WO2014116376A1 - Low shrinkage dielectric films - Google Patents

Abstract

Methods of forming a dielectric layer on a substrate are described, and may include introducing a first precursor into a remote plasma region fluidly coupled with a substrate processing region of a substrate processing chamber A plasma may be formed in the remote plasma region to produce plasma effluents. The plasma effluents may be directed into the substrate processing region. A silicon-containing precursor may be introduced into the substrate processing region, and the silicon-containing precursor may include at least one silicon-silicon bond. The plasma effluents and silicon-containing precursor may be reacted in the processing region to form a silicon-based dielectric layer that is initially flowable when formed on the substrate.

Description

LOW SHRINKAGE DIELECTRIC FILMS

CROSS-REFERENCES TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Nonpro visional Patent Application No.

13/834,333, filed March 15, 2013, which claims the benefit of U.S. Provisional Application No. 61/756,762, filed January 25, 2013, entitled "Low Shrinkage Dielectric Films." The entire disclosure of each is incorporated herein by reference for all purposes.

TECHNICAL FIELD

[0002] The present technology relates to semiconductor processes and equipment. More specifically, the present technology relates to forming dielectric materials. BACKGROUND

[0003] As integrated circuit chipmakers continue increasing the density of circuit elements on each chip, filling the gaps that separate those elements becomes more challenging. The increased circuit element density has necessitated shorter widths between adjacent elements. As the width of these gaps shrink faster than their height, the ratio of height to width (known as the aspect ratio) proportionally increases. It is more difficult to fill a tall and narrow gap (i.e., a high aspect ratio gap) with a uniform film of dielectric material than a shallow and wide gap (i.e., a low aspect ratio gap).

[0004] One commonly encountered difficulty with filling high aspect ratio gaps is the formation of voids. In high aspect ratio gaps, there is a tendency of the dielectric material filling the gap to deposit at a faster rate around the top end of the gap. Often the dielectric material will close the top before the gap has been completely filled, leaving a void. Even when the top of the gap does not close prematurely, the uneven growth rate of the dielectric film down the sidewalls of the gap can create a weak seam in the middle of the gapfill. These seams can later result in cracks that adversely affect the physical integrity and dielectric properties of the device. [0005] One technique to avoid the formation of voids and weak seams in dielectric gapfills is to fill the gap at a lower deposition rate. Lower deposition rates can give the dielectric material more time to redistribute on the inside surfaces of the gap to reduce the chances of excessive topside growth. A lower deposition rate may also be the result of increased etching or sputtering that occur at the same time as the dielectric deposition. For example, in HDPCVD dielectric material at the top corners of the gap etch away faster than material on the sidewalls and bottom portion of the gap. This increases the chances that the topside of the gap will remain open so the sidewalls and bottom can completely fill with dielectric material. However, reducing the dielectric deposition rate also results in the deposition taking longer to complete. The longer deposition times decrease the rate at which substrate wafers are processed through the deposition chamber, resulting in a reduced efficiency for chamber.

[0006] Thus, there is a need for improved systems and methods for filling short-width, high aspect ratio gaps with a void free dielectric film. These and other problems are addressed by the systems and methods of the present invention.

SUMMARY

[0007] Methods of forming a dielectric layer on a substrate are described, and may include introducing a first precursor into a remote plasma region f uidly coupled with a substrate processing region of a substrate processing chamber A plasma may be formed in the remote plasma region to produce plasma effluents. The plasma effluents may be directed into the substrate processing region. A silicon-containing precursor may be introduced into the substrate processing region, and the silicon-containing precursor may include at least one silicon-silicon bond. The plasma effluents and silicon-containing precursor may be reacted in the processing region to form a silicon-based dielectric layer that is initially flowable when formed on the substrate.

[0008] The silicon-containing precursors may include at least two silicon-silicon bonds, and may include three or more. The first precursor may include one or more precursors selected from the group including ammonia, nitrogen, H₂, Ar, and He, and may include additional carrier gases or combinations of precursors as well. The plasma effluents and silicon-containing precursor may be introduced into the processing region through a showerhead configured to maintain separation of the precursors so that they do not contact each other until they enter the substrate processing region. The substrate may be maintained at a distance less than or at about 3 inches from the showerhead, and may be maintained closer or further away in disclosed embodiments. The substrate processing region may be plasma-free during the deposition process, and in alternative arrangements a direct plasma may be provided within the processing region.

[0009] The silicon-containing precursor may have the formula Si_xH_y, where x is greater than or equal to 2, and y is 2x+n or greater, where n is any number less than or equal to 2. The silicon- containing precursor may also be introduced into the processing region in a substantially vapor phase. The method for deposition may be performed at a temperature of less than or equal to about 30°C, and the pressure during the process may be less than or equal to about 5 Torr. The as-formed film produced by the described processes may have a density greater than or equal to about 1.4 g/cc. [0010] The methods may also include stopping the introduction of the silicon-containing precursor after the silicon-based dielectric layer is formed. The plasma effluents may be continuously directed into the substrate processing region, however, in order to densify the formed dielectric layer. The methods may further include annealing the formed silicon-based dielectric layer, and during the anneal, the formed silicon-based dielectric layer may shrink by less than about 20%.

[0011] Methods are also described for forming a dielectric layer on a substrate in a substrate processing region of a processing chamber. The methods may include introducing a first precursor into a remote plasma region fluidly coupled with the substrate processing region while forming a plasma in the remote plasma region to produce plasma effluents. The methods may also include directing the plasma effluents into the substrate processing region, and introducing a silicon-containing precursor into the substrate processing region. The silicon-containing precursor may include at least one silicon-silicon bond in disclosed embodiments. The methods may also include reacting the plasma effluents and silicon-containing precursor in the substrate processing region to form a silicon-based dielectric layer that is initially flowable when formed on the substrate. The methods may further include curing the formed silicon-based dielectric layer with at least one additional precursor.

