Method for depositing silicon-free carbon-containing film as gap-fill layer by pulse plasma-assisted deposition

Method for depositing silicon-free carbon-containing thin films as gap-filling layers by pulsed plasma-assisted deposition

METHOD FOR DEPOSITING SILICON-FREE CARBON-CONTAINING FILM AS GAP-FILL LAYER BY PULSE PLASMA-ASSISTED DEPOSITION

This invention generally relates to a method of depositing a silicon-free carbon-containing film as a gap-filling layer in a trench by pulsed plasma assisted deposition.

In the manufacturing of integrated circuits such as those used for shallow trench isolation, inter-metal dielectric layers, passivation layers, etc., it is often necessary to use insulating materials to fill trenches (usually with an aspect ratio of 1 or higher any recess). However, with the miniaturization of the wiring pitch of large integrated circuit (Large Scale Integration, LSI) components, due to the limitations of the existing deposition process, hole-free filling of high aspect ratio spaces (for example, aspect ratio (AR) 3) has become a problem. It becomes more and more difficult.

Figure 2 schematically illustrates a schematic cross-sectional view of a trench undergoing a conventional plasma-enhanced CVD process that undergoes gap filling in sequence (a) and (b). In the traditional plasma-enhanced CVD process, since the plasma reaction occurs in the gas phase and the reaction products accumulate on the surface of the substrate, the film at the top of the trench 103 of the substrate 101 grows faster than inside the trench 103 . Therefore, when layer 102 is deposited, protrusions 104 are necessarily formed as shown in (a). In addition, since in the traditional CDV process, deposition is performed layer by layer, so when the next layer 105 is deposited on this layer 102, the upper opening of the trench 103 is closed, leaving a hole 106 inside the trench 103, as shown in (b) shown.

3 schematically illustrates a schematic cross-sectional view of a trench undergoing a conventional gap filling process using inhibitors in order (a), (b) and (c). By depositing the inhibitor 202 in the trench 201 and inhibiting the reaction product from accumulating on the surface coated with the inhibitor, as shown in (b), the reaction product will not accumulate on the top surface and top of the trench 201 , but accumulates at the bottom of the trench 201 to achieve bottom-up fill 203, as shown in Figure (c). However, it is difficult to find the appropriate combination of inhibitors and activators and process conditions suitable for deposition. In many cases this is impractical.

Figure 4 schematically illustrates a schematic cross-sectional view of a trench undergoing a conventional gap filling process in the order of (a) and (b) using a highly anisotropic process. The highly anisotropic process is usually an ion-driven deposition method, in which layers are deposited by plasma reaction through ion bombardment of ion-containing plasma, so the anisotropic deposition layer 302 is on the top surface and the deposition layer 303 is on the trench 301 The inside is used as bottom growth filler, as shown in (b). However, when the trench is deep, in order to use ions to bombard the bottom region of the trench, it is necessary to make the mean free path of the ions longer to reach the bottom region by, for example, significantly reducing the high vacuum pressure, which is usually costly and impractical.

Figure 5 schematically illustrates a schematic cross-sectional view of a trench undergoing a conventional void filling process in the order of (a) and (b), or (c) and (d) using a volume expansion process ((d) shows the loading effect). After depositing layer 402 on the surface of substrate 405 having trenches 401 as shown in (a), the layer can be expanded, for example by oxidizing it, thereby increasing the volume or thickness of the layer and closing the voids. (Trench) 401, as shown in (b). However, as shown in (c), when the trench is composed of a narrow trench 401 and a wide trench 403, due to the loading effect (that is, the change in filling speed depending on the pattern density is called the "loading effect"), Even when the narrow trench is closed, the wide trench remains significantly open 404, as shown in (d). Furthermore, as the layers expand and close the trench, the facing layers push against each other, thus exerting stress on the sidewalls of the trench as indicated by the arrows in (d), often causing the trench to Partial or visibly collapsed structure.

