KR20170132666A - Technique to deposit sidewall passivation for high aspect ratio cylinder etch - Google Patents

Abstract

Various embodiments of the present disclosure are directed to methods, apparatus, and systems for forming recessed features in a dielectric material on a semiconductor substrate. Separate etch operations and depot operations are employed in a recursive manner. Each of the etching operations partially etches the features. Each of the depot actions forms a protective coating on the sidewalls of the feature to prevent lateral etching of the dielectric material during the etching operations. The protective coating may be deposited using methods that cause formation of a protective coating substantially along the entire length of the side walls. The protective coating may be deposited using specific reactants and / or reaction mechanisms that do not use a plasma and that generate a substantially complete sidewall coating at relatively low temperatures. In some cases, the protective coating is deposited using molecular layer deposition techniques. In certain embodiments, the protective coating is fluorinated.

Description

TECHNICAL FIELD [0001] The present invention relates to a technique for depalletizing a side wall passivation for high aspect ratio cylinder etching. BACKGROUND OF THE INVENTION < RTI ID = 0.0 > [0001]

One process that is commonly employed during fabrication of semiconductor devices is the formation of etched cylinders in dielectric materials. Exemplary backgrounds in which such a process may occur include, but are not limited to, memory applications such as DRAM and 3D NAND structures. As the semiconductor industry advances and device dimensions become smaller, it becomes increasingly more difficult to etch these cylinders, especially for high aspect ratio cylinders with narrow widths and / or deep depths, in a uniform manner.

Certain embodiments herein relate to methods and apparatus for forming an etched feature in a stack comprising a dielectric material on a semiconductor substrate. The disclosed embodiments may utilize specific techniques to depress the passivating material on the sidewalls of the etched features, thereby causing the etch to occur at high aspect ratios. In multiple embodiments, specific reactants or classes of reactants may be used to depot passivating material. For example, one or more of the reactants may be a fluorine-containing reactant, and the resulting passivating material may include fluorine, among other elements.

In one aspect of the disclosed embodiments, there is provided a method of forming an etched feature in a stack comprising a dielectric material on a semiconductor substrate, the method comprising: (a) generating a first plasma comprising an etch reactant, Exposing to the plasma, and partially etching the features in the stack; (b) after step (a): (i) exposing the substrate to a first reactant material and causing the first reactant material to adsorb on the substrate; (ii) exposing the substrate to a second reactant material; and iii) depalletizing the protective film on the sidewalls of the feature by repeating (i) and (ii) until the protective film reaches the target thickness, wherein the first and second reactive materials are in contact with each other Depositing a protective film on the sidewalls of the feature, wherein the protective film is a fluorinated organic polymer film and is substantially deposited along the entire depth of the feature; And (c) repeating steps (a) and (b) until the feature is etched to a final depth, wherein the deposited protective film in step (b) And repeating steps (a) and (b), wherein the features have an aspect ratio of at least about 5 at the final depth of the feature.

In various embodiments, depositing the protective film in step (b) may be accomplished without exposing the substrate to plasma energy. In some cases, the first reactant may comprise an acyl halide or acid anhydride, and the second reactant may comprise at least one of a diamine, a diol, a thiol, and a trifunctional compound, At least one of the reactant and the second reactant may be a fluorine-containing reactant. The first reactant may comprise a diacyl chloride. For example, the first reactant may comprise a fluorinated analog of malonyl chloride and / or malonyl chloride. In certain instances, the second reactant may comprise a diamine. In some cases, the second reactant may comprise a fluorinated analog of ethylenediamine and / or ethylenediamine. In these or other instances, the first reactant may comprise a fluorinated analog of malonyl chloride and / or malonyl chloride.

In certain embodiments, the first reactant is selected from the group consisting of ethanedioyl dichloride, a fluorinated analog of ethanedioyl dichloride, malonyl chloride, a fluorinated analog of malonyl chloride, succinyl dichloride, succinyl di Fluorinated analogs of chlorides, fluorinated analogs of chlorides, fluorinated analogs of chlorides, pentanedioyl dichlorides, fluorinated analogs of pentanedioyl dichlorides, maleic anhydrides, and fluorinated analogs of maleic anhydrides ; And the second reactant is selected from the group consisting of 1,2-ethanediamine, a fluorinated analog of 1,2-ethanediamine, 1,3-propanediamine, a fluorinated analog of 1,3-propanediamine, Fluorinated analogues of 1,4-butanediamine, ethylene glycol, fluorinated analogs of ethylene glycol, 1,3-propanediol, fluorinated analogs of 1,3-propanediol, 1,4-butanediol, Fluorinated analogs of 1,4-butanediol, 1,2-ethanedithiol, fluorinated analogs of 1,2-ethanedithiol, 1,3-propanedithiol, 1,3-propanedithiol, (±) -3-amino-1,2-propanediol, (±) -3-amino-1,2-dicarboxylic acid, Fluorinated analogues of propanediol, glycerol, fluorinated analogues of glycerol, bis (hexamethylene) triamine, fluorinated analogues of bis (hexamethylene) triamine, melamine, melamine Fluorinated analogs of diethylenetriamine, diethylenetriamine, fluorinated analogues of diethylenetriamine, (±) -1,2,4-butanetriol, (±) -1,2,4- Analogs, cyanuric chloride, and fluorinated analogs of cyanuric chloride. In various instances, the protective film may comprise a fluorinated polyamide and / or a fluorinated polyester.

In various embodiments, the step of depalletizing the protective film of step (b) occurs in the reaction chamber. In some such cases, the step of depalletizing the protective film of step (b) may further comprise purging the reaction chamber at least once during each iteration of step (b). Similarly, the step of depalletizing the protective film of step (b) may comprise purging the reaction chamber at least twice during each iteration of step (b), wherein the transfer of the first reactant in the first purging (i) Between the transfer of the second reactant in the second spreading (ii) and the subsequent transfer of the first reactant in the subsequent iteration of (i) Occurs.

When the feature reaches the final depth of the feature, the feature may have a maximum critical dimension that is (i) not less than about 20 aspect ratios and (ii) not greater than about 10% greater than the critical dimension at the bottom of the feature . The features may have an aspect ratio of about 50 or more at the final depth of the feature. The features may be formed during formation of the VNAND device in some embodiments, and in such cases the stack may comprise (i) a silicon oxide material, and (ii) alternating layers of a silicon nitride material or a polysilicon material It is possible. The features may also be formed during formation of the DRAM device, and the dielectric material may comprise silicon oxide. In various embodiments, step (a) and step (b) may be repeated at least once, wherein step (b) may or may not be performed using the same reactants during each iteration.

In another aspect of the disclosed embodiments, an apparatus is provided for forming an etched feature in a stack including a dielectric material on a semiconductor substrate. At least one reaction chamber is designed or configured to perform etching and at least one reaction chamber is designed or configured to perform a deposition and each of the reaction chambers is configured to react At least one reaction chamber comprising an inlet for introduction into the chamber and an outlet for removing material from the reaction chamber; (A) an instruction to generate an etch plasma comprising an etch reactant, expose the substrate to an etch plasma, and partially etch the feature in the stack, wherein the instruction (a) (A) performed in a configured reaction chamber; (b) after instruction (a): (i) exposing the substrate to a first reactant material and causing the first reactant material to adsorb on the substrate; (ii) exposing the substrate to a second reactant material; and iii) instructions for depalletizing the protective film on the sidewalls of the feature by repeating (i) and (ii) until the protective film reaches the target thickness, wherein the first and second reactive materials form a protective film (B) for depositing a protective film on the sidewalls of the feature, wherein the protective film is a fluorinated organic polymer film and is substantially deposited along the entire depth of the feature; And (c) instructions for repeating instructions (a) and (b) until the feature is etched to a final depth, wherein the protective film deposited in instruction (b) comprises a lateral etch of the feature during instruction (A) and (c) for repeating the instruction (b), wherein the feature substantially avoids and the feature has an aspect ratio of at least about 5 at the final depth of the feature.

In certain embodiments, a reaction chamber designed or constructed to perform etching such that both instruction (a) and instruction (b) occur in the same reaction chamber may be the same as the reaction chamber designed or constructed to perform the deposition . In other embodiments, a reaction chamber designed or constructed to perform etching may be different from a reaction chamber designed or configured to perform deposition, and the controller may be configured to perform a deposition with a reaction chamber designed or configured to perform etching Further comprising instructions for transferring the substrate between the designed or configured reaction chambers. In certain embodiments, the controller includes instructions for depotting the protective film in instruction (b) without using a plasma.

In a further aspect of the disclosed embodiments, there is provided a method of forming an etched feature in a stack comprising a dielectric material on a semiconductor substrate, the method comprising: (a) generating a first plasma comprising an etch reactant, 1 < / RTI > plasma, and partially etching the features in the stack; (b) depressurizing the protective film on the sidewalls of the feature after step (a), wherein the protective film is a fluorinated organic polymer film and is substantially deposited on the sidewalls of the feature Depositing a protective film on the substrate; And (c) repeating steps (a) and (b) until the feature is etched to a final depth, wherein the deposited protective film in step (b) And repeating steps (a) and (b), wherein the features have an aspect ratio of at least about 5 at the final depth of the feature.

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

Figure 1 illustrates an etched cylinder with undesirable bowing due to over-etching of the sidewalls.
2A shows a flow diagram of a method for forming an etched feature on a semiconductor substrate in accordance with various disclosed embodiments.
Figure 2B shows a flow diagram of a method of depalletizing a protective film on sidewalls of a partially etched feature in accordance with certain embodiments.
Figures 2c and 2d illustrate specific deposition reactions for forming a protective film, wherein the reactants used include malonyl chloride and ethylenediamine.
Figure 2e illustrates a specific deposition reaction for forming a protective film, wherein the reactants used include a fluorinated analog of malonyl chloride and a fluorinated analog of ethylenediamine.
Figures 3A-3D illustrate etched cylinders in a semiconductor substrate as the cylinders are circularly etched and coated with a protective sidewall coating, in accordance with various embodiments.
Figures 3e and 3f show graphs illustrating percent saturation of malonyl chloride (Figure 3e) and ethylenediamine (Figure 3f) during some doses.
Figure 3g illustrates a mass change over time for 100 cycles for a coupon processed in a reaction chamber using the method of Figure 2b using a set of reactants.
Figure 3h illustrates the close-up version of Figure 3g focused on about four of the 100 cycles shown in Figure 3g.
Figure 3i illustrates data showing the composition of the protective film formed for Figures 3g and 3h.
Figures 4A-4C illustrate reaction chambers that may be used to perform the etching processes described herein in accordance with certain embodiments.
Figure 5 illustrates a reaction chamber that may be used to perform the deposition processes described herein in accordance with certain embodiments.
Figure 6 illustrates a multi-station device that may be used to perform deposition processes in certain implementations.
Figure 7 shows a cluster tool that may be used to implement both deposition and etching in accordance with certain embodiments.

In this application, the terms "semiconductor wafer", "wafer", "substrate", "wafer substrate", and "partially fabricated integrated circuit" are used interchangeably. Those skilled in the art will appreciate that the term "partially fabricated integrated circuit" may refer to a silicon wafer during any of the many stages of integrated circuit fabrication thereon. The wafer or substrate used in the semiconductor device industry typically has a diameter of 200 mm, or 300 mm, or 450 mm. The following detailed description assumes that the present invention is implemented on a wafer. However, the present invention is not so limited. The workpiece may be of various shapes, sizes, and materials. In addition to semiconductor wafers, other workpieces that may take advantage of the present invention may be used in various applications such as printed circuit boards, magnetic recording media, magnetic recording sensors, mirrors, optical elements, micro-mechanical devices, It includes various articles.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the embodiments provided. The disclosed embodiments may be practiced without some or all of these specific details. In other instances, well-known process operations have not been described in detail in order not to unnecessarily obscure the disclosed embodiments. While the disclosed embodiments will be described in conjunction with specific embodiments, it will be understood that they are not intended to limit the disclosed embodiments.

I. Techniques for etching high aspect ratio features in dielectric materials

The manufacture of specific semiconductor devices involves etching the features into a dielectric material or materials. The dielectric material may be a single layer of material or a stack of materials. In some cases, the stack includes alternating layers of dielectric materials (e.g., silicon nitride and silicon oxide). One exemplary etched feature is a cylinder that may have a high aspect ratio. As the aspect ratio of these features continues to increase, it becomes increasingly difficult to etch features into dielectric materials. One problem that arises during etching of high aspect ratio features is a non-uniform etch profile. That is, the features are not etched in a straight downward direction. Instead, the sidewalls of the features are often bowed such that the middle portion of the etched feature is wider (i.e., more etched) than the top and / or bottom portion of the feature. This over-etching near the middle portion of the features can result in compromised structural and / or electronic integrity of the remaining material. The portion of the feature that bows outwardly may occupy a relatively small portion of the total feature depth, or a relatively larger portion. The portion of the feature that bowed outward is where the critical dimension (CD) of the feature is at its maximum. The critical dimension corresponds to the diameter of the feature at a given spot. It is generally preferred that the maximum CD of the feature be approximately the same as the CD somewhere in the feature, e.g., at the bottom of the feature or near the bottom of the feature.

