Patent Grant
9611544
Various thin film layers for semiconductor devices may be deposited with atomic layer deposition (ALD) processes. However, existing ALD processes may not be suitable for depositing highly conformal dielectric films.
Various aspects disclosed herein pertain to methods of depositing a film on a substrate surface. In certain embodiments, the methods include depositing a film by surface mediated reactions in which the film is grown over one or more cycles of reactant adsorption and reaction. In one aspect, the method is characterized by intermittent delivery of dopant species to the film between the cycles of adsorption and reaction.
In one aspect, a disclosed method deposits a nitrogen and/or carbon doped dielectric film on a substrate surface in a reaction chamber. The method may be characterized by the following sequence: (a) introducing a silicon oxide or silicon nitride precursor into the reaction chamber under conditions allowing the precursor to adsorb onto the substrate surface; (b) thereafter purging the precursor from the reaction chamber while the precursor remains adsorbed on the substrate surface; (c) exposing the substrate surface to plasma to drive a reaction of the dielectric precursor on the substrate surface to form a portion of the dielectric film; (d) introducing a carbon and/or nitrogen-containing dopant species into the reaction chamber under conditions allowing the dopant precursor to contribute nitrogen and/or carbon to the dielectric film; and (e) repeating (a)-(c). In various embodiments, the dopant species introduced in (d) is not introduced during (a)-(c). In some implementations, the substrate is held at a temperature of between about 100° C. and 350° C. during (a)-(e). In certain embodiments, the substrate surface is exposed to the carbon and/or nitrogen-containing dopant species prior to (a)-(c).
In certain embodiments, an oxidant flows into the reaction chamber prior to and during (a)-(c). In some cases, the silicon oxide or silicon nitride precursor and the oxidant co-exist in vapor phase in the reaction chamber. In such cases, the precursor and the oxidant may not appreciably react with one another in the reaction chamber until exposure to plasma in (c).
Reactants of various types may be employed. For example, in certain embodiments, the oxidant is nitrous oxide. In some embodiments, the silicon oxide precursor is BTBAS or BDEAS. In some embodiments, the silicon nitride precursor is dichlorosilane, BTBAS or BDEAS. In some cases, the dopant containing material is a hydrocarbon, alcohol, ketone, aldehyde, ether, ester, carboxylic acid, oxolane, or furan. Specific examples include methane, ethane, propane, acetylene, ethylene, propylene, t-amyl alcohol, ethanol, propanol, ethyleneglycol, and propyne. In some cases, the dopant containing material is ammonia or an amine, nitrile, amide, nitrogen-containing heterocyclic compound, or amino alcohol. Specific examples include ammonia, hydrazine, elemental nitrogen, acetonitrile, t-butylamine, ethanolamine, ethylamine, and triethylamine.
In the above method, an additional operation (f) of reacting the carbon and/or nitrogen-containing dopant species may be employed. This operation introduces a dopant to the film. In certain embodiments, operation (f) involves exposing the carbon and/or nitrogen-containing dopant species to a plasma.
In certain embodiments, the method additionally includes repeating (d) and (e) one or more times. In some cases, (a)-(c) are repeated multiple times prior repeating (d). And in some examples, (d) is performed at intervals between one or more repetitions of (a)-(c), where such intervals vary over the course of depositing the nitrogen and/or carbon doped dielectric film.
The film deposited during (a)-(c) may be between about 0.5 to 5 Angstroms in some cases. Further, in some examples, the total film thickness is between about 10-20000 Angstroms.
In some aspects, the disclosed embodiments concern an apparatus for depositing a nitrogen and/or carbon doped dielectric film on a substrate surface. Such apparatus may contain the following features: a reaction chamber comprising a device for holding the substrate during deposition of the doped dielectric film; one or more process gas inlets coupled to the reaction chamber; and a controller designed or configured to cause the apparatus to perform various operations. The operations may include the following: (a) introducing a silicon oxide or silicon nitride precursor into the reaction chamber under conditions allowing the precursor to adsorb onto the substrate surface; (b) thereafter purging the precursor from the reaction chamber while the precursor remains adsorbed on the substrate surface; (c) exposing the substrate surface to plasma to drive a reaction of the dielectric precursor on the substrate surface to form a portion of the dielectric film; (d) introducing a carbon and/or nitrogen-containing dopant species, not introduced during (a)-(c), into the reaction chamber under conditions allowing the dopant precursor to contribute nitrogen and/or carbon to the dielectric film; and (e) repeating (a)-(c). Certain aspects of the controller's operations may include details as described above in the context of the method operations.
In a further aspect, a method includes the following operations: (a) providing a substrate in a reaction chamber; (b) introducing a first reactant in vapor phase into the reaction chamber under conditions allowing the first reactant to adsorb onto the substrate surface; (c) introducing a second reactant in vapor phase into the reaction chamber while the first reactant is adsorbed on the substrate surface; (d) exposing the substrate surface to plasma to drive a reaction between the first and second reactants on the substrate surface to form a portion of the film; (e) repeating (b)-(d) at least once; (f) introducing a third reactant, not introduced during (b)-(e), into the reaction chamber under conditions allowing the third reactant to adsorb onto the substrate surface; (g) reacting the third reactant to produce a dopant for the film; and (h) repeating (b)-(d).
These and other features will be described in more detail below with reference to the associated drawings.
Manufacture of semiconductor devices typically involves depositing one or more thin films on a non-planar substrate in an integrated fabrication process. In some aspects of the integrated process it may be useful to deposit thin films that conform to substrate topography. For example, a silicon nitride film may be deposited on top of an elevated gate stack to act as a spacer layer for protecting lightly-doped source and drain regions from subsequent ion implantation processes.
In spacer layer deposition processes, chemical vapor deposition (CVD) processes may be used to form a silicon nitride film on the non-planar substrate, which is then anisotropically etched to form the spacer structure. However, as a distance between gate stacks decreases, mass transport limitations of CVD gas phase reactions may cause “bread-loafing” deposition effects. Such effects typically exhibit thicker deposition at top surfaces of gate stacks and thinner deposition at the bottom corners of gate stacks. Further, because some die may have regions of differing device density, mass transport effects across the wafer surface may result in within-die and within-wafer film thickness variation. These thickness variations may result in over-etching of some regions and under-etching of other regions. This may degrade device performance and/or die yield.
Some approaches to addressing these issues involve atomic layer deposition (ALD). In contrast with a CVD process, where thermally activated gas phase reactions are used to deposit films, ALD processes use surface-mediated deposition reactions to deposit films on a layer-by-layer basis. In one example ALD process, a substrate surface, including a population of surface active sites, is exposed to a gas phase distribution of a first film precursor (P1). Some molecules of P1 may form a condensed phase atop the substrate surface, including chemisorbed species and physisorbed molecules of P1. The reactor is then evacuated to remove gas phase and physisorbed P1 so that only chemisorbed species remain. A second film precursor (P2) is then introduced to the reactor so that some molecules of P2 adsorb to the substrate surface. The reactor may again be evacuated, this time to remove unbound P2. Subsequently, thermal energy provided to the substrate activates surface reactions between adsorbed molecules of P1 and P2, forming a film layer. Finally, the reactor is evacuated to remove reaction by-products and possibly unreacted P1 and P2, ending the ALD cycle. Additional ALD cycles may be included to build film thickness.
Depending on the exposure time of the precursor dosing steps and the sticking coefficients of the precursors, each ALD cycle may deposit a film layer of, in one example, between one-half and three angstroms thick. Thus, ALD processes may be time consuming when depositing films more than a few nanometers thick. Further, some precursors may have long exposure times to deposit a conformal film, which may also reduce wafer throughput time.
Conformal films may also be deposited on planar substrates. For example, antireflective layers for lithographic patterning applications may be formed from planar stacks comprising alternating film types. Such antireflective layers may be approximately 100 to 1000 angstroms thick, making ALD processes less attractive than CVD processes. However, such anti-reflective layers may also have a lower tolerance for within-wafer thickness variation than many CVD processes may provide. For example, a 600-angstrom thick antireflective layer may tolerate a thickness range of less than 3 angstroms.
Accordingly, various embodiments are provided herein providing processes and equipment for plasma-activated conformal film deposition (CFD) on non-planar and planar substrates. These embodiments incorporate various features employed in some but not all CFD processes. Among these features are (1) eliminating or reducing the time required to “sweep” one or both reactants from the reaction chamber, (2) providing a continuous flow of at least one reactant while a different reactant is intermittently flowed into the reaction chamber, (3) igniting plasma while one of the reactants is present in the gas phase, rather than when all reactants are cleared from the reaction chamber, (4) treating deposited CFD films with a plasma to modify the film properties, (5) depositing a portion of a film by PECVD after depositing a first portion of the film by CFD, typically in the same reaction chamber, (6) etching a partially deposited film between CFD stages, and (7) doping the CFD film by interspersing dopant delivery cycles with film only deposition cycles. Of course, this list is not exhaustive. Various other CFD features will be apparent when considering the remainder of the specification.
The concept of a CFD “cycle” is relevant to the discussion of various embodiments herein. Generally a cycle is the minimum set of operations required to perform a surface deposition reaction one time. The result of one cycle is production of at least a partial film layer on a substrate surface. Typically, a CFD cycle will include only those steps necessary to deliver and adsorb each reactant to the substrate surface, and then react those adsorbed reactants to form the partial layer of film. Of course, the cycle may include certain ancillary steps such as sweeping one of the reactants or byproducts and/or treating the partial film as deposited. Generally, a cycle contains only one instance of a unique sequence of operations. As an example, a cycle may include the following operations: (i) delivery/adsorption of reactant A, (ii) delivery/adsorption of reactant B, (iii) sweep B out of the reaction chamber, and (iv) apply plasma to drive a surface reaction of A and B to form the partial film layer on the surface.
The seven above-mentioned features will now be discussed further. In the following descriptions, consider a CFD reaction in which one or more reactants adsorb to the substrate surface and then react to form a film on the surface by interaction with plasma.
Feature 1 (Continuous flow of a reactant)—Reactant A continues to flow to a reaction chamber during one or more portions of a CFD cycle when the reactant would not normally flow in conventional ALD. In conventional ALD, reactant A flows only for the purpose of having the reactant adsorb onto the substrate surface. At other phases of an ALD cycle, reactant A does not flow. In accordance with certain CFD embodiments described herein, however, reactant A flows not only during phases associated with its adsorption but also during phases of a CFD cycle that perform operations other than adsorption of A. For example, in many embodiments, reactant A flows into the reactor while the apparatus is dosing a second reactant (reactant B herein). Thus, during at least a portion of a CFD cycle, reactants A and B coexist in the gas phase. Further, reactant A may flow while plasma is applied to drive a reaction at the substrate surface. Note that the continuously flowing reactant may be delivered to the reaction chamber in conjunction with a carrier gas—e.g., argon.
One advantage of the continuous flow embodiment is that the established flow avoids the delays and flow variations caused by transient initialization and stabilization of flow associated with turning the flow on and off.
As a specific example, an oxide film may be deposited by a conformal film deposition process using a principal reactant (sometimes referred to as a “solid component” precursor or, in this example, simply “reactant B”). Bis(tert-butylamino)silane (BTBAS) is one such principal reactant. In this example, the oxide deposition process involves delivery of an oxidant such as oxygen or nitrous oxide, which flows initially and continuously during delivery of the principal reactant in distinct exposure phases. The oxidant also continues to flow during distinct plasma exposure phases. See for example the sequence depicted in
In some specific examples, the reactant that flows continuously is an “auxiliary” reactant. As used herein, an “auxiliary” reactant is any reactant that is not a principal reactant. As suggested above, a principal reactant contains an element that is solid at room temperature, which element is contributed to the film formed by CFD. Examples of such elements are metals (e.g., aluminum and titanium), semiconductors (e.g., silicon and germanium), and non-metals or metalloids (e.g., boron). Examples of auxiliary reactants include oxygen, ozone, hydrogen, carbon monoxide, nitrous oxide, ammonia, alkyl amines, and the like.