[0012] The at least one additional precursor utilized may include an oxygen-containing precursor, a nitrogen-containing precursor, or a carbon-containing precursor. The methods may also include directing the plasma effluents into the substrate processing region to densify the cured dielectric layer. The silicon-containing precursor utilized may have the formula Si_xH_y, where x is greater than or equal to 2, and y is 2x+n or greater, where n is any number less than or equal to 2, and where the silicon-containing precursor is introduced into the processing region in a substantially vapor phase. The precursors introduced into the processing chamber to form the silicon-based dielectric layer may include one or more inert precursors and a silicon-containing precursor having silicon-silicon and silicon-hydrogen containing bonds. The methods may also include the step of annealing the formed silicon-based dielectric layer. When performed, the annealing may shrink the formed dielectric layer by less than about 20% during the annealing.

[0013] Such technology may provide numerous benefits over conventional techniques. For example, the deposition processes disclosed may produce denser and higher quality films. As such, film shrinkage may be reduced or prevented during annealing or post-formation operations. These and other embodiments, along with many of their advantages and features, are described in more detail in conjunction with the below description and attached figures. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] A further understanding of the nature and advantages of the disclosed technology may be realized by reference to the remaining portions of the specification and the drawings.

[0015] FIG. 1 shows a flow chart of a process for forming a dielectric film according to disclosed embodiments.

[0016] FIG. 2 shows another flow chart of a process for forming a dielectric film according to disclosed embodiments.

[0017] FIG. 3A shows a schematic cross-sectional view of a portion of a substrate processing chamber according to the disclosed technology. [0018] FIG. 3B shows a bottom plan view of a showerhead according to the disclosed technology.

[0019] FIG. 4 shows a top plan view of an exemplary substrate processing system according to the disclosed technology.

[0020] In the appended figures, similar components and/or features may have the same numerical reference label. Further, various components of the same type may be distinguished by following the reference label by a letter that distinguishes among the similar components and/or features. If only the first numerical reference label is used in the specification, the description is applicable to any one of the similar components and/or features having the same first numerical reference label irrespective of the letter suffix. DETAILED DESCRIPTION

[0021] The present technology includes improved processes and chemistry profiles for depositing silicon-based materials on substrates. While conventional processes may deposit films of similar materials, the films may suffer from reduced quality and density. Accordingly, when lower quality films are densified to produce a higher quality film, film shrinkage may occur that may have an adverse effect on the underlying device. For example, as device geometries are reduced, the silicon or device base may have thinner wall profiles. When a film is deposited within the structures and densified, the shrinking film may exert stress on the underlying structures that can deform the patterning. The present technology, however, may form flowable films that fundamentally shrink less than conventional films. In so doing, more intricate patterns can be covered. For example, trenches within the device may have very high aspect ratios, such as having a heightwidth ratio greater than or about 5: 1, 8:1, 10: 1, etc. or more, and as such a flowable dielectric film may be required to provide a bottom-up fill profile. If these films also shrink less when densified, less stress is exerted on the underlying structure, and overall process quality may be improved.

[0022] Methods of forming a dielectric layer on a substrate are described, and may include introducing a first precursor into a remote plasma region f uidly coupled with a substrate processing region of a substrate processing chamber A plasma may be formed in the remote plasma region to produce plasma effluents. The plasma effluents may be directed into the substrate processing region. A silicon-containing precursor may be introduced into the substrate processing region, and the silicon-containing precursor may include at least one silicon-silicon bond. The plasma effluents and silicon-containing precursor may be reacted in the processing region to form a silicon-based dielectric layer that is initially flowable when formed on the substrate.

[0023] Precursors used in deposition of silicon-based films may include a variety of additional molecules that affect the quality of the deposited film. For example, the presence of hydroxyl groups may increase the fiowability of a deposited film. However, it may be desirable to remove these groups in the final film to produce higher quality films. The removal of these groups, or the substitution with other materials including oxygen, nitrogen, and carbon, for example, may reduce the overall density of the deposited or formed film. Accordingly, when later processing steps used to density the film are performed, the film may shrink, which may produce unwanted stresses on the underlying structure. The inventors have advantageously determined that by reducing the inclusion of materials beyond silicon in the utilized precursors, the resulting film may have improved quality and may have reduced shrinking as compared to conventional films based on more varied precursor groups.

[0024] In order to better understand and appreciate the invention, reference is now made to FIG. 1, which shows a flow chart of a process for forming a dielectric film according to disclosed embodiments. Prior to the first operation, a substrate may be delivered into a process chamber, such as those described below. The substrate may be previously patterned or relatively clean. Various front end processing may have been performed including the formation of gates, vias, trenches, and other structures. These structures may be on the nanometer scale, and for example, trenches or gaps that require filling may have widths of less than about 100 nm, and may alternatively be less than or about 75 nm, 50 nm, 40 nm, 30 nm, 25 nm, 20 nm, 10 nm, etc. or less. The patterned substrate may then be delivered to a substrate processing region for deposition of a dielectric material. In disclosed embodiments, the substrate may already be located in the processing region if a previous operation was performed in the same chamber in which the deposition process is to occur. At operation 110, a first precursor may be introduced into a plasma region of the processing chamber that is separate or removed from the processing region of the chamber in which the substrate resides. The first precursor may include one of several precursor materials. For example, the first precursor may be one or more inert gases including argon, helium, nitrogen, etc. Additional gases may alternatively or additionally be used, and may include ammonia (NH₃), hydrogen, or nitrogen and/or hydrogen-containing gases. In disclosed embodiments, the first precursor may exclusively include inert gases, and in an exemplary process argon or helium is delivered to the plasma region.