It is believed that over-etching in the middle of the cylinder or other features without any theory or mechanism of action occurs at least partially because the side walls of the cylinder are insufficiently protected from etching. Conventional etch chemistries utilize fluorocarbon etchants to form the cylinders in the dielectric material. Fluorocarbon etaners are excited by plasma exposure, which results in the formation of various fluorocarbon fragments including, for example, CF, CF ₂ , and CF ₃ . The reactive fluorocarbon fragments cleanly etch the dielectric material at the bottom of the feature (e.g., cylinder) with the help of ions. Other fluorocarbon fragments are deposited on the sidewalls of the cylinder being etched to form a protective polymer sidewall coating. This protective sidewall coating facilitates preferential etching at the bottom of the feature as opposed to the sidewalls of the feature. Without this sidewall protection, the features begin to take on a non-uniform profile with a wider etch / cylinder width that is inadequate to protect the sidewall.

Side wall protection is particularly difficult to achieve in high aspect ratio features. One reason for this difficulty is that conventional fluorocarbon-based processes can not form deep protective polymer side wall coatings in the etched cylinder. FIG. 1 shows a view of a cylinder 102 that is etched into a dielectric material 103 coated with a patterned mask layer 106. While the following discussion sometimes references cylinders, the concepts apply to other feature shapes such as rectangles and other polygons. The protective polymer side wall coating 104 is concentrated near the top portion of the cylinder 102. The C _x F _y chemistry provides both the reactive material (s) for forming the protective polymer side wall coating 104 as well as the etching reactive material (s) for vertically etching the cylinder. The middle portion of the cylinder 102 is wider than the upper portion of the cylinder 102 because the protective polymer side wall coating 104 does not extend deeply into the cylinder (i.e., there is insufficient deposition on the sidewall). The wider intermediate portion of the cylinder 102 is referred to as the bowing 105. Boeing can be described numerically in terms of a comparison between the critical dimension of the feature in the Boeing area (relatively larger area) and the critical dimension of the feature under the Boeing area. Boeing can be used to determine the distance (e.g., the critical dimension at the narrowest portion of the feature below the critical dimension subtracting bowing at the widest portion of the feature) or the ratio / percentage (at the widest portion of the feature below the critical dimension division Boing The critical dimension at the narrowest portion of the feature of the feature). This Boeing 105, and associated non-uniform etch profile, is undesirable. Because of the high ion energies often used in this type of etching process, the Boeing is often created when etching cylinders of high aspect ratios. In some applications, the Boeons are created with even aspect ratios as low as about five. As such, conventional fluorocarbon etch chemistries are typically limited to forming relatively low aspect ratio cylinders in dielectric materials. Some modern applications require cylinders with higher aspect ratios than cylinders that can be achieved with conventional etching chemistries.

II. Background and applications

In various embodiments herein, the features are etched in a substrate (typically a semiconductor wafer) having a dielectric material on the surface. Etch processes are generally plasma-based etch processes. The entire feature formation process may occur in the following stages: one stage relates to etching the dielectric material and another stage relates to forming the protective sidewall coating without substantially etching the dielectric material. The protective sidewall coating passivates the sidewalls and prevents the features from being over-etched (i.e., the sidewall coating prevents lateral etching of the features). These two stages can be repeated until the feature is etched to the final depth of the feature. By circulating these two stages, the diameter of the feature can be controlled over the entire depth of the feature, thereby forming features with more uniform diameters / improved profiles.

The feature is a recess in the surface of the substrate. The features may have many different shapes, including, but not limited to, cylinders, rectangles, squares, other polygonal recesses, trenches, and the like.

Aspect ratios are a comparison of the depth of the feature to the critical dimension of the feature (often the width / diameter of the feature). For example, cylinders having a depth of 2 [mu] m and a width of 50 nm have an aspect ratio of 40: 1, often referred to simply as 40. [ As the features may have non-uniform critical dimensions over the depth of the features, the aspect ratio may vary depending on where the dimensions are measured. For example, sometimes the etched cylinder may have a wider intermediate portion than the top and bottom portions. This wider intermediate section may also be referred to as Boeing, as mentioned above. The aspect ratio measured based on the critical dimension at the top (i.e., neck) of the cylinder will be higher than the aspect ratio measured based on the critical dimension at the wider mid / bowing of the cylinder. As used herein, aspect ratios are measured based on a critical dimension adjacent to the opening of the feature, unless otherwise specified.

The features formed through the disclosed methods may be high aspect ratio features. In some applications, the high aspect ratio features include features having an aspect ratio of at least about 5, at least about 10, at least about 20, at least about 30, at least about 40, at least about 50, at least about 60, at least about 80, to be. The critical dimensions of the features formed through the disclosed methods may be less than about 200 nm, such as less than about 100 nm, less than about 50 nm, or less than about 20 nm.

The material from which the features are etched may be dielectric material in various instances. Exemplary materials include, but are not limited to, silicon oxides, silicon nitrides, silicon carbides, oxynitrides, oxycarbides, carbo-nitrides, combinations of these materials (e.g., boron, phosphorus, Doped versions), and laminates from any combination of these materials. Specific exemplary materials are stoichiometrically agent and the ratio of _{SiO 2, SiN, SiON, SiOC} , SiCN, and so on - and a stoichiometric formulations. The material or materials to be etched may contain other elements, for example hydrogen, in various cases. In some embodiments, the nitride and / or oxide material being etched has a composition comprising hydrogen. As used herein, silicon oxide materials, silicon nitride materials, etc., include both stoichiometric and non-stoichiometric versions of these materials, and such materials may be used in combination with other elements It will be appreciated.

One application for the disclosed methods is in the context of forming a DRAM device. In this case, the feature may be mainly etched in silicon oxide. The substrate may also comprise one, two or more layers of, for example, silicon nitride. In one example, the substrate comprises a silicon oxide layer sandwiched between two silicon nitride layers, wherein the silicon oxide layer is about 800-1200 nm thick and the at least one silicon nitride layer is about 300-400 nm thick to be. The etched features may be cylinders having a final depth of 1 to 3 占 퐉, for example, about 1.5 to 2 占 퐉. The cylinder may have a width of about 20 to 50 nm, for example about 25 to 30 nm. After the cylinder is etched, the capacitor memory cell may be formed inside the cylinder.

Another application for the disclosed methods is in the context of forming a vertical NAND (VNAND, also referred to as 3D NAND) device. In this case, the material from which the features are etched may have a repeating layered structure. For example, the materials may include oxides (e.g., SiO ₂₎ and nitrides alternating layers (e.g., SiN), or oxide (e.g., SiO ₂₎ with alternating layers of polysilicon . Alternating layers form pairs of materials. In some cases, the number of pairs may be at least about 20, at least about 30, at least about 40, at least about 60, or at least about 70. The oxide layers may have a thickness of about 20 to 50 nm, for example about 30 to 40 nm. The nitride layer or polysilicon layer may have a thickness of about 20 to 50 nm, for example about 30 to 40 nm. The features etched into the alternating layer may have a depth of about 2 to 6 [mu] m, for example about 3 to 5 [mu] m. The features may have a width of about 50 to 150 nm, for example about 50 to 100 nm.

III. Etching Process / Deposition Process

2A shows a flow diagram of a method 200 of forming an etched feature in a semiconductor substrate. The operations shown in Figure 2A are described with respect to Figures 3A-3D, which shows a partially fabricated semiconductor substrate when a feature is etched. In operation 201, features 302 are etched to a first depth in a substrate having a dielectric material 303 and a patterned mask layer 306. This first depth is only part of the final desired depth of the feature. The chemical used to etch the feature may be a fluorocarbon-based chemical (C _x F _y ). Other etch chemistries may be used. This etching operation 201 may also result in the formation of the first sidewall coating 304. The first sidewall coating 304 may be a polymer sidewall coating, as described in connection with FIG. The first sidewall coating 304 extends toward the first depth but in many cases the first sidewall coating 304 does not actually reach the bottom of the features 302. [

The first side wall the coating 304 because doing depot on the carbon species / fragment to the side wall of the object in a specific fluoro (i.e., the carbon species in a particular fluorinated deulim precursors for the first side wall coating 304) C _x F _y etch chemistry. One reason why the first sidewall coating 304 does not reach the bottom of the features 302 may be related to the sticking coefficient of the precursors that form the coating. In particular, for certain etchants, the adhesion coefficient of these first sidewall coating precursors is very high, which is believed to cause substantially the majority of the precursor molecules to adhere to the sidewalls immediately after entering the feature. As such, there are few sidewall coating precursor molecules that can penetrate deep into the advantageous features of the sidewall protection. Thus, the first sidewall coating 304 provides only partial protection against over-etching of the sidewalls of the features 302. In some embodiments, the etching conditions provide little sidewall protection.

Next, in operation 203, the etching process is stopped. After the etching stops, the second sidewall coating 310 is deposited at operation 205. In some cases, the second sidewall coating 310 may be substantially a first sidewall coating. Although this deposition is not limited thereto, it is contemplated that chemical vapor deposition (CVD) methods, atomic layer deposition (ALD) methods (any of which may be plasma-assisted or plasma-free), and MLD deposition methods. < / RTI > MLD methods may also deposit thin films of organic polymers using ALD-like cycles with two half-reactions. In some cases, MLD methods may be driven in a less adsorptive-limited manner than conventional ALD methods. For example, certain MLD methods may utilize the unsaturation or supersaturation of the reactants. ALD and MLD methods are particularly well suited for forming conformal films that line the sidewalls of the features in certain embodiments. For example, ALD and MLD methods are useful for delivering reactants deep into the features due to the adsorption-related properties of these methods. Embodiments of the present disclosure are not limited to those in which the second sidewall coating 310 is deposited via cyclic layer-by-layer deposition methods such as ALD and MLD, but the second sidewall coating 310) should allow the protective layer to be formed deep within the etched features 302. The etched features 302 are then removed from the etched features 302, CVD and other deposition processes may be suitable in various implementations.

FIG. 2B illustrates a flow diagram of a method 250 for depositing an organic polymer second protective sidewall coating 310 through an MLD process. As noted, ALD and CVD methods may also be used, as described further below. Method 250 begins with operation 251 where the first reactant flows into the reaction chamber and adsorbs onto the substrate surface. The reactive material may penetrate deeply into the partially etched features and adsorb onto the sidewalls of the features. In some embodiments, the first reactant is a diacyl halide, such as diacyl chloride. In a particular embodiment, the first reactant may be malonyl chloride (C ₃ H ₂ Cl ₂ O ₂ , sometimes also referred to as malonyl dichloride, with the structure Cl-CO-CH ₂ -CO-Cl). An example in which malonyl chloride is the first reactant is further discussed with reference to Figures 2c and 2d. In another embodiment, the first reactant may be a fluorinated analog of malonyl chloride or another diacyl halide. For example, in any of the first reactants listed herein, one or more CH bonds may be replaced by a CF bond. In a particular embodiment, the first reactant comprises C ₃ F ₂ Cl ₂ O ₂ (having the structure Cl-CO-CF ₂ -CO-Cl), and / or C ₃ HFCl ₂ O ₂ -CO-Cl < / RTI >). An example in which the first reactant is a fluorinated analog of malonyl chloride is further discussed with respect to Figure 2e. The first reactant forms an adsorbed layer, as shown by the adsorbed precursor layer 312 in Figure 3b.

Next, at operation 253, the reaction chamber may be selectively purged to remove excess first reactant material from the reaction chamber. Next, at operation 255, the second reactant is delivered to the reaction chamber. In some embodiments, the second reactant may be a diamine, a diol, a thiol, or a trifunctional compound. In certain embodiments, the second reactant may be ethylenediamine (C ₂ H ₈ N ₂ ). Figures 2c and 2d show examples in which the second reactant is ethylenediamine. For any of the second reactants of the second reactants listed herein, one or more of the CH bonds may be replaced by a CF bond. For example, in certain embodiments, the second reactant may be a fluorinated diamine, a fluorinated diol, a fluorinated thiol, or a fluorinated trifunctional compound. In a particular example, the second reactant is C ₂ H ₄ F ₄ N ₂ (having the structure NH ₂ -CF ₂ -CF ₂ -NH ₂ ). That is, the second reactant may be a diaminoethane in which CH bonds are replaced with CF bonds. In some implementations, less CH bonds than all CH bonds may be replaced with CF bonds. For example, the second reactant may be, in any combination, NH ₂ -CHF-CH ₂ -NH ₂ , NH ₂ -CH ₂ -CF ₂ -NH ₂ , NH ₂ -CHF-CF ₂ -NH ₂ , and / or it may include _{NH 2 -CHF-CHF-NH 2} . An example in which the second reactant is a fluorinated analog of ethylenediamine is further discussed with respect to Figure 2e.