The continuously flowing reactant may be provided at a constant flow rate or at varied but controlled flow rate. In the latter case, as an example, the flow rate of an auxiliary reactant may drop during an exposure phase when the primary reactant is delivered. For example, in oxide deposition, the oxidant (e.g., oxygen or nitrous oxide) may flow continuously during the entire deposition sequence, but its flow rate may drop when the primary reactant (e.g., BTBAS) is delivered. This increases the partial pressure of BTBAS during its dosing, thereby reducing the exposure time needed to saturate the substrate surface. Shortly before igniting the plasma, the flow of oxidant may be increased to reduce the likelihood that BTBAS is present during the plasma exposure phase. In some embodiments, the continuously flowing reactant flows at a varied flow rate over the course of two or more deposition cycles. For example, the reactant may flow at a first flow rate during a first CFD cycle and at a second flow rate during a second CFD cycle.
When multiple reactants are employed and the flow of one of them is continuous, at least two of them will co-exist in the gas phase during a portion of the CFD cycle. Similarly, when no purge step is performed after delivery of the first reactant, two reactants will co-exist. Therefore, it may be important to employ reactants that do not appreciably react with one another in the gas phase absent application of activation energy. Typically, the reactants should not react until present on the substrate surface and exposed to plasma or another appropriate non-thermal activation condition. Choosing such reactants involves considerations of at least (1) the thermodynamic favorability (Gibb's free energy <0) of the desired reaction, and (2) the activation energy for the reaction, which should be sufficiently great so that there is negligible reaction at the desired deposition temperature.
Feature 2 (Reduce or eliminate a sweep step)—In certain embodiments, the process dispenses with or reduces the time associated with a sweep step that would normally be performed in conventional ALD. In conventional ALD, a separate sweep step is performed after each reactant is delivered and adsorbed onto the substrate surface. Little or no adsorption or reaction occurs in a conventional ALD sweep step. In a CFD cycle, the sweep step is reduced or eliminated after delivery of at least one of the reactants. An example of a process sequence in which a sweep step is removed is presented in
The concept of a CFD “sweep” step or phase appears in the discussion various embodiments herein. Generally, a sweep phase removes or purges one of the vapor phase reactant from a reaction chamber and typically occurs only after delivery of such reactant is completed. In other words, that reactant is no longer delivered to the reaction chamber during sweep phase. However, the reactant remains adsorbed on the substrate surface during the sweep phase. Typically, the sweep serves to remove any residual vapor phase reactant in the chamber after the reactant is adsorbed on the substrate surface to the desired level. A sweep phase may also remove weakly adsorbed species (e.g., certain precursor ligands or reaction by-products) from the substrate surface. In ALD, the sweep phase has been viewed as necessary to prevent gas phase interaction of two reactants or interaction of one reactant with a thermal, plasma or other driving force for the surface reaction. In general, and unless otherwise specified herein, a sweep phase may be accomplished by (i) evacuating a reaction chamber, and/or (ii) flowing gas not containing the species to be swept out through the reaction chamber. In the case of (ii), such gas may be, for example, an inert gas or an auxiliary reactant such as a continuously flowing auxiliary reactant.
Elimination of the sweep phase may be accomplished with or without continuous flow of the other reactant. In the embodiment depicted in
In various embodiments where two or more reactants are employed, the reactant which has its sweep step eliminated or reduced is an auxiliary reactant. As an example, auxiliary reactant is an oxidant or a nitrogen source and the primary reactant is a silicon, boron, or germanium containing precursor. Of course, a sweep of the principal reactant may also be reduced or eliminated. In some examples, no sweep step is performed after delivery of an auxiliary reactant but a sweep step is optionally performed after delivery of a principal reactant.
As mentioned, the sweep phase need not be fully eliminated but simply reduced in duration in comparison to sweep phases in conventional ALD processes. For example, the sweep phase of a reactant such as an auxiliary reactant during a CFD cycle may be performed for about 0.2 seconds or less, e.g., for about 0.001 to 0.1 seconds.
Feature 3 (Igniting plasma while one of the reactants is present in the gas phase)—With this feature, a plasma is ignited before all reactants have been cleared from the reaction chamber. This is contrary to conventional ALD, where the plasma activation or other reaction driving operation is provided only after the vapor phase reactants are no longer present in the reaction chamber. Note that this feature would necessarily occur when reactant A flows continuously during the plasma portion of a CFD cycle as depicted in
For example, a sequence might be (i) introduce reactant A, (ii) purge A, (iii) introduce reactant B and while B is flowing strike a plasma, and (iv) purge. In such embodiments, the process employs a plasma activated reactant species from the gas phase. This is a general example where CFD is not constrained to a sequence of sequential steps.
If the activation plasma is provided during the time when the solid component precursor (primary reactant) is supplied to the reactor, the step coverage may become less conformal, but the deposition rate will typically increase. However if plasma activation occurs only during delivery of one an auxiliary reactant this is not necessarily the case. The plasma can activate the vapor phase auxiliary component to render it more reactive and thereby increase its reactivity in the conformal film deposition reaction. In certain embodiments, this feature is employed when depositing a silicon containing film such as an oxide, nitride, or carbide.
Feature 4 (Plasma treatment of deposited CFD films)—In these embodiments, the plasma may serve two or more roles in the conformal film deposition process. One of its roles is to activate or drive the film formation reaction during each CFD cycle. Its other role is to treat the film after the CFD film has been partially or fully deposited following one or more CFD cycles. The plasma treatment is intended to modify one or more film properties. Typically, though not necessarily, the plasma treatment phase is conducted under conditions that are different from those employed to activate the film formation reaction (i.e., to drive the film formation reaction). As an example, the plasma treatment may be performed in the presence of a reducing or oxidizing environment (e.g., in the presence of hydrogen or oxygen), while this need not be the case during the activation portion of a CFD cycle.
The plasma treatment operation may be performed during every cycle of the CFD process, during every other cycle, or on some less frequent basis. The treatment may be performed on regular intervals, tied to a fixed number of CFD cycles, or it may be performed variably (e.g., at varying intervals of CFD cycles) or even randomly. In a typical example, film deposition is performed for a few CFD cycles, to reach appropriate film thickness, and then the plasma treatment is employed. Thereafter, film deposition is again performed for a number of CFD cycles without plasma treatment before the treatment is again performed. This super-sequence of x number of CFD cycles, followed by plasma treatment (film modification) may be repeated until the film is completely formed by CFD.
In certain embodiments, the plasma treatment may be performed before initiation of CFD cycling to modify one or more properties of the surface on which the CFD film is deposited. In various embodiments, the surface is made from silicon (doped or undoped) or a silicon containing material. The modified surface may be better able to produce a high quality interface with the subsequently deposited CFD film. The interface may provide, e.g., good adhesion, reliable electrical properties through, e.g., defect reduction, etc.
The pretreatment of the substrate prior to CFD is not limited to any particular plasma treatment. In certain embodiments, the pre-treatment involves exposure to hydrogen-plasma, nitrogen-plasma, nitrogen/hydrogen-plasma, ammonia-plasma, argon-plasma, helium-plasma, helium anneal, hydrogen-anneal, ammonia-anneal, and UV-cure in the presence of helium, hydrogen, argon, nitrogen, hydrogen/nitrogen-forming gas, and/or ammonia. Plasma processing may be enabled with various plasma generators including, though not limited to, microwave, ICP-remote, direct and others known to those in the art.
Overall, the treatment may occur before, during and after CFD cycling. When occurring during CFD cycling, the frequency of treatment may be chosen for the appropriate deposition conditions. Typically, the treatment will occur not more often than once per cycle.
As an example, consider a process for forming silicon nitride from precursors having some carbon present. Examples of such precursors include BTBAS. As a consequence of the carbon present in the precursor, the as deposited nitride film includes some carbon impurity, which may degrade the electrical properties of the nitride. To counteract this problem, after a few CFD cycles with the carbon-containing precursor, the partially deposited film is exposed to hydrogen in the presence of plasma to reduce and ultimately remove the carbon impurity.
The plasma conditions employed to modify the film surface may be chosen to effect a desired change in film properties and/or composition. Among the plasma conditions that can be selected and/or tailored for the desired modification are oxidizing conditions, reducing conditions, etching conditions, power used to generate the plasma, frequency used to generate the plasma, use of two or more frequencies to generate the plasma, plasma density, the distance between the plasma and the substrate, etc. Examples of CFD film properties that can be modified by plasma treatment include, internal film stress, etch resistance, density, hardness, optical properties (refractive index, reflectivity, optical density, etc.), dielectric constant, carbon content, electrical properties (Vfb spread, etc.), and the like.
In some embodiments, a treatment other than a plasma treatment is employed to modify the properties of the as deposited film. Such treatments include electromagnetic radiation treatments, thermal treatments (e.g., anneals or high temperature pulses), and the like. Any of these treatments may be performed alone or in combination with another treatment, including a plasma treatment. Any such treatment can be employed as a substitute for any of the above-described plasma treatments. In a specific embodiment, the treatment involves exposing the film to ultraviolet radiation. As described below, in a specific embodiment, the method involves the application of UV-radiation to an oxide CFD film in situ (i.e., during formation of the film) or post deposition of the oxide. Such treatment serves to reduce or eliminate defect structure and provide improved electrical performance.
In certain specific embodiments, a UV treatment can be coupled with a plasma treatment. These two operations can be performed concurrently or sequentially. In the sequential option, the UV operation optionally takes place first. In the concurrent option, the two treatments may be provided from separate sources (e.g., an RF power source for the plasma and a lamp for the UV) or from a single source such as a helium plasma that produces UV radiation as a byproduct.
Feature 5 (Depositing by CFD and then transitioning to PECVD)—In such embodiments, the completed film is generated in part by CFD and in part by a CVD process such as PECVD. Typically, the CFD portion of the deposition process if performed first and the PECVD portion is performed second, although this need not be the case. Mixed CFD/CVD processes can improve the step coverage over that seen with CVD alone and additionally improve the deposition rate over that seen with CFD alone. In some cases, plasma or other activation is applied while one 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 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 CFD, followed by an intermediate portion of the film being deposited by CVD, and a final portion of the film deposited by 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 CFD.
A transition phase may be employed between the CFD and CVD phases. The conditions employed during such transition phase different from those employed in either the CFD or the CVD phases. Typically, though not necessarily, the conditions permit simultaneous CFD surface reactions and CVD type gas phase reaction. 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 a low flow rate, i.e., a rate that is significantly lower than that employed in the corresponding CFD phase of the process.
Feature 6 (Deposit by CFD, etch, and then further deposit by CFD)—In such embodiments, CFD deposition is performed for one or more cycles (typically a number of cycles) and then the resulting film is etched to remove, for example, some excess film at or near a recess entrance (a cusp), followed by further cycles of CFD deposition. Other examples of structural features in the deposited film that may be etched in a similar manner. The etchant chosen for this process will depend on the material to be etched. In some cases, the etch operation may be performed with a fluorine containing etchant (e.g., NF3) or hydrogen.
In certain embodiments, a remote plasma is employed to produce the etchant. Generally, a remote plasma etches in a more isotropic fashion than a direct plasma. A remote plasma generally provides a relatively high fraction of radicals to the substrate. The reactivity of these radicals may vary with the vertical position within the recess. At the top of the feature, the radicals are more concentrated and consequently will etch at a higher rate, while further down the recess and at the bottom, some radicals will have been lost and therefore they will etch at a lower rate. This is of course a desirable reactivity profile for addressing the problem of too much deposition occurring at the recess opening. An additional benefit of using a remote plasma in etching is that the plasma is relatively gentle and hence unlikely to damage the substrate layer. This can be particularly beneficial when the underlying substrate layer is sensitive oxidation or other damage.
Feature 7 (Tailoring the film composition with additional reactant)—Many of the examples presented herein concern CFD processes employing one or two reactants. Further, many of the examples employ the same reactants in every CFD cycle. However, this need not be the case. First, many CFD processes may employ three or more reactants. Examples include (i) CFD of tungsten using as reactants diborane, tungsten hexafluoride, and hydrogen, and (ii) CFD of silicon oxide using as reactants diborane, BTBAS, and oxygen. The diborane can be removed from the growing film or it can be incorporated into the film if appropriate.