[0025] The separate plasma region may be referred to as a remote plasma region herein and may be within a distinct module separate from the processing chamber, or as a compartment within the processing chamber. A plasma may be formed within the remote plasma region thereby generating plasma effluents from the first precursor. At operation 120, the generated plasma effluents are directed into the substrate processing region. This may be effected in a number of ways, including with a pressure differential, generated electric field, or some other known mechanism for directing the flow of ions and/or electrons into the processing region. Before, after, or concurrently with operation 120, a silicon-containing precursor may be introduced into the substrate processing region. In disclosed embodiments, the silicon-containing precursor includes at least one silicon-silicon bond.

[0026] The plasma effluents and silicon-containing precursor may be reacted in the substrate processing region to form a silicon based dielectric layer on the substrate. The formed material may be initially flowable when formed or when deposited initially, which may allow the material to flow down into trenches to fill defined patterns on the substrate. The dielectric material may be based on reactions between the plasma species and the silicon-containing precursor. The precursors may begin reacting directly upon contacting one another, and accordingly the precursors may be separated until entering the substrate processing region. Such separation may be performed by components such as a dual-channel showerhead as described further below. The showerhead may be configured to maintain separation of the precursors so as to prevent the precursors from contacting one another until they enter or are delivered into the substrate processing region. Previous technologies may have relied on the inclusion of water or hydroxyl groups in the as deposited film to potentially impart the flowability of the film. As previously stated, though, these groups may produce weaker films that may shrink unacceptably upon densification. The present technology, however, utilizes a variety of parameters that may synergistically allow flowability to occur. [0027] Without being bound to a particular theory, the number of silicon-silicon bonds in the deposited film may directly correspond to the amount of shrinking of the produced film. For example, the more silicon-silicon bonds in the film, the less shrinking may occur as a result of densification because less additional polymerization may be imparted along with less removal of unwanted species. Such as when a silicon oxide film is being formed, after the initial deposition, the formed film may be oxidized or reacted with additional material so as to incorporate oxygen into the polymer matrix, and remove residual materials such as hydrogen, nitrogen, carbon, etc. The more materials that are removed from the film may leave pores within the film that are removed during densification, such as annealing. The removal of these pores may compress the film imparting stress along surfaces contacted by the film. These stresses may overcome a threshold that allows the structure to deform, which may destroy the underlying structure.

Accordingly, the present technology may utilize silicon-containing precursors that maximize the number of silicon-silicon bonds, and minimize additional molecular bonding. In this way, less material may need to be removed during curing or other operations, which may reduce the amount of shrinking of the final film.

[0028] In disclosed embodiments, the technology may utilize silanes and polysilanes as the silicon-containing precursor. These materials may include or exclusively consist of silicon- silicon and silicon-hydrogen bonds. Exemplary precursors may include at least one silicon- silicon bond, at least two silicon-silicon bonds, at least three silicon-silicon bonds, etc. For example, the precursors may be selected from any of the polysilane homologues beginning with disilane. The silicon-containing precursor may also be selected from a variety of isomers of the polysilanes. For example, if the silicon-containing precursor has five silicon atoms, the composition could include any of n-pentasilane, isopentasilane, neopentasilane, 2-silyltetrasilane, 2,2-disilyltrisilane, etc. The silicon-containing precursors may include cyclic forms or cyclosilanes, such as cyclohexasilane, for example. The polysilanes may also include any saturated or unsaturated compound such as silenes and silynes. The silicon-containing precursor may also be of a general formula such as Si_xH_y. X may be any number of two or greater up to infinity, and Y may be any number of two or greater up to infinity. For example, such a minimal formula would denote disilyne (S1₂H₂). Y may also be any factor based on X. For example, Y may be 2X, or 2X + N, where n=2, 0, -2, -4, -6, etc., or N may be any number less than or equal to 2. Exemplary silanes used in the technology can include disilane, tetrasilane, cyclohexasilane, etc.

[0029] The vapor pressure of many of these disclosed materials is such that the materials may be in a substantially liquid phase under many operating conditions. Although the silicon- containing precursors may be used in liquid form in the disclosed technology, in embodiments the silicon-containing precursors may be introduced into the processing chamber in a vapor or substantially vapor form. However, this may require the use of additional components to ensure that the materials are introduced in a vapor form. Many different mechanisms may be employed to deliver vapor phase silicon-containing precursors. For example, vapor draw with or without a heated ampoule, a bubbler, or direct liquid injection may be utilized among a variety of other technology. However, depending on the precursor utilized, additional issues may occur. For example, if higher order silanes are delivered in liquid phase to an injection nozzle, the injection nozzle may be heated to deliver the material into the substrate processing region as a vapor.

However, the vaporization temperature of higher order silanes and the polymerization

temperature of higher order silanes may be relatively close, such that the technique may clog the nozzle. Additionally, a bubbler may utilize an inert gas in the delivery of the vapor, but also introduces the additional inert gas. In so doing, further mechanisms may be needed to ensure that an adequate flow of the actual silicon-containing precursor is delivered to provide adequate film formation rates. Higher order silicon-containing precursors or silanes have more silicon-silicon bonds which may lead to less shrinking of the films, but may additionally have very low vapor pressures which may require additional components or mechanisms to provide a vapor phase silicon-containing precursor to the substrate processing region.