The second reactant reacts with the first reactant to form a protective film on the substrate. The formed protective film may be the second sidewall coating 310 as shown in Figs. 3C and 3D. The protective film may be formed through a thermal reaction without dependence on any plasma.

Next, at operation 257, the reaction chamber may be selectively purged. The purges of operations 253 and 257 may occur by sweeping the reaction chamber with a non-reactive gas, evacuating the reaction chamber, or some combination thereof. The purpose of the purge is to remove all unadsorbed reactants and by-products from the reaction chamber. Although both purge operations 253 and 257 are selectable, purge operations 253 and 257 may help prevent unwanted gas phase reactions and may result in improved deposition results.

Next, at operation 259, it is determined whether the protective film is sufficiently thick. This determination may be made based on the thickness deposited per cycle and the number of cycles performed. In various embodiments, each cycle depots a film of about 0.1 to 1 nm, and the thickness is determined by the length of time the reactants flow into the reaction chamber and the level at which the reactant saturation occurs. If the film is not yet thick enough, the method 250 is repeated from operation 251 to build additional film thickness by depalletizing the additional layers. Otherwise, the method 250 is completed. In subsequent iterations, operation 251 includes both adsorption of an additional first reactant material on the substrate and the reaction of the first reactant and the second reactant, which may be due to a previous iteration of operation 255 It may be accompanied. That is, after the first cycle, both operations 251 and 255 may involve a reaction between the first reactant and the second reactant. After the protective film is sufficiently thick, the substrate may undergo another etching process as shown in operation 211 of FIG. 2A.

Deposition method 250 may be used to form a layer of an organic polymer film in a plurality of cases. Figure 2c illustrates steps 251 to 257 of Figure 2b in a particular context in which the first reactant is malonyl chloride and the second reactant is ethylenediamine. In operation 251, malonyl chloride, which is the first reactant, flows into the reaction chamber in a vapor phase and adsorbs onto the substrate 260. The portion of the substrate 260 shown in Figure 2C is the side wall of the partially etched cylinder. At operation 253, the reaction chamber is selectively purged, for example, by flowing a non-reactive purge gas through the reaction chamber. At operation 255, ethylenediamine, a second reactant, flows into the reaction chamber in a vapor phase. The first and second reactants react to form a layer of the organic polymer film on the exposed surfaces of the substrate 260, for example along the sidewalls of the partially etched features. Next, at operation 257, the reaction chamber may be selectively purged by, for example, flowing another purge gas into the reaction chamber. These operations can be repeated until the organic polymer film is grown to the desired thickness.

Figure 2D further illustrates the reaction that occurs at operation 255 where the first reactant is malonyl chloride and the second reactant is ethylenediamine. These reactants may be particularly useful in applications where a protective film is desired to form at relatively low temperatures. These reactants are shown to react effectively and efficiently with each other at temperatures well below the temperatures typically used in similar MLD and ALD reactions. For example, malonyl chloride and ethylenediamine are shown to react with each other at temperatures as low as about 50 캜 and react with each other at room temperature (e.g., as low as about 20 캜 or 25 캜) without the use of plasma It is expected. Many similar thermal ALD reactions (without plasma) are performed at much higher temperatures, e.g., at least about 200 < 0 > C. Low temperature deposition is particularly useful in certain contexts. In some cases, the use of a low temperature non-plasma deposition may help enable deposition to occur in the same reaction chamber as the etching reaction, so that transfer between two different reaction chambers is not required. MLD processes are described in U.S. Patent Application Serial No. 14 / 446,427, filed July 30, 2014, entitled " METHOD OF CONDITIONING VACUUM CHAMBER OF SEMICONDUCTOR SUBSTRATE PROCESSING APPARATUS ", which is incorporated herein by reference in its entirety. Further discussed.

Figure 2e is, for the fluorinated analogues of the carbonyl chloride, the first reaction material words (e. _{G., Cl-CO-CF 2 -CO} -Cl) and the second reactant is ethylenediamine fluorinated analogs (e.g., NH ₂ -CF ₂ -CF ₂ -NH ₂ ). FIG. When these reactants are used, fluorinated organic polymers (e.g., fluorinated polyamides) having the composition [C ₅ O ₄ N ₂ H ₂ F ₆ ] _n are formed. The use of fluorinated protective membranes is further discussed below.

The disclosed MLD method 250 of FIG. 2B is well suited for forming a conformal film coating the entire sidewalls of the feature. One reason MLD methods may be particularly useful is that MLD methods can achieve a very high degree of conformality because the reaction is driven by thermal energy rather than by plasma energy. When the plasmas are used to generate one or more reactive materials in a plasma-assisted ALD manner, the resulting reactants may be radical species with high surface reactivity. Therefore, this approach may produce reactive materials with limited ability to penetrate into high aspect ratio features and thus result in poorer conformality and / or higher dosage requirements as compared to thermal methods. Also, because the plasma used in semiconductor fabrication is not uniform in the reaction chamber, plasma non-uniformities can cause non-uniform deposition results across the substrate. In contrast, it is easier to deliver uniform heat energy to the substrate, for example, by providing a uniform heat source on the substrate support. Plasma energy is often used to drive reactions at relatively low temperatures (e.g., less than about 200 ° C). Often, semiconductor devices have a specific thermal budget during fabrication, and management may need to be done to process the substrate at lower temperatures to conserve the thermal budget and thus prevent damage to the device. However, the use of plasmas may also have detrimental effects on conformality and / or uniformity, as noted. In various embodiments herein, certain reactive materials are used to depalletize the protective layer at relatively low temperatures, thereby capturing both the uniformity gains associated with thermal processing and the low temperature / thermal budget gains often associated with plasma processing do. An example of a pair of reactive materials that may be used at relatively low temperatures to depalletize the protective layer includes malonyl chloride and ethylenediamine, as discussed in connection with Figures 2c and 2d.

Referring back to FIG. 2A, the method continues at operation 207 where the deposition process is aborted. The method may then include the act of partially etching the features in the substrate (operation 211, similar to operation 201), stopping the etching (operation 213, similar to operation 203), applying a protective coating on the sidewalls of the partially etched features (Operation 215, similar to operation 205), and stopping the deposition (operation 217, similar to operation 207). Next, at operation 219, it is determined whether the feature has been completely etched. If the features have not been completely etched, the method is repeated from operation 211 with additional etch and deposition of protective coatings. The etch operation 211 may change the second sidewall coating 310 to form a film that is much more etch resistant than the films deposited in operations 205 and 215. [ In one example, deposition operation 205 is performed through method 250 to form an organic polymer film comprising carbon, nitrogen, oxygen, and hydrogen. Once the features are completely etched, the method is complete.

In various embodiments, the etching operation 201 and the protective sidewall coating deposition operation 205 are cyclically repeated a plurality of times. For example, these operations may each occur at least twice (e.g., as shown in FIG. 2A), such as at least about three times, or at least about five times. In some cases, the number of cycles (including the etching operation 201 and the protective sidewall coating deposition operation 205, along with the etching operation 211 and the deposition operation 215, where each cycle is counted as the second cycle) is about 2 to 10, For example from about 2 to about 5. Every time an etching operation occurs, the etching depth increases. The etched distance may be uniform between cycles, or may be non-uniform. In certain embodiments, the etched distance in each cycle decreases because additional etchings are performed (i.e., later etch operations may etch less extensively than previously performed etch operations). The thickness of the second sidewall coating 310 deposited in each of the deposition operations 205 may be uniform between cycles, or the thickness of such coatings may vary. Exemplary thicknesses for the second sidewall coating 310 during each cycle may range from about 1 to 10 nm, for example from about 3 to 5 nm. In addition, the type of coating to be formed may be uniform between cycles, or the type of coating to be formed may vary.

The etching operation 201 and the deposition operation 205 may occur in the same reaction chamber or in different reaction chambers. In one example, an etching operation 201 occurs in the first reaction chamber and a deposition operation 205 occurs in the second reaction chamber, and the first and second reaction chambers together form a multi-chamber processing apparatus such as a cluster tool. Load locks and other suitable vacuum seals may be provided for transferring the substrate between the associated chambers in certain instances. The substrate may be transported by a robot arm or other mechanical structure. The reaction chamber used for etching, for example, may be a reaction chamber from Flex ™ 2300 ^® Flex ™ product family, available from Lam Research Corporation of Fremont, California materials. The reaction chamber used for the deposition may be a chamber from the Vector ^® family or from the Altus ^® family, available from Lam Research Corporation. The use of a combined reactor for both etching and deposition may be advantageous in certain embodiments because it avoids the need to transport the substrate. The use of different reactors for etching and deposition may be advantageous in other embodiments where it is desired that the reactors be specifically optimized for each of the operations. In a particular embodiment, both the etching operation and the deposition operation occur in the same reaction chamber (e.g., a Flex ™ reaction chamber), and the deposition reaction occurs via an MLD method such as the method 250 of FIG. 2B. The low temperature thermally driven deposition reactions may be particularly well suited to perform in a reaction chamber designed to perform different etching. Related reaction chambers are discussed further below.

As mentioned, the deposition operation aids in optimizing the etching operation by forming a deeply penetrating protective layer that minimizes or prevents lateral etching of the features during the etching operation. This facilitates the formation of etched features with very vertical sidewalls that barely or not at all. In certain embodiments, the final etched feature with an aspect ratio of at least about 80 is less than about 60% (measured as the narrowest critical dimension below 100 * (the widest critical dimension below) / the narrowest critical dimension below) It has Boeing. For example, a feature with a 50 nm wideest CD and a 40 nm narrowest CD (40 nm CD placed below 50 nm CD in the feature) is 25% (100 * (50 nm-40 nm) / 40 Nm = 25%). In another embodiment, the final etched feature having an aspect ratio of at least about 40 has less than about 20% Boeing.

IV. Materials and parameters of process operations

A. Substrate

The methods disclosed herein are particularly useful for etching semiconductor substrates having dielectric materials on top. Exemplary dielectric materials include, but are not limited to, silicon oxides, silicon nitrides, silicon carbides, oxynitrides, oxycarbides, carbo-nitrides, these materials (e.g. doped with boron, Doped versions, and stacks from any combination of these materials. Specific exemplary materials are stoichiometrically agent and the ratio of _{SiO 2, SiN, SiON, SiOC} , SiCN, and so on - and a stoichiometric formulations. As noted above, the etched dielectric material may comprise more than one type / layer of material. In certain cases, the dielectric material may be provided in the alternating layers of SiN and SiO _2, or alternating layers of polysilicon and SiO _2. Additional details have been provided above. The substrate may have a top mask layer that defines where the features are etched. In certain instances, the mask layer may be Si and the mask layer may have a thickness of about 500-1500 nm.

B. Etching process

In various embodiments, the etching process includes flowing a chemical etchant into the reaction chamber (often through a showerhead), among other things , creating a plasma from the etchant, and reactive ions Etching process. The plasma dissociates the etchant compound (s) into neutral species and ionic species (e.g., charged materials or neutral materials such as CF ₄ , CF _2, and CF ₃ ). Plasma is a capacitively coupled plasma in many cases, but other types of plasma may be used as appropriate. The ions in the plasma are directed towards the wafer and cause the dielectric material to be cleanly etched during impact.

Exemplary devices that may be used to perform the etching process include the 2300 ^® FLEX ™ family of reactive ion etching reactors available from Lam Research Corporation of Fremont, California. Etch reactors of this type are further described in the following US patents: U.S. Patent No. 8,552,334 and U.S. Patent No. 6,841,943, each of which is incorporated herein by reference in its entirety.

Various reactive material options can be used to etch features into the dielectric material. In certain instances, the etch chemistry comprises one or more fluorocarbons. In these or other instances, the etch chemistry may include other etchants such as NF ₃ . One or more co-reactants may also be provided. In some cases oxygen (O ₂ ) is provided as a co-reactant. The oxygen may help to control the formation of the protective polymer side wall coating (e.g., the first side wall coating 304 of FIGS. 3A-3D).