Further, some examples may employ additional reactants in only some CFD cycles. In such examples, a basic CFD process cycle employs only the reactants to create the base film composition (e.g., silicon oxide or silicon carbide). This basic process is performed in all or nearly all CFD cycles. However, some of the CFD cycles are executed as variant cycles and they deviate from the conditions of the normal deposition cycles. For example, they may employ one or more additional reactants. These variant cycles may also employ the same reactants employed in the basic CFD process, although this need not be the case.
Such CFD processes are particularly beneficial in preparing doped oxides or other doped materials as CFD films. In some implementations, dopant precursors are included as the “additional” reactant in only a small fraction of the CFD cycles. The frequency of adding the dopant is dictated by the desired concentration of dopant. For example, the dopant precursor may be included in every 10th cycle of the base material deposition.
Unlike many other deposition processes, particularly those requiring thermal activation, the CFD process may be conducted at a relatively low temperature. Generally, the CFD temperature will be between about 20 and 400 C. Such temperature may be chosen to permit deposition in the context of a temperature sensitive process such as deposition on a photoresist core. In a specific embodiment, a temperature of between about 20 and 100 C is used for double patterning applications (using, e.g., photoresist cores). In another embodiment, a temperature of between about 200 and 350 C is employed for memory fabrication processing.
As suggested above, CFD is well suited for depositing films in advanced technology nodes. Thus, for example, CFD processing may be integrated in processes at the 32 nm node, the 22 nm node, the 16 nm node, the 11 nm node, and beyond any of these. These nodes are described in the International Technology Roadmap for Semiconductors (ITRS), the industry consensus on microelectronic technology requirements for many years. Generally they reference one-half pitch of a memory cell. In a specific example, the CFD processing is applied to “2X” devices (having device features in the realm of 20-29 nm) and beyond.
While most examples of CFD films presented herein concern silicon based microelectronic devices, the films may also find application in other areas. Microelectronics or optoelectronics using non-silicon semiconductors such as GaAs and other III-V semiconductors, as well as II-VI materials such as HgCdTe may profit from using the CFD processes disclosed herein. Applications for conformal dielectric films in the solar energy field, such as photovoltaic devices, in the electrochromics field, and other fields are possible.
In the depicted embodiment, reactant gases A and B may co-exist in the gas phase without reacting. Accordingly, one or more of the process steps described in the ALD process may be shortened or eliminated in this example CFD process. For example, sweep steps after A Exposure Phases 120A and 120B may be eliminated.
The CFD process may be employed to deposit any of a number of different types of film. While most of the examples presented herein, concern dielectric materials, the disclosed CFD processes may be employed to form films of conductive and semiconductor materials as well. Nitrides and oxides are featured dielectric materials, but carbides, oxynitrides, carbon-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).
In some embodiments, a silicon nitride film may be formed by reaction of a silicon-containing reactant and one or more of a nitrogen-containing reactant and/or a nitrogen-containing reactant blend. Example silicon-containing reactants include, but are not limited to, bis(tertiarybutylamino)silane (SiH2(NHC(CH3)3)2 or BTBAS), dichlorosilane (SiH2Cl2), and chlorosilane (SiH3Cl). Example nitrogen-containing reactants include, but are not limited to, ammonia, nitrogen, and tert-butyl amine ((CH3)3CNH2 or t-butyl amine). An example nitrogen-containing reactant blend, includes, but is not limited to, a blend of nitrogen and hydrogen.
Selection of one or more reactants may be driven by various film and/or hardware considerations. For example, in some embodiments, a silicon nitride film may be formed from reaction of dichlorosilane and plasma-activated nitrogen. Chemisorption of dichlorosilane to a silicon nitride surface may create a silicon-hydrogen terminated surface, liberating hydrogen chloride (HCl). An example of this chemisorption reaction is schematically depicted in Reaction 1.
The cyclic intermediate shown in Reaction 1 may then be transformed into a silicon amine terminated surface via reaction with plasma-activated nitrogen.
However, some molecules of dichlorosilane may chemisorb by alternative mechanisms. For example, surface morphology may hinder the formation of the cyclic intermediate depicted in Reaction 1. An example of another chemisorption mechanism is shown schematically in Reaction 2.
During subsequent plasma activation of nitrogen, the remaining chlorine atom of the intermediate species shown in Reaction 2 may be liberated and may become activated by the plasma. This may cause etching of the silicon nitride surface, potentially causing the silicon nitride film to become rough or hazy. Further, the residual chlorine atom may readsorb, physically and/or chemically, potentially contaminating the deposited film. This contamination may alter physical and/or electrical properties of the silicon nitride film. Further still, the activated chlorine atom may cause etch damage to portions of the process station hardware, potentially reducing the service life of portions of the process station.
Thus, in some embodiments, chlorosilane may be substituted for dichlorosilane. This may reduce film contamination, film damage, and/or process station damage. An example of the chemisorption of chlorosilane is schematically shown in Reaction 3.
While the example depicted in Reaction 3 uses chlorosilane as the silicon-containing reactant, it will be appreciated that any suitable mono-substituted halosilane may be used.
As explained above, the depicted intermediate structures may react with a nitrogen source to form a silicon amine terminated surface of silicon nitride. For example, ammonia may be activated by a plasma, forming various ammonia radical species. The radical species react with the intermediate, forming the silicon amine terminated surface.
However, ammonia may physisorb strongly to surfaces of the reactant delivery lines, process station, and exhaust plumbing, which may lead to extended purge and evacuation times. Further, ammonia may have a high reactivity with some gas phase silicon-containing reactants. For example gas-phase mixtures of dichlorosilane (SiH2Cl2) and ammonia may create unstable species such as diaminosilane (SiH2(NH2)2). Such species may decompose in the gas phase, nucleating small particles. Small particles may also be formed if ammonia reacts with hydrogen chloride generated during chemisorption of a halosilane. Such particles may accumulate in the process station where they may contaminate substrate surfaces, potentially leading to integrated device defects, and where they may contaminate process station hardware, potentially leading to tool down time and cleaning. The small particles may also accumulate in exhaust plumbing, may clog pumps and blowers, and may create a need for special environmental exhaust scrubbers and/or cold traps.
Thus, in some embodiments, a substituted amine may be used as a nitrogen-containing reactant. For example, various radicals formed from plasma activation of an alkyl substituted amine, such as t-butyl amine, may be supplied to the process station. Substituted amines such as t-butyl amine may have a lower sticking coefficient on process hardware than ammonia, which may result in comparatively lower phyisorbption rates and comparatively lower process purge time.
Further, such nitrogen-containing reactants may form halogenated salts that are comparatively more volatile than ammonium chloride. For example, t-butylammonium chloride may be more volatile than ammonium chloride. This may reduce tool down time, device defect creation, and environmental abatement expense.
Further still, such nitrogen-containing reactants may form other amine precursors via various byproduct reactions. For example, the reaction of t-butyl amine with dichlorosilane may form BTBAS. Thus, the side products may provide alternate routes to form silicon nitride, potentially increasing film yield. In another example, substituted amines may provide low temperature thermally activated routes to silicon nitride films. For example, t-butyl amine decomposes thermally at temperatures above 300° C. to form isobutylene and ammonia.
While the illustrative example provided above describes silicon nitride film formation using t-butyl amine, it will be appreciated that any suitable substituted amine may be employed within the scope of the present disclosure. Suitable substituted amines may be selected, in some embodiments, based on thermodynamic characteristics and/or reactivity characteristics of the reactant. For example, the relative volatility of halogenated salts formed from the reactant may be considered, as may the existence and selectivity of various thermal decomposition paths at relevant temperatures.
Further, while the examples provided above describe the deposition of silicon nitride films, it will be appreciated that the principles discussed above apply generally to the deposition of other films. For example, some embodiments may use suitable halosilanes in combination with a suitable oxygen-containing reactant species, such as an oxygen plasma, to deposit silicon oxides.
A non-limiting list of reactants, product films, and film and process property ranges are provided in Table 1.
A CFD cycle typically contains an exposure phase for each reactant. During this “exposure phase,” a reactant is delivered to a process chamber to cause adsorption of the reactant on the substrate surface. Typically, at the beginning of an exposure phase, the substrate surface does not have any appreciable amount of the reactant adsorbed. In
Continuously supplying reactant A to the process station may reduce or eliminate a reactant A flow rate turn-on and stabilization time compared to an ALD process where reactant A is first turned on, then stabilized and exposed to the substrate, then turned off, and finally removed from a reactor. While the embodiment shown in
In some embodiments, reactant A exposure phase 120A may have a duration that exceeds a substrate surface saturation time for reactant A. For example, the embodiment of
At Reactant B exposure phase 140A of the embodiment shown in
In some embodiments, plasma activation of deposition reactions may result in lower deposition temperatures than in thermally-activated reactions, potentially reducing consumption of the available thermal budget of an integrated process. For example, in some embodiments, a plasma activated CFD process may occur at room temperature.
While the CFD process embodiment depicted in
Further, while many examples discussed herein include two reactants (A and B), it will be appreciated that any suitable number of reactants may be employed within the scope of the present disclosure. In some embodiments, a single reactant and an inert gas used to supply plasma energy for a surface decomposition reaction of the reactant may be used. Alternatively, as discussed above in the context of feature 7, some embodiments may use three or more reactants to deposit a film.
In some scenarios, surface adsorbed B species may exist as discontinuous islands on the substrate surface, making it difficult to achieve surface saturation of reactant B. Various surface conditions may delay nucleation and saturation of reactant B on the substrate surface. For example, ligands released on adsorption of reactants A and/or B may block some surface active sites, preventing further adsorption of reactant B. Accordingly, in some embodiments, continuous adlayers of reactant B may be provided by modulating a flow of and/or discretely pulsing reactant B into the process station during reactant B exposure phase 140A. This may provide extra time for surface adsorption and desorption processes while conserving reactant B compared to a constant flow scenario.
Additionally or alternatively, in some embodiments, one or more sweep phases may be included between consecutive exposures of reactant B. For example, the embodiment of
Returning to the embodiment of
Sweep phase 160A may have any suitable duration. In some embodiments, increasing a flow rate of a one or more sweep gases may decrease the duration of sweep phase 160A. For example, a sweep gas flow rate may be adjusted according to various reactant thermodynamic characteristics and/or geometric characteristics of the process station and/or process station plumbing for modifying the duration of sweep phase 160A. In one non-limiting example, the duration of a sweep phase may be optimized by adjustment of the sweep gas flow rate. This may reduce deposition cycle time, which may improve substrate throughput.
A CFD cycle, typically includes an “activation phase” in addition to the exposure and optional sweep phases described above. The activation phase serves to drive the reaction of the one or more reactants adsorbed on the substrate surface. At plasma activation phase 180A of the embodiment shown in
In some embodiments, the plasma ignited in plasma activation phase 180A may be formed directly above the substrate surface. This may provide a greater plasma density and enhanced surface reaction rate between reactants A and B. For example, plasmas for CFD processes may be generated by applying a radio frequency (RF) field to a low-pressure gas using two capacitively coupled plates. In alternative embodiments, a remotely generated plasma may be generated outside of the main reaction chamber.
Any suitable gas may be used to form the plasma. In a first example, and inert gas such as argon or helium may be used to form the plasma. In a second example, a reactant gas such as oxygen or ammonia may be used to form the plasma. In a third example, a sweep gas such as nitrogen may be used to form the plasma. Of course, combinations of these categories of gases may be employed. Ionization of the gas between the plates by the RF field ignites the plasma, creating free electrons in the plasma discharge region. These electrons are accelerated by the RF field and may collide with gas phase reactant molecules. Collision of these electrons with reactant molecules may form radical species that participate in the deposition process. It will be appreciated that the RF field may be coupled via any suitable electrodes. Non-limiting examples of electrodes include process gas distribution showerheads and substrate support pedestals. It will be appreciated that plasmas for CFD processes may be formed by one or more suitable methods other than capacitive coupling of an RF field to a gas.
