 2009 A1
20100022099 Van Nooten et al. Jan 2010 A1
20100025824 Chen et al. Feb 2010 A1
20100048011 Yeh et al. Feb 2010 A1
20100051578 Chang et al. Mar 2010 A1
20100051579 Kobayashi Mar 2010 A1
20100078316 Edakawa et al. Apr 2010 A1
20100096687 Balseanu et al. Apr 2010 A1
20100096688 Balseanu et al. Apr 2010 A1
20100099236 Kwon et al. Apr 2010 A1
20100099271 Hausmann et al. Apr 2010 A1
20100102417 Ganguli et al. Apr 2010 A1
20100120262 Vorsa et al. May 2010 A1
20100124618 Kobayashi et al. May 2010 A1
20100124621 Kobayashi et al. May 2010 A1
20100126667 Yin et al. May 2010 A1
20100136260 Matsunaga et al. Jun 2010 A1
20100136313 Shimizu et al. Jun 2010 A1
20100144162 Lee et al. Jun 2010 A1
20100167555 Maula et al. Jul 2010 A1
20100173494 Kobrin Jul 2010 A1
20100190353 Nguyen et al. Jul 2010 A1
20100197129 Ishikawa Aug 2010 A1
20100216268 Katayama et al. Aug 2010 A1
20100221925 Lee et al. Sep 2010 A1
20100244114 Konno et al. Sep 2010 A1
20100255218 Oka 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
20110003445 Murata et al. Jan 2011 A1
20110014795 Lee et al. Jan 2011 A1
20110014796 Wallick et al. Jan 2011 A1
20110014798 Mallick et al. Jan 2011 A1
20110042744 Cheng et al. Feb 2011 A1
20110064969 Chen et al. Mar 2011 A1
20110086516 Lee et al. Apr 2011 A1
20110121354 Schmid et al. May 2011 A1
20110124187 Afzali-Ardakani et al. May 2011 A1
20110139176 Cheung et al. Jun 2011 A1
20110143548 Cheung et al. Jun 2011 A1
20110151142 Seamons et al. Jun 2011 A1
20110151246 Ramon Moreno et al. Jun 2011 A1
20110151674 Tang et al. Jun 2011 A1
20110151678 Ashtiani et al. Jun 2011 A1
20110159202 Matsushita et al. Jun 2011 A1
20110159673 Hanawa et al. Jun 2011 A1
20110171775 Yamamoto et al. Jul 2011 A1
20110176967 Okuda et al. Jul 2011 A1
20110198756 Thenappan et al. Aug 2011 A1
20110201210 Sato et al. Aug 2011 A1
20110207323 Ditizio Aug 2011 A1
20110215445 Yang et al. Sep 2011 A1
20110256726 LaVoie et al. Oct 2011 A1
20110256734 Hausmann et al. Oct 2011 A1
20110298099 Lee et al. Dec 2011 A1
20110309475 Lee Dec 2011 A1
20120009802 LaVoie et al. Jan 2012 A1
20120009803 Jung et al. Jan 2012 A1
20120021252 Lee Jan 2012 A1
20120028454 Swaminathan et al. Feb 2012 A1
20120028469 Onizawa et al. Feb 2012 A1
20120058282 Hong et al. Mar 2012 A1
20120064682 Jang et al. Mar 2012 A1
20120074844 York et al. Mar 2012 A1
20120077349 Li et al. Mar 2012 A1
20120086048 Park et al. Apr 2012 A1
20120108079 Mahajani May 2012 A1
20120113672 Dubrow et al. May 2012 A1
20120161405 Mohn et al. Jun 2012 A1
20120164846 Ha et al. Jun 2012 A1
20120193693 Kanaya Aug 2012 A1
20120213940 Mallick Aug 2012 A1
20120258261 Reddy et al. Oct 2012 A1
20120280200 Tada et al. Nov 2012 A1
20120282418 Chou et al. Nov 2012 A1
20120315394 Ito Dec 2012 A1
20130040447 Swaminathan et al. Feb 2013 A1
20130043512 Huang et al. Feb 2013 A1
20130058161 Yamanaka et al. Mar 2013 A1
20130058162 Yamanaka et al. Mar 2013 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
20130189854 Hausmann et al. Jul 2013 A1
20130196516 Lavoie et al. Aug 2013 A1
20130252437 Sano et al. Sep 2013 A1
20130309415 Swaminathan et al. Nov 2013 A1
20130319329 Li et al. Dec 2013 A1
20130323923 Koehler et al. Dec 2013 A1
20130344248 Clark Dec 2013 A1
20140030444 Swaminathan Jan 2014 A1
20140049162 Thomas et al. Feb 2014 A1
20140051262 Lavoie et al. Feb 2014 A9
20140087066 Wang et al. Mar 2014 A1
20140094035 Ji et al. Apr 2014 A1
20140106574 Kang et al. Apr 2014 A1
20140113457 Sims et al. Apr 2014 A1
20140120270 Tour et al. May 2014 A1
20140120737 Swaminathan et al. May 2014 A1
20140134827 Swaminathan et al. May 2014 A1
20140141542 Kang et al. May 2014 A1
20140141626 Hausmann et al. May 2014 A1
20140170853 Shamma et al. Jun 2014 A1
20140182619 Goto et al. Jul 2014 A1
20140209562 LaVoie et al. Jul 2014 A1
20140216337 Swaminathan et al. Aug 2014 A1
20140239462 Shamma et al. Aug 2014 A1
20140262038 Wang et al. Sep 2014 A1
20140264555 Ahn et al. Sep 2014 A1
20140273428 Shero et al. Sep 2014 A1