Figure 6 shows the deposition used in (a), dry etching using different etchants in (b) to (d), and (e) to (g) corresponding to (b) to (d) respectively. STEM image of a cross-sectional view of a trench undergoing a conventional gap-fill process for the second deposited combination. By combining deposition and etching, the layout or geometry of the gap-fill trenches can be tuned. However, as shown in Figure 6, regardless of the type of etchant ((b) and (e) (CF ₄, CHF in (c) and (f) ₃, and C in (d) and (g) ₄F ₈), etching and subsequent deposition do not fill the initial holes in the narrow trenches. In addition, as shown in Figure 6, the loading effect is obvious. In addition, this process is time consuming since at least the deposition is repeated with etching in between.

Figure 7 schematically illustrates a schematic cross-sectional view of a trench undergoing a conventional gap filling process in sequence (a) and (b) using a flowable material. Since liquid or viscous gas is flowable and naturally moves to the bottom of the trench, by using this liquid or viscous gas, the trench 502 formed in the substrate 501 can be filled with the flowable material to form a bottom growth filler. 503, as shown in figure (b). Typically, to keep the material flowable, the substrate temperature is kept at a low temperature, such as 50°C or lower. This process is very fast and efficient. Although loading effects are evident, this is usually not a problem as all trenches can be overfilled, followed by CMP. However, this material is often of poor quality and requires additional curing steps. Furthermore, when the trench is narrow, the surface tension of the flowable material interferes with or even prevents the flowable material from entering the trench interior. Figure 8 schematically illustrates a schematic cross-sectional view of a trench undergoing a conventional gap filling process using a flowable material, and illustrates the aforementioned issues. In this process, the flowable state of the precursor is achieved by polymerization in the reaction chamber, which occurs when another precursor is mixed in the gas phase above the substrate, that is, before reaching the substrate surface and/or Occurs immediately after contact with the top surface of the substrate. By polymerization with another precursor in the gas phase, said precursor changes to a flowable state immediately before reaching the substrate surface and/or upon contact with the top surface of the substrate while its temperature is maintained at a very low temperature. In any case, the flowable state is always achieved before entering the trench. Therefore, as shown in Figure 8, the flowable material 504 does not enter the trench 502 of the substrate 501, and due to the surface tension of the flowable material 504, the top opening of the trench 502 is blocked by the mass 505 and prevents the flowable material 504 Enter trench 502. Additionally, to create a flowable state of the precursor, the process always uses oxygen and nitrogen, sometimes hydrogen chemistry, and/or the precursor must have a very low vapor pressure.

In view of traditional gap filling techniques, one embodiment of the present invention provides complete gap filling through plasma-assisted deposition using hydrocarbon precursors, during which virtually no formation occurs without the need for nitrogen, oxygen or hydrogen plasma. holes. Embodiments may address one or more of the previously discussed issues.

Any discussion of related problems and solutions in the related art is included in this specification merely to provide a background for the present invention, and it should not be considered that any or all discussions were known at the time of completion of the present invention.

In certain embodiments, it is an object of the present invention to provide a silicon (Si)-free carbon (C) film with filling capabilities. In certain embodiments, this can be accomplished by forming a viscous polymer in the gas phase by striking an Ar or He plasma in a chamber filled with a volatile unsaturated or cyclic hydrocarbon precursor, which can be The precursor polymerizes during plasma shock within certain parameters that define the dominant partial pressure and wafer temperature. The viscose phase flows at the bottom of the trench and fills the trench with a thin film with seamless bottom growth capabilities. In some embodiments, this process is best demonstrated using cyclopentene as a precursor; however, many other unsaturated or cyclic hydrocarbon compounds can be used alone or in any combination. In some embodiments, preferably, the process uses only silicon-free hydrocarbon precursors and inert gases to impact the plasma. In some embodiments, preferably, the process uses ALD-like process conditions (recipe) (for example, feeding/blowing/plasma impact/blowing), in which the blowing after feeding is automatically strict. Shorten to leave a high partial pressure of precursor during plasma shock. This is clearly different from ALD chemistry or agency.

The aforementioned process may be based on pulsed plasma CVD, which also provides good filling capabilities for the resulting film, although ALD-like process conditions may be more beneficial, as discussed below.

In certain embodiments, critical aspects of flowability of the deposited film include: <br/>) High enough partial pressure during the entire RF-ON period for the polymerization/chain growth of the process; <br/>) Enough energy to activate the reaction (defined by RF-ON cycle and RF power), the RF-ON cycle will not be too long; and <br/>) The temperature and pressure of polymerization/chain growth are set above the melting point of the mobile phase but below the boiling point of the deposited material.