Plasma activation phase 180A may have any suitable duration. In some embodiments, plasma activation phase 180A may have a duration that exceeds a time for plasma-activated radicals to interact with all exposed substrate surfaces and adsorbates, forming a continuous film atop the substrate surface. For example, the embodiment shown in
As explained more fully below, and as suggested in the discussion of feature 4 above, extending a plasma exposure time and/or providing a plurality of plasma exposure phases may provide a post-reaction treatment of bulk and/or near-surface portions of the deposited film. In one scenario, decreasing surface contamination by plasma treatment may prepare the surface for adsorption of reactant A. For example, a silicon nitride film formed from reaction of a silicon-containing reactant and a nitrogen-containing reactant may have a surface that resists adsorption of subsequent reactants. Treating the silicon nitride surface with a plasma may create hydrogen bonds for facilitating subsequent adsorption and reaction events.
In some embodiments, film properties, such as film stress, dielectric constant, refractive index, etch rate may be adjusted by varying plasma parameters, which will be discussed in more detail below. Table 3 provides an example list of various film properties for three example CFD silicon dioxide films deposited at 400 degrees Celsius. For reference purposes, Table 3 also includes film information for an example PECVD silicon dioxide film deposited at 400 degrees Celsius.
For example,
At plasma activation phase 380 shown in
While the embodiment of
Plasma treatment of the deposited film may alter one or more physical characteristics of the film. In one scenario, a plasma treatment may densify a newly deposited film. Densified films may be more etch-resistant than non-densified films. For example,
In another scenario, plasma treatment of a film may vary the stress characteristics of the film. For example,
In another scenario, plasma treatment of a deposited film may provide transient differential removal of trace film contaminants (e.g., hydrogen, nitrogen and/or carbon in an example silicon dioxide film) relative to other film constituents (e.g., silicon and/or oxygen in an example silicon dioxide film). For example,
While the plasma treatment discussed above relates to an oxygen plasma treatment, it will be appreciated that any suitable plasma treatment may be employed without departing from the scope of the present embodiment. For example, in some embodiments a substituted amine may be employed as a nitrogen-containing reactant in a suitable CFD process in place of NH3. Although replacement of NH3 with a substituted amine (e.g., an alkyl amine like t-butyl amine) for conformal SiN deposition may provide a number of benefits, in some instances, the deposited film may include carbon residue originating from the alkyl amine reactant (e.g., carbon residue from the three methyl groups included each t-butyl amine molecule (NH2—(CH3)3)). This in-film carbon may result in electrical leakage and may render the film unusable for some dielectric barrier applications.
Thus, in some embodiments, igniting a hydrogen plasma during SiN film deposition may reduce carbon residue in the SiN film, which may comparatively improve the insulating character of the film. In some examples, the reduction in carbon residue may be readily observable in FTIR spectra. For example, the SiN:C—H levels may be reduced from approximately 10% atomic to approximately 1% atomic.
Therefore, in some embodiments, a silicon nitride film may be deposited with a CFD process using an alkyl amine or a mixture of alkyl amines included in the nitrogen-containing reactant and one or more instances of a hydrogen plasma treatment. It will be appreciated that any suitable hydrogen plasma may be employed without departing from the scope of the present disclosure. Thus, in some embodiments, an admixture of H2 with a gas such as He or Ar, or other H-containing gases, or active H atoms produced by a remote plasma source, may be used to treat the deposited film. Further, in some embodiments, the carbon content of the film may be tuned to any suitable concentration by varying one or more of the number of treatment pulses and their duration, the intensity of the treatment plasma, the substrate temperature, and the treatment gas composition.
While the hydrogen plasma treatment discussed above relates to a silicon nitride film, it will be appreciated that application of a suitable hydrogen plasma treatment may be used to adjust the carbon content of other CFD deposited films, including, but not limited to, SiOx, GeOx, and SiOxNy.
Certain embodiments disclosed herein pertain to ultraviolet treatment (with or without plasma treatment) of oxide CFD films. The treatment may mitigate defects in the oxide and improve electrical properties such as CV characteristics of a gate dielectric. Device and package applications employing CFD oxides that can benefit from such treatment include thru-silicon vias, logic technology employing gate oxides, shallow trench isolation (STI), thin thermal oxidation formed after STI-photoresist strip, sacrificial oxide (e.g., ˜60 A) before a P-well implant, post “well” thermal oxide growth, gate/channel oxide, DRAM PMD PECVD Oxide.
In some cases, untreated CFD oxide films have been observed to have relatively poor electrical performance due to, it is believed, fixed charge in the as deposited film. For example, some films have been found to have significant within-wafer Vfb variations. Such problems have been resolved by using a post-deposition treatment with UV-radiation and/or a thermal anneal in the presence of hydrogen. It is believed that this process passivates and/or alleviates defects related to fixed charge at the (1) oxide to silicon interface or (2) within the deposited dielectric film or (3) at the air to oxide surface (surface charge). Using such treatment, the Vfb spread for as deposited oxide has been tightened from 8.3V to about 1.5V after UV cure.
While the these embodiments are primarily concerned with improving oxide films, the disclosed method may be applied generally to the growth of dielectrics, metals, metal to dielectric interface engineering. Specific dielectric materials include, for example, silicon oxides, including doped silicon oxides, silicon carbides, silicon oxycarbides, silicon nitrides, silicon oxynitrides, and ashable hard mask materials.
Examples of treatments that may be applied to improve dielectric properties include the following:
(A) Post deposition treatment of dielectric films synthesized by CFD with UV cure and then hydrogen-anneal. In the simplest embodiment, UV treatment may be used alone to reduce fixed charge.
(B) Pre-treatment of the substrate prior to CFD-dielectric film deposition with treatments including: H2-plasma, N2-plasma, N2/H2-plasma, NH3-plasma, Ar-plasma, He-plasma, He anneal, H2-anneal, NH3-anneal, and UV cure in the presence of He, H2, Ar, N2, H2/N2-forming gas, NH3. Plasma processing may be enabled with various plasma generators including, though not limited to, microwave, ICP-remote, direct and the like.
(C) Concurrent treatment (curing during deposition) with treatments including: H2-plasma, N2-plasma, N2/H2-plasma, NH3-plasma, Ar-plasma, He-plasma, He anneal, H2-anneal, NH3-anneal, and UV cure in the presence of He, H2, Ar, N2, H2/N2-forming gas, NH3. Plasma processing may be implemented with various plasma generators including, though not limited to, microwave, ICP-remote, direct and others known to those in the art. Isotropic and directional processing may be applied including, though not limited to, remote plasma, UV exposure, direct plasma, and microwave plasma. An example method includes intermittent treatment of the film between groups of CFD cycles. A group of CFD cycles may vary from about 1 to 10000 cycles. A typical scenario includes: (1) 5 cycles of CFD oxide growth followed by (2) one or more film treatments with any of the methods described above (e.g., He-plasma, UV-treatment), followed by (3) 5 cycles of CFD oxide growth. This method may be used to grow a film of any desired thickness.
(D) UV treatment imparted as byproduct by any plasma listed above (e.g., a helium plasma emits UV radiation).
One example of a procedure for in situ “cure” during the CFD cycling involves the following operations:
UV treatment via He-plasma
BTBAS dose
Purge
O2/Ar—RF plasma activation
Purge
Repeat steps 1-5 to yield a film of desired thickness.
A range of UV cure conditions may be employed in any of the listed contexts. Generally, the pedestal temperature will be maintained between about 250 and 500 C during the cure. For many device fabrication applications, the upper temperature will be limited to 450 C or even 400 C. The ambient employed during the cure may be inert or reactive. Examples of gases that may be present during the cure include helium, argon, nitrogen, forming gas, and ammonia. The flow rate of such gases may be about 2 to 20,000 sccm, preferably about 4000 to 18,000 sccm. The power of the UV lamp may, for example, about 2-10 kW, and preferably between about 3.5 and 7 kW. An appropriate duration of exposure to UV from such source is between about 20 and 200 seconds (e.g., about 90 seconds). Finally, the pressure may be held at a level between 0 Torr and about 40 Torr.
In a specific embodiment, an effective treatment of CFD oxide was obtained using the following conditions:
Pedestal temperature=400 C
Ambient=He
Pressure=40 Torr He
Flow rate=10,000 sccm
In some embodiments, a thermal anneal of the oxide is performed after the UV cure operation. In one example, the following conditions were used in the anneal:
Ped T=400 C
Ambient=H2+N2
Pressure=2.5 Torr
Flow rates=750 sccm H2; 3000 sccm N2
The physical and electrical characteristics of the deposited film may also be altered by adjusting other process parameters, such as deposition temperature. For example, correlation 700 of the embodiment depicted in
It will be appreciated that variation of physical and/or electrical film characteristics, like those discussed above, may provide opportunities to adjust device performance and yield, as well as opportunities to modify aspects of device manufacturing process integration. As one non-limiting example, the ability to tune etch rate characteristics of a CFD silicon dioxide film may make the film a candidate for etch stop, hard mask, and other process integration applications. Accordingly, various embodiments of CFD-produced films are provided herein for application throughout an integrated semiconductor device fabrication process.
In one scenario, a CFD process may deposit a conformal silicon dioxide film on a non-planar substrate. For example, a CFD silicon dioxide film may be used for gap fill of structures, such as a trench fill of shallow trench isolation (STI) structures. While the various embodiments described below relate to a gap fill application, it will be appreciated that this is merely a non-limiting, illustrative application, and that other suitable applications, utilizing other suitable film materials, may be within the scope of the present disclosure. Other applications for CFD silicon dioxide films include, but are not limited to, interlayer dielectric (ILD) applications, intermetal dielectric (IMD) applications, pre-metal dielectric (PMD) applications, dielectric liners for through-silicon via (TSV) applications, resistive RAM (ReRAM) applications, and/or stacked capacitor fabrication in DRAM applications.
Doped silicon oxide may be used as a diffusion source for boron, phosphorus, or even arsenic dopants. For example, a boron doped silicate glass (BSG), a phosphorus doped silicate glass (PSG), or even a boron phosphorus doped silicate glass (BPSG) could be used. Doped CFD layers can be employed to provide conformal doping in, for example, three-dimensional transistor structures such as multi-gate FinFET's and three-dimensional memory devices. Conventional ion implanters cannot easily dope sidewalls, especially in high aspect ratio structures. CFD doped oxides as diffusion sources have various advantages. First, they provide high conformality at low temperature. In comparison, low-pressure CVD produced doped TEOS (tetraethylorthosilicate) is known but requires deposition at high temperature, and sub-atmospheric CVD and PECVD doped oxide films are possible at lower temperature but have inadequate conformality. Conformality of doping is important, but so is conformality of the film itself, since the film typically is a sacrificial application and will then need to be removed. A non-conformal film typically faces more challenges in removal, i.e. some areas can be overetched. Additionally, CFD provides extremely well controlled doping concentration. As mentioned, a CFD process can provide from a few layers of undoped oxide followed by a single layer of doping. The level of doping can be tightly controlled by the frequency with which the doped layer is deposited and the conditions of the doping cycle. In certain embodiments, the doping cycle is controlled by for instance using a dopant source with significant steric hindrance. In addition to conventional silicon-based microelectronics, other applications of CFD doping include microelectronics and optoelectronics based on III-V semiconductors such as GaAs and II-VI semiconductors such as HgCdTe, photovoltaics, flat panel displays, and electrochromic technology.
Some gap fill processes involve two film deposition steps performed on different deposition tools, requiring a vacuum break and air exposure between deposition processes.
As depicted in
Further, while gap 802C may have an aspect ratio suitable for a gas-phase deposition process, 802B may have an aspect ratio that may lead to incomplete filling by a higher deposition rate process and may form a keyhole void. For example,
Some approaches to addressing high aspect ratio gaps such as gap 802B include providing device design rules that avoid creation of such gaps. However, such design rules may require additional masking steps, may make device design difficult, and/or may lead to increased integrated semiconductor device area, which may increase manufacturing cost. Thus, in some embodiments, a CFD process may include an in-situ transition from a CFD process to a CVD and/or a PECVD process. For example,
In some embodiments, a plasma generator may be controlled to provide intermittent pulses of plasma energy during plasma activation phase 904B. For example, the plasma may be pulsed at one or more frequencies including, but not limited to, frequencies between of 10 Hz and 150 Hz. This may enhance step coverage by reducing a directionality of ion bombardment in comparison to a continuous plasma. Further, this may reduce ion bombardment damage to the substrate. For example, photoresist substrates may be eroded by ion bombardment during a continuous plasma. Pulsing the plasma energy may reduce photoresist erosion.