20140273528 Niskanen et al. Sep 2014 A1
20140295084 Shirai et al. Oct 2014 A1
20140302686 Pan et al. Oct 2014 A1
20150041867 Han Feb 2015 A1
20150048740 Valcore, Jr. et al. Feb 2015 A1
20150093902 Huang et al. Apr 2015 A1
20150109814 Chen et al. Apr 2015 A1
20150126042 Pasquale et al. May 2015 A1
20150147483 Fukazawa May 2015 A1
20150159271 Lee et al. Jun 2015 A1
20150170900 LaVoie Jun 2015 A1
20150206719 Swaminathan et al. Jul 2015 A1
20150235835 Swaminathan et al. Aug 2015 A1
20150243883 Swaminathan et al. Aug 2015 A1
20150249013 Arghavani et al. Sep 2015 A1
20150294905 Wu et al. Oct 2015 A1
20160020092 Kang et al. Jan 2016 A1
20160064211 Swaminathan et al. Mar 2016 A1
20160079037 Hirano et al. Mar 2016 A1
20160118246 Kang et al. Apr 2016 A1
20160148800 Henri et al. May 2016 A1
20160148806 Henri et al. May 2016 A1
20160155676 Kang et al. Jun 2016 A1
20160163539 Kang et al. Jun 2016 A9
20160163972 Swaminathan et al. Jun 2016 A1
20160240428 Tung et al. Aug 2016 A1
20160251756 Lansalot-Matras et al. Sep 2016 A1
20160260584 Marakhtanov et al. Sep 2016 A1
20160293385 Kapoor et al. Oct 2016 A1
20160293398 Danek et al. Oct 2016 A1
20160293838 Swaminathan et al. Oct 2016 A1
20160322215 Shaikh Nov 2016 A1
20160322371 Yonemochi Nov 2016 A1
20160329206 Kumar et al. Nov 2016 A1
20160329423 Kawahara et al. Nov 2016 A1
20160336178 Swaminathan et al. Nov 2016 A1
20160340782 Chandrasekharan et al. Nov 2016 A1
20160365425 Chen et al. Dec 2016 A1
20160379826 Arghavani et al. Dec 2016 A9
20170009346 Kumar et al. Jan 2017 A1
20170062204 Suzuki et al. Mar 2017 A1
20170092735 Hashemi et al. Mar 2017 A1
20170103891 Lee et al. Apr 2017 A1
20170110364 Song et al. Apr 2017 A1
20170110533 Huang et al. Apr 2017 A1
20170117134 Henri et al. Apr 2017 A1
20170117150 Liao et al. Apr 2017 A1
20170140926 Pore et al. May 2017 A1
20170148628 Swaminathan et al. May 2017 A1
20170170026 Hudson et al. Jun 2017 A1
20170221718 Tapily Aug 2017 A1
20170226637 Lubomirsky et al. Aug 2017 A1
20170250068 Ishikawa et al. Aug 2017 A1
20170263437 Li et al. Sep 2017 A1
20170263450 Swaminathan et al. Sep 2017 A1
20170316940 Ishikawa et al. Nov 2017 A1
20170316988 Kang et al. Nov 2017 A1
20170323786 Kang et al. Nov 2017 A1
20180005801 Singhal et al. Jan 2018 A1
20180005814 Kumar et al. Jan 2018 A1
20180061628 Ou et al. Mar 2018 A1
20180138028 Henri et al. May 2018 A1
20180247875 Kang et al. Aug 2018 A1
20180269061 Arghavani et al. Sep 2018 A1
20180323057 Kumar et al. Nov 2018 A1
20190057858 Hausmann et al. Feb 2019 A1
20190080903 Abel et al. Mar 2019 A1
20190385820 Singhal et al. Dec 2019 A1
20190385850 Arghavani et al. Dec 2019 A1
Foreign Referenced Citations (143)
Number Date Country
1732288 Feb 2006 CN
1768158 May 2006 CN
1841676 Oct 2006 CN
1926668 Mar 2007 CN
101006195 Jul 2007 CN
101255548 Sep 2008 CN
101328578 Dec 2008 CN
101378007 Mar 2009 CN
101416293 Apr 2009 CN
101535524 Sep 2009 CN
101736326 Jun 2010 CN
101889331 Nov 2010 CN
102005462 Apr 2011 CN
102191479 Sep 2011 CN
102471885 May 2012 CN
102687249 Sep 2012 CN
102906304 Jan 2013 CN
103137864 Jun 2013 CN
103928396 Jul 2014 CN
105391427 Mar 2016 CN
105719954 Jun 2016 CN
0 277 766 Aug 1988 EP
0 541 212 May 1993 EP
1 081 754 Jul 2001 EP
1 703 552 Sep 2006 EP
2 278 046 Jan 2011 EP
S48-043472 Jun 1973 JP
H02-093071 Apr 1990 JP
H03-011635 Jan 1991 JP
05-226279 Sep 1993 JP
H06-177120 Jun 1994 JP
07-81271 Mar 1995 JP
H07-176084 Jul 1995 JP
H09-102494 Apr 1997 JP
H09-219401 Aug 1997 JP
10-98032 Apr 1998 JP
H10-189467 Jul 1998 JP
H11-172439 Jun 1999 JP
2001-274404 Oct 2001 JP
2001-338922 Dec 2001 JP
2002-009072 Jan 2002 JP
2002-134497 May 2002 JP
2002-164345 Jun 2002 JP
2002-539640 Nov 2002 JP
2005-210076 Aug 2005 JP
2005-310927 Nov 2005 JP
2006-032695 Feb 2006 JP
2006-060091 Mar 2006 JP
2006-303431 Nov 2006 JP
2007-165883 Jun 2007 JP
2007-180362 Jul 2007 JP
2007-189173 Jul 2007 JP
2007-521658 Aug 2007 JP
2007-287889 Nov 2007 JP
2007-287890 Nov 2007 JP
2008-500742 Jan 2008 JP
2008-506262 Feb 2008 JP