[0030] Again without being bound to any particular theory, flowability of the dielectric material with the disclosed technology may be based on a combination of process parameters including the temperature and pressure of the process in relation to the silicon-containing precursor, plasma power used, and distance between the showerhead or mechanism delivering the precursors and the substrate on which the films are to be formed. During the processing, the substrate processing region may be relatively, substantially, or completely plasma- free during the deposition.

Although the plasma effluents of the first precursor may be delivered into the substrate processing region, the plasma used to generate the effluents may be contained externally to the substrate processing region. The greatest amount of reactions may occur directly under the showerhead, or where the precursors initially interact. The plasma effluents may have had the least amount of time to recombine, and thus greater reactions between the precursors may occur. These gas phase reactions may be affected further by the material used. Silicon- silicon bonds may be weaker bonds than silicon-hydrogen, silicon-oxygen, and other silicon-based bonds. Accordingly, where these greater reactions occur, or where a higher plasma power is utilized, for the silicon- containing precursors of the present technology, a greater number of bonds may be broken. As a possible result, the dielectric material formed in this region may have reduced or no flowability when deposited on the substrate. As the distance of the substrate from the showerhead increases, the amount of interactions may be reduced slightly or more substantially. For example, potentially only one out of two or one out of three silicon-silicon bonds may be broken, and thus the polymerization may include longer chains of silicon groups, which may at least partially impart flowability to the deposited material.

[0031] Accordingly, the substrate may be maintained at a distance from the showerhead, or region where the interactions between the precursors begin, that is less than or about three inches. The substrate may be maintained at least 0.1 inches from the showerhead in disclosed

embodiments. The substrate may also be maintained at a distance less than or about 2 inches, 1 inch, 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, or less inches, or be maintained between about 3 inches and about 0.01 inches, 2 and 0.1 inches, 1 and 0.2 inches, 0.8 and 0.2 inches, etc. The distance may also be determined in conjunction with the process parameters and silicon- containing precursor or precursors being used.

[0032] During the deposition process, the substrate may be maintained at or below about 400°C, and may be maintained at or below about 300°C, 200°C, 100°C, 80°C, 75°C, 50°C, 25°C, 10°C, 0°C, -10°C, -20°C, -30°C, or less, between about 30°C and -30°C, etc. The processing chamber may be maintained at or below about 100 Torr during the processes, and may be maintained at or below about 50 Torr, 25 Torr, 15 Torr, 5 Torr, 1 Torr, 0.1 Torr, etc., or between about 0.1 mTorr and about 10 Torr. The temperature and pressure may also be set based at least partially on the vapor pressure of the silicon-containing precursor or precursors being used. As one non-limiting example, if tetrasilane is used as the silicon-containing precursor, and the chamber temperature is about -10°C, the vapor pressure of tetrasilane may be below about 3 Torr. As such, if the chamber pressure is greater than about 3 Torr, then condensation of the tetrasilane may occur. The interaction of the plasma effluents with the tetrasilane may also impart energy that overcomes the condensation point. Additionally, as the distance from the plasma source increases, and the plasma power decreases either or both from distance or actual generation power, the amount of silicon-silicon bond breaking may be reduced, which may allow longer polymer chains to be formed. The combination of improved polymerization, i.e. longer silicon- silicon chains, along with the benefit of operations at or near the condensation point of the precursors may at least partially impart flowability to the films. The process may also create longer silicon polymer chains with reduced additional material, which may reduce the amount of shrinking of the final film. The plasma source used in the technology may include plasma generated in the chamber, but remote from and fluidly coupled with the substrate processing region, or alternatively generated in a module separate from but fluidly coupled with the processing chamber. The plasma may be from any known or later developed technology, and may produce plasma power between about 0 and 2000 Watts. In disclosed embodiments, the plasma power may be less than or about 1000 Watts, or about 500, 300, 250, 200, 150, 100, 80, 60, 40, 20 Watts, etc. or less. [0033] Utilizing the described processes, a synergistic combination may be produced where an amount of condensation and an amount of polymerization occur to produce flowable films from silicon-containing precursors that may only include silicon and hydrogen bonding. The resultant films may have flowability when initially formed on the substrate, but may be composed of mostly silicon-silicon and silicon-hydrogen bonds. These films that may have more silicon atoms in the matrix, and more silicon-silicon bonding in the deposited film, may shrink less than conventional films. Advantageously, the inventors have additionally determined that these films may have increased density as formed over conventional films. The as-deposited films may have a density greater than or equal to about 1.2 g/cc. The films may also have densities greater than or equal to about 1.3 g/cc, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, etc. or greater. [0034] After an amount of dielectric material has been formed on the substrate, additional processes may be performed. One or more densifying operations may be performed to increase the quality of the dielectric material. In disclosed embodiments, once a determined amount of dielectric material has been formed, the introduction and flow of the silicon-containing precursor may be stopped. However, the plasma effluents may be continued to be produced and directed into the substrate processing region at the formed dielectric layer to densify the formed dielectric material. Additionally or alternatively, the formed silicon-based dielectric layer may be annealed to further densify the film. The annealing may be a dry anneal, such as with nitrogen, or a steam anneal that may occur at temperatures between about 200°C and higher, above or about 400°C, above or about 900°C, etc. or greater. During the anneal, the amount or film shrinking may be less than conventional films. For example, the film may shrink by less than 50% during the anneal. Additionally, the films produced by the disclosed technology may shrink by less than or about 40%, 30%, 25%, 20%, 15%, 10%, 5%, 0%, -5%, -10%, etc. or less. In exemplary methods and processes, the inventors have determined that negative shrinking may occur. This negative shrinking may imply that the film expands during the processing. [0035] The above example process as described in conjunction with FIG. 1 may produce a substantially silicon based film, and may be used to produce polysilicon films of various structure and characteristics. The processes may be further adjusted to incorporate additional materials to produce oxides, nitrides, carbides, and other compositions useful in semiconductor processing. A further example of the disclosed technology incorporating additional materials is described with respect to FIG. 2. FIG. 2 shows another flow chart of a process for forming a dielectric film according to disclosed embodiments. The process may include similar operations as described with respect to FIG. 1. In disclosed embodiments, at operation 210 a first precursor may be introduced into a remote plasma region fluidly coupled with a substrate processing region while forming a plasma in the remote plasma region to produce plasma effluents. The first precursor may include one or more of any of the previously described precursors, and may consist exclusively of one or more inert precursors such as argon, helium, or nitrogen. At operation 220, the plasma effluents may be directed into the substrate processing region. [0036] A silicon-containing precursor may be introduced into the substrate processing region at operation 230, and the silicon-containing precursor may have at least one silicon-silicon bond. The silicon-containing precursor may include one or more of any of the previously discussed precursors. For example, the silicon-containing precursor may have the formula Si_xH_y, where x may be greater than or equal to 2, and y is 2x+n or greater, and where n may be any number less than or equal to 2. Additionally, the silicon-containing precursor may be introduced into the processing region in a substantially vapor phase. In disclosed embodiments, the precursors introduced into the processing chamber to form the silicon-based dielectric layer may consist of one or more inert precursors and a silicon-containing precursor consisting or silicon-silicon and silicon-hydrogen containing bonds. For example, the first precursor may consist of argon or helium. At operation 240, the plasma effluents and silicon-containing precursors may be reacted to form a silicon-based dielectric layer on the substrate. These operations may be performed in any of the ways previously described. After the initial film has been formed, a curing operation may optionally be performed at operation 250 that cures the formed silicon-based dielectric layer with at least one additional precursor. [0037] The additional precursor may include one or more of an oxygen-containing precursor, such as ozone, a nitrogen-containing precursor, or a carbon-containing precursor. The precursors may be introduced or utilized with or without the plasma effluents directed into the substrate processing region. The additional precursors may be used to additionally substitute material into the silicon-based dielectric material. For example, ozone or another oxygen-containing precursor may be used to provide oxygen that is incorporated into the silicon matrix to produce a silicon oxide film. This may help pack the formed matrix with additional material that may further help reduce shrinkage on annealing or densifying operations. A variety of films may be formed in this way, including oxides, nitrides, carbides, oxycarbides, oxynitrides, carbonitrides, etc. The additional precursors may be flowed after the formation of the silicon-based dielectric, near the end of the formation, and may be introduced with or without the silicon-containing precursors and/or the first precursor. The temperature and/or pressure of the chamber may be changed during the curing operation. For example, if the temperature of the film forming operation is less than 30°C, for example, the chamber temperature may be raised to above or about 30°C, 50°C, 100°C, 200°C, etc., or higher.