In the embodiment shown in
In some embodiments, a CFD process may include an in-situ etch for selectively removing a re-entrant portion of deposited film. Non-limiting parameter ranges for an example silicon dioxide deposition process including an in-situ etch for a gap fill CFD process are provided in Table 5.
At etch phase 1104 of the embodiment of
In some embodiments, incompatible gas phase species may be removed from the process station before and after etching the film. For example, the embodiment of
At the conclusion of etch phase 1104, a deposition phase 1106 begins, further filling gaps on the non-planar substrate. Deposition phase 1106 may be any suitable deposition process. For example, deposition phase 1106 may include one or more of a CFD process, a CVD process, a PECVD process, etc. While the embodiment of
In the embodiment depicted in
Another embodiment of an in-situ etch process is shown in
Other example applications for CFD films include, but are not limited to conformal low-k films (e.g., k approximately 3.0 or lower in some non-limiting examples) for back-end-of-line interconnect isolation applications, conformal silicon nitride films for etch stop and spacer layer applications, conformal antireflective layers, and copper adhesion and barrier layers. Many different compositions of low-k dielectrics for BEOL processing can be fabricated using CFD. Examples include silicon oxides, oxygen doped carbides, carbon doped oxides, oxynitrides, and the like.
In another example, in one integrated process scenario, a silicon dioxide spacer layer may be deposited over a photoresist “core.” Use of a photoresist core instead of an alternative core material (such as a silicon carbide layer) may eliminate a patterning step in the integrated process. The process may involve patterning photoresist using normal lithographic techniques and then depositing a thin layer of CFD oxide directly over that core. A directional dry etch process may be then used to remove the CFD oxide film at the top of the patterned photoresist and at the bottom leaving only material along the sidewall of the patterned photoresist (consider trenches). At this stage, simple ashing can be used to remove the exposed core leaving behind the CFD oxide. Where once there was a single photoresist line, now there are two CFD-oxide lines. In this manner the process doubles the pattern density; hence it is sometimes referred to as “double patterning”. Unfortunately, use of a photoresist core may limit a spacer layer deposition temperature to less than 70 degrees Celsius, which may be less than deposition temperatures for conventional CVD, PECVD, and/or ALD processes. Thus, in some embodiments, a low temperature CFD silicon dioxide film may be deposited at temperatures below 70 degrees Celsius. It will be appreciated that other potential integrated process applications exist for suitable CFD-generated films within the scope of the present disclosure. Additionally, in various embodiments, a nitride such as a silicon nitride deposited as above may be employed as a conformal diffusion barrier layer and/or etch stop in various stages of semiconductor device manufacture.
While the various CFD deposition processes described above have been directed at depositing, treating, and/or etching single film types, it will be appreciated that some CFD processes within the scope of the present disclosure may include in-situ deposition of a plurality of film types. For example, alternating layers of film types may be deposited in-situ. In a first scenario, a double spacer for a gate device may be fabricated by in-situ deposition of a silicon nitride/silicon oxide spacer stack. This may reduce cycle time and increase process station throughput, and may avoid interlayer defects formed by potential film layer incompatibility. In a second scenario, an antireflective layer for lithographic patterning applications may be deposited as a stack of SiON or amorphous silicon and SiOC with tunable optical properties.
In certain embodiments, a doped dielectric layer is formed by a conformal film deposition process. The layer typically includes a silicon oxide or silicon nitride base material or matrix which is doped with carbon and/or nitrogen. Many useful doped dielectric layer compositions may be provided by carefully tuning the amount and timing of carbonaceous or nitrogenous dopant delivered during CFD. The resulting doped conformal films may be silicon oxycarbides (sometimes termed oxygen doped silicon carbides), silicon oxynitrides (SiON), nitrogen doped silicon carbides (SiCN), and the like. These layers have numerous applications in integrated circuits and other devices. Examples include dielectric liners, gate electrode spacers, and input/output gate oxides.
The type of precursor is chosen for its ability to produce an undoped dielectric of the desired composition. The precursor may be introduced in a vapor phase together with an oxidant. In some embodiments, the oxidant is initially delivered to the reaction chamber and its flow is established prior to delivery of the dielectric precursor. Further, the underlying substrate surface may be first treated with a dopant containing compound prior to exposure to the dielectric precursor. Examples of such embodiments are discussed below.
Examples of suitable oxidants include elemental oxygen (e.g., O2 or O3), nitrous oxide (N2O), water, and carbon dioxide. The oxidant is typically delivered to the reaction chamber together with a carrier gas such as an inert gas (e.g., argon) or nitrogen.
In one example, BTBAS or BDEAS (where BDEAS is bisdiethylaminosilane or (Et2N)2SiH2) serves as the precursor for producing a silicon oxide (such as a silicate glass). Other examples include various other bisalkylaminosilanes, where the alkyl groups may contain 1-6 carbon groups. Each amine group may be, separately, mono or di-substituted with alkyl groups. Alkenyl and alkynyl variations may be employed. In some cases, different alkyl groups may be employed on the molecule (e.g., one amine may be substituted with a methyl group and the other amine may be substituted with an ethyl group. In certain embodiments, the one or more alkyl groups provides steric hindrance of the silane core.
In the case of silicon nitride CFD films, BTBAS or a similar silicon and nitrogen containing compounds are examples of suitable precursors. In another example, a combination of silicon and nitrogen containing precursors (such as silane and tert-butylamine) is sometimes used to produce silicon nitride. Examples of some additional suitable silicon nitride precursors and their deposition conditions are provided in US patent application Ser. No. 13/084,305, filed Apr. 11, 2011, which is incorporated herein by reference in its entirety. Specific examples include tetraethyl orthosilicate (C8H20O4Si), and analogues thereof (e.g., Si(OR)4, where R may be any suitable alkyl group, such as a methyl group, an ethyl group, a propyl group, etc.); alkoxysilanes such as methyltriethoxysilane (MTEOS), methyltrimethoxysilane (MTMOS), dimethyldimethoxysilane (DMDMOS), trimethylmethoxysilane (TMMOS), dimethyldiethoxysilane (DMDEOS); alkylsilanes such as Tetramethylsilane (4MS); Trimethylsilane (3MS); Dimethylsilane (2MS); cyclic siloxanes such as 2,4,6,8-Tetramethylcyclotetrasiloxane (TOMCAT), octamethylcyclotetrasiloxane (OMCAT), tetravinyltetramethylcyclotetrasiloxane (TVTMCTS); alkynylsilanes such as Trimethylsilylacetylene (TMSA); dichlorosilane, trichlorosilane and mixtures of these precursorsTEOS). These compounds are used with nitriding co-reactants. As discussed in Ser. No. 13/084,305, examples of such co-reactants include tert-butylamine (TBA), triethylamine (Et3N), trimethylamine (Me3N), ammonia, tert-amylamine, isopropylamine, and the like.
At the conclusion of operation A, the flow of dielectric precursor into the chamber is terminated and an operation B begins as depicted. During operation B, the oxidant which was introduced into the chamber during phase A continues to flow and serves to purge the chamber of precursor. In certain embodiments, the oxidant continues to flow at the same rate as during operation A.
After the purge is completed during operation B, the precursor is reacted on the substrate surface to form a portion of the dielectric film (see operation C). In various embodiments, a plasma is applied to drive the reaction of the adsorbed dielectric precursor. In some examples, this reaction is an oxidation reaction. Some of the oxidant previously flowing into the reaction chamber is adsorbed onto the surface along with the dielectric precursor, thus providing an immediately available oxidizing agent for the plasma-mediated surface reaction. After the surface reaction is complete, the plasma or other source of activation energy is turned off and the reactor is again purged by continuously flowing oxidant. See operation D.
Operations A through D collectively provide a single cycle of the dielectric film deposition process. It should be understood that other CFD cycle sequences described herein may be used in place of the basic cycle depicted here. In the depicted embodiment, the deposition cycle (A through D) is performed without introduction of any dopant species. In various embodiments, the cycle represented by operations A through D is repeated one or more times in succession prior to introduction of a dopant species. This is illustrated in phase E of
At some point in the process, the cycles of dielectric deposition are interrupted by introduction of a dopant species such as, e.g., a hydrocarbon. This is illustrated as an operation F in the figure. When carbides or carbon doped dielectrics are to be formed, examples of dopant species for the dielectric source film includes one or more hydrocarbons (alkanes, alkenes, alkynes, and aromatic hydrocarbons), alcohols, ketones, aldehydes, ethers, esters, carboxylic acids, oxolanes, furans, and the like. Specific examples of such dopant species include methane, ethane, propane, acetylene, ethylene, propylene, t-amyl alcohol, ethanol, propanol, ethyleneglycol, propyne, and the like. Examples of nitrogenous doping species that may be provided in the dielectric source film include inorganic and organic compounds such as ammonia, amines (primary, secondary, tertiary, and quaternary), nitriles, amides, nitrogen-containing heterocyclic compounds (including azoles, pyrroles, etc.), amino alcohols, and the like. Specific examples of such doping species include ammonia, hydrazine, elemental nitrogen (N2), acetonitrile, tert-butylamine, ethanolamine, and the like. Examples of nitrogen-containing carbonaceous doping species that may be provided in the dielectric source film include amines, nitriles, amides, nitrogen-containing heterocyclic compounds, substituted hydrazines, amino alcohols, and the like. Specific examples of such doping species include acetonitrile, tert-butylamine, ethylamine, dimethylhydrazine triethylamine, and the like.
In a specific embodiment, the dopant species is provided to the reaction chamber in mixture with a carrier gas such as an inert gas (e.g., argon or helium), but not with an oxidant or other reactant. In other embodiments, the oxidant used in the basic cycle continues to flow during delivery of the dopant species but at a reduced rate. Thus, in this baseline example, flow of the oxidant is reduced or ceases during operation F. In other embodiments, the precursor is introduced together with a reducing agent or an oxidizing agent.
The dopant species is supplied under conditions suitable for efficiently delivery to the substrate. As an example, the dopant species may be delivered to a chamber having a total pressure of about 0.5-5 Torr. In some embodiments, the substrate temperature ranges from about 100-550 C, or about 350-450 C, during delivery of the dopant species.
In certain embodiments, the dopant species attaches to the substrate surface by a surface limited mechanism, as with ALD. In alternative embodiments, the precursor may deposit by CVD-type process rather than an ALD (surface adsorption limited) process.
Optionally the dopant precursor is purged from the reaction chamber prior to further processing of the dielectric film. Additionally, as depicted in the
In the depicted baseline process, the cycles of dielectric deposition and intermittent dopant delivery (operations A through G) may be performed multiple times as shown in a phase H of the figure. The actual number of times that the process sequence is repeated depends upon the desired total thickness of the film and the thickness of the dielectric deposited per cycle, as well as the amount of dopant incorporated into the film. In some embodiments, operations A-G are repeated at least twice, or at least three times, or at least five times, or at least about ten times.
After the dielectric film is completely deposited, it may be further processed to impart desired physical or chemical properties appropriate for the fabrication technology for which it is used. This may involve, for example, etching the deposited film on a device structure as depicted at an operation I of
Numerous variations on this baseline process may be realized. Some of these variations have as their goal controlling or tuning the amount of dopant species in the dielectric film. Specific variations are designed to control the wet etch rate of the dielectric film. Other variations are designed to control the within wafer dopant uniformity, step-coverage (e.g., about 70-100%), dielectric constant (e.g., about 2.5-10), film leakage, refractive index, etc. For example, increased carbon dopant may decrease dielectric constant, reduce wet etch rate, and increase refractive index.
In certain embodiments, the cycle frequency with which a dopant is introduced into a growing dielectric film is controlled. More frequent dopant species delivery cycles result in an overall greater level of doping in the final dielectric film. This may also result in a relatively even distribution of dopant throughout the film. When fewer dopant precursor delivery cycles are inserted into the deposition process, the regions of high dopant concentration in the film are more widely separated than is the case when the dopant delivery cycles are more frequent.