2008-060455 Mar 2008 JP
2008-109093 May 2008 JP
2008-517479 May 2008 JP
2008-522405 Jun 2008 JP
2008-182199 Aug 2008 JP
2008-258591 Oct 2008 JP
2008-294260 Dec 2008 JP
2008-306093 Dec 2008 JP
2009-65203 Mar 2009 JP
2009-170823 Jul 2009 JP
2009-540128 Nov 2009 JP
4364320 Nov 2009 JP
2010-10497 Jan 2010 JP
2010-043081 Feb 2010 JP
2010-103484 May 2010 JP
2010-118664 May 2010 JP
2010-152136 Jul 2010 JP
2010-183069 Aug 2010 JP
2010-530127 Sep 2010 JP
2010-245518 Oct 2010 JP
2010-251654 Nov 2010 JP
2010-283388 Dec 2010 JP
2010-539730 Dec 2010 JP
2011-023576 Feb 2011 JP
2011-023655 Feb 2011 JP
2011-054968 Mar 2011 JP
11-067744 Apr 2011 JP
2011-187934 Sep 2011 JP
2012-506640 Mar 2012 JP
2012-199306 Oct 2012 JP
2013-102130 May 2013 JP
2013-166965 Aug 2013 JP
2013-196822 Sep 2013 JP
2013-225655 Oct 2013 JP
2013-240042 Nov 2013 JP
2014-532304 Dec 2014 JP
10-2001-0111448 Dec 2001 KR
10-0356473 Oct 2002 KR
10-2004-0001036 Jan 2004 KR
2004-0097219 Nov 2004 KR
10-2006-0056883 May 2006 KR
10-0721503 May 2007 KR
10-2007-0060104 Jun 2007 KR
10-0734748 Jul 2007 KR
2008-0052499 Jun 2008 KR
10-2009-0057665 Jun 2009 KR
10-2009-0080019 Jul 2009 KR
10-2009-0081396 Jul 2009 KR
10-2009-0116433 Nov 2009 KR
10-2010-0133377 Dec 2010 KR
2011-0016916 Feb 2011 KR
10-2011-0086090 Jul 2011 KR
10-2013-0056608 May 2013 KR
2013-0057409 May 2013 KR
10-2014-0069326 Jun 2014 KR
10-2015-0025224 Mar 2015 KR
10-1762978 Jul 2017 KR
188537 Apr 2013 SG
483103 Apr 2002 TW
200701341 Jan 2007 TW
200721306 Jun 2007 TW
201009942 Mar 2010 TW
201042706 Dec 2010 TW
201113934 Apr 2011 TW
201140695 Nov 2011 TW
201144475 Dec 2011 TW
201621974 Jun 2016 TW
WO 2004032196 Apr 2004 WO
WO 2006014471 Feb 2006 WO
WO 2006018441 Feb 2006 WO
WO 2006026350 Mar 2006 WO
WO 2006104741 Oct 2006 WO
WO 2007043709 Apr 2007 WO
WO 2007118026 Oct 2007 WO
WO 2011087580 Jul 2011 WO
WO 2011087850 Jul 2011 WO
WO 2011130326 Oct 2011 WO
WO 2011130397 Oct 2011 WO
WO 2012040317 Mar 2012 WO
WO 2012048094 Apr 2012 WO
WO 2012087737 Jun 2012 WO
WO 2013032786 Mar 2013 WO
WO 2013043330 Mar 2013 WO
WO 2013065806 May 2013 WO
WO 2013095396 Jun 2013 WO
WO 2013112727 Aug 2013 WO
Non-Patent Literature Citations (277)
Entry
U.S. Office Action dated Mar. 15, 2013 issued in U.S. Appl. No. 13/084,399.
U.S. Final Office Action dated Sep. 13, 2013 issued in U.S. Appl. No. 13/084,399.
U.S. Notice of Allowance dated Jan. 15, 2014 issued in U.S. Appl. No. 13/084,399.
U.S. Office Action dated Jan. 2, 2015 issued in U.S. Appl. No. 14/231,554.
U.S. Final Office Action dated Jun. 10, 2015 issued in U.S. Appl. No. 14/231,554.
U.S. Notice of Allowance dated Aug. 31, 2015 issued in U.S. Appl. No. 14/231,554.
U.S. Office Action dated Sep. 14, 2012 issued in U.S. Appl. No. 13/084,305.
U.S. Final Office Action dated Apr. 25, 2013 issued in U.S. Appl. No. 13/084,305.
U.S. Office Action dated Apr. 13, 2011 issued in U.S. Appl. No. 12/889,132.
U.S. Notice of Allowance dated Sep. 30, 2011 issued in U.S. Appl. No. 12/889,132.
U.S. Office Action dated Aug. 1, 2012 issued in U.S. Appl. No. 13/011,569.
U.S. Final Office Action dated Feb. 26, 2013 issued in U.S. Appl. No. 13/011,569.
U.S. Notice of Allowance dated May 6, 2013 issued in U.S. Appl. No. 13/011,569.
U.S. Office Action dated Jul. 1, 2016 issued in U.S. Appl. No. 13/963,212.
U.S. Office Action dated Jan. 12, 2017 issued in U.S. Appl. No. 13/963,212.
U.S. Final Office Action dated Jun. 28, 2017 issued in U.S. Appl. No. 13/963,212.
U.S. Office Action dated Jan. 24, 2018 issued in U.S. Appl. No. 13/963,212.
U.S. Office Action dated Apr. 4, 2013 issued U.S. Appl. No. 13/242,084.
U.S. Notice of Allowance dated Jun. 19, 2013 issued U.S. Appl. No. 13/242,084.
U.S. Notice of Allowance dated Sep. 19, 2013 issued U.S. Appl. No. 13/242,084.
U.S. Office Action dated Sep. 21, 2015 issued U.S. Appl. No. 14/607,997.
U.S. Final Office Action dated Mar. 18, 2016 issued U.S. Appl. No. 14/607,997.
U.S. Notice of Allowance dated Jun. 16, 2016 issued U.S. Appl. No. 14/607,997.