In certain embodiments, the etch chemistry comprises a combination of fluorocarbons and oxygen. For example, in one example, the etch chemistry includes C ₄ F ₆ , C ₄ F ₈ , N ₂ , CO, CF ₄ , and O ₂ . Other conventional etching chemistries may also be used, and non-conventional chemistries may be used. The fluorocarbons may flow at rates of about 0 to 500 sccm, such as about 10 to 200 sccm. When C ₄ F ₆ and C ₄ F ₈ are used, the flow of C ₄ F ₆ may range from about 10 to 200 sccm, and the flow of C ₄ F ₈ may range from about 10 to 200 sccm. The flow of oxygen may range from about 0 to 500 sccm, for example from about 10 to 200 sccm. The flow of nitrogen may range from about 0 to 500 sccm, for example from about 10 to 200 sccm. The flow of tetrafluoromethane may range from about 0 to 500 sccm, for example from about 10 to 200 sccm. The flow of carbon monoxide may range from about 0 to 500 sccm, for example from about 10 to 200 sccm. These rates are appropriate at a reactor volume of about 50 liters.

In some embodiments, the substrate temperature during etching is about 30 to 200 占 폚. In some embodiments, the pressure during etching is about 5 to 80 mTorr. The ion energy may be relatively high, for example about 1 to 10 kV. The ion energy is determined by the applied RF power. In various instances, the dual-frequency RF power is used to generate the plasma. Thus, the RF power may comprise a first frequency component (e.g., about 2 MHz) and a second frequency component (e.g., about 60 MHz). Different powers may be provided for each of the frequency components. For example, a first frequency component (e.g., about 2 MHz) may be provided at a power of about 3 to 24 kW, e.g., about 10 kW, and a second frequency component (e.g., about 60 MHz may be provided at lower power, for example, about 0.5 to 10 kW, for example about 2 kW. In some embodiments, three different frequencies of RF power are used to generate the plasma. For example, the combination may be 2 MHz, 27 MHz, and 60 MHz. The power levels for the third frequency component (e.g., about 27 MHz) may be similar to those described above for the second frequency component. These power levels assume that the RF power is delivered to a single 300 mm wafer. The power levels can be linearly scaled based on the substrate area for additional substrates and / or substrates of different sizes (thereby maintaining a uniform power density delivered to the substrate). In some embodiments, the RF power applied during etching may be adjusted between higher power and lower power at a repetition rate of about 100 to 40,000 Hz.

Each cycle of the etching process etches the dielectric material to some extent. The etched distance during each cycle may be from about 10 to 500 nm, for example from about 50 to 200 nm. The total etch depth will depend on the particular application. The total etch depth for some cases (e.g., DRAM) may be about 1.5 to 2 micrometers. For other cases (e.g., VNAND), the total etch depth may be at least about 3 microns, e.g., at least about 4 microns. In these or other cases, the total etch depth may be less than or equal to about 5 탆.

As described in the discussion of FIGS. 3A-3D, the etch process may produce a first sidewall coating (e. G., A first sidewall coating 304, which may be a polymer). However, the depth of the sidewall coating may be limited to the area near the upper portion of the feature, and the sidewall protection may not extend completely downward into the required features. Thus, the individual deposition operations are performed to form a sidewall coating that substantially covers the entire depth of the etched features, as described herein.

C. Deposition Process

The deposition process is mainly performed to deposit the protective layer on the sidewalls in the etched features. This protective layer must extend deep into the features, even high aspect ratio features. The formation of a deep passivation layer in high aspect ratio features may be enabled by the reactants having relatively low adhesion coefficients. In addition, reaction mechanisms that require adsorption of reactants (e.g., ALD and MLD reactions) can facilitate the formation of a deep protective layer in the etched features. Deposition of the protective layer begins after the feature is partially etched. As noted in the discussion of FIG. 2A, the deposition operation may be cycled with the etching operation to create additional sidewall protection as the features are etched deeper into the dielectric material. In some cases, the deposition of the protective layer is initiated when the feature is etched or etched by at least about 1/3 of the final depth of the feature. In some embodiments, the deposition of the protective layer begins when the feature reaches an aspect ratio of at least about 2, at least about 5, at least about 10, at least about 15, at least about 20, or at least about 30. In these or other instances, the deposition may be initiated before the feature reaches an aspect ratio of about 4, about 10, about 15, about 20, about 30, about 40, or about 50. In some embodiments, the deposition is initiated after the feature is at least about 1 占 퐉 depth, or at least about 1.5 占 퐉 depth (e.g., in VNAND embodiments where the final feature depth is between 3 and 4 占 퐉). In other embodiments, the deposition is initiated after the feature is at least about 600 nm deep, or at least about 800 nm deep (e.g., in DRAM embodiments with a final feature depth of 1.5-2 μm depth). The optimal time for initiating the deposition of the protective layer is just before the sidewalls are over-etched to form a bowing. The exact timing of this generation depends on the shape of the etched features, the material being etched, the chemicals used to etch and deposit the protective layer, and the process conditions used to etch and deposit the associated materials.

The protective layer formed during the deposition process may have various compositions. As described, the protective layer must penetrate deep into the etched features and be relatively resistant to the etch chemistry used to etch the features. In some cases, the protective layer is a ceramic material or an organic polymer. Exemplary organic materials may include polyolefins, for example polyfluoroolefins in some cases. One particular example is polytetrafluoroethylene. The precursor fragments used to form some of the polyfluoroolefins have a very low adhesion coefficient and thus may penetrate deeply into the etched features, resulting in CF ₂ (in certain cases, HFPO (hexafluoropropylene oxide) ) to be.

In certain embodiments, the protective layer formed during the deposition process is an organic polymer. In some cases, the organic polymer is a polyamide, polyester, polyimide, polyurea, polythiourea, polyurethane, or polyazomethine. In multiple instances, the organic polymer may be in the fluorinated form of any of the listed polymers. In certain cases, the polyamide protective layer is formed from a combination of an acyl chloride and a diamine. In some implementations the fluorinated polyamide protective layer is formed from a combination of an acyl chloride and a diamine, and one or both of the acyl chloride and the diamine may be completely or partially fluorinated. In some other cases, the polyamide protective layer may be formed from a combination of an acid anhydride and a diamine. In some implementations, the fluorinated polyamide protective layer may be formed from a combination of an acid anhydride and a diamine, and either or both of the acid anhydride and the diamine may be completely or partially fluorinated. Exemplary acid anhydrides include, but are not limited to, maleic anhydride. In certain other embodiments, the polyester protective layer may be formed from a combination of an acyl chloride and a diol. In some implementations, the fluorinated polyester protective layer may be formed from a combination of an acyl chloride and a diol, and one or both of the acyl chloride and the diol may be completely or partially fluorinated. In some embodiments, the polyester protective layer may be formed from a combination of an acid anhydride and a diol. In some implementations, the polyester protective layer may be formed from a combination of an acid anhydride and a diol, and either or both of the acid anhydride and the diol may be completely or partially fluorinated. In some specific examples, the protective layer is a polyamide layer formed from a combination of malonyl dichloride and ethylenediamine. In some analogous examples, the protective layer may be a fluorinated polyamide layer formed from a combination of malonyl dichloride and ethylenediamine, and either or both of malonyl dichloride and ethylenediamine may be fluorinated. Other combinations may also be used to form the fluorinated organic polymers as desired. These reactants may be used in an MLD process to form a protective layer in various embodiments, for example, as shown in Figures 2C-2E.

One issue that may occur in certain implementations is premature etch stop or slow vertical etch at some of the otherwise recessed features. Because the protective film may be formed on the bottom of the partially etched feature (if the film is not useful) in addition to the sidewalls of the partially etched feature (if the film is useful), the etching operation may be such that the feature is further etched in the vertical direction It may be necessary to etch the protective film at the bottom of the feature before it can be removed. In the context of FIG. 2A, operation 211 may initially involve etching through the depressed protective layer at the bottom of the partially etched feature during operation 205. In some embodiments, a separate breakthrough step may be performed to etch through the protective film, followed by another etching process to further etch the features in the underlying material. In other embodiments, no separate breakthrough step is performed.

The protective film at the bottom of the feature may slow (or even stop) the etching process in the feature, which may result in incomplete etching over a specific time frame and / or features with undesirably small critical dimensions at the bottom of the features . Even a small feature rate can be a problem because one of the objectives of the etching process is to uniformly etch all features on the substrate. In certain instances, acceptable tolerance levels acceptable for defective / incompletely etched features may be less than about 1 per 100 million etched features.

Certain protective film materials may be better suited to minimize the risk of etch stop or slow down. For example, fluorine-containing organic protective films may reduce the risk of etch stop or deceleration at the bottom of the features while simultaneously providing ampoule protection to the sidewalls of the features. At least partially, the material on the bottom is directly impacted by the ions, but because the sidewalls are only indirectly impacted due to the geometry of the features and the orientation of the ions, the material at the bottom of the features is the same It is easier to etch than material. In various instances, the etching processes (e.g., operations 201 and 211 of FIG. 2A) may be optimized to etch the silicon-containing material. These processes may not be well suited for etching hydrocarbon materials such as the protective film materials described in connection with Figures 2c and 2d. Indeed, various hydrocarbon polymers may inhibit the etching of silicon-containing materials. By tailoring the composition of the protective film to better promote etching at the bottom of the feature, the risk of etch stop or deceleration can be reduced.

Fluorine-containing protective membranes are particularly advantageous because they do not interfere with the theory or mechanism of action and because the fluorine (or fluorine-containing species) in the film can be liberated when these films are directly impacted by ions It is believed to be possible. The exposed fluorine (or fluorine-containing species) may directly etch the features (e.g., the protective film at the bottom of the feature, or the underlying material below the protective film) ) May be combined with other species to etch the features (e.g., to form fluorocarbons). The liberated fluorine (or fluorine-containing species) may be concentrated at the bottom of the feature, where it is most useful to further etch the feature in a precisely vertical direction.

It is believed that films with relatively higher fluorine content and relatively lower hydrogen content are particularly well suited to the etching methods described herein. In certain embodiments, the protective film has a composition with an F: H ratio of at least about 0.25: 1, or at least about 0.5: 1, or at least about 1: 1, or at least about 2: 1, or at least about 3: It is possible. Highly fluorinated membranes may be particularly advantageous when etching silicon or silicon oxide, while less fluorinated membranes may be useful when etching silicon nitride. It may be desirable to substitute CF bonds for less CH bonds than all CH bonds in the reactants because silicon nitride is better etched in the presence of some hydrogen, thereby promoting silicon nitride etch There will be available hydrogen. However, hydrogen can also be provided separately (e.g., as H ₂ or as part of another species in the etch chemistry), so highly fluorinated protective films can also be used when etching silicon nitride .

As mentioned above, Figure 2e illustrates an example of an MLD reaction between a fluorinated analog of malonyl chloride and a fluorinated analog of ethylenediamine. In this example, all of the C-H bonds in the reactants are replaced with C-F bonds. The resulting protective film is a fluorinated organic polymer having the structure shown in Figure 2E. In this example, the protective film is a fluorinated polyamide. In some other embodiments, the protective film may be a fluorinated polyimide, a fluorinated polyurea, a fluorinated polythiourea, a fluorinated polyurethane, a fluorinated polyazomethine, a fluorinated polyester, etc. .

To form the fluorine-containing protective film, one or more of the reactive materials used to form the protective film may comprise fluorine. Any of the reactants described herein may be modified to include fluorine. In some cases, one or more C-H bonds in the reactants described herein may be substituted with C-F bonds. In certain embodiments, all C-H bonds in the reactants described herein are substituted with C-F bonds. In these or other instances, one or more N-H bonds in the reactants described herein may be substituted with N-F bonds. One or both of the reactants used to form the protective film may be fluorinated. In addition, each of the reactants may be completely or partially fluorinated.

In another example, the fluorinated polyamide protective membrane is a mixture of malonyl chloride (Cl-CO-CH ₂ -CO-Cl) and a fluorinated analog of diaminoethane (NH ₂ -CF ₂ -CF ₂ -NH ₂ ) May be formed from combinations. The fluorinated polyamide protective film may have a composition of [C ₅ O ₄ N ₂ H ₄ F ₄ ] _n . In another example, the fluorinated polyamide protective membrane is a mixture of a fluorinated analog of malonyl chloride (Cl-CO-CF ₂ -CO-Cl) and diaminoethane (NH ₂ -CH ₂ -CH ₂ -NH ₂ ) May be formed from combinations. The fluorinated polyamide protective film may have a composition of [C ₅ O ₄ N ₂ H ₆ F ₂ ] _n .