In one embodiment, the dopant species is delivered to the growing dielectric film one time for each cycle of dielectric deposition. In another embodiment, the dopant species is delivered once during every other cycle of dielectric deposition. In other embodiments, less frequent dopant species delivery cycles are incorporated in the process. For example, the dopant species may be delivered once during every third, fourth, or fifth cycle of dielectric deposition. In some cases, the dopant species is delivered at a frequency of about once during every 5-20 dielectric deposition cycles.
It should be understood that the frequency of the dopant delivery cycles need not be consistent over the course of the dielectric film deposition. With this in mind, the resulting dielectric film may have a graded composition of dopant such that the average concentration of dopant over the thickness of the deposit dielectric film is nonuniform. In one embodiment, the concentration of dopant is greater on one side or the other of the dielectric film. Of course, the dopant concentration gradient in the dielectric film can be tailored as desired by carefully varying the frequency of dopant delivery cycles over the course of the entire dielectric deposition process.
Another variation on the baseline process involves adjusting the amount of dopant species delivered during any dopant delivery cycle. The amount of dopant delivered during any given dopant delivery cycle will be determined by the concentration of dopant species delivered to the reaction chamber as well as the duration of the exposure of the substrate to the delivered dopant species. Of course, if accumulation of dopant species is a surface limited process, as with ALD, the total amount of dopant delivered is somewhat constrained. To the extent that greater amounts of dopant species are delivered during any dopant delivery cycle, the overall concentration of dopant in the dielectric film increases. This may offset the effect of having relatively infrequent dopant delivery cycles in the overall process. However, it must be understood that increasing the amount of dopant delivered during any given dopant species delivery cycle results in a relatively high local concentration of dopant in the film. Of course, such dopant concentration spike can be softened by annealing or other operation through which the dopant concentration is made more uniform in the dielectric film.
In the case of carbon being the dopant, the amount of hydrocarbon or other carbon containing species delivered during a typical dopant delivery cycle may provide between about 108 and 1022 atoms per cm2. In the case of nitrogen being the dopant, the amount of nitrogenous compound delivered during a typical dopant delivery cycle may provide between about 108 and 1022 atoms per cm2
In some embodiments, the amount of dopant species delivered in each dopant delivery cycle is not constant throughout the growth of the full dielectric film. Thus, the amount of dopant species delivered per cycle can be tailored to produce a desired dopant concentration gradient in the dielectric film. For example, it may be desirable to provide greater amounts of dopant species in those dopant delivery cycles that occur at locations in the dielectric film that are relatively close to the underlying device structure or, alternatively at locations that are relatively near the center or outer surface of the film.
In general, the concentration profile of the dopant in the dielectric film can be tailored as appropriate. In one embodiment, the dopant concentration spikes to a high level at the edge of the film adjacent to the structure to be doped. In some embodiments, the concentration increases and decreases intermittently throughout the film thickness.
The base oxide or nitride matrix in which the dopant species reside may itself be tailored to affect the properties of the final doped film. For example, the density and/or chemical composition of the oxide or nitride may be controlled to produce a desired impact on final film properties. In some approaches, the entire dielectric thickness possesses the same density or composition such that the tailored properties are invariant throughout the film thickness. In other approaches, the film properties are tailored such that one or more such properties vary across the film thickness. Examples include modulation of band-gap and tunneling capacity over the thickness.
The deposition temperature employed during formation of the dielectric film also influences the film properties. In general, it has been found that dielectric deposited at relatively low temperatures by CFD processing generally provides relatively low density films. Lower density films permit faster diffusion of dopants, higher etch rates, and other interesting properties. Examples of the relatively low temperatures associated with relatively low density films are temperatures in the range of about 100 to 450° C., or more specifically between about 200 to 250° C. Of course, these temperature ranges depend upon the choice of dielectric precursor and other deposition parameters. The temperatures presented here are associated with use of BTBAS or BDEAS as the dielectric precursor.
By contrast, dielectric deposited at relatively higher temperatures tends to have a relatively higher density. Using BTBAS as the dielectric precursor, relatively high temperatures associated with relatively low dopant diffusion rates are in the range of about 500 to 1200° C., or more specifically between about 800 to 950° C. Of course, these temperatures may be applied to other precursors.
In various embodiments, the deposition temperature is controlled by heating and/or cooling a pedestal or chuck that holds the substrate during CFD. Examples of suitable pedestals are described in U.S. patent application Ser. No. 12/435,890 (published application no. US-2009-0277472), filed May 5, 2009, and US patent application Ser. No. 13/086,010, filed Apr. 13, 2011, both of which are incorporated herein by reference in their entireties.
In certain embodiments, the substrate surface on which the dielectric film is to be formed is pretreated prior to deposition of the dielectric film. In one example, the pretreatment involves exposure to a plasma such as a reducing plasma. Such treatment may be appropriate when, for example, the substrate features to be doped contains silicon. Typically silicon contains a small quantity of native oxide which could be detrimental in later fabrication operations. In a specific embodiment, the substrate surface is pretreated with a reducing plasma such as an ammonia or hydrogen containing plasma. In some embodiments, the pretreatment reduces the defects in the underlying device structure. For example, a helium plasma may be employed to reduce charge trapping defects in the underlying material. A helium plasma treatment may be done in a variety of ways including: (1) alternating CFD cycles and He-plasma cycles or (2) X # of CFD cycles followed by a helium plasma cycle where X is between about 1-200 or (3) inclusion of helium flow during the RF plasma step. Alternative gases include argon, ammonia, nitrogen, neon, xenon, hydrogen. RF plasma power may range from about 100 W to 3000 W with flows ranging from about 500 sccm to 20,000 SLM.
In general, the process depicted in
In various embodiments, a partially fabricated dielectric film itself is pretreated with a plasma or other activating treatment prior to exposure to the dopant species. This serves to change the concentration of charge trapping defects in the film. Alternatively, or in addition, the process may be used to increase either positive or negative charge in a film thus leading to control over flat-band-voltage position ranging from about −40V to 30V. The process conditions presented above for treating the underlying structure prior to film deposition may be employed as well for treating the partially deposited film.
An optional post deposition anneal may be employed. After the source layer is formed (or during its formation), the film may be annealed. In certain embodiments, the anneal is performed at a temperature of between about 100 and 1200° C. for about 0.5 to 60 minutes, or between about 700 and 900° C. for about 1 to 5 minutes.
The dielectric film serving as a source of dopant species will have various characteristics. In various embodiments, the film thickness is between about 10 and 20,000 Angstroms. For thru-silicon vias, film thicknesses ranging from 500 to 20,000 A may be appropriate. For transistor applications, film thicknesses ranging from 5 to 1000 A may be appropriate. The average concentration of dopant atoms (or other dopant species) in the dielectric film depends upon various factors including the total amount of dopant species per unit surface area of the film as well as the application.
In various embodiments, a nitrogen-doped silicon carbide film has a density of between about 2.6-3.5. In certain embodiments, silicon oxycarbide and silicon oxynitride films have a density of between 1.6-3.0. Compositionally, Si:O:N films may contain between about 2-35 atomic % nitrogen and about 2-35 atomic % oxygen with the balance being all or substantially all silicon. Compositionally, Si:O:C films may contain between about 2-35 atomic % carbon and about 2-35 atomic % oxygen with the balance being all or substantially all silicon. Compositionally, Si:N:C films may contain between about 2-35 atomic % nitrogen and 2-35 atomic % carbon with the balance being all or substantially all silicon.
Various apparatus may be designed to deposit the doped dielectric films as described here. Generally, the apparatus will contain a process chamber for holding a substrate during deposition of the doped film. The process chamber will include one or more inlets for admitting process gases, including dielectric precursors, oxidants, carrier gases or inerts, dopant species and the like. In various embodiments, the apparatus will additionally include features for generating a plasma having properties suitable for creating the dielectric layer, incorporating dopant into the dielectric layer, treating the dielectric layer to modify the electrical, optical, mechanical, and/or chemical properties of the layer, and the like. Typically, the apparatus will include a vacuum pump or provisions for connecting to such pump. Still further, the apparatus will have a controller or controllers configured or designed for controlling the apparatus to accomplish the sequence of doped dielectric deposition operations described here. The controller may include instructions for controlling various features of the apparatus including the valving to deliver of process gases and to control pressure, the power supply for generating plasmas, and the vacuum source. The instructions may control the timing and sequence of the various operations. In various embodiments, the apparatus may have features as provided in the Vector™ family of deposition tools available from Novellus Systems of San Jose, Calif. Other features of suitable apparatus for depositing doped dielectric films are described elsewhere herein.
The substrate surface on which the dielectric source layer is formed may require a highly conformal deposition. In certain examples, the dielectric source film conformably coats features having an aspect ratio of between about 500:1 and 20:1 for TSV and DRAM applications. For logic technology, the films may be deposited on features having aspect ratios ranging from about 10:1 to 2:1. In some examples, the featured have widths of no greater than about 2 micrometer for TSV applications. And for logic, critical dimensions ranging from about 200 nm down to 5 nm may be appropriate. Doping using dielectric source layers of the types described herein will find particular application in devices formed according to the 45 nm technology node and beyond, including the 22 nm technology node, the 16 nm technology node, 11 nm, 7 nm, etc.
Doped CFD films have various applications including serving as etchable layers used at various stages in integrated circuit fabrication such as in transistor and/or self-aligned contacts fabrication. In certain embodiments, the etchable layer is a glass layer having tunable wet etching rates, where the etch rate is tunable by the level of doping. In other words, the level of doping is chosen to provide a pre-defined etch rate. In specific embodiments, the etchable layer is a silicate glass layer containing a dopant such as phosphorus, boron, or combinations thereof. Etch rates may range from about 5:1 to 0.5:1 with respect to a typical thermal oxide; the etch rate for such oxide is about 1.
Among the device structures that may be contacted with doped CFD layers of the types described herein are front end of line structures such as gate electrodes or back end of line features such as planarized metallization layers and liners for low k dielectrics used for intermetal dielectrics.
In certain embodiments, the carbon or nitrogen doped structures described herein can be used as gate spacers in which a conformal dielectric layer is first deposited over the gate structure and then isotropically etched to leave sidewall spacers.
A specific example is depicted in the table presented in
Of interest, this example begins with a pretreatment of the substrate, prior to beginning the first CFD cycle. The pretreatment begins with exposure to an RF plasma, followed by evacuation of the reaction chamber (optional pump to base), and finally a purge. The chamber pressure is initially 3 Torr and it holds at that level during the plasma treatment, then during the evacuation operation, the pressure drops to 0.2 Torr, and finally the pressure returns to 3 Torr during the purge. The duration of each operation is 1.8 seconds for the plasma treatment, 10 seconds for the pump to base, and 5 seconds for the purge. The plasma treatment is conducted at an energy of 200 or 500 W. Oxygen flows during the entire pretreatment sequence, first at 2 SLM during the plasma and pump down operations and then at 4 SLM during the purge (in preparation for the first CFD cycle). Argon flows at 5 SLM during the evacuation and purge operations. The plasma treatment may be accompanied by helium if the goal is to mitigate defects in the substrate or ammonia if the goal is provide nitrogen dopant. In either case, the gas flows at 7.5 SLM. In the latter case, the resulting dielectric is a nitrogen doped silicon oxide (SiON). The number of cycles may be tailored based on the desired films thickness. Typical deposition rates may vary from 0.4-1.4 A/cycle and typically 0.9-1.1 A/cycle. All processing may be done in any vacuum chamber and such as the Vector™ class of chambers (available from Novellus Systems, of San Jose, Calif.) for PECVD. Ammonia may be used as a co-reactant during the course of a deposition aimed toward generating SiON or SiCN films. The techniques and methods described herein are application to any wafer size including, though not limited to 200 mm, 300 mm, 450 mm.
It will be appreciated that any suitable process station may be employed with one or more of the embodiments described above. For example,
CFD process station 1300 fluidly communicates with reactant delivery system 1301 for delivering process gases to a distribution showerhead 1306. Reactant delivery system 1301 includes a mixing vessel 1304 for blending and/or conditioning process gases for delivery to showerhead 1306. One or more mixing vessel inlet valves 1320 may control introduction of process gases to mixing vessel 1304.