U.S. Notice of Allowance dated Sep. 27, 2016 issued U.S. Appl. No. 14/607,997.
U.S. Office Action dated Sep. 26, 2017 issued in U.S. Appl. No. 15/426,889.
U.S. Notice of Allowance dated Mar. 28, 2018 issued in U.S. Appl. No. 15/426,889.
U.S. Notice of Allowance dated Aug. 7, 2014 issued U.S. Appl. No. 14/133,239.
U.S. Notice of Allowance dated Nov. 26, 2014 issued U.S. Appl. No. 14/133,239.
U.S. Office Action dated Apr. 29, 2013 issued U.S. Appl. No. 13/224,240.
U.S. Final Office Action dated Nov. 22, 2013 issued U.S. Appl. No. 13/224,240.
U.S. Examiner's Answer to Appeal Brief (filed May 22, 2014) Before the Patent Trial and Appeal Board dated Aug. 14, 2014 issued U.S. Appl. No. 13/224,240.
U.S. Patent Board Decision on Appeal Before the Patent Trial and Appeal Board (Examiner Affirmed) dated Aug. 11, 2016 issued U.S. Appl. No. 13/224,240.
U.S. Notice of Allowance dated Nov. 17, 2016 issued U.S. Appl. No. 13/224,240.
U.S. Notice of Allowance (Supplemental Notice of Allowability) dated Feb. 21, 2017 issued U.S. Appl. No. 13/224,240.
U.S. Office Action dated Jun. 7, 2013 issued U.S. Appl. No. 13/414,619.
U.S. Notice of Allowance dated Jul. 26, 2013, issued U.S. Appl. No. 13/414,619.
U.S. Office Action dated May 24, 2013 issued U.S. Appl. No. 13/472,282.
U.S. Notice of Allowance dated Oct. 4, 2013 issued U.S. Appl. No. 13/472,282.
U.S. Office Action dated May 21, 2014 issued in U.S. Appl. No. 13/607,386.
U.S. Notice of Allowance dated Oct. 8, 2014 issued in U.S. Appl. No. 13/607,386.
U.S. Notice of Allowance dated Nov. 19, 2014 issued in U.S. Appl. No. 13/607,386.
U.S. Office Action dated Jun. 13, 2014 issued in U.S. Appl. No. 13/953,616.
U.S. Final Office Action dated Nov. 24, 2014 issued in U.S. Appl. No. 13/953,616.
U.S. Office Action dated Dec. 11, 2014 issued in U.S. Appl. No. 14/074,596.
U.S. Office Action dated Dec. 24, 2015 issued in U.S. Appl. No. 14/074,596.
U.S. Notice of Allowance dated Feb. 12, 2016 issued in U.S. Appl. No. 14/074,596.
U.S. Office Action dated May 15, 2015 issued in U.S. Appl. No. 14/074,617.
U.S. Notice of Allowance dated Nov. 20, 2015 issued in U.S. Appl. No. 14/074,617.
U.S. Office Action dated Dec. 30, 2016 issued in U.S. Appl. No. 15/015,952.
U.S. Notice of Allowance dated Jun. 15, 2017 issued in U.S. Appl. No. 15/015,952.
U.S. Notice of Allowance dated Jan. 29, 2018 issued in U.S. Appl. No. 15/650,662.
U.S. Office Action dated Aug. 14, 2015 issued in U.S. Appl. No. 14/061,587.
U.S. Notice of Allowance dated Feb. 11, 2016 issued in U.S. Appl. No. 14/061,587.
U.S. Notice of Allowance [Supplemental Notice of Allowability] dated Mar. 1, 2016 issued in U.S. Appl. No. 14/061,587.
U.S. Office Action dated Mar. 2, 2015 issued in U.S. Appl. No. 14/137,860.
U.S. Notice of Allowance dated Oct. 1, 2015 issued in U.S. Appl. No. 14/137,860.
U.S. Notice of Allowance [Supplemental Notice of Allowability] dated Oct. 22, 2015 issued in U.S. Appl. No. 14/137,860.
U.S. Office Action dated Feb. 3, 2017 issued in U.S. Appl. No. 14/987,542.
U.S. Notice of Allowance dated Jun. 20, 2017 issued in U.S. Appl. No. 14/987,542.
U.S. Notice of Allowance dated Aug. 22, 2017 issued in U.S. Appl. No. 14/987,542.
U.S. Office Action dated Nov. 9, 2018 issued in U.S. Appl. No. 15/654,186.
U.S. Notice of Allowance dated Mar. 7, 2019 issued in U.S. Appl. No. 15/654,186.
U.S. Office Action dated Jul. 10, 2014 issued in U.S. Appl. No. 14/144,107.
U.S. Final Office Action dated Jan. 15, 2015 issued in U.S. Appl. No. 14/144,107.
U.S. Notice of Allowance dated Mar. 19, 2015 issued in U.S. Appl. No. 14/144,107.
U.S. Office Action dated Oct. 21, 2015 issued in U.S. Appl. No. 14/194,549.
U.S. Final Office Action dated Nov. 1, 2016 issued in U.S. Appl. No. 14/194,549.
U.S. Office Action dated Apr. 19, 2017 issued in U.S. Appl. No. 14/194,549.
U.S. Final Office Action dated Sep. 20, 2017 issued in U.S. Appl. No. 14/194,549.
U.S. Notice of Allowance dated Feb. 14, 2018 issued in U.S. Appl. No. 14/194,549.
U.S. Office Action dated Mar. 21, 2019 issued in U.S. Appl. No. 15/976,793.
U.S. Notice of Allowance dated Aug. 5, 2015 issued in U.S. Appl. No. 14/183,287.
U.S. Office Action dated Aug. 1, 2016 issued in U.S. Appl. No. 14/932,869.
U.S. Office Action dated Jul. 2, 2015 issued in U.S. Appl. No. 14/187,145.