In cases where the protective film comprises nitrogen - for example, a nitrogen-containing polymer, a nitrogen-containing reactant may be used. The nitrogen-containing reactants may include at least one nitrogen such as nitrogen, ammonia, hydrazine, methylamine, dimethylamine, ethylamine, ethylenediamine, isopropylamine, t- Butylamine, diisopropylamine, diethylisopropylamine, di-t-butylhydrazine, and di-t-butylhydrazine, in the presence of a base such as triethylamine, diisopropylamine, (For example, amines bearing carbon), as well as aromatic containing amines such as anilines, pyridines, and benzylamines. Amines may be primary, secondary, tertiary or quaternary (e.g., tetraalkylammonium compounds). The nitrogen-containing reactant may contain heteroatoms other than nitrogen, for example, hydroxylamine, t-butyloxycarbonylamine and Nt-butylhydroxylamine are nitrogen-containing reactants . Another example is nitrous oxide.

In the case where the protective film comprises oxygen-for example, an oxygen-containing polymer-, an oxygen-containing reactant may be used. Oxygen - for example, by containing the reaction materials are not limited to, oxygen, ozone, nitrous oxide, nitrogen monoxide, nitrogen dioxide, carbon monoxide, carbon dioxide, sulfur, sulfur dioxide, an oxygen-containing hydrocarbon of (C _x H _y O _z), water , Acyl halides, acid anhydrides, mixtures thereof, and the like. The disclosed precursors are not intended to be limiting.

In certain embodiments where the protective coating comprises an organic polymer, the first reactant may be an acyl halide (e.g., a diacyl halide) such as acyl chloride (e.g., diacyl chloride), (other acyl halides May be used in some cases). Fluorinated acyl halide analogs (e. G., Fluorinated analogs of diacyl halide, e. G., Fluorinated analogs of diacyl chlorides) may be used in some embodiments. In various embodiments, the first reactant material of the diacyl chloride is ethanedioyl dichloride (also referred to as oxalyl dichloride, ClCOCOCl), malonyl dichloride (also referred to as malonyl chloride, CH ₂ ) _2), succinyl dichloride (also referred to as succinyl chloride, ClCOCH ₂ CH ₂ COCl), pentanedionate days dichloride (also referred to as glutaryl chloride, ClCO (CH _{2) 3} COCl), or their . ≪ / RTI > Similarly, in some embodiments, the first reactant is a fluorinated analog of ethanedioyl dichloride, a fluorinated analog of malonyl chloride, a fluorinated analog of succinyl dichloride, a fluorine of pentanedioyl dichloride, Or an analogue thereof, or combinations thereof. In some other embodiments, the first reactant may be an acid anhydride such as an anhydride of a dicarboxylic acid generating all of the above diacyl chlorides. Fluorinated analogs of acid anhydrides may also be used. An example of an acid anhydride which may be used is maleic anhydride (or a fluorinated analog of maleic anhydride). In other embodiments, the first reactant may be an organometallic-containing precursor, and an example of an organometallic-containing precursor is TMA (trimethylaluminum).

In these or other embodiments in which the protective coating comprises an organic polymer, the second reactive material may be a diamine. In certain embodiments, the diamine is fluorinated. In some cases, the diamine is 1,2-ethane diamine (also referred to as ethylene _{diamine, (NH 2 (CH 2)} 2 NH 2)), 1,3- propanediamine _{(NH 2 (CH 2) 3} NH 2) , 1,4-butane diamine _{(NH 2 (CH 2) 4} NH 2), 1,2- ethane diamine of fluorinated analog of the fluorine of 1, 3-propanediamine Chemistry analog of the 1,4-butanediamine Fluorinated analogs, or combinations thereof. The second reactant may in some cases be a diol. The diols may or may not be fluorinated. Exemplary diols include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, fluorinated analogs of ethylene glycol, fluorinated analogs of 1,3-propanediol, Or analogues thereof, or combinations thereof. The second reactant may be thiol in some cases. The thiol may or may not be fluorinated. Exemplary thiols include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, fluorinated analogs of 1,2-ethanedithiol, 1,3-propanedithiol Fluorinated analogs, fluorinated analogs of 1,4-butanedithiol, or combinations thereof. In certain embodiments, the second reactant is a selectively fluorinated trifunctional compound such as (±) -3-amino-1,2-propanediol, glycerol, bis (hexamethylene) triamine, melamine , Diethylenetriamine, (±) -1,2,4-butanetriol, cyanuric chloride, fluorinated analogues of (±) -3-amino-1,2-propanediol, fluorinated Analogs, fluorinated analogues of bis (hexamethylene) triamine, fluorinated analogs of melamine, fluorinated analogs of diethylenetriamine, fluorination of (±) -1,2,4-butanetriol , Fluorinated analogs of cyanuric chloride, or combinations thereof.

In various embodiments, any combination of bidentate reactive materials that enable MLD may be used to form a protective film. One or both of the bidentate reactants may comprise fluorine. The fluorine may be present in one or more C-F bonds and / or N-F bonds.

In certain embodiments, malonyl chloride may be used with ethylenediamine to form a polyamide protective coating. In another example, either or both of malonyl chloride and ethylenediamine are provided in a fluorinated form to form a fluorinated polyamide protective coating.

Although it is not limited to the exemplary purge gas comprises He, Ar, Ne, H _2, N _2, and combinations thereof.

Other reactive materials may also be used as known by those skilled in the art. For example, where the protective film comprises a metal, a carbon-containing reactive material may be used where a metal-containing reactive material may be used and the protective film comprises carbon.

Some specific examples of reactant combinations will be provided, but these examples are not intended to be limiting. In one example, malonyl chloride is adsorbed onto the surface of the substrate to form a precursor film. The precursor film may be exposed to ethylenediamine to form a protective organic polymer film as shown in Figs. 2C and 2D. In another example described in connection with FIG. 2e, the fluorinated analog of malonyl chloride may be adsorbed onto the surface of the substrate to form a precursor film, and the precursor film may then be subjected to a thermal treatment to form a fluorinated protective organic polymer film Lt; / RTI > is exposed to the fluorinated analog. The reaction may occur without exposure to the plasma, but instead requires thermal energy to drive the reaction. These reactants appear to react without plasma energy at relatively low temperatures, as described above.

As noted above, the precursor (s) used to form the protective layer may have relatively low adhesion coefficients, thereby enabling the precursors to penetrate deeply into the etched features. In some cases, the adhesion coefficient (in the related deposition conditions) of the precursors may be less than or equal to about 0.05, e.g., less than or equal to about 0.001.

The choice of reactants may be influenced by a plurality of factors. These factors may include toxicity, flammability, availability, cost, quality life, ease of delivery / use, and the like. Generally, the fluorinated analogues of the various reactants described herein may be somewhat less volatile than the corresponding non-substituted portions. As such, one or more reactive materials may be vaporized or otherwise atomized prior to delivery to the reaction chamber. Reactant delivery systems commonly used in connection with liquid reactants in ALD / CVD systems may be readily configured for this purpose.

In certain embodiments, the inner surfaces of the reaction chamber may be heated during one or more steps. For example, the reaction chamber surfaces may be heated during deposition of the protective film and / or during etching. The use of heated reaction chamber surfaces may minimize the extent to which the reactants condense on these surfaces. That is, heating the inner surfaces of the reaction chamber helps to keep these inner surfaces as clean as possible, and reduces the risk that any build on these surfaces will adversely affect the entire etching process. In certain embodiments, the inner chamber surfaces (e.g., one or more of the chamber walls, the ceiling, the substrate support, the showerhead, etc.) may be maintained at a temperature of about 40 to about 200 DEG C during the deposition of the protective film and / And may be heated to a temperature of 60 to 150 ° C.

The reaction mechanism may be cyclical (e. G., ALD or MLD) or continuous (e. G., CVD). Any deposition method that results in the formation of the protective sidewall film with high aspect ratios may be used. As noted, ALD and MLD reactions may be particularly well suited for this purpose due to conformal and adsorption-based mechanisms. However, other types of reactions may be used as long as the film can be formed with high aspect ratios to deeply protect the sidewalls in the etched features.

Briefly, plasma-assisted ALD reactions include the following actions: (a) transfer of a first reactant to form an adsorbed precursor layer, (b) selective purge operation to remove a first reactant from the reaction chamber, (c) transfer of a second reactant (often provided in the form of a plasma), wherein the plasma energy drives the reaction between the first reactant and the second reactant, (d) And (e) repeating (a) to (d) until the film reaches the desired thickness.

Similarly, the MLD reaction can be carried out in a variety of manners including: (a) transfer of a first reactant to form an adsorbed precursor layer, (b) selectable purge operation to remove a non-adsorbed first reactant from the reaction chamber, c) driving the reaction between the first reactant and the second reactant to transfer the second reactant, wherein the thermal energy forms a protective film; d) activating a selectable purge for removal of unadsorbed reactants and by- (E) repeating (a) - (d) until the protective film reaches the desired thickness. The first reactant and the second reactant may be delivered in a gas phase, and the reaction may occur without the use of a plasma.

Since the reactants are provided at individual times and the reaction is a surface reaction in the case of ALD and MLD methods, the membrane may be adsorbed to some extent. The adsorption-based regime results in the formation of highly conformal films that can significantly lining the entire depth of the features. In various instances, the protective coating may be partially deposited along a substantial portion of the length / depth of the etched features. In some cases, the protective film may be deposited along at least about 80%, at least about 90%, or at least about 95% of the length / depth of the features. In certain embodiments, the protective film is deposited along the entire length / depth of the feature. In contrast, plasma-assisted CVD reactions involve continuously transferring the reactant (s) to the substrate while the substrate is exposed to the plasma. CVD reactions are gas phase reactions that depress reaction products on the substrate surface.

The following reaction conditions may be used in certain embodiments in which the deposition reaction occurs via MLD methods. The conditions are described with respect to the method 250 shown in FIG. 2B. In operation 251, the first reactant may flow into the reaction chamber. In certain embodiments, the first reactant may flow at a rate of about 0.1 to 5000 sccm, such as about 500 to 2000 sccm, for a duration of about 0.1 to 30 s, such as about 0.2 to 5 s . In operation 253, the reaction chamber may be selectively purged for a duration of about 0.05 to 10 s, for example, about 0.2 to 3 s. Or may be generated by evacuating the evacuating reaction chamber and / or by flowing an inert gas through the reaction chamber. When an inert gas is used, the inert gas may flow at rates of about 20 to 5000 sccm in some cases. Next, at operation 255, the second reactant material may flow into the reaction chamber. In certain embodiments, the second reactant may flow at a rate of about 10 to 5000 sccm, or about 500 to 2000 sccm, for a duration of about 0.1 to 30 s, such as about 0.2 to 5 s.

The thermal energy may be provided to drive the reaction between the first reactant and the second reactant. The thermal energy can be used mainly to the extent that it is controlled by the temperature of the substrate. In some cases, the thermal energy may be regulated by controlling the substrate temperature through the substrate support / pedestal. In these or other instances, the thermal energy may be provided by transferring reactants at specific temperatures. In some cases, the temperature of the substrate may be maintained at about -10 to 350 캜, such as about 0 to 200 캜, or about 10 to 100 캜, or about 20 to 50 캜. In certain embodiments, the substrate is maintained at a temperature of about 200 DEG C or less, about 100 DEG C or less, about 50 DEG C or less, or about 30 DEG C or less. In these or other embodiments, the temperature of one or both of the reactant gases delivered to the reaction chamber (and / or the inert gases used to purge) may correspond to the substrate temperatures listed in this paragraph. At operation 257, the reaction chamber may be selectively purged using the conditions described above with respect to operation 253. At act 259, it is determined whether the protective film is sufficiently thick. If not, the method may be repeated from operation 251. In certain instances, the pressure in the reaction chamber may be about 1 to 4 Torr. In various instances, in each iteration of act 205 or 215 in Figure 2a, the protective film may be depotted for a duration of less than about 10 minutes.

In certain embodiments, the ends of the molecules forming the organic polymer film form a hydroxyl, amine, or thiol. For example, if a diamine is used as the second reactant, -NH ₂ may form the ends of the molecules forming the organic polymer film. If a diol is used as the second reactant, -OH may form the ends of the molecules forming the organic polymer film. Similarly, if a thiol is used as the second reactant, -SH may form the ends of the molecules forming the organic polymer film.

In certain embodiments, the first reactant and the second reactant, which are used to form the organic polymer film, are deposited on the plasma or process gas exposed surface of the vacuum chamber such that the deposited organic polymer film layer has a maximum thickness, Or the first reactant and the second reactant may flow into the vacuum chamber until about 100% saturation is reached on the process gas exposed surface. Unfolding and supersaturation may also be performed in some embodiments, for example, to tailor the deposition rate as desired.