Certain objects and advantages of the invention are described herein for the purpose of briefly describing aspects of the invention and advantages achieved over the prior art. Of course, it is to be understood that not all such objects or advantages may necessarily be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will appreciate that the invention may be embodied or carried out in a manner that achieves or optimizes an advantage or set of advantages as taught in this specification, rather than in a manner that achieves as may be taught or suggested in this specification. Other purposes or advantages.

The aspects, features and advantages of the present invention will become more apparent from the following embodiments.

In this specification, "gas" may include evaporated solids and/or liquids, and may consist of a single gas or a mixture of certain gases, depending on the implementation context. Likewise, depending on the context of implementation, the quantifier "a" means a species or a genus that includes multiple species. In the present invention, the process gas introduced into the reaction chamber through the gas showerhead (showerhead) may consist of, substantially consist of, or consist of the silicone-free precursor and the additive gas. The added gas may include a plasma-generated gas that excites the precursor to deposit amorphous carbon when RF power is applied to the added gas. The added gas can be an inert gas, which can be fed into the reaction chamber as a carrier gas and/or a diluent gas. The added gas may not include reactive gases for oxidizing or nitriding the precursor. Alternatively, the added gas may comprise a reactive gas for oxidizing or nitriding the precursor to an extent that does not interfere with plasma polymerization to form an amorphous carbon-based polymer. Furthermore, in certain embodiments, the added gas only contains inert gases. Precursors and additional gases can be introduced into the reaction space as mixed gases or as separate gases. A carrier gas such as a rare gas can be used to introduce the precursor. Gases other than process gases (ie, gases not introduced through the gas shower heads) may be used, for example, to seal the reaction space, including sealing gases such as rare gases. In certain embodiments, the term "precursor" generally refers to a compound that participates in a chemical reaction to generate another compound, and specifically refers to a compound that constitutes the film matrix or the main skeleton of the film, whereas the term "reactant" means something other than Compounds other than precursors that activate precursors, modify precursors, or catalyze reactions of precursors, where the reactants can provide elements (such as N, C) to the film matrix and become part of the film matrix when RF power is applied part. The term "noble gas" means a plasma-generated gas that excites precursors when RF power is applied, but unlike the reactants, does not become part of the film matrix.

In certain embodiments, "thin film" means a layer that extends substantially continuously in a direction perpendicular to the thickness direction, without pinholes, covering the entire target or associated surface; or a layer that only covers the target or associated surface. In certain embodiments, "layer" means a structure having a specific thickness formed on the surface of a film or non-film structure or the like. A film or layer may consist of a discrete single film or layer, or multiple films or layers, having certain characteristics, and the boundaries between adjacent films or layers may or may not be opaque and may be based on physics, chemistry, and/or or any other feature, formation process or sequence, and/or function or purpose of adjacent films or layers. Furthermore, in this specification, any two variable numbers may constitute a feasible range of the variable, since the feasible range may be determined based on conventional work, and any range specified may include or exclude endpoint values. In addition, any value for a specified variable (whether or not expressed as "about") may be considered an exact value or an approximation and includes equivalent values, and in some embodiments may refer to an average, median, or representative value. , majority, etc. Furthermore, in the present disclosure, in some embodiments, the terms "consisting of and "having independently mean "generally or broadly including, "comprising, "consisting essentially of or "consisting of. In this specification, in certain embodiments, any defined meaning does not necessarily exclude a common and customary meaning.

In this specification, "continuous" means no vacuum is broken; no timeline is interrupted; no material is intervening in a step; no processing conditions are changed, followed by no change in processing conditions as the next step; or except in certain embodiments. There is no intervening discrete physical or chemical structure between the two structures other than the two structures in .