U.S. Final Office Action dated Dec. 16, 2015 issued in U.S. Appl. No. 14/187,145.
U.S. Notice of Allowance dated Feb. 25, 2016 issued in U.S. Appl. No. 14/187,145.
U.S. Office Action dated Jun. 9, 2017 issued in U.S. Appl. No. 15/224,347.
U.S. Notice of Allowance dated Oct. 4, 2017 issued in U.S. Appl. No. 15/224,347.
U.S. Notice of Allowance [Corrected Notice of Allowability] dated Nov. 28, 2017 issued in U.S. Appl. No. 15/224,347.
U.S. Office Action dated Jun. 14, 2016 issued in U.S. Appl. No. 15/019,904.
U.S. Notice of Allowance dated Oct. 13, 2016 issued in U.S. Appl. No. 15/019,904.
U.S. Office Action dated Nov. 25, 2016 issued in U.S. Appl. No. 15/178,474.
U.S. Notice of Allowance dated Feb. 10, 2017 issued in U.S. Appl. No. 15/178,474.
U.S. Notice of Allowance dated Mar. 27, 2017 issued in U.S. Appl. No. 15/178,474.
U.S. Notice of Allowance dated Apr. 18, 2017 issued in U.S. Appl. No. 15/178,474.
U.S. Office Action dated Aug. 22, 2017 issued in U.S. Appl. No. 15/609,864.
U.S. Final Office Action dated Dec. 4, 2017 issued in U.S. Appl. No. 15/609,864.
U.S. Notice of Allowance dated Mar. 9, 2018 issued in U.S. Appl. No. 15/609,864.
U.S. Office Action dated Apr. 13, 2015 issued in U.S. Appl. No. 14/335,785.
U.S. Final Office Action dated Aug. 24, 2016 issued in U.S. Appl. No. 14/335,785.
U.S. Notice of Allowance dated Nov. 4, 2016 issued in U.S. Appl. No. 14/335,785.
U.S. Notice of Allowance dated Feb. 22, 2017 issued in U.S. Appl. No. 14/335,785.
U.S. Notice of Allowance dated Mar. 21, 2017 issued in U.S. Appl. No. 14/335,785.
U.S. Notice of Allowance [Corrected Notice of Allowability] dated Apr. 19, 2017 issued in U.S. Appl. No. 14/335,785.
U.S. Office Action dated May 25, 2016 issued in U.S. Appl. No. 14/552,011.
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. Notice of Allowance dated Jul. 15, 2016 issued in U.S. Appl. No. 14/678,736.
U.S. Office Action dated Aug. 18, 2017 issued in U.S. Appl. No. 15/201,221.
U.S. Notice of Allowance dated Apr. 9, 2018 issued in U.S. Appl. No. 15/201,221.
U.S. Office Action dated Mar. 21, 2019 issued in U.S. Appl. No. 16/034,022.
U.S. Office Action dated Oct. 6, 2017 issued in U.S. Appl. No. 15/253,301.
U.S. Notice of Allowance dated Mar. 26, 2018 issued in U.S. Appl. No. 15/253,301.
U.S. Office Action dated Jan. 26, 2018 issued in U.S. Appl. No. 15/683,397.
U.S. Final Office Action dated Nov. 16, 2018 issued in U.S. Appl. No. 15/683,397.
U.S. Notice of Allowance dated Mar. 28, 2019 issued in U.S. Appl. No. 15/683,397.
U.S. Office Action dated Jul. 18, 2018 issued in U.S. Appl. No. 15/703,917.
U.S. Notice of Allowance dated Dec. 5, 2018 issued in U.S. Appl. No. 15/703,917.
PCT International Search Report and Written Opinion, dated Oct. 20, 2011, issued in Application No. PCT/US2011/032186.
PCT International Preliminary Report on Patentability, dated Oct. 26, 2012, issued in Application No. PCT/US2011/032186.
Korean Office Action, dated Feb. 7, 2017, issued in Application No. KR 10-2012-7004925.
Korean Office Action, dated Aug. 23, 2017, issued in Application No. KR 10-2017-7020548.
Taiwan Office Action dated Apr. 27, 2016 issued in Application No. TW 100113041.
PCT Invitation to Pay Additional Fees; Communication Re Partial International Search, dated Dec. 16, 2011, issued in Application No. PCT/US2011/032303.
PCT International Search Report and Written Opinion, dated Feb. 20, 2012, issued in PCT/US2011/032303.
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 May 2, 2012 issued in Application No. PCT/US2011/052537.
PCT International Preliminary Report on Patentability and Written Opinion dated Apr. 4, 2013 issued in Application No. PCT/US2011/052537.
Chinese First Office Action dated Jun. 2, 2015 issued in Application No. CN 201180045808.6.
Chinese Second Office Action dated Feb. 2, 2016 issued in Application No. CN 201180045808.6.
Korean Office Action, dated May 23, 2017, issued in Application No. KR 10-2013-7010291.
Korean Office Action, dated Nov. 27, 2017, issued in Application No. KR 10-2013-7010291.
Korean Decision for Grant of Patent, dated Jul. 25, 2018, issued in Application No. KR 10-2013-7010291.
Taiwan Office Action dated May 5, 2016 issued in Application No. TW 100134208.
Taiwan Office Action dated Oct. 19, 2017 issued in Application No. TW 105130207.
PCT International Search Report and Written Opinion dated Dec. 18, 2012, issued in Application No. PCT/US2012/052769.
PCT International Preliminary Report on Patentability and Written Opinion dated Apr. 3, 2014, issued in Application No. PCT/US2012/052769.
Chinese First Office Action dated Nov. 19, 2015 issued in Application No. CN 201280046487.6.
Chinese Second Office Action dated Aug. 22, 2016 issued in Application No. CN 201280046487.6.
Japanese Office Action dated Aug. 23, 2016 issued in Application No. JP 2014-531838.
Korean First Office Action dated Oct. 2, 2018 issued in Application No. KR 10-2014-7010949.