[0038] Subsequent to the optional introduction of additional precursor material, the cured or otherwise formed dielectric may be optionally densified at operation 260. The flow of the silicon-containing precursor and/or the additional precursor may be stopped, and then the flow of the first precursor may be performed, or continued in various embodiments. Plasma effluents developed from the first precursor may be directed into the substrate processing region to densify the formed or cured dielectric layer. In disclosed embodiments the densifying operation may be performed prior to the curing operation such that operation 260 is performed prior to operation 250. Additional operations may be performed optionally in the process including an anneal at operation 270. The formed, cured, and/or densified dielectric may be annealed as previously discussed to improve the final quality of the film. Further post-deposition treatments may be performed that may include one or more of a variety of operations including UV, e-beam, and other curing or annealing type operations. During the anneal, the silicon-based dielectric layer may shrink by less than or about 50%. The films produced by the disclosed technology may shrink by less than or about 40%, 30%, 25%, 20%, 15%, 10%, 5%, etc. or less. All optional operations may be performed in the same or a different chamber than the film forming or deposition operation. By maintaining the substrate in a chamber without breaking vacuum, moisture and other effects on the formed film may be reduced or prevented.

[0039] The technology also encompasses delivery of the silicon-containing precursor into the remote plasma region. Alternatively, the silicon-containing precursor may be activated by a direct plasma applied either in a remote region of the chamber, or alternatively in the processing region of the chamber, where the silicon-containing precursor is delivered to the area in which a plasma is developed. In disclosed embodiments, a silicon-containing precursor may be delivered into a processing region or a plasma region of a chamber and activated with a plasma, such as a type of plasma previously defined. The silicon-containing precursor may be delivered with additional fluids such as inert carriers that may include argon and may include hydrogen in disclosed embodiments as well. The process may be performed at a variety of the temperatures, pressures, and plasma powers previously described. For example, the plasma power applied directly may be less than 500W, and may also be less than or about 300W, 200W, 100W, 80W, 70W, 60W, 50W, etc. or less, and the temperatures may be below or about 100°C, and may also be less than or about 75°C, 50°C, 25°C, 15°C, 10°C, 5°C, 0°C, -5°C, etc. or less. Additionally, in this and other disclosed embodiments, the pedestal on which the substrate resides may be electrically biased. Biasing of the pedestal may provide an electrical field that may be used to direct radical species to the surface of the substrate. [0040] The described processes synergistically utilize silicon-containing precursors having silicon-silicon bonding, temperature, pressure, plasma, and deposition distances to produce flowable films of improved qualities and reduced shrinking. By accounting for the phase transition profiles of the silicon-containing precursors, the technology advantageously may remove nitrogen, carbon, water, hydroxyl groups, and other additional materials that may reduce the density, and increase the shrinking of the formed films. As would be understood, additional modifications to chamber parameters and plasma power may be used to further tune the deposition processes as may be required. Advantageously, tuning these processes may be performed without the need to break vacuum conditions or move the substrate to an additional chamber. This may reduce overall processing times and save costs over conventional techniques. Additional examples of deposition process parameters, chemistries, and components are disclosed in the course of describing an exemplary processing chamber and system below.