In this specification, the term "filling ability" means filling that is substantially free of holes (for example, no holes with a diameter of about 5 nm or more) and slits (for example, no slits with a length of about 5 nm or more). Void capability, where a seamless/void-free bottom upward growth of a layer is observed, with growth at the void bottom being at least about 1.5 times faster than growth on the void sidewalls and on the top surface with voids. Films with filling capabilities are also called "flowable films" or "sticky films." The flowable or viscous behavior of the film often manifests itself as a concave surface at the bottom of the trench. For example, FIG. 13 shows a STEM photograph of a cross-sectional view of a trench having different opening sizes (widths) undergoing a gap filling cycle, in accordance with one embodiment of the present invention. As shown in Figure 13, flowable films exhibit growth rates at least about 1.5 times faster on the trench bottom than on the trench sidewalls and top surfaces. For comparison, for example, Figure 23 shows STEM pictures of cross-sectional views of trenches with different opening sizes (widths) where a film without filling capability was deposited (using the same precursor as in Figure 13). As shown in Figure 23, the non-flowable film showed growth at the bottom of the trench at about the same rate as the top surface and showed no substantial concavity at the bottom.

Liquidity can be determined by the following table: &lt;br/&gt;1 <tables><table><table border="1" borderColor="#000000" width="85%"><tbody><tr><td>Bottom/Top Ratio (B/T) &lt;br/&gt;</td><td>fluidity &lt;br/&gt;</td></tr><tr><td>0&lt;B/T&lt;1 &lt;br/&gt;</td><td>none &lt;br/&gt;</td></tr><tr><td>1 B/T &lt;1.5 &lt;br/&gt;</td><td>bad &lt;br/&gt;</td></tr><tr><td>1.5 B/T &lt;2.5 &lt;br/&gt;</td><td>good &lt;br/&gt;</td></tr><tr><td>2.5 B/T &lt;3.5 &lt;br/&gt;</td><td>very good &lt;br/&gt;</td></tr><tr><td>3.5B/T &lt;br/&gt;</td><td>very good &lt;br/&gt;</td></tr></tbody></table></table></tables>

B/T means the ratio of the thickness of the film deposited at the bottom of the trench to the thickness of the film deposited on the top surface forming the trench before filling the trench. Typically, wide trenches with an aspect ratio of about 1 or less are used to evaluate flowability, typically since the higher the aspect ratio of the trench, the higher the B/T ratio becomes. For example, Figure 11 shows a middle and wide trench undergoing a gap fill cycle in (a), a middle and narrow trench undergoing a gap fill cycle in (b), and a narrow trench undergoing a gap fill cycle in (c) STEM pictures of cross-sectional views of trenches where the narrow trench, the middle trench, and the wide trench have the dimensions shown in Table 2 below. As shown in Figure 11, since the B/T ratio becomes higher when the aspect ratio of the trench is high, flowability is usually evaluated when films are deposited in wide trenches with an aspect ratio of about 1 or less. .

Table 2 (Values are approximate) <tables><table><table border="1" borderColor="#000000" width="85%"><tbody><tr>&lt;td /&gt;<td>opening [nm] &lt;br/&gt;</td><td>Depth[nm] &lt;br/&gt;</td><td>Aspect Ratio (AR) &lt;br/&gt;</td></tr><tr><td>narrow &lt;br/&gt;</td><td>30 &lt;br/&gt;</td><td>90 &lt;br/&gt;</td><td>3 &lt;br/&gt;</td></tr><tr><td>Moderate &lt;br/&gt;</td><td>70 &lt;br/&gt;</td><td>90 &lt;br/&gt;</td><td>1.3 &lt;br/&gt;</td></tr><tr><td>Width &lt;br/&gt;</td><td>100 &lt;br/&gt;</td><td>90 &lt;br/&gt;</td><td>0.9 &lt;br/&gt;</td></tr></tbody></table></table></tables>

As mentioned above, once the trench is filled, the "growth" rate defined by thickness decreases; however, since this is a flowable process, volumetric growth should be considered. Usually, every nm ³The growth of is constant throughout the deposition step, although the Z (vertical) direction growth becomes faster the narrower the trench. Furthermore, as the precursor flows to the bottom of the recesses, once all trenches, holes or other recesses are filled, growth proceeds in a typical manner through a planarization effect regardless of geometry, resulting in a substantially flat surface as shown in Figure 10. 10 shows a deep trench undergoing a gap filling cycle repeated 242 times in (a) and a trench with different opening sizes (widths) undergoing a gap filling cycle repeated 242 times in (b), according to one embodiment of the present invention. STEM photo of a cross-sectional view of the trench. In certain embodiments, the growth rate of a conventional flowable film on a flat surface (eg, blanket deposition) is in the range of 0.01 to 10 nm/cycle.