Singapore Supplementary Examination Report dated Jun. 1, 2016 issued in Application No. SG 11201400633R.
Taiwan Notice of Allowance and Search Report dated Dec. 18, 2015 issued in Application No. TW 101134692.
Taiwan First Office Action dated Mar. 14, 2018 issued in Application No. TW 106122777.
Taiwan Second Office Action dated Dec. 14, 2018 issued in Application No. TW 106122777.
PCT International Search Report and Written Opinion dated Feb. 28, 2013, issued in Application No. PCT/US2012/051740.
PCT International Preliminary Report on Patentability and Written Opinion dated Mar. 13, 2014, issued in Application No. PCT/US2012/051740.
Chinese First Office Action dated Nov. 6, 2015 issued in Application No. CN 201280053888.4.
Chinese Second Office Action dated Aug. 16, 2016 issued in Application No. CN 201280053888.4.
Korean First Office Action dated Oct. 31, 2017 issued in Application No. KR 10-2014-7008696.
Korean Second Office Action dated Sep. 20, 2018 issued in Application No. KR 10-2014-7008696.
Korean Decision for Grant of Patent, dated May 17, 2019 issued in Application No. KR 10-2014-7008696.
Taiwan Office Action and Search Report dated Jan. 27, 2016 issued in Application No. TW 101131556.
Taiwan Office Action and Search Report dated Nov. 9, 2016 issued in Application No. TW 101131556.
Chinese First Office Action dated May 19, 2016 issued in Application No. CN 201310021460.8.
Chinese Second Office Action dated Apr. 13, 2017 issued in Application No. CN 201310021460.8.
Chinese Third Office Action dated Oct. 17, 2017 issued in Application No. CN 201310021460.8.
Chinese Fourt Office Action dated May 16, 2018 issued in Application No. CN 201310021460.8.
European Extended Search Report dated Apr. 14, 2014 issued in Application No. EP 13 15 2046.
European Examination Report dated Dec. 11, 2017 issued in Application No. EP 13 15 2046.
Japanese Office Action dated Jan. 10, 2017 issued in Application No. JP 2013-007612.
Japanese Decision of Rejection dated Jan. 9, 2018 issued in Application No. JP 2013-007612.
Japanese Reason for Refusal dated Apr. 2, 2019 issued in Application No. JP 2013-007612.
Korean Notice of Provisional Rejection dated Dec. 6, 2013 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 Decision from the Patent Tribunal of the KIPO (description) dated May 26, 2015 issued in Application No. KR 10-2012-0043797.
Taiwan Examination Report dated Mar. 29, 2017 issued in Application No. TW 102102054.
PCT International Search Report and Written Opinion dated May 27, 2013, issued in Application No. PCT/US2013/022977.
PCT International Preliminary Report on Patentability and Written Opinion dated Aug. 7, 2014, issued in Application No. PCT/US2013/022977.
Chinese First Office Action dated Feb. 22, 2016 issued in Application No. CN 201380006994.1.
Chinese Second Office Action dated Feb. 6, 2017 issued in Application No. CN 201380006994.1.
Japanese Notification of Reasons for Rejection dated Jan. 10, 2017 issued in Application No. JP2014-554825.
Japanese Decision of Refusal dated Dec. 5, 2017 issued in Application No. JP2014-554825.
Japanese Notice of Reason for Refusal dated Jul. 24, 2018 issued in Application No. JP 2017-159931.
Singapore Supplementary Examination Report dated Aug. 11, 2016 issued in Application No. SG 11201404315R.
Taiwan Office Action and Search Report dated Jul. 20, 2016 issued in Application No. TW 102102879.
Taiwan Office Action dated Oct. 25, 2016 issued in Application No. TW 102117772.
Taiwan Rejection Decision dated Aug. 17, 2017 issued in Application No. TW 102117772.
Japanese First Office Action dated Oct. 31, 2017 issued in Application No. JP 2013-230782.
Japanese Second Office Action dated May 22, 2018 issued in Application No. JP 2013-230782.
Japanese Decision to Grant dated Sep. 10, 2018 issued in Application No. JP 2013-230782.
Japanese Office Action dated Dec. 5, 2017 issued in Application No. JP 2013-231188.
Japanese Second Office Action [Decision of Rejection] dated Dec. 4, 2018 issued in Application No. JP 2013-231188.
Taiwan Examination Report dated Jul. 13, 2017 issued in Application No. TW 102140721.
Taiwan First Office Action dated Sep. 20, 2018 issued in Application No. TW 106140906.
Taiwan Examination Report dated Jan. 11, 2017 issued in Application No. TW 102138326.
Chinese First Office Action dated Nov. 28, 2016 issued in Application No. CN 201410521390.7.
Taiwan First Office Action dated May 3, 2018 issued in Application No. TW 103133765.
Japanese First Office Action dated Dec. 18, 2018 issued in Application No. JP 2014-262248.
Singapore Eligibility to Grant w/Supplemental Examinatinon Report dated Apr. 23, 2019 issued in Application No. SG 10201408801Q.
Taiwan First Office Action dated Jun. 26, 2018 issued in Application No. TW 103145386.
Chinese First Office Action dated May 27, 2017 issued in Application No. CN 201510091775.9.
Chinese Second Office Action dated Mar. 26, 2018 issued in Application No. CN 201510091775.9.
Chinese Third Office Action dated Oct. 15, 2018 issued in Application No. CN 201510091775.9.
Chinese Fourth Office Action dated Mar. 27, 2019 issued in Application No. CN 201510091775.9.
Taiwanese First Office Action dated Sep. 14, 2018 issued in Application No. TW 104106165.
Chinese First Office Action dated Apr. 11, 2016 issued in Application No. CN 201510086588.1.
Chinese Second Office Action dated Mar. 20, 2017 issued in Application No. CN 201510086588.1.