Exemplary Processing System

[0041] Deposition chambers that may implement embodiments of the present invention may include high-density plasma chemical vapor deposition (HDP-CVD) chambers, plasma enhanced chemical vapor deposition (PECVD) chambers, sub-atmospheric chemical vapor deposition (SACVD) chambers, and thermal chemical vapor deposition chambers, among other types of chambers. Specific examples of CVD systems that may implement embodiments of the invention include the CENTURA ULTIMA® HDP-CVD chambers/systems, and PRODUCER® PECVD chambers/systems, available from Applied Materials, Inc. of Santa Clara, Calif. [0042] Examples of substrate processing chambers that can be used with exemplary methods of the invention may include those shown and described in co-assigned U.S. Provisional Patent App. No. 60/803,499 to Lubomirsky et al, filed May 30, 2006, and titled "PROCESS CHAMBER FOR DIELECTRIC GAPFILL," the entire contents of which is herein incorporated by reference for all purposes. Additional exemplary systems may include those shown and described in U.S. Pat. Nos. 6,387,207 and 6,830,624, which are also incorporated herein by reference for all purposes.

[0043] FIG. 3A shows a schematic cross-sectional view of a portion of a substrate processing chamber 301 according to the disclosed technology. A remote plasma system (RPS) 310 may process a gas which then travels through a gas inlet assembly 311. Two distinct gas supply channels may be present within the gas inlet assembly 311. A first channel 312 may carry a gas that passes through the remote plasma system (RPS) 310, while a second channel 313 may bypass the RPS 310. The first channel 312 may be used for the process gas and the second channel 313 may be used for a treatment gas in disclosed embodiments. The lid or conductive top portion 321 and a perforated partition, such as showerhead 353, are shown with an insulating ring 324 disposed between, which may allow an AC potential to be applied to the lid 321 relative to showerhead 353. The process gas may travel through first channel 312 into chamber plasma region 320 and may be excited by a plasma in chamber plasma region 320 alone or in

combination with RPS 310. The combination of chamber plasma region 320 and/or RPS 310 may be referred to as a remote plasma system herein. The perforated partition or showerhead 353 may separate chamber plasma region 320 from a substrate processing region 370 beneath showerhead 353. Showerhead 353 may allow a plasma present in chamber plasma region 320 to avoid directly exciting gases in substrate processing region 370, while still allowing excited species to travel from chamber plasma region 320 into substrate processing region 370. [0044] Showerhead 353 may be positioned between chamber plasma region 320 and substrate processing region 370 and allow plasma effluents or excited derivatives of precursors or other gases created within chamber plasma region 320 to pass through a plurality of through-holes 356 that traverse the thickness of the plate or plates included in the showerhead. The showerhead 353 may also have one or more hollow volumes 351 that can be filled with a precursor in the form of a vapor or gas, such as a silicon-containing precursor, and pass through small holes 355 into substrate processing region 370, but not directly into chamber plasma region 320. Showerhead 353 may be thicker than the length of the smallest diameter 350 of the through-holes 356 in disclosed embodiments. In order to maintain a significant concentration of excited species penetrating from chamber plasma region 320 to substrate processing region 370, the length 326 of the smallest diameter 350 of the through-holes may be restricted by forming larger diameter portions of through-holes 356 part way through the showerhead 353. The length of the smallest diameter 350 of the through-holes 356 may be the same order of magnitude as the smallest diameter of the through-holes 356 or less in disclosed embodiments.

[0045] In the embodiment shown, showerhead 353 may distribute, via through-holes 356, process gases which contain a plasma vapor/gas such as argon, for example. Additionally, the showerhead 353 may distribute, via smaller holes 355, a silicon-containing precursor that is maintained separately from the plasma region 320. The process gas or gases and the silicon- containing precursor may be maintained fluidly separate via the showerhead 353 until the precursors separately enter the processing region 370. The precursors may contact one another once they enter the processing region and react to form a flowable dielectric material on a substrate 380.

[0046] In embodiments, the number of through-holes 356 may be between about 60 and about 2000. Through-holes 356 may have a variety of shapes but may be made round. The smallest diameter 350 of through-holes 356 may be between about 0.5 mm and about 20 mm or between about 1 mm and about 6mm in disclosed embodiments. There is also latitude in choosing the cross-sectional shape of through-holes, which may be made conical, cylindrical or a combination of the two shapes. The number of small holes 355 used to introduce a gas into substrate processing region 370 may be between about 100 and about 5000 or between about 500 and about 2000 in different embodiments. The diameter of the small holes 355 may be between about 0.1 mm and about 2 mm.

[0047] FIG. 3B shows a bottom plan view of a showerhead 353 according to the disclosed technology. Showerhead 353 corresponds with the showerhead shown in FIG. 3 A. Through- holes 356 are depicted with a larger inner-diameter (ID) on the bottom of showerhead 353 and a smaller ID at the top. Small holes 355 are distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 356 which may help to provide more even mixing than other embodiments described herein.

[0048] An additional dual channel showerhead, as well as this processing system and chamber, are more fully described in patent application Ser. No. 13/251,714 filed on Oct. 3, 2011, which is hereby incorporated by reference for all purposes to the extent not inconsistent with the claimed features and description herein.