In this specification, recesses between adjacent protruding structures and any other recess patterns are referred to as "grooves." That is, the trench is any recessed pattern containing holes/vias, and in certain embodiments, the holes/vias have a width of about 20 nm to about 100 nm (typically about 30 nm to about 50 nm) (where When the length of the trench is essentially the same as its width, it is called a hole/via, and its diameter is approximately 20 nm to approximately 100 nm), its depth is approximately 30 nm to approximately 100 nm (typically approximately 40 nm to approximately 60 nm), and Aspect ratio is about 2 to about 10 nm (usually about 2 to about 5). The appropriate size of the trench can vary based on process conditions, film composition, intended application, etc.

When, for example, volatile hydrocarbon precursors are polymerized and deposited on the substrate surface through plasma, the fluidity of the film is temporarily obtained, in which the gaseous monomers (precursors) are activated or segmented by the energy provided by the plasma gas discharge, so Polymerization is initiated, and when the resulting polymeric material is deposited on the substrate surface, the material displays temporarily flowable behavior. When the deposition step is completed, the flowable film is no longer flowable but solidified, so a separate solidification process is not required.

It is often difficult to schematically illustrate the reaction equations when hydrocarbons polymerize because plasma chemistry is very complex and the exact nature of the plasma reactions is difficult to characterize and is largely unknown.

Depositing flowable films is known in the art; however, conventional deposition of flowable films uses chemical vapor deposition (CVD) with the continuous application of RF power, because pulsed plasma-assisted deposition methods such as PEALD are difficult to deposit conformal films. It is well known that the conformal film is a film having characteristics diametrically opposed to those of a flowable film. I In certain embodiments, the flowable film is a silicon-free, carbon-containing film composed of an amorphous carbon polymer, and although any suitable hydrocarbon precursor or precursors may be used, in certain embodiments, the precursor Includes unsaturated or cyclic hydrocarbons with a vapor pressure of 1,000 Pa or higher at 25°C. In certain embodiments, the precursor is at least one selected from the group consisting of: C2-C8 alkynes (C _nH _2n-2), C2-C8 alkenes (C _nH _2n), C2-C8 dienes (C _nH _n+2), C3-C8 cycloalkenes (cycloalkenes), C3-C8 annulene (C _nH _n), C3-C8 cycloalkanes and the aforementioned alternative hydrocarbons. In certain embodiments, the precursor is ethylene, acetylene, propene, butadiene, pentene, cyclopentene, benzene, Styrene, toluene, cyclohexene and/or cyclohexane.

If there are no desired halide, N or O contaminants in the film, it is best if the precursor does not have this element in its functional groups. However, if this is not a problem, hydrocarbon compounds having amine, alcohol, acid functional groups, etc. can be used as precursors.

Saturated hydrocarbons are generally not preferred; however, they can be used as long as they polymerize at high partial pressures of plasma activation.

For liquids, the vapor pressure is preferably higher than 1,000 Pa, preferably higher than 10,000 Pa at 25°C. For example, at 25°C, the vapor pressure of cyclopentene is 53,000 Pa.

In certain embodiments, volatile hydrocarbon precursors polymerize within specific parameters defined primarily by precursor partial pressure during plasma shock, wafer temperature, and reaction chamber pressure. In order to adjust the "precursor partial pressure", an indirect process knob (dilution gas flow) is usually used to control the precursor partial pressure. In order to control the fluidity of the deposited film, the absolute value of the precursor partial pressure is not required. Instead, the ratio of the precursor flow rate to the remaining gas flow rate at the reference temperature and the total pressure of the reaction space can be used as actual control parameters. If the precursor is very dilute, chain growth stops before the liquid behavior of a liquid-rich phase can be exhibited, or, as in standard plasma CVD deposition, polymerization does not occur at all. If the precursor gas ratio (ratio of precursor flow rate to total gas flow rate) is low during the entire period of plasma shock, no or little bottom-up growth fill (Bottom-up) is observed, assuming constant total pressure and temperature. fill) (this assumption applies when discussing precursor gas ratios unless otherwise stated). At low precursor gas ratios, polymerization may occur to some extent, but the supply is too low to form long enough polymer chains to have liquid-like behavior. In certain embodiments, the precursor gas ratio is in the range of about 10% to about 100%, preferably about 50% to about 90%.