Japanese Office Action dated Apr. 19, 2016 issued in Application No. JP 2015-21804.
Korean First Office Action dated Feb. 19, 2016, issued in Application No. KR 10-2015-0022610.
Korean Final Office Action dated Jun. 29, 2016, issued in Application No. KR 10-2015-0022610.
Taiwan Notice of Allowance and Search Report dated Aug. 30, 2018 issued in Application No. TW 104104471.
Singapore Search Report and Written Opinion dated Mar. 14, 2019 issued in Application No. SG 10201807090Q.
Taiwan First Office Action dated Sep. 13, 2018, issued in Application No. TW 104104648.
Chinese Third Office Action dated Dec. 22, 2017, issued in Application No. CN 201380006994.1.
Taiwanese First Office Action dated Nov. 9, 2018 issued in Application No. TW 104122669.
Chinese First Office Action dated Mar. 30, 2018 issued in Application No. CN 201610206201.6.
Chinese Second Office Action dated Jan. 24, 2019 issued in Application No. CN 201610206201.6.
Chinese First Office Action dated Oct. 8, 2018 issued in Application No. CN 201710522311.8.
PCT International Search Report and Written Opinion dated Feb. 25, 2019 issued in Application No. PCT/US2018/050049.
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.
Choi, Gyu-Jin et al., (2009) “Plasma-enhanced atomic layer deposition of TiO2 and AI-doped TiO2 films using N2O and O2 reactants,” Journal of the Electrochemical Society, 156(9):G138-G143.
Faraz et al., (2015) “Atomic Layer Etching. What Can We Learn from Atomic Layer Deposition?,” ECS Journal of Solid State Science and Technology, 4(6):N5023-N5032.
Hausmann et al., (2002) “Atomic Layer Deposition of Hafnium and Zirconium Oxides Using Metal Amide Precursors,” Chem. Mater. 14(10):4350-4358.
Elam et al., (2003) “Growth of ZnO/Al2O3 Alloy Films Using Atomic Layer Deposition Techniques,” Chemistry of Materials, 2003, vol. 15, No. 4, pp. 1020-1028. <doi:10.1021/cm020607+>.
Kim, H., et al., (2002) “The Growth of Tantalum Thin Films by Plasma-Enhanced Atomic Layer Deposition and Diffusion Barrier Properties,” Mat. Res. Soc. Symp. Proc. 716:B8.5.1-B8.5.6.
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).
Ko, Myoung-Gyun, et al., “Characterization of ruthenium thin film deposited by rf-direct plasma atomic layer deposition,” 209th ECS Meeting, Abstract #50, p. 1 [Downloaded on Jun. 9, 2014].
Ko, Myoung-Gyun, et al., (Oct. 2008) “Correlation of Carbon Content with the Thermal Stability of Ruthenium Deposited by Using RF-Direct Plasma-Enhanced Atomic-Layer Deposition,” Journal of the Korean Physical Society, 53(4):2123-2128.
Lavareda et al., (2004) “Properties of a-Si:H TFTs using silicon carbonitride as dielectric,” Journal of Non-Crystalline Solids, 338-340:797-801.
Lee et al., (2005) “Chemically conformal deposition of SrTiO3 thin films by Atomic Layer Deposition using conventional metal organic precursors and remote-plasma activated H2O,” School of Materials Science and Engineering, and Inter-university Semiconductor Research Center, Seoul National University, Microelectronic Engineering 80:158-161.
Lee, Jong Ju, (2005) “Low-impurity, highly conformal atomic layer deposition of titanium nitride using NH3—Ar—H2 plasma treatment for capacitor electrodes,” Materials Letters, 59:615-617.
Li, Xingcun, et al., (2011) “Atomic Layer Deposition Al203 Thin Films in Magnetized Radio Frequency Plasma Source,” Physics Procedia 18:100-106.
Man P.F. et al., (Feb. 11-15, 1996) “Elimination of Post-Release Adhesion in Microstructures Using Conformal Fluorocarbon Coatings,” MEMS '96 Proceedings, IEEE, pp. 55-60.
Nguyen, S.V. et al., (Jan./Mar. 1999) “Plasma-assist chemical vapor deposition of dielectric thin films for ULSI semiconductor circuits,” IBM J.Res.Develop. 43(1.2):5-38.
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.
“PlasmaPro™ NGP® 80 Range,” Oxford Instruments (2010), 8 pages.
Pritchett, Merry, (May 2004) “Adherence/Diffusion Barrier Layers for Copper Metallization: Amorphous Carbon: Silicon Polymerized Films,” Dissertation Prepared for the Degree of Doctor of Philosophy, University of Texas, 113pp.
Puurunen, Riikka L. (2005) “Surface chemistry of atomic layer deposition: A case study for the trimethylaluminum/water process,” Journal of Applied Physics, 97:121301-1-121301-52.
van der Straten et al., (2004) “Atomic layer deposition of tantalum nitride for ultrathin liner applications in advanced copper metallization schemes,” Journal of Materials Research, 19(2):447-453.
U.S. Appl. No. 16/036,784, filed Jul. 16, 2018, Ou et al.
U.S. Office Action dated Jul. 30, 2019 issued in U.S. Appl. No. 15/847,744.
Japanese Second Office Action dated Jun. 17, 2019 issued in Application No. JP 2017-159931.
Japanese First Office Action dated May 29, 2019 issued in Application No. JP 2018-090402.
Korean First Office Action dated Jun. 28, 2019 issued in Application No. KR 10-2013-0056776.
Chinese Second Office Action dated Jun. 13, 2019 issued in Application No. CN 201710522311.8.
Korean First Office Action dated Aug. 19, 2019 issued in Application No. KR 10-2019-7012231.
Office Action dated Mar. 6, 2019, issued in U.S. Appl. No. 15/681,268.
Final Office Action dated Sep. 16, 2019, issued in U.S. Appl. No. 15/681,268.