[0049] An exemplary film may be created on a substrate supported by a pedestal, such as pedestal 375 having a substrate 380 disposed thereon, within substrate processing region 370 when plasma effluents arriving through through-holes 356 in showerhead 353 combine with a silicon-containing precursor arriving through the small holes 355 originating from hollow volumes 351. Though substrate processing region 370 may be equipped to support a plasma for other processes such as curing, no plasma may be present during the growth or deposition of the exemplary films.

[0050] A plasma may be ignited either in chamber plasma region 320 above showerhead 353 or substrate processing region 370 below showerhead 353. Alternatively, no plasma may be formed in any portion of the chamber, and may be only formed in RPS unit 310. A plasma may be present in chamber plasma region 320 to produce the radical plasma effluents, such as from an inflow of one or more of argon, helium, hydrogen, or ammonia. An AC voltage typically in the radio frequency (RF) range is applied between the conductive top portion, such as lid 321, of the processing chamber and showerhead 353 to ignite a plasma in chamber plasma region 320 during deposition. An RF power supply generates a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency. [0051] The top plasma may be left at low or no power when the bottom plasma in the substrate processing region 370 may be turned on during the formation of the dielectric layer or while cleaning the interior surfaces bordering substrate processing region 370. A plasma in substrate processing region 370 may be ignited by applying an AC voltage between showerhead 353 and the pedestal 375 or bottom of the chamber. A cleaning gas may be introduced into substrate processing region 370 while the plasma is present.

[0052] The pedestal 375 may be moveable, and may be configured to be raised or lowered in disclosed embodiments, and may similarly be configured to rotate. The pedestal 375 may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate. This configuration allows the substrate temperature to be cooled or heated to maintain relatively low temperatures, such as from about 0°C or lower up to about 200°C or higher. The heat exchange fluid may comprise ethylene glycol, water, or some other fluid capable of introducing or removing heat from the system. The wafer support platter of the pedestal may also be resistively heated in order to achieve relatively high temperatures from about 200°C or lower up to about 1100°C or higher using an embedded resistive heating element. An outer portion of the heater element may run adjacent to a perimeter of the support platter, while an inner portion runs on the path of a concentric circle having a smaller radius. The resistive heating element may additionally be coiled through the platter to provide more uniform temperatures. The wiring to the heater element may pass through the stem of the pedestal.

[0053] The chamber plasma region or a region in an RPS may be referred to as a remote plasma region. In embodiments, the radical precursor, e.g. an argon precursor, may be created in the remote plasma region and travel into the substrate processing region to combine with the silicon- containing precursor. In embodiments, the silicon-containing precursor is excited only by the radical-argon precursor. Plasma power may essentially be applied only to the remote plasma region, in embodiments, to ensure that the radical-argon precursor provides the dominant excitation to the silicon-containing precursor.

[0054] In embodiments employing a chamber plasma region, the excited plasma effluents may be generated in a section of the substrate processing region partitioned from a deposition region. The deposition region, also known herein as the substrate processing region, may be where the plasma effluents mix and react with the silicon-containing precursor to deposit dielectric material on the substrate, e.g., a semiconductor wafer. The excited plasma effluents may also be accompanied by additional gases including other inert gases or ammonia, for example. The silicon-containing precursor may not pass through a plasma before entering the substrate plasma region, in embodiments. The substrate processing region may be described herein as "plasma- free" during the deposition of the dielectric material. "Plasma-free" does not necessarily mean the region is devoid of plasma. Ionized species and free electrons created within the plasma region may travel through pores or apertures in the partition or showerhead, but the silicon- containing precursor may not be substantially excited by the plasma power applied to the plasma region. The borders of the plasma in the chamber plasma region are hard to define and may encroach upon the substrate processing region through the apertures in the showerhead. In the case of an inductively-coupled plasma, a small amount of ionization may be effected within the substrate processing region directly. Furthermore, a low intensity plasma may be created in the substrate processing region without eliminating desirable features of the forming film. All causes for a plasma having much lower intensity ion density than the chamber plasma region, or a remote plasma region, during the creation of the excited plasma effluents do not deviate from the scope of "plasma-free" as used herein.

[0055] Plasma power can be a variety of frequencies or a combination of multiple frequencies. In the exemplary processing system, the plasma may be provided by RF power delivered to lid 321 relative to showerhead 353. The RF power may be between about 10 watts and about

2000 watts, between about 100 watts and about 2000 watts, between about 200 watts and about 1500 watts, less than or about 100 Watts, or less than or about 500 watts in different

embodiments. The RF frequency applied in the exemplary processing system may be low RF frequencies less than about 200 kHz, high RF frequencies between about 10 MHz and about 15 MHz, or microwave frequencies greater than or about 1 GHz in different embodiments. The plasma power may be capacitively-coupled (CCP) or inductively-coupled (ICP) into the remote plasma region.

[0056] Substrate processing region 370 can be maintained at a variety of pressures during the flow of precursors, any carrier gases, and plasma effluents into substrate processing region 370. The pressure may be maintained between about 0.1 mTorr and about 100 Torr, between about 1 Torr and about 20 Torr, less than about 5 Torr, or less than about 3 Torr in different

embodiments. [0057] Embodiments of the deposition systems may be incorporated into larger fabrication systems for producing integrated circuit chips. FIG. 3 shows one such system 400 of deposition, etching, baking, and curing chambers according to disclosed embodiments. In the figure, a pair of front opening unified pods (FOUPs) 402 supply substrates of a variety of sizes that are received by robotic arms 404 and placed into a low pressure holding area 406 before being placed into one of the substrate processing chambers 408a-f. A second robotic arm 410 may be used to transport the substrate wafers from the holding area 406 to the substrate processing chambers 408a-f and back. Each substrate processing chamber 408a-f, can be outfitted to perform a number of substrate processing operations including the deposition processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation, and other substrate processes.