For example, FIG. 3e shows a graph of percent saturation of the first reactant (malonyl chloride) to be deposited on the surface of the coupon in a vacuum chamber with a sustained pressure of about 2 Torr. The first reactant flows into the doses each lasting about 1 second and the purge gas flows between each of the doses of the first reactant for about 5 seconds. As shown in Figure 3E, malonyl chloride, the first reactant, reaches about 100% saturation at about 8 dots.

Figure 3f shows a graph of percent saturation of a second reactant (ethylenediamine) to be deposited on the surface of the coupon in a vacuum chamber with a sustained pressure of about 2 Torr. The second reactant flows into the doses each lasting about 1 second and the purge gas flows between each of the doses of the second reactant for about 5 seconds. As shown in Figure 3F, the second reactant, ethylenediamine, reaches about 100% saturation at about 3 dots.

3g is a graph of mass change (ng / cm2) versus time (seconds) during about one hundred deposition cycles, wherein each cycle comprises the delivery of malonyl chloride, the first reactant flowing for about one second, And a final purge flow of about 5 seconds wherein the deposition cycles are carried out in a vacuum chamber having a sustained pressure of about 2 Torr, the surface of the coupon To form an organic polymer film. As shown in Figure 3g, the mass change is directly proportional to the number of cycles performed.

Figure 3h is an exploded view of the graph of Figure 3g and shows a graph of mass change (ng / cm2) over time (seconds) of about four deposition cycles of the 100 deposition cycles of Figure 3g. In this figure, R1 corresponds to the times at which the first reactant (malonyl chloride) is delivered, and R2 corresponds to the times at which the second reactant (ethylenediamine) is delivered.

Figure 3i shows the organic polymer film composition of the deposited film in accordance with the flow periods shown in Figures 3g and 3h. As shown in Figure 3i, the organic polymer film comprises N-H, C-H, C = O, and C-N bonds and is consistent with the configuration of the polyamide material.

The reaction conditions herein are provided as guidance and are not intended to be limiting.

V. apparatus

The methods described herein may be performed by any suitable device or combination of devices. Suitable devices include hardware for achieving process operations and a system controller having instructions for controlling process operations according to the present invention. For example, in some embodiments, the hardware may include one or more process stations included in the process tool. One process station may be an etching station and another process station may be a deposition station. In yet another embodiment, etching and deposition occurs within a single station / chamber.

4A-4C illustrate an embodiment of an adjustable gap capacitively coupled limited RF plasma reactor 400 that may be used to perform the etching operations described herein. As shown, the vacuum chamber 402 includes a chamber housing 404 enclosing an interior space for housing the lower electrode 406. In the upper portion of the chamber 402, the upper electrode 408 is vertically spaced from the lower electrode 406. The planar surfaces of the upper and lower electrodes 408 and 406 are substantially parallel and orthogonal to the vertical direction between the electrodes. Preferably, the upper and lower electrodes 408 and 406 are circular and coaxial with respect to the vertical axis. The lower surface of the upper electrode 408 faces the upper surface of the lower electrode 406. The spaced apart electrode surfaces define an adjustable gap 410 between the electrode surfaces. During operation, the lower electrode 406 is supplied with RF power by an RF power supply (matching) 420. RF power is supplied to the lower electrode 406 via the RF supply conduit 422, the RF strap 424 and the RF power member 426. The ground shield 436 may surround the RF power member 426 to provide a more uniform RF field to the lower electrode 406. The wafer is inserted through the wafer port 482 and is in contact with the gap 410 on the lower electrode 406 for processing, as described in co-owned U. S. Patent 7,732, 728, the entire content of which is incorporated herein by reference. And the process gas is supplied to the gap 410 and excited into the plasma state by the RF power. The upper electrode 408 may be powered or grounded.

In the embodiment shown in Figs. 4A to 4C, the lower electrode 406 is supported on the lower electrode support plate 416. Fig. An insulator ring 414 interposed between the lower electrode 406 and the lower electrode support plate 416 insulates the lower electrode 406 from the support plate 416.

The RF bias housing 430 supports the lower electrode 406 on the RF bias housing bowl 432. The ball 432 is connected to the conduit support plate 438 via an opening in the chamber wall plate 418 by the arm 434 of the RF bias housing 430. In the preferred embodiment, the RF bias housing ball 432 and the RF bias housing arm 434 are integrally formed into one component, while the arm 434 and ball 432 are also two bolted together or joined together May be individual components.

The RF bias housing arm 434 is connected to the RF power supply and to the outside of the vacuum chamber 402 in the space on the backside of the lower electrode 406 for RF power and facilities, e.g., gas coolant, liquid coolant, RF energy, And one or more hollow passageways for passing electrical signals and electrical monitoring from the vacuum chamber 402 into the vacuum chamber 402. RF supply conduit 422 is isolated from RF bias housing arm 434 and RF bias housing arm 434 provides a return path for RF power to RF power supply 420. The facility conduit 440 provides a path for the facility components. Additional details of the facility components are described in U.S. Patent Nos. 5,948,704 and 7,732,728 and are not shown here for the sake of brevity. The gap 410 is preferably surrounded by a confinement ring assembly or a shroud (not shown), the details of which can be found in commonly owned U. S. Patent No. 7,740, 736, incorporated herein by reference . The interior of the vacuum chamber 402 is maintained at a low pressure by connection to a vacuum pump through a vacuum portal (480).

The conduit support plate 438 is attached to an actuation mechanism 442. Details of the operating mechanism are described in co-owned U.S. Patent No. 7,732,728, incorporated herein by reference. An actuating mechanism 442, such as a servo motor, stepper motor or the like, is attached to the vertical linear bearing 444 by a screw gear 446, such as a ball screw, and a motor for rotating the ball screw. During operation to resize the gap 410, the actuation mechanism 442 moves along the vertical linear bearing 444. 4A illustrates an apparatus when the actuation mechanism 442 is in a high position on a linear bearing 444 generating a small gap 410a. 4B illustrates the device when the actuation mechanism 442 is in an intermediate position on the linear bearing 444. [ As shown, the lower electrode 406, the RF bias housing 430, the conduit support plate 438, and the RF power supply 420 both move lower toward the chamber housing 404 and the upper electrode 408 and it generates an intermediate-size gap (410 b).

Figure 4c illustrates a larger gap (410 c) when the operating mechanism (442) is in a low position on the linear bearing. Preferably, the upper and lower electrodes 408, 406 remain coaxial during the gap adjustment and the opposing surfaces of the upper and lower electrodes remain parallel across the gap.

This embodiment can be applied to the CCP chamber 402 during multi-step process recipes (BARC, HARC, and STRIP, etc.) to maintain a uniform etch across large diameter substrates or flat panel displays, for example 300 mm wafers. And the gap 410 between the lower and upper electrodes 406, 408 within the cavity. In particular, the chamber belongs to a machine that allows linear movement, which is essential to provide an adjustable gap between the lower and upper electrodes 406,408.

FIG. 4A illustrates bellows 450 deflected to the side, sealed to the conduit support plate 438 at the proximal end and to the stepped flange 428 of the chamber wall plate 418 at the distal end. The inner diameter of the stepped flange defines an opening 412 in the chamber wall plate 418 through which the RF bias housing arm 434 passes. The distal end of the bellows 450 is clamped by the clamp ring 452.

The laterally biased bellows 450 provides a vacuum seal while allowing vertical movement of the RF bias housing 430, the conduit support plate 438, and the actuation mechanism 442. RF bias housing 430, conduit support plate 438, and actuation mechanism 442 may be referred to as cantilever assemblies. Preferably, the RF power supply 420 may move with the cantilever assembly and be attached to the conduit support plate 438. 4B shows the bellows 450 in the neutral position when the cantilever assembly is in the intermediate position. 4C shows the bellows 450 deflected sideways when the cantilever assembly is in the low position.

A labyrinth seal 448 provides a particle barrier between the bellows 450 and the interior of the plasma processing chamber housing 404. The fixed shield 456 is removable from the chamber wall plate 418 to the chamber housing (not shown) to provide a labyrinth groove 460 (slot) in which the movable shield plate 458 moves vertically to receive the vertical movement of the cantilever assembly 404). ≪ / RTI > The outer portion of the removable shield plate 458 remains in the slot at all the vertical positions of the lower electrode 406.

The labyrinth seal 448 is affixed to the inner surface of the chamber wall plate 418 at the periphery of the opening 412 in the chamber wall plate 418 defining the labyrinth ridge groove 460. In this embodiment, Shielding portion 456. A removable shield plate 458 is attached and extends radially from the RF bias housing arm 434 through which the arm 434 passes through the opening 412 in the chamber wall plate 418. While the movable shield plate 458 is spaced from the shield 456 fixed by the first gap and away from the inner surface of the chamber wall plate 418 by a second gap, which allows the cantilever assembly to move vertically, Extend into the rinse groove (460). The labyrinth seal 448 is moved into the bellows 450, which blocks the movement of broken particles from the bellows 450 and enters the vacuum chamber interior 405 and allows the radicals to form later breaking deposits Thereby blocking radicals from the process gas plasma.

Figure 4a is a cantilever assembly and location shows a (small gaps (410 a)) movable shield plate 458 at a position higher than in the RF bias housing arm 434, labyrinth groove 460 above, when it is in . Figure 4c is a cantilever assembly is shown a low position (large gap (410 c)) movable shield plate 458 at a lower position than in the RF bias housing arm 434, labyrinth groove 460 above, when it is in . Figure 4b is a cantilever assembly is the middle position when in the (intermediate gap (410 b)) showing a movable shield plate 458 in the neutral or intermediate position in the labyrinth groove 460. Although the labyrinth seal 448 is shown symmetrical with respect to the RF bias housing arm 434, in other embodiments the labyrinth seal 448 may be asymmetric with respect to the RF bias arm 434. [

Figure 5 provides a simplified block diagram illustrating various reactor components arranged to implement the deposition methods described herein. As shown, the reactor 500 is operative to include a plasma generated by a capacitive-discharge type system including a showerhead 514 that cooperates with a grounded heater block 520, And enclosing process chamber 524. A high frequency (HF) radio frequency (RF) generator 504 and a low frequency (LF) RF generator 502 may be coupled to the matching network 506 and the showerhead 514. The frequency and power supplied by the matching network 506 may be sufficient to generate a plasma from the process gases supplied to the process chamber 524. For example, the matching network 506 may provide HFRF power of 50 W to 500 W. [ In some instances, the matching network 506 may provide HFRF power of 100 W to 5000 W and LFRF power total energy of 100 W to 5000 W. In a typical process, the HFRF component may be 5 MHz to 60 MHz, e.g., 13.56 MHz. In operations with an LF component, the LF component may be from about 100 kHz to 2 MHz, for example, 430 kHz.

Within the reactor, the wafer pedestal 518 may support the substrate 516. The wafer pedestal 518 may include a chuck, fork, or lift pins (not shown) for holding and moving the substrate between the deposition and / or plasma treatment reactions and during deposition and / Not shown). The chuck may be an electrostatic chuck, a mechanical chuck or various other types of chuck that can be used in industry and / or research.

Various process gases may be introduced through the inlet 512. A plurality of source gas lines (510) are connected to the manifold (508). The gases may or may not be premixed. Appropriate valve and mass flow control mechanisms may be employed to ensure that the correct process gases are delivered during the deposition and plasma processing phases of the process. In the case where the chemical precursor (s) are delivered in liquid form, liquid flow control mechanisms may be employed. The liquid may then be vaporized and mixed with other process gases during its movement in the heated manifold above the vaporization point of the chemical precursor supplied in liquid form prior to reaching the deposition chamber.

The process gases may exit the chamber 524 through the outlet 522. A vacuum pump, such as a one- or two-stage mechanical drying pump and / or a turbomolecular pump 504, draws process gases from the process chamber 524 and generates a throttle valve May be used to maintain a suitable low pressure within the process chamber 524 by using a closed loop controlled flow rate limiting device such as a pendulum valve.

As discussed above, techniques for the deposition discussed herein may be implemented in a multi-station or single station tool. In specific implementations, a 300 mm Lam Vector ^TM tool with a 4-station deposition scheme or a 200 mm Sequel ^TM tool with a 6-station deposition scheme may be used. In some implementations, tools for processing 450 mm wafers may be used. In various implementations, it may be indexed after each deposition and / or post-deposition plasma treatment, or may be indexed after etch operations if etch chambers or stations are part of the same tool, Tasks and processes may be performed in a single station prior to indexing the wafer.