Some reactants, like BTBAS, may be stored in liquid form prior to vaporization at and subsequent delivery to the process station. For example, the embodiment of
In some embodiments, reactant liquid may be vaporized at a liquid injector. For example, a liquid injector may inject pulses of a liquid reactant into a carrier gas stream upstream of the mixing vessel. In one scenario, a liquid injector may vaporize reactant by flashing the liquid from a higher pressure to a lower pressure. In another scenario, a liquid injector may atomize the liquid into dispersed microdroplets that are subsequently vaporized in a heated delivery pipe. It will be appreciated that smaller droplets may vaporize faster than larger droplets, reducing a delay between liquid injection and complete vaporization. Faster vaporization may reduce a length of piping downstream from vaporization point 1303. In one scenario, a liquid injector may be mounted directly to mixing vessel 1304. In another scenario, a liquid injector may be mounted directly to showerhead 1306.
Showerhead 1306 and pedestal 1308 electrically communicate with RF power supply 1314 and matching network 1316 for powering a plasma. In some embodiments, the plasma energy may be controlled by controlling one or more of a process station pressure, a gas concentration, an RF source power, an RF source frequency, and a plasma power pulse timing. For example, RF power supply 1314 and matching network 1316 may be operated at any suitable power to form a plasma having a desired composition of radical species. Examples of suitable powers include, but are not limited to, powers between 100 W and 5000 W for a 300 mm wafer. Likewise, RF power supply 1314 may provide RF power of any suitable frequency. In some embodiments, RF power supply 1314 may be configured to control high- and low-frequency RF power sources independently of one another. Example low-frequency RF frequencies may include, but are not limited to, frequencies between 50 kHz and 500 kHz. Example high-frequency RF frequencies may include, but are not limited to, frequencies between 1.8 MHz and 2.45 GHz. It will be appreciated that any suitable parameters may be modulated discretely or continuously to provide plasma energy for the surface reactions. In one non-limiting example, the plasma power may be intermittently pulsed to reduce ion bombardment with the substrate surface relative to continuously powered plasmas.
In some embodiments, the plasma may be monitored in-situ by one or more plasma monitors. In one scenario, plasma power may be monitored by one or more voltage, current sensors (e.g., VI probes). In another scenario, plasma density and/or process gas concentration may be measured by one or more optical emission spectroscopy sensors (OES). In some embodiments, one or more plasma parameters may be programmatically adjusted based on measurements from such in-situ plasma monitors. For example, an OES sensor may be used in a feedback loop for providing programmatic control of plasma power. It will be appreciated that, in some embodiments, other monitors may be used to monitor the plasma and other process characteristics. Such monitors may include, but are not limited to, infrared (IR) monitors, acoustic monitors, and pressure transducers.
In some embodiments, pedestal 1308 may be temperature controlled via heater 1310. Further, in some embodiments, pressure control for CFD process station 1300 may be provided by butterfly valve 1318. As shown in the embodiment of
As described above, one or more process stations may be included in a multi-station processing tool.
The depicted processing chamber 2414 comprises four process stations, numbered from 1 to 4 in the embodiment shown in
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, wafer temperature, target power levels, RF power levels, 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. 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 CFD process may include one or more instructions for execution by system controller 2450. The instructions for setting process conditions for a CFD process phase may be included in a corresponding CFD recipe phase. In some embodiments, the CFD recipe phases may be sequentially arranged, so that all instructions for a CFD process phase are executed concurrently with that process phase.
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 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.
The apparatus/process described hereinabove may be used in conjunction with lithographic patterning tools or processes, for example, for the fabrication or manufacture of semiconductor devices, displays, LEDs, photovoltaic panels and the like. Typically, though not necessarily, such tools/processes will be used or conducted together in a common fabrication facility. Lithographic patterning of a film typically includes some or all of the following operations, each operation enabled with a number of possible tools: (1) application of photoresist on a workpiece, i.e., substrate, using a spin-on or spray-on tool; (2) curing of photoresist using a hot plate or furnace or UV 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; (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.
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 subcombinations 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.
This application claims priority under 35 U.S.C. §120 as a continuation in part of US patent application Ser. No. 13/084,399, filed Apr. 11, 2011, which claims benefit of U.S. provisional patent application No. 61/324,710, filed Apr. 15, 2010, and U.S. provisional patent application No. 61/372,367, filed Aug. 10, 2010, and U.S. provisional patent application No. 61/379,081, filed Sep. 1, 2010, and U.S. provisional patent application No. 61/417,807, filed Nov. 29, 2010. Each of the above patent applications is incorporated herein by reference in its entirety and for all purposes. This application is also a continuation in part of US patent application Ser. No. 13/084,305, filed Apr. 11, 2011, and incorporated herein by reference in its entirety and for all purposes.
| Number | Name | Date | Kind |
|---|---|---|---|
| 4500563 | Ellenberger et al. | Feb 1985 | A |
| 5223443 | Chinn et al. | Jun 1993 | 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 |
| 5932286 | Beinglass et al. | Aug 1999 | A |
| 6100202 | Lin et al. | Aug 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 |
| 6416822 | Chiang et al. | Jul 2002 | B1 |
| 6428859 | Chiang et al. | Aug 2002 | B1 |
| 6468924 | Lee et al. | Oct 2002 | B2 |
| 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 | 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 |
| 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 | Vaartstra | 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 |
| 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 |
| 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 |
| 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 |
| 8956983 | Swaminathan et al. | Feb 2015 | B2 |
| 8999859 | Swaminathan et al. | Apr 2015 | B2 |
| 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 et al. | Mar 2016 | B2 |
| 9355839 | Swaminathan et al. | May 2016 | B2 |
| 9355886 | Swaminathan et al. | May 2016 | B2 |
| 9373500 | Swaminathan et al. | Jun 2016 | B2 |
| 20020076507 | Chiang et al. | Jun 2002 | A1 |
| 20030008070 | Seutter et al. | Jan 2003 | A1 |
| 20030024477 | Okuda et al. | Feb 2003 | A1 |
| 20030143839 | Raaijmakers et al. | Jul 2003 | A1 |
| 20030200917 | Vaartstra | Oct 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 |
| 20040219746 | Vaartstra et al. | Nov 2004 | A1 |
| 20040231799 | Lee et al. | Nov 2004 | A1 |
| 20050042865 | Cabral et al. | Feb 2005 | A1 |
| 20050079661 | Cho et al. | Apr 2005 | A1 |
| 20050109276 | Iyer et al. | May 2005 | A1 |
| 20050118837 | Todd et al. | Jun 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 |
| 20050233553 | Kountz et al. | Oct 2005 | A1 |
| 20050260347 | Narwankar et al. | Nov 2005 | A1 |
| 20050276099 | Horng et al. | Dec 2005 | A1 |
| 20050287775 | Hasebe et al. | Dec 2005 | A1 |
| 20060030148 | Seutter et al. | Feb 2006 | A1 |
| 20060084283 | Paranjpe et al. | Apr 2006 | A1 |
| 20060088985 | Haverkort et al. | Apr 2006 | A1 |
| 20060165890 | Kaushal et al. | Jul 2006 | A1 |
| 20060199357 | Wan et al. | Sep 2006 | A1 |
| 20060228868 | Ahn et al. | Oct 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 |
| 20070065576 | Singh et al. | Mar 2007 | A1 |
| 20070087581 | Singh et al. | Apr 2007 | A1 |
| 20070116887 | Faguet | 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 |
| 20070251444 | Gros et al. | Nov 2007 | A1 |
| 20070259110 | Mahajani et al. | Nov 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 |
| 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 |
| 20080213479 | Chou et al. | Sep 2008 | A1 |
| 20080242116 | Clark | 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 |
| 20090163012 | Clark et al. | Jun 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 |
| 20100022099 | Van Nooten et al. | Jan 2010 | A1 |
| 20100025824 | Chen et al. | Feb 2010 | A1 |
| 20100051578 | Chang et al. | Mar 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 |
| 20100124618 | Kobayashi et al. | May 2010 | A1 |
| 20100124621 | Kobayashi et al. | May 2010 | A1 |
| 20100136260 | Matsunaga et al. | Jun 2010 | A1 |
| 20100136313 | Shimizu et al. | Jun 2010 | A1 |
| 20100167555 | Maula et al. | Jul 2010 | A1 |
| 20100221925 | Lee et al. | Sep 2010 | A1 |
| 20100255218 | Oka et al. | Oct 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 | Hayashi | 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 |
| 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 |
| 20110198756 | Thenappan et al. | Aug 2011 | A1 |
| 20110201210 | Sato et al. | 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 |
| 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 |
| 20120077349 | Li et al. | Mar 2012 | A1 |
| 20120108079 | Mahajani | May 2012 | A1 |
| 20120113672 | Dubrow et al. | May 2012 | A1 |
| 20120164846 | Ha et al. | Jun 2012 | A1 |
| 20120193693 | Kanaya | Aug 2012 | A1 |
| 20120213940 | Mallick | Aug 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 |
| 20130058161 | Yamanaka et al. | Mar 2013 | A1 |
| 20130058162 | Yamanaka et al. | Mar 2013 | A1 |
| 20130071580 | Weidman et al. | Mar 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 |
| 20130344248 | Clark | Dec 2013 | A1 |
| 20140030444 | Swaminathan et al. | Jan 2014 | A1 |
| 20140051262 | Lavoie et al. | Feb 2014 | A9 |
| 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 |
| 20140182619 | Goto et al. | Jul 2014 | A1 |
| 20140209562 | LaVoie et al. | Jul 2014 | A1 |
| 20140216337 | Swaminathan et al. | Aug 2014 | A1 |
| 20140264555 | Ahn et al. | Sep 2014 | A1 |
| 20140273428 | Shero et al. | Sep 2014 | A1 |
| 20140295084 | Shirai et al. | Oct 2014 | A1 |
| 20140302686 | Pan et al. | Oct 2014 | 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 |
| 20160020092 | Kang et al. | Jan 2016 | A1 |
| 20160064211 | Swaminathan et al. | Mar 2016 | A1 |
| 20160118246 | Kang et al. | Apr 2016 | A1 |
| 20160148800 | 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 |
| 20160293398 | Danek et al. | Oct 2016 | A1 |
| 20160293838 | Swaminathan et al. | Oct 2016 | A1 |
| Number | Date | Country |
|---|---|---|
| 1732288 | Feb 2006 | CN |
| 1926668 | Mar 2007 | CN |
| 101255548 | Sep 2008 | CN |
| 101378007 | Mar 2009 | CN |
| 101416293 | Apr 2009 | CN |
| 101535524 | Sep 2009 | CN |
| 101889331 | Nov 2010 | CN |