In some embodiments, this parameter range is adjusted as shown in the following table: &lt;br/&gt;3 (Values are approximate) <tables><table><table border="1" borderColor="#000000" width="85%"><tbody><tr><td> &lt;br/&gt;</td><td>Low <b>←</b>sticky <b>→</b>high &lt;br/&gt;</td></tr><tr><td>Precursor partial pressure (Pa) &lt;br/&gt;</td><td>&gt;50 &lt;br/&gt;</td><td>Preferably &gt;200 &lt;br/&gt;</td></tr><tr><td>Wafer temperature (°C) &lt;br/&gt;</td><td>-10 to 200 &lt;br/&gt;</td><td>Preferably 50 to 150 &lt;br/&gt;</td></tr><tr><td>Total pressure (Pa) &lt;br/&gt;</td><td>300 to 101325 &lt;br/&gt;</td><td>Preferably &gt;500 &lt;br/&gt;</td></tr></tbody></table></table></tables>

As for pressure, high pressure is best for flowability because gravity is the driving force for the film to flow at the bottom. As for temperature, low temperatures are best for flow (this is not intuitive), although high temperatures favor polymer chain growth rates. For example, the phase transition between gas precursor and solidification can be shown in the following table: &lt;br/&gt;4 <tables><table><table border="1" borderColor="#000000" width="85%"><tbody><tr><td>chain length &lt;br/&gt;</td><td>X &lt;br/&gt;</td><td>5x &lt;br/&gt;</td><td>10x &lt;br/&gt;</td></tr><tr><td>state &lt;br/&gt;</td><td>gaseous &lt;br/&gt;</td><td>liquid &lt;br/&gt;</td><td>solid state &lt;br/&gt;</td></tr></tbody></table></table></tables>

Alternatively or more, curing can occur upon contact with the substrate, where the reaction is thermally activated. As for the precursor gas ratio, a high precursor gas ratio is best for mobility because at low precursor partial pressures, although polymerization may occur, the supply is too low to form long enough polymer chains to have a liquid-like state the behavior of. As for the RF-on time, the RF-on time is optimal. Above or below it, the ability to flow to the bottom is reduced (best depends on other process parameters). It should be noted that changing these process parameters significantly changes the bottom-up growth process tolerance. For example, when observing the fluidity of a deposited film at 50°C and a pressure of 500 Pa, one needs to change the pressure to at least 700 Pa at 75°C while keeping all other parameters constant. The same goes for pressure, temperature, and precursor gas ratios.

Figure 12 shows a diagram showing a schematic relationship between process parameters and flowability obtained using the data analysis software JMP® according to an embodiment of the present invention (PEALD-like method). The upper vertical axis ("top/bottom") means the ratio of (top thickness of isolation area)/(bottom thickness of isolation area), which is the reciprocal of the B/T ratio, where a ratio of 1 means that the deposited film has no flow, While a ratio of 0 indicates that the deposited film has full or complete fluidity. The lower vertical axis ("Desirability") means the degree of desired mobility on a scale of 0 to 1, where 1 represents completely satisfactory mobility and 0 represents completely unsatisfactory mobility. These graphs were obtained using the data analysis software JMP®, which determines the impact of each process parameter on flow based on available experimental data through modeling and statistical analysis. This software allows this information without complete data at each parameter set point (e.g., to obtain the void effect of fluidity, complete data at each pressure, each temperature, etc., and combinations thereof would not be required) . For example, the middle graph shows the relationship between pressure (total pressure) and T/B ratio, which shows that a pressure of 1100 Pa is optimal in this data set. Likewise, the graph shows that a He flow rate of 0.5 slm, a gap of 16 mm and a temperature of 50°C is optimal.