In some embodiments, an apparatus configured to perform the techniques described herein may be provided. Appropriate devices may include a system controller 530 having instructions for controlling process operations in accordance with the disclosed embodiments as well as hardware for performing various process operations. The system controller 530 is configured to execute instructions to perform the techniques in accordance with the disclosed embodiments and to communicate with the various process control equipment, e.g., valves, RF generators, wafer handling systems, One or more memory devices and one or more processors coupled to the memory array. A machine-readable medium including instructions for controlling process operations in accordance with the present disclosure may be coupled to the system controller 530. [ The system controller 530 may be coupled to various hardware devices, such as mass flow controllers, valves, RF generators, etc., to facilitate control of various process parameters associated with deposition operations, Vacuum pumps, etc. < / RTI >

In some embodiments, the system controller 530 may control all of the activities of the reactor 500. The system controller 530 may execute system control software stored on a mass storage device, loaded into a memory device, and executed on a processor. The system control software may include instructions for controlling the timing of gas flows, wafer movement, RF generator activation, etc., as well as instructions for controlling the chamber and / or station pressure, chamber and / or station temperature, wafer temperature, , RF power levels, substrate pedestal, chuck, and / or susceptor locations, and other parameters of the particular process performed by the reactor apparatus 500. The system control software may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of the process tool components required to perform the various process tool processes. The system control software may be coded in any suitable computer readable programming language.

The system controller 530 may typically include one or more memory devices and one or more processors configured to execute instructions for a device to perform the techniques in accordance with the present disclosure. A machine-readable medium containing instructions for controlling process operations in accordance with the disclosed embodiments may be coupled to the system controller 530. [

One or more process stations may be included in the multi-station processing tool. Figure 6 shows a schematic diagram of an embodiment of a multi-station processing tool 600 having an inbound load lock 602 and an outbound load lock 604, one or both of which may include a remote plasma source. At atmospheric pressure, the robot 606 is configured to move wafers from the cassettes loaded through the pods 608 to the inbound load lock 602 via the atmospheric port 610. [ The wafer is placed on the pedestal 612 in the inbound load lock 602 by the robot 606 and the standby port 610 is closed and the load lock is pumped down. If the inbound load lock 602 includes a remote plasma source, the wafer may be exposed to remote plasma processing in the loadlock before it is introduced into the processing chamber 614. In addition, the wafer may also be heated in the inbound load lock 602, for example, to remove moisture and adsorbed gases. Next, the chamber transfer port 616 to the processing chamber 614 is opened and another robot (not shown) places the wafer in the reactor on the pedestal of the first station shown in the reactor for processing. It will be appreciated that the illustrated embodiment includes loadlocks, but in some embodiments a wafer may be provided directly into the process station.

The illustrated processing chamber 614 includes four process stations numbered from 1 to 4 in the embodiment shown in FIG. Each station has a heated pedestal (shown as 618 for station 1), and gas line inflows. It will be appreciated that, in some embodiments, each of the process stations may have different or multiple purposes. For example, each of the process stations 1 to 4 may be a chamber for performing one or more of ALD, CVD, CFD, or etching (any of which may be plasma assisted). In one embodiment, at least one of the process stations is a deposition station having a reaction chamber as shown in Fig. 5, and at least one of the other process stations has a reaction chamber as shown in Figs. 4A to 4C Etching station. It will be appreciated that although the illustrated processing chamber 614 includes four stations, the processing chamber according to this disclosure may have any suitable number of stations. For example, in some embodiments, the processing chamber may have five or more stations, while in other embodiments, the processing chamber may have three or fewer stations.

Figure 6 also illustrates one embodiment of a wafer handling system 609 for transferring wafers within the processing chamber 614. [ In some embodiments, the wafer handling system 609 may transfer wafers between various process stations and / or between the process station and the load lock. It will be appreciated that any suitable wafer handling system may be employed. Non-limiting examples include wafer carousels and wafer handling robots. Figure 6 also illustrates one embodiment of a system controller 650 that is employed to control process conditions and hardware states of the process tool 600. [ The system controller 650 may include one or more memory devices 656, one or more mass storage devices 654, and one or more processors 652. The processor 652 may include a CPU or computer, analog input / output connections and / or digital input / output connections, stepper motor controller boards, and the like.

In some implementations, the controller is part of a system that may be part of the above described examples. Such systems may include semiconductor processing equipment, including processing tools or tools, chambers or chambers, processing platforms or platforms, and / or specific processing components (wafer pedestal, gas flow system, etc.) . These systems may be integrated into an electronic device for controlling their operation prior to, during, and after the processing of a semiconductor wafer or substrate. An electronic device may also be referred to as a "controller" that may control various components or sub-components of the system or systems. The controller may control the delivery of, for example, processing gases, temperature settings (e.g., heating and / or cooling), pressure settings, vacuum settings, power RF configuration parameters, RF matching circuit settings, frequency settings, flow rate settings, fluid delivery settings, location and operation settings, tools and other delivery tools And / or any of the processes disclosed herein, including wafer transfers into and out of load locks that are interfaced or interfaced with a particular system.

Generally speaking, the controller may be implemented with various integrated circuits, logic, memory, and / or software that receive instructions and issue instructions, control operations, enable cleaning operations, enable endpoint measurements, May be defined as an electronic device. The integrated circuits may be implemented as chips that are in the form of firmware that stores program instructions, digital signal processors (DSPs), chips that are defined as application specific integrated circuits (ASICs), and / or one that executes program instructions (e.g., Microprocessors, or microcontrollers. The program instructions may be instructions that are passed to the controller or to the system in the form of various individual settings (or program files) that define operating parameters for executing a particular process on a semiconductor wafer or semiconductor wafer. In some embodiments, the operating parameters are configured to achieve one or more processing operations during fabrication of one or more layers, materials, metals, oxides, silicon, silicon dioxide, surfaces, circuits, and / It may be part of the recipe specified by the process engineer.

The controller, in some implementations, may be coupled to or be part of a computer that is integrated into the system, coupled to the system, or otherwise networked to the system, or a combination thereof. For example, the controller may be all or part of a factory host computer system capable of remote access to wafer processing, or may be in a "cloud ". The computer monitors the current progress of manufacturing operations, examines the history of past manufacturing operations, examines trends or performance metrics from a plurality of manufacturing operations, changes parameters of current processing, and performs processing steps following current processing Or may enable remote access to the system to start a new process. In some instances, a remote computer (e.g., a server) may provide process recipes to the system via a network that may include a local network or the Internet. The remote computer may include a user interface that enables input or programming of parameters and / or settings to be communicated from the remote computer to the system at a later time. In some instances, the controller receives instructions in the form of data that specify parameters for each of the processing operations to be performed during one or more operations. It should be appreciated that these parameters may be specific to the type of tool that is configured to control or interfere with the controller and the type of process to be performed. Thus, as described above, the controllers may be distributed, for example, by including one or more individual controllers networked together and cooperating together for common purposes, e.g., for the processes and controls described herein. An example of a distributed controller for this purpose is one or more integrated on a chamber communicating with one or more integrated circuits located remotely (e. G., At the platform level or as part of a remote computer) Circuits.

Exemplary systems include, but are not limited to, a plasma etch chamber or module, a deposition chamber or module, a spin-rinse chamber or module, a metal plating chamber or module, a cleaning chamber or module, a bevel edge etch chamber or module, a physical vapor deposition ) Chambers or modules, chemical vapor deposition chambers or modules, atomic layer deposition (ALD) chambers or modules, MLD (molecular layer deposition) chambers or modules, atomic layer etch chambers or modules, A track chamber or module, and any other semiconductor processing systems that may be used or associated with manufacturing and / or fabrication of semiconductor wafers.

As described above, depending on the process operations or operations to be performed by the tool, the controller may be used to transfer materials to move the containers of wafers to / from tool positions and / or load ports in a semiconductor manufacturing plant. May communicate with one or more of other tool circuits or modules, other tool components, cluster tools, other tool interfaces, adjacent tools, neighboring tools, tools located all over the plant, main computer, other controllers or tools.

In certain embodiments, the controller has instructions for performing the operations shown and described with respect to FIG. 2A. For example, the controller can include: (a) instructions for performing an etching operation to partially etch a feature on a substrate, (b) instructions for depositing a protective sidewall coating in the etched feature without substantially etching the substrate Instructions. The instructions may relate to performing these processes using the disclosed reaction conditions. The instructions may also, in some implementations, relate to transferring the substrate between the etch chamber and the deposition chamber.

Returning to the embodiment of FIG. 6, in some embodiments, the system controller 650 controls all of the activities of the process tool 600. The system controller 650 executes the system control software 658 stored in the mass storage device 654 and loaded into the memory device 656 and executed on the processor 652. [ Alternatively, the control logic may be hard-coded in the system controller 650. Applications Specific Integrated Circuits (ASICs), Programmable Logic Devices (PLDs) (e.g., field-programmable gate arrays, or FPGAs), etc. may be used for these purposes. In the following discussion, when "software" or "code" is used, functionally comparable hardcoded logic may be used in place. The system control software 658 may control the timing and / or the temperature of the substrate and / or the substrate, the chamber and / or the station pressure, the chamber and / or station temperature, the wafer temperature, the target power levels, the RF power levels, Or susceptor locations, and other parameters of the particular process performed in the process tool 600. [ The system control software 658 may be configured in any suitable manner. For example, various process tool component subroutines or control objects may be written to control the operation of the process tool components required to perform the various process tool processes. The system control software 658 may be coded in any suitable computer readable programming language.

In some embodiments, the system control software 658 may include input / output control (IOC) sequencing instructions for controlling the various parameters described above. For example, each of the phases of the ALD undercoating deposition process may include one or more instructions for execution by the system controller 650. Instructions for setting process conditions for ALD process phases may be included in the corresponding ALD recipe phase. In some embodiments, ALD recipe phases may be serially arranged such that all instructions for the ALD process phase are executed concurrently with this process phase.

Other computer software and / or programs stored in mass storage device 654 and / or memory device 656 associated with system controller 650 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.

The substrate positioning program may include program code for process tool components used to load the substrate on the pedestal 618 and to control the space between the substrate and other portions of the process tool 600.

The process gas control program may include code for controlling gas composition and flow rates and for selectively flowing gas into one or more process stations prior to deposition to stabilize pressure within the process station. In some embodiments, the controller includes instructions for depalletizing the nanolaminate protective layer on the core layer, and instructions for depoforming the conformal layer over the protective layer.

The pressure control program may include code for controlling the pressure in the process station, for example, by adjusting the throttle valve of the exhaust system of the process station, the gas flow to the process station, and the like. In some embodiments, the controller includes instructions for depalletizing the nanolaminate protective layer on the core layer, and instructions for depoforming the conformal layer over the protective layer.

The heater control program may include a code for controlling the current to the heating unit used to heat the substrate. Alternatively, the heater control program may control the transfer of heat transfer gas (such as helium) to the substrate. In certain embodiments, the controller includes instructions for depalletizing the nanolaminate protective layer to a first temperature, and instructions for depalletizing the conformal layer over the protective layer to a second temperature, wherein the second temperature is Is higher than the first temperature.

The plasma control program may include code for setting RF power levels and exposure times within one or more process stations in accordance with the embodiments herein. In some embodiments, the controller includes instructions for depalletizing the nanolaminate protection layer with a first RF power level and a first RF duration, and a second RF power level and a second RF duration, Lt; RTI ID = 0.0 > layer < / RTI > The second RF power level and / or the second RF duration may be higher / higher than the first RF power level / first duration.

In some embodiments, there may be a user interface associated with the system controller 650. The user interface may include graphical software displays of a display screen, device and / or process conditions, and user input devices such as pointing devices, keyboards, touchscreens, microphones,

In some embodiments, the parameters adjusted by the system controller 650 may be related to process conditions. Non-limiting examples include process gas composition and flow rates, temperature, pressure, plasma conditions (such as RF bias power levels and exposure times), and the like. These parameters may be provided to the user in the form of a recipe, which may be entered using a user interface.

Signals for monitoring the process may be provided by the analog input and / or digital input connections of system controller 650 from various process tool sensors. Signals for controlling the process may be output on the analog output interface and the digital output interface of the process tool 600. Non-limiting examples of process tool sensors that may be monitored include mass flow controllers, pressure sensors (such as manometers), thermocouples, and the like. Properly programmed feedback and control algorithms may be used with data from these sensors to maintain process conditions.

The system controller 650 may provide program instructions for implementing the above described deposition processes. The program instructions may control various process parameters such as DC power level, RF bias power level, pressure, temperature, and so on. The instructions may control these parameters to operate the in-sequence positions of the film stacks in accordance with various embodiments described herein.

The system controller will typically include one or more memory devices and one or more processors configured to execute instructions to perform the method according to the present invention. A machine-readable, non-volatile medium including instructions for controlling process operations in accordance with the disclosed embodiments may be coupled with the system controller.