[0058] The substrate processing chambers 408a-f may include one or more system components for depositing, annealing, curing and/or etching a dielectric film on the substrate wafer. In one configuration, two pairs of the processing chambers, e.g., 408c-d and 408e-f, may be used to deposit dielectric material on the substrate, and the third pair of processing chambers, e.g., 408a- b, may be used to etch the deposited dielectric. In another configuration, all three pairs of chambers, e.g., 408a-f, may be configured to deposit, cure, and density a dielectric film on the substrate. Any one or more of the processes described may be carried out in chamber(s) separated from the fabrication system shown in different embodiments.

[0059] In the preceding description, for the purposes of explanation, numerous details have been set forth in order to provide an understanding of various embodiments of the present invention. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details. [0060] Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosed embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.

[0061] Where a range of values is provided, it is understood that each intervening value, to the smallest fraction of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of those smaller ranges may independently be included or excluded in the range, and each range where either, neither, or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

[0062] As used herein and in the appended claims, the singular forms "a", "an", and "the" include plural references unless the context clearly dictates otherwise. Thus, for example, reference to "an aperture" includes a plurality of such apertures, and reference to "the plate" includes reference to one or more plates and equivalents thereof known to those skilled in the art, and so forth.

[0063] Also, the words "comprise(s)", "comprising", "contain(s)", "containing", "include(s)", and "including", when used in this specification and in the following claims, are intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups.

Claims

WHAT IS CLAIMED IS:

1. A method of forming a dielectric layer on a substrate in a substrate processing region of a processing chamber, the method comprising:

introducing a first precursor into a remote plasma region fluidly coupled with the substrate processing region while forming a plasma in the remote plasma region to produce plasma effluents;

directing the plasma effluents into the substrate processing region; introducing a silicon-containing precursor into the substrate processing region, wherein the silicon-containing precursor includes at least one silicon-silicon bond; and

reacting the plasma effluents and silicon-containing precursor in the substrate processing region to form a silicon-based dielectric layer that is initially flowable when formed on the substrate.

2. The method of claim 1, wherein the silicon-containing precursor includes at least two silicon-silicon bonds.

3. The method of claim 1, wherein the first precursor includes one or more precursors selected from the group consisting of ammonia, nitrogen, H₂, Ar, and He.

4. The method of claim 1, wherein the plasma effluents and silicon- containing precursor are introduced into the processing region through a showerhead configured to maintain separation of the precursors so that they do not contact each other until they enter the substrate processing region.

5. The method of claim 4, wherein the substrate is maintained at a distance less than or at about 3 inches from the showerhead.

6. The method of claim 1, wherein the substrate processing region is plasma- free during the deposition process.

7. The method of claim 1, wherein the silicon-containing precursor has the formula Si_xH_y, wherein x is greater than or equal to 2, and y is 2x+n or greater, wherein n is any number less than or equal to 2, and wherein the silicon-containing precursor is introduced into the processing region in a substantially vapor phase.

8. The method of claim 1 , wherein the method is performed at a temperature of less than or equal to about 30°C.

9. The method of claim 1 , wherein the method is performed at a pressure of less than or equal to about 5 Torr.

10. The method of claim 1, wherein the as-formed film has a density greater than or equal to about 1.4 g/cc.

11. The method of claim 1 , further comprising stopping the introduction of the silicon-containing precursor after the silicon-based dielectric layer is formed, and directing the plasma effluents into the substrate processing region to densify the formed dielectric layer.

12. The method of claim 1, further comprising annealing the formed silicon- based dielectric layer.

13. The method of claim 12, wherein the formed silicon-based dielectric layer shrinks by less than about 20% during the annealing.

14. A method of forming a dielectric layer on a substrate in a substrate processing region of a processing chamber, the method comprising:

introducing a first precursor into a remote plasma region fluidly coupled with the substrate processing region while forming a plasma in the remote plasma region to produce plasma effluents;

directing the plasma effluents into the substrate processing region; introducing a silicon-containing precursor into the substrate processing region, wherein the silicon-containing precursor includes at least one silicon-silicon bond;

reacting the plasma effluents and silicon-containing precursor in the substrate processing region to form a silicon-based dielectric layer that is initially flowable when formed on the substrate; and

curing the formed silicon-based dielectric layer with at least one additional precursor.

15. The method of claim 14, wherein the at least one additional precursor comprises an oxygen-containing precursor, a nitrogen-containing precursor, or a carbon- containing precursor.

16. The method of claim 14, further comprising directing the plasma effluents into the substrate processing region to densify the cured dielectric layer.

17. The method of claim 14, wherein the silicon-containing precursor has the formula Si_xH_y, wherein x is greater than or equal to 2, and y is 2x+n or greater, wherein n is any number less than or equal to 2, and wherein the silicon-containing precursor is introduced into the processing region in a substantially vapor phase.

18. The method of claim 14, wherein the precursors introduced into the processing chamber to form the silicon-based dielectric layer consist of one or more inert precursors and a silicon-containing precursor consisting of silicon-silicon and silicon-hydrogen containing bonds.

19. The method of claim 14, further comprising annealing the formed silicon- based dielectric layer.

20. The method of claim 14, wherein the formed silicon-based dielectric layer shrinks by less than about 20% during the annealing.