Flowable films can be deposited by Plasma-enhanced Atomic Layer Deposition (PEALD) and by Plasma-enhanced Chemical Vapor Deposition using pulsed plasma. PECVD) deposition. Typically, however, pulse feeds (on-off pulses) are used PECVD of pulse)) is not the best because when no precursor is fed to the reaction space while RF power is applied to the reaction space, the precursor partial pressure becomes too low. The precursor partial pressure at the reference temperature used to deposit flowable films should be greater than the precursor partial pressure used to deposit non-flowable films because a relatively high molar concentration of the precursor is required at the reference temperature while applying RF power to make the plasma Polymerize so that the plasma reaction product is continuously formed in the gas phase by PECVD and is continuously deposited on a substrate in which trenches form holes (as shown in Figure 2), or when the plasma reaction product is transmitted through PEALD The surface reaction is only formed on the surface (where the bottom growth type structure cannot be formed in the trench), and a flowable film can be deposited. In some embodiments, in PEALD, by shortening the duration of the blow, the precursor on the top surface can be mainly removed, while the precursor in the trench can remain in the trench and the precursor is exposed to When plasma is applied, a more viscous polymer is formed in the trench than on the top surface, and the viscous polymer also flows to the bottom of the trench, thus forming a layer with a concave surface at the bottom. As mentioned previously, in PEALD, by substantially deficient or shortening the purge after precursor feed, the molar concentration of the precursor in the trench can remain relatively high at the reference temperature when RF power is applied to the reaction space. In certain embodiments, the purge after the precursor feed is so shortened that the precursor partial pressure at the reference temperature in the trench after the shortened purge can be considered to be substantially the same as the current precursor feed to the reaction. Precursor partial pressure at reference temperature in space. It should be noted that the foregoing process is obviously different from traditional PEALD; however, for convenience, in this specification, the foregoing process may be referred to as a PEALD-like process or simply PEALD, where PEALD refers to a process using a device for PEALD.

In certain embodiments, the purge duration (in seconds) after precursor feeding during the ALD cycle is 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0 , 3.0, 4.0, 5.0, and the range is between any two aforementioned values, which depends on the chamber volume, the distance between the upper and lower electrodes, feeding time, blowing time, total gas flow, and vapor pressure of the precursor (The dose also depends on the ambient temperature and the amount of precursor remaining in the storage bottle, etc.) etc., which can be determined by a person skilled in the art through traditional experiments based entirely on this specification. In some embodiments, in a PEALD-like process and PECVD using continuous or pulsed plasma, the precursor flow rate (sccm) is 50, 100, 150, 200, 300, 400, 500, 600, 700, and ranges Between any two of the aforementioned values, it also depends on the aforementioned factors. In certain embodiments, the precursor feed duration (in seconds) in the ALD cycle is 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, 3.0, 4.0, 5.0 , and in a PEALD-like process, the range is between any two aforementioned values, which also depends on the aforementioned factors. In certain embodiments, the RF power is applied for a duration (in seconds) of 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, 3.0, 4.0, 5.0, and a range Between any two of the aforementioned values, it also depends on the aforementioned factors. In certain embodiments, the blowout duration (in seconds) after RF power application is 0.0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, 3.0, 4.0 , 5.0, and the range is between any two of the aforementioned values, which also depends on the aforementioned factors.

9 schematically illustrates the aforementioned PEALD-like process, which shows a schematic cross-sectional view of a trench undergoing a gap filling process in sequence (a), (b), and (c) according to one embodiment of the present invention. In (a), the substrate 31 with trenches 32 is placed in the reaction space, and in (b), the precursor is fed into the reaction space, so that the gas phase precursor 33 is used to fill the trenches 32. Thereafter, the gas phase precursor is exposed to plasma impact, thereby forming a viscous phase directly in the trench 32 (not before reaching the trench, as with standard PECVD, nor after reaching the trench, as with standard PEALD), which is deposited in the trench 32, but also flows into the trench 32, where the viscous substance (polymer) 36 accumulates at the bottom of the trench 32 (for illustrative purposes, the surface is schematically represented as a plane), however little is observed on the side walls of deposition 35, and in (c) only a thin layer 34 is deposited on the top surface. This plasma polymerization process does not require nitrogen, oxygen, or hydrogen as reactants; or chamber pressure limitations.