The various hardware and method embodiments described above may be used in conjunction with lithographic patterning tools or processes for manufacturing or fabricating, for example, semiconductor devices, displays, LEDs, photoelectric panels, and the like. Typically, these tools / processes are not necessarily, but will be used or implemented together in a common manufacturing facility.

7 illustrates a semiconductor process cluster architecture with various modules for interfacing with a vacuum transfer module (VTM) The configuration of transport modules for "transporting " substrates between a plurality of storage facilities and processing modules may be referred to as a" cluster tool architecture "system. An airlock 730, also known as a loadlock or transfer module, is shown in the VTM 738 with four processing modules 720a through 720d, each of which may be optimized to perform various manufacturing processes. By way of example, processing modules 720a through 720d perform laser metrology and other defect detection methods and defect identification methods as well as substrate etching, depot, ion implantation, substrate cleaning, sputtering, and / or other semiconductor processes . One or more of the processing modules (any of 720a through 720d) may be configured to deposit protective films on the sidewalls of the recessed features, as described herein, i.e., to etch the recessed features into the substrates , And for other suitable functions in accordance with the disclosed embodiments. The air lock 730 and process modules 720a through 720d may be referred to as "stations ". Each of the stations has a facet 736 that interfaces the station to the VTM 738. Within the facets, sensors 1 through 18 are used to detect the passage of substrate 726 as it is moved between respective stations.

A robot 722 transports substrates between stations. In one implementation, the robot may have one arm, and in another embodiment, the robot may have two arms, each arm picking an end effector 724 for transfer I have. The front-end robot 732 in the atmospheric transfer module (ATM) 740 transfers the substrates from the cassette or a front opening unified pod (FOUP) 734 in the load port module (LPM) 742 to the air lock 730 Or the like. The module center 728 within the process modules 720a through 720d may be in one position for disposing the substrate. The aligner 744 in the ATM 740 may be used to align the substrates.

In an exemplary processing method, the substrate is disposed within one of the FOUPs 734 in the LPM 742. The front-end robot 732 transfers the substrate from the FOUP 734 to the aligner 744, which causes the substrate 726 to be properly centered before the substrate is etched, . After alignment, the substrate is moved into the air lock 730 by the front-end robot 732. Because the airlock modules have the ability to match the environment between ATM and VTM, the substrate can move between two pressure environments without being damaged. From the airlock module 730 the substrate is moved by the robot 722 through the VTM 738 and into one of the process modules 720a through 720d, for example, the process module 720a. To achieve this substrate movement, the robot 722 uses end effectors 724 on each of the arms of the robot. In process module 720a, the substrate undergoes etching as described herein to form a partially etched feature. Next, the robot 722 moves the substrate from the processing module 720a into the VTM 738 and then into the different processing module 720b. In processing module 720b, the protective film is deposited on the sidewalls of the partially etched feature. The robot 722 moves the substrate from the processing module 720b into the VTM 738 and into the processing module 720a where the partially etched features are further etched. The etching / deposition can be repeated until the feature is completely etched.

It should be noted that computer control of substrate movement may be local to the cluster architecture, or may be external to the cluster architecture within the production floor or within a remote location and connected to the cluster architecture via the network.

Lithographic patterning of the film typically includes some or all of the following operations, each enabled using a plurality of possible tools, which may include: (1) using a spin-on tool or a spray-on tool, For example, an operation of applying a photoresist on a substrate having a silicon nitride film formed on the substrate; (2) curing the photoresist using a hot plate or furnace or other suitable curing tool; (3) exposing the photoresist to visible or ultraviolet or x-ray light using a tool such as a wafer stepper; (4) selectively removing resist using a tool such as a wet bench or a spray developer to develop the resist to pattern it; (5) transferring the resist pattern to a film or workpiece placed thereunder by using a dry or plasma assisted etching tool; And (6) removing the resist using a tool such as a RF or microwave plasma resist stripper. In some embodiments, an ashable hardmask layer (e.g., an amorphous carbon layer) and another suitable hard mask (e.g., antireflective layer) may be deposited prior to applying the photoresist.

It is to be understood that the configurations and / or methods described herein are exemplary in nature and that these particular embodiments or examples should not be construed as limiting because a plurality of variations are possible. The particular routines or methods described herein may represent one or more of any number of processing strategies. As such, the various operations illustrated may be performed in an exemplary sequence, in a different sequence, in parallel, or may be omitted in some cases. Likewise, the order of the processes described above may be varied.

It is to be understood that the subject matter of the present disclosure is not limited to all of the novel and obvious combinations of the various processes, systems and configurations, and other features, functions, operations, and characteristics disclosed herein as well as all equivalents thereof, Sub-combinations.

Claims (22)

A method of forming an etched feature in a stack comprising a dielectric material on a semiconductor substrate,
The method comprises:
(a) generating a first plasma including an etch reactant, exposing the substrate to the first plasma, and partially etching the feature within the stack;
(b) after said step (a)
(i) exposing the substrate to a first reactive material and causing the first reactive material to adsorb onto the substrate,
(ii) exposing the substrate to a second reactant, and
(iii) depalletizing the protective film on the sidewalls of the feature by repeating (i) and (ii) until the protective film reaches the target thickness,
The first reactant and the second reactant react with each other to form the protective film, and
Depressurizing the protective film on the sidewalls of the feature, the protective film being a fluorinated organic polymer film and being substantially deposited along the entire depth of the feature; And
(c) repeating steps (a) and (b) until the feature is etched to a final depth, wherein the protective film deposited in step (b) (A) and (b) substantially avoiding lateral etching of the features, and wherein the features have an aspect ratio of at least about 5 at a final depth of the feature. ≪ / RTI > The method according to claim 1,
Wherein depositing the protective film in step (b) is accomplished without exposing the substrate to plasma energy. 3. The method of claim 2,
Wherein the first reactant comprises an acyl halide or an acid anhydride and the second reactant comprises at least one of a diamine, a diol, a thiol, and a trifunctional compound, and wherein the first reactant and the second Wherein at least one of the reactants is a fluorine-containing reactant. The method of claim 3,
Wherein the first reactive material comprises a diacyl chloride. 5. The method of claim 4,
Wherein the first reactive material comprises a fluorinated analog of malonyl chloride or malonyl chloride. The method of claim 3,
Wherein the second reactive material comprises a diamine. The method according to claim 6,
Wherein the second reactive material comprises a fluorinated analog of ethylenediamine or ethylenediamine. 8. The method of claim 7,
Wherein the first reactive material comprises a fluorinated analog of malonyl chloride or malonyl chloride. The method of claim 3,
Wherein the first reactant is selected from the group consisting of ethanedioyl dichloride, a fluorinated analog of ethanedioyl dichloride, malonyl chloride, a fluorinated analog of malonyl chloride, succinyl dichloride, succinyl dichloride, At least one material selected from the group consisting of analogs, pentanedioyl dichloride, fluorinated analogs of pentanedioyl dichloride, maleic anhydride, and fluorinated analogs of maleic anhydride; And the second reactant is selected from the group consisting of 1,2-ethanediamine, a fluorinated analog of 1,2-ethanediamine, 1,3-propanediamine, a fluorinated analog of 1,3-propanediamine, 1,4- Fluorinated analogues of 1,4-butanediamine, ethylene glycol, fluorinated analogs of ethylene glycol, 1,3-propanediol, fluorinated analogs of 1,3-propanediol, 1,4-butanediol, Fluorinated analogs of 1,4-butanediol, 1,2-ethanedithiol, fluorinated analogs of 1,2-ethanedithiol, 1,3-propanedithiol, 1,3-propanedithiol, (±) -3-amino-1,2-propanediol, (±) -3-amino-1,2-dicarboxylic acid, Fluorinated analogues of propanediol, glycerol, fluorinated analogues of glycerol, bis (hexamethylene) triamine, fluorinated analogues of bis (hexamethylene) triamine, melamine, melamine Fluorinated analogs of diethylenetriamine, diethylenetriamine, fluorinated analogues of diethylenetriamine, (±) -1,2,4-butanetriol, (±) -1,2,4- The fluorinated analog of the cyanuric chloride, the analog, the cyanuric chloride, and the fluorinated analog of cyanuric chloride. 10. The method according to any one of claims 1 to 9,
Wherein the protective film comprises a fluorinated polyamide and / or a fluorinated polyester. The method of claim 3,
Depositing the protective film of step (b) occurs in the reaction chamber, and depalletizing the protective film of step (b) comprises at least one reaction during the respective repetition of step (b) ≪ / RTI > further comprising purging the chamber. 10. The method according to any one of claims 1 to 9,
Depositing the protective film of step (b) comprises purging the reaction chamber at least twice during each iteration of step (b), wherein the first spreading comprises purging the first reaction material in step (i) (Ii), and a second spread occurs between the transfer of the second reactant and the subsequent transfer of the second reactant in (ii) and subsequent to the transfer of the second reactant in (ii) A method for forming an etched feature in a stack that occurs between transfers of reactive material. 10. The method according to any one of claims 1 to 9,
At the final depth, the features may include (i) an aspect ratio of at least about 20, and (ii) a feature having a maximum critical dimension not greater than about 10% greater than the critical dimension at the bottom of the feature Lt; / RTI > 10. The method according to any one of claims 1 to 9,
The feature is formed during formation of the VNAND device, and wherein the stack comprises (i) a silicon oxide material, and (ii) alternating layers of a silicon nitride material or a polysilicon material to form an etched feature in the stack Way. 10. The method according to any one of claims 1 to 9,
Wherein the features are formed during formation of a DRAM device, and wherein the dielectric material comprises silicon oxide. 10. The method according to any one of claims 1 to 9,
Wherein the features have an aspect ratio of at least about 50 at a final depth of the features. 10. The method according to any one of claims 1 to 9,
Wherein said step (a) and said step (b) are repeated at least once, and said step (b) comprises the step of applying an etched feature in the stack, which may or may not be performed using the same reactants during each iteration Lt; / RTI > An apparatus for forming an etched feature in a stack comprising a dielectric material on a semiconductor substrate,
The apparatus comprises:
Wherein the at least one reaction chamber is designed or configured to perform etching and the at least one reaction chamber is designed or configured to perform deposition,
An inlet for introducing process gases into the reaction chamber, and
An outlet for removing material from the reaction chamber, the at least one reaction chamber; And
As a controller,
(a) instructions for generating an etch plasma comprising an etch reactant, exposing the substrate to the etch plasma, and partially etching the feature in the stack, wherein the instruction (a) is designed to perform etching Or in the reaction chamber configured;
(b) after said instruction (a)
(i) exposing the substrate to a first reactive material and causing the first reactive material to adsorb onto the substrate,
(ii) exposing the substrate to a second reactant, and
(iii) instructions for depalletizing the protective film on the sidewalls of the feature by repeating (i) and (ii) until the protective film reaches the target thickness,
The first reactant and the second reactant react with each other to form the protective film, and
The protective film is a fluorinated organic polymer film and is substantially deposited along the entire depth of the feature; instructions (b) for depalletizing the protective film on the sidewalls of the feature; And
(c) instructions to repeat the instruction (a) and the instruction (b) until the feature is etched to a final depth, wherein the protective film deposited in the instruction (b) (A) and (b) instructions for repeating said instruction (b) substantially preventing lateral lateral etching of said feature and said feature having an aspect ratio of at least about 5 at a final depth of said feature And the controller. ≪ Desc / Clms Page number 17 > 19. The method of claim 18,
The reaction chamber designed or constructed to perform etching such that both the instruction (a) and the instruction (b) occur in the same reaction chamber is the same as the reaction chamber designed or constructed to perform the deposition, Device for forming a feature. 19. The method of claim 18,
The reaction chamber designed or constructed to perform etching is different from the reaction chamber designed or configured to perform deposition and the controller is configured to perform a deposition with the reaction chamber designed or configured to perform etching, Further comprising instructions for transferring the substrate between reaction chambers. ≪ RTI ID = 0.0 > 8. < / RTI > 21. The method according to any one of claims 18 to 20,
Wherein the controller comprises instructions for depalletizing the protective film in the instruction (b) without the use of plasma. A method of forming an etched feature in a stack comprising a dielectric material on a semiconductor substrate,
The method comprises:
(a) generating a first plasma including an etch reactant, exposing the substrate to the first plasma, and partially etching the feature within the stack;
(b) depositing a protective film on the sidewalls of the feature after said step (a), said protective film being a fluorinated organic polymer film and being substantially deposited along the entire depth of the feature, Depalletizing the protective film on the sidewalls of the feature; And
(c) repeating steps (a) and (b) until the feature is etched to a final depth, wherein the protective film deposited in step (b) (A) and (b) substantially avoiding lateral etching of the features, and wherein the features have an aspect ratio of at least about 5 at a final depth of the feature. ≪ / RTI >

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