| 103137864 | Jun 2013 | CN |
| 0 277 766 | Aug 1988 | EP |
| 0 541 212 | May 1993 | EP |
| 1 703 552 | Sep 2006 | EP |
| 2 278 046 | Jan 2011 | EP |
| H02-093071 | Apr 1990 | JP |
| H06-177120 | Jun 1994 | JP |
| 2001-338922 | Dec 2001 | JP |
| 2002-134497 | May 2002 | JP |
| 2002-164345 | Jun 2002 | JP |
| 2007-180362 | Jul 2007 | JP |
| 2007-287889 | Nov 2007 | JP |
| 2007-287890 | Nov 2007 | JP |
| 2008-500742 | Jan 2008 | JP |
| 2008-109093 | May 2008 | JP |
| 4364320 | Aug 2009 | JP |
| 2009-540128 | Nov 2009 | JP |
| 2010-10497 | Jan 2010 | JP |
| 2010-245518 | Oct 2010 | JP |
| 2011-023576 | Feb 2011 | JP |
| 2013225655 | Oct 2013 | JP |
| 10-2001-0111448 | Dec 2001 | KR |
| 10-2004-0001036 | Jan 2004 | KR |
| 10-0734748 | Jul 2007 | KR |
| 10-2009-0057665 | Jun 2009 | KR |
| 10-2009-0080019 | Jul 2009 | KR |
| 10-2009-0081396 | Jul 2009 | KR |
| 201009942 | Mar 2010 | TW |
| 201042706 | Dec 2010 | TW |
| WO 2004032196 | Apr 2004 | WO |
| WO 2006026350 | Mar 2006 | WO |
| WO 2006104741 | Oct 2006 | WO |
| WO 2007043709 | Apr 2007 | WO |
| WO 2007118026 | Oct 2007 | 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 2013112727 | Aug 2013 | WO |
| Entry |
|---|
| International Search Report and Written Opinion, dated Feb. 20, 2012, issued in PCT/US2011/032303. |
| Lee, Jong Ju, Low-impurity, highly conformal atomic layer deposition of titanium nitride using NH3—Ar—H2 plasma treatment for capacitor electrodes, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA (2004). |
| “PlasmaPro,” Oxford Instruments (2010). |
| Cecchi et al., “Ultra-thin conformal pore-sealing of low-k materials by plasma-assisted ALD,” University of New Mexico, Albuquerque, NM, Sandia National Labs, Albuquerque, NM (2007). |
| Lee et al., “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 (2005). |
| Plasma Enhanced Atomic Layer Deposition (PEALD), Website: http://www.asm.com/index.php?option=com—content&task=view&id=19&Itemid=161 (2010). |
| International Search Report and Written Opinion, dated Oct. 20, 2011, issued in PCT/US2011/032186. |
| Invitation to Pay Additional Fees; Communication Re Partial International Search, dated Dec. 16, 2011, issued in PCT/US2011/032303. |
| King, Sean W., “Plasma enhanced atomic layer deposition of SiNx:H and SiO2,” J. Vac. Sci. Technol. A 29(4), Jul./Aug. 2011 . |
| U.S. Appl. No. 13/242,084, filed Sep. 23, 2011, entitled “Plasma Activated Conformal Dielectric Film Deposition”. |
| U.S. Appl. No. 13/963,212, filed Aug. 9, 2013, entitled “Plasma-Activated Deposition of Conformal Films”. |
| U.S. Appl. No. 13/953,616, filed Jul. 29, 2013, entitled “High Pressure, High Power Plasma Activated Conformal Film Deposition”. |
| US Office Action dated Mar. 15, 2013 issued in U.S. Appl. No. 13/084,399. |
| US Office Action dated Sep. 14, 2012 issued in U.S. Appl. No. 13/084,305. |
| US Final Office Action dated Apr. 25, 2013 issued in U.S. Appl. No. 13/084,305. |
| US Office Action dated Apr. 13, 2011 issued in U.S. Appl. No. 12/889,132. |
| US Notice of Allowance dated Sep. 30, 2011 issued in U.S. Appl. No. 12/889,132. |
| US Office Action dated Aug. 1, 2012 issued in U.S. Appl. No. 13/011,569. |
| US Final Office Action dated Feb. 26, 2013 issued in U.S. Appl. No. 13/011,569. |
| US Notice of Allowance dated May 6, 2013 issued in U.S. Appl. No. 13/011,569. |
| US Office Action dated Apr. 4, 2013 issued U.S. Appl. No. 13/242,084. |
| US Notice of Allowance dated Jun. 19, 2013 issued U.S. Appl. No. 13/242,084. |
| US Office Action dated Jun. 7, 2013 issued U.S. Appl. No. 13/414,619. |
| US Notice of Allowance dated Jul. 26, 2013, issued U.S. Appl. No. 13/414,619. |
| US Office Action dated May 24, 2013 issued U.S. Appl. No. 13/472,282. |
| PCT International Preliminary Report on Patentability dated Oct. 26, 2012, issued in PCT/US2011/032186. |
| 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. |
| PCT International Search Report and Written Opinion dated Dec. 18, 2012, issued in Application No. PCT/US2012/052769. |
| PCT International Search Report and Written Opinion dated Feb. 28, 2013, issued in Application No. PCT/US2012/051740. |
| PCT International Search Report and Written Opinion dated May 27, 2013, issued in Application No. PCT/US2013/022977. |
| 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 ISS, 9 pp, G138-G143. |
| Man P.F. et al., “Elimination of Post-Release Adhesion in Microstructures Using Conformal Fluorocarbon Coatings,” MEMS '96 Proceedings, IEEE Feb. 11-15, 1996, pp. 55-60. |
| Nguyen, S.V. et al., Plasma-assist chemical vapor deposition of dielectric thin films for ULSI semiconductor circuits, IBM J.Res.Develop. vol. 43, No. 1.2, Jan./Mar. 1999, pp. 5-38. |
| U.S. Appl. No. 15/224,347, filed Jul. 29, 2016, entitled “Plasma Assisted Atomic Layer Deposition of Multi-Layer Films for Patterning Applications.” |
| U.S. Appl. No. 14/552,011, filed Nov. 24, 2014, entitled “Selective Inhibition in Atomic Layer Deposition of Silicon-Containing Films.” |
| U.S. Appl. No. 15/201,221, filed Jul. 1, 2016, entitled “Selective Atomic Layer Deposition with Post-Dose Treatment.” |
| U.S. Appl. No. 15/253,301, filed Aug. 31, 2016, entitled “Selective Atomic Layer Deposition for Gapfill Using Sacrificial Underlayer.” |
| U.S. Appl. No. 15/199,608, filed Jun. 30, 2016, entitled “Apparatus and Method for Deposition and Etch in Gap Fill.” |
| US Final Office Action dated Sep. 13, 2013 issued in U.S. Appl. No. 13/084,399. |
| US Notice of Allowance dated Jan. 15, 2014 issued in U.S. Appl. No. 13/084,399. |
| US Office Action dated Jan. 2, 2015 issued in U.S. Appl. No. 14/231,554. |
| US Final Office Action dated Jun. 10, 2015 issued in U.S. Appl. No. 14/231,554. |
| US Notice of Allowance dated Aug. 31, 2015 issued in U.S. Appl. No. 14/231,554. |
| US Office Action dated Jul. 1, 2016 issued in U.S. Appl. No. 13/963,212. |
| US Notice of Allowance dated Sep. 19, 2013 issued U.S. Appl. No. 13/242,084. |
| US Office Action dated Sep. 21, 2015 issued U.S. Appl. No. 14/607,997. |
| US Final Office Action dated Mar. 18, 2016 issued U.S. Appl. No. 14/607,997. |
| US Notice of Allowance dated Jun. 16, 2016 issued U.S. Appl. No. 14/607,997. |
| US Notice of Allowance dated Sep. 27, 2016 issued U.S. Appl. No. 14/607,997. |
| US Notice of Allowance dated Aug. 7, 2014 issued U.S. Appl. No. 14/133,239. |
| US Notice of Allowance dated Nov. 26, 2014 issued U.S. Appl. No. 14/133,239. |
| US Notice of Allowance dated Oct. 4, 2013 issued U.S. Appl. No. 13/472,282. |
| US Office Action dated May 21, 2014 issued in U.S. Appl. No. 13/607,386. |
| US Notice of Allowance dated Oct. 8, 2014 issued in U.S. Appl. No. 13/607,386. |
| US Notice of Allowance dated Nov. 19, 2014 issued in U.S. Appl. No. 13/607,386. |
| US Office Action dated Jun. 13, 2014 issued in U.S. Appl. No. 13/953,616. |
| US Final Office Action dated Nov. 24, 2014 issued in U.S. Appl. No. 13/953,616. |
| US Office Action dated Dec. 11, 2014 issued in U.S. Appl. No. 14/074,596. |
| US Office Action dated Dec. 24, 2015 issued in U.S. Appl. No. 14/074,596. |
| US Notice of Allowance dated Feb. 12, 2016 issued in U.S. Appl. No. 14/074,596. |
| US Office Action dated May 15, 2015 issued in U.S. Appl. No. 14/074,617. |
| US Notice of Allowance dated Nov. 20, 2015 issued in U.S. Appl. No. 14/074,617. |
| US Office Action dated Aug. 14, 2015 issued in U.S. Appl. No. 14/061,587. |
| US Notice of Allowance dated Feb. 11, 2016 issued in U.S. Appl. No. 14/061,587. |
| US Notice of Allowance [Supplemental Notice of Allowability] dated Mar. 1, 2016 issued in U.S. Appl. No. 14/061,587. |
| US Office Action dated Mar. 2, 2015 issued in U.S. Appl. No. 14/137,860. |
| US Notice of Allowance dated Oct. 1, 2015 issued in U.S. Appl. No. 14/137,860. |
| US Notice of Allowance [Supplemental Notice of Allowability] dated Oct. 22, 2015 issued in U.S. Appl. No. 14/137,860. |
| US Office Action dated Jul. 10, 2014 issued in U.S. Appl. No. 14/144,107. |
| US Final Office Action dated Jan. 15, 2015 issued in U.S. Appl. No. 14/144,107. |
| US Notice of Allowance dated Mar. 19, 2015 issued in U.S. Appl. No. 14/144,107. |
| US Office Action dated Oct. 21, 2015 issued in U.S. Appl. No. 14/194,549. |
| US Final Office Action dated Nov. 1, 2016 issued in U.S. Appl. No. 14/194,549. |
| US Notice of Allowance dated Aug. 5, 2015 issued in U.S. Appl. No. 14/183,287. |
| US Office Action dated Aug. 1, 2016 issued in U.S. Appl. No. 14/932,869. |
| US Office Action dated Jul. 2, 2015 issued in U.S. Appl. No. 14/187,145. |
| US Final Office Action dated Dec. 16, 2015 issued in U.S. Appl. No. 14/187,145. |
| US Notice of Allowance dated Feb. 25, 2016 issued in U.S. Appl. No. 14/187,145. |
| US Office Action dated Jun. 14, 2016 issued in U.S. Appl. No. 15/019,904. |
| US Notice of Allowance dated Oct. 13, 2016 issued in U.S. Appl. No. 15/019,904. |
| US Office Action dated Apr. 13, 2015 issued in U.S. Appl. No. 14/335,785. |
| US Final Office Action dated Aug. 24, 2016 issued in U.S. Appl. No. 14/335,785. |
| US Office Action dated May 25, 2016 issued in U.S. Appl. No. 14/552,011. |
| US Notice of Allowance dated Sep. 26, 2016 issued in U.S. Appl. No. 14/552,011. |
| US Notice of Allowance dated Jul. 15, 2016 issued in U.S. Appl. No. 14/678,736. |
| Taiwan Office Action dated Apr. 27, 2016 issued in Application No. TW 100113041. |
| 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. |
| Taiwan Office Action dated May 5, 2016 issued in TW 100134208. |
| 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. |
| Singapore Supplementary Examination Report dated Jun. 1, 2016 issued in SG 11201400633R. |
| Taiwan Notice of Allowance and Search Report dated Dec. 18, 2015 issued in Application No. TW 101134692. |
| 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. |
| Taiwan Office Action and Search Report dated Jan. 27, 2016 issued in Application No. TW 101134692. |
| Chinese First Office Action dated May 19, 2016 issued in CN 201310021460.8. |
| European Extended Search Report dated Apr. 14, 2014 issued in Application No. EP 13 15 2046. |
| 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. |
| 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. |
| Singapore Supplementary Examination Report dated Aug. 11, 2016 issued in SG 11201404315R. |
| Taiwan Office Action and Search Report dated Jul. 20, 2016 issued in Application No. TW 102102879. |
| Chinese First Office Action dated Apr. 11, 2016 issued in Application No. CN 201510086588.1. |
| Japanese Office Action dated Apr. 19, 2016 issued in Application No. JP 201521804. |
| 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. |
| Hausmann et al., (2002) “Atomic Layer Deposition of Hafnium and Zirconium Oxides Using Metal Amide Precursors,” Chem. Mater. 14(10):4350-4358. |
| 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. |
| 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. |
| Li, Xingcun, et al., (2011) “Atomic Layer Deposition Al203 Thin Films in Magnetized Radio Frequency Plasma Source,” Physics Procedia 18:100-106. |
| 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. |
| Taiwan Office Action and Search Report dated Nov. 9, 2016 issued in Application No. TW 101131556. |
| Number | Date | Country | |
|---|---|---|---|
| 20120009802 A1 | Jan 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| 61324710 | Apr 2010 | US | |
| 61372367 | Aug 2010 | US | |
| 61379081 | Sep 2010 | US | |
| 61417807 | Nov 2010 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13084399 | Apr 2011 | US |
| Child | 13224240 | US | |
| Parent | 13084305 | Apr 2011 | US |
| Child | 13084399 | US |