Wikipedia “Density” via https://en.wikipedia.org/wiki/Density; pp. 1-11; 2019.
Denser—definition of denser by the Free Dictionary via https://www.thefreedictionary.com /denser; pp. 1-5; 2003.
Chemicool Dictionary “Definition of Step Coverage” via https://www.chemicool.com/definition/step_coverage.html ; 1 page; 2017.
U.S. Appl. No. 16/453,237, filed Jun. 26, 2019, Singhal et al.
U.S. Appl. No. 16/556,122, filed Aug. 29, 2019, Arghavani et al.
U.S. Office Action dated Oct. 1, 2019 issued in U.S. Appl. No. 15/965,628.
U.S. Notice of Allowance dated Mar. 30, 2020 issued in U.S. Appl. No. 15/965,628.
U.S. Notice of Allowance dated Oct. 3, 2019 issued in U.S. Appl. No. 15/976,793.
U.S. Office Action dated Apr. 1, 2020 issued in U.S. Appl. No. 16/556,122.
U.S. Final Office Action dated Sep. 25, 2020 issued in U.S. Appl. No. 16/556,122.
U.S. Final Office Action dated Jan. 21, 2020 issued in U.S. Appl. No. 15/847,744.
U.S. Notice of Allowance dated May 28, 2020 issued in U.S. Appl. No. 15/847,744.
U.S. Final Office Action dated Sep. 27, 2019 issued in U.S. Appl. No. 16/034,022.
Notice of Allowance dated Feb. 7, 2020 issued in U.S. Appl. No. 16/034,022.
U.S. Office Action dated Feb. 14, 2020 issued in U.S. Appl. No. 16/453,237.
U.S. Final Office Action dated Aug. 20, 2020 issued in U.S. Appl. No. 16/453,237.
Chinese First Office Action dated Jan. 20, 2020 issued in Application No. CN 201710347032.2.
Chinese Second Office Action dated Aug. 14, 2020 issued in Application No. CN 201710347032.2.
Singapore Search Report and Written Opinion dated May 19, 2020 issued in Application No. SG 10201607194P.
Japanese Third Office Action dated Mar. 10, 2020 issued in Application No. JP 2017-159931.
Chinese Notification of Reexamination dated Apr. 17, 2020 issued in Application No. CN 201310021460.8.
Japanese Second Office Action [Decision of Rejection] dated Jan. 14, 2020 issued in Application No. JP 2018-090402.
Korean First Office Action dated May 14, 2020 issued in Application No. KR 10-2013-0135905.
Korean First Office Action dated Jan. 15, 2020 issued in Application No. KR 10-2013-0135907.
Korean Decision for Grant of Patent dated Sep. 7, 2020 issued in Application No. KR 10-2013-0135907.
Korean First Office Action dated May 27, 2020 issued in Application No. KR 10-2013-0126834.
Chinese First Office Action dated Jul. 10, 2020 issued in Application No. CN 201710839679.7.
Chinese Fifth Office Action dated Jun. 30, 2020 issued in Application No. CN 201510091775.9.
Singapore Second Written Opinion dated Jan. 24, 2020 issued in Application No. SG 10201807090Q.
Taiwan Notice of Allowance dated Jul. 2, 2020, issued in Application No. TW 108119661.
Taiwan First Office Action dated Oct. 16, 2019 issued in Application No. TW 105109955.
PCT International Preliminary Report on Patentability dated Mar. 26, 2020 issued in Application No. PCT/US2018/050049.
Notice of Allowance dated Jan. 14, 2020, in U.S. Appl. No. 15/681,268.
Notice of Allowance dated Apr. 29, 2020, in U.S. Appl. No. 15/681,268.
International Search Report and Written Opinion issued in Application No. PCT/US2018/000331 dated Feb. 11, 2019.
U.S. Notice of Allowance dated Nov. 4, 2020 issued in U.S. Appl. No. 16/453,237.
Chinese Third Office Action dated Jan. 6, 2021 issued in Application No. CN 201710347032.2.
Chinese Reexamination Decision dated Sep. 11, 2020 issued in Application No. CN 201310021460.8.
Korean Decision for Grant of Patent dated Oct. 20, 2020 issued in Application No. KR 10-2013-0126834.
Singapore Notice of Eligibility and Examination Report dated Nov. 6, 2020 issued in Application No. SG 10201807090Q.
Taiwanese First Office Action dated Dec. 21, 2020 issued in Application No. TW 106121191.
Kwon, J., et al., (Nov. 2011) “Tracking by Sampling Trackers” 2011 International Conference on Computer Vision. IEEE, 2011, pp. 1195-1202.
Profijt, et al., (2011) “Plasma-Assisted Atomic Layer Deposition: Basics, Opportunities, and Challenges” Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films vol. 29, pp. 1-27.
Korean First Office Action dated Apr. 7, 2021 issued in Application No. KR 10-2021-0020087.
Korean First Office Action dated May 21, 2021 issued in Application No. Kr 10-2015-0028413.
Korean First Office Action dated Apr. 21, 2021, issued in Application No. KR 10-2015-0023868.
Chinese Second Office Action dated Apr. 12, 2021 issued in Application No. CN 201710839679.7.
Korean First Office Action dated Apr. 21, 2021 issued in Application No. KR 10-2014-0131380.
Related Publications (1)
Number Date Country
20190311897 A1 Oct 2019 US
Provisional Applications (5)
Number Date Country
61884923 Sep 2013 US
61417807 Nov 2010 US
61379081 Sep 2010 US
61372367 Aug 2010 US
61324710 Apr 2010 US
Divisions (1)
Number Date Country
Parent 14987542 Jan 2016 US
Child 15654186 US
Continuations (2)
Number Date Country
Parent 15654186 Jul 2017 US
Child 16428067 US
Parent 14137860 Dec 2013 US
Child 14987542 US
Continuation in Parts (1)
Number Date Country
Parent 13084399 Apr 2011 US
Child 14137860 US