Although flowable films can be deposited by a PEALD-like process and can be deposited by PECVD using constant plasma or pulsed plasma, there are benefits to using a PEALD-like process. For example, it is beneficial when the precursor intermittently changes from gas to liquid phase during deposition, as a constant liquid phase will be more likely to have surface tension problems (which are highly dependent on structure and the narrower the trenches, the more severe the problem becomes ), as shown in Figure 8. In addition, PECVD using pulsed plasma is obviously more precursor-consuming than the PEALD-like process.

As mentioned above, in order to achieve the mobility of the precursor, the partial pressure of the precursor at the reference temperature is one of the important parameters in the reaction space, because the molar concentration of the precursor can be expressed as follows: &lt;br/&gt;/V = p/RT (ideal gas law) &lt;br/&gt;where T: thermodynamic temperature, P: pressure, n: mass of substance, V: volume, and R: gas constant.

Therefore, if the deposition temperature becomes higher, the partial pressure of the precursor used for deposition should also become higher to maintain the same molar concentration. If the temperature is constant, the molar concentration of the precursor directly corresponds to the partial pressure of the precursor, which can be regarded as a control process parameter. In addition, if the RF power application period is extended in a PEALD-like process, the molar concentration of the precursor in the trench will decrease toward the end of the period, resulting in insufficient molecular weight of the precursor in the trench when exposed to the plasma, resulting in slower deposition. Little or almost no flowable material, or solidification of deposited flowable material, or cessation of the flowability of the material. On the other hand, if the RF power is applied for too short a period of time, sufficient plasma polymerization cannot occur and, therefore, a flowable film cannot be formed or deposited in the trench. In some embodiments, the RF power application period (period of exposure to plasma) may be in the range of about 0.7 seconds to about 2.0 seconds (preferably about 1.0 seconds to about 2.0 seconds), which range may be applied to PEALD process and PECVD process using pulsed plasma. The plasma exposure time can also be adjusted by changing the distance between the upper and lower electrodes (conductively coupled parallel electrodes), where by increasing the distance, the precursor remains in the reaction space between the upper and lower electrodes The retention time can be extended when the flow rate of the precursor into the reaction space is constant. In some embodiments, the distance (in mm units) between the upper electrode and the lower electrode is 5, 10, 15, 20, 25, 30, and ranges between any two of the aforementioned values. In certain embodiments, the RF power (W) for flowable film deposition (eg, 13.56 MHz) is 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 10,000, and the same Measured for 300-mm wafers, the range is between any two of the aforementioned values, both in a PEALD-like process and a PECVD process using pulsed plasma, which can be converted into units of W/ for wafers of different sizes cm ²。

In the present invention where conditions and/or structures are not specified, in view of the present invention, those skilled in the art can easily provide such conditions and/or structures based on traditional experiments.

In all disclosed embodiments, any element used in the embodiment may be substituted for any equivalent element thereof for the intended purpose, including such elements as are expressly, necessary, or essentially disclosed in this specification. Furthermore, the present invention is equally applicable to devices and methods.

The examples will be explained in conjunction with preferred embodiments. However, the present invention is not limited to the preferred embodiments.

Certain embodiments provide a method for pulsed plasma-assisted deposition of a Si-free C-containing film with filling capabilities using a hydrocarbon precursor in a reaction space to fill patterned recesses in a substrate, wherein when taking When the hydrocarbon precursor is supplied to the reaction space by providing a first partial pressure of the precursor on the patterned recesses of the substrate under process conditions, the Si-free C-containing film without filling capability can use the hydrocarbon precursor in the reaction space. Depositing a reference film on the substrate, the method includes: (i) supplying the hydrocarbon precursor to the reaction space by providing a second partial pressure of the precursor on the patterned recessed portion of the substrate under a second process condition, Wherein when deposited under the second process conditions, the second partial pressure is higher than the first partial pressure to a certain extent that provides a film filling capability; (ii) the substrate is deposited under the second process conditions. Exposing the patterned recesses to a plasma to deposit a Si-free C-containing film with filling capability, wherein the partial pressure of the precursor remains higher than the first partial pressure during the entire period of exposure of the patterned recesses of the substrate to the plasma , so the bottom growth method is used to fill the recessed portion, in which step (ii) is performed intermittently by plasma pulse treatment; and step (i) is performed continuously or intermittently without the overlapping step of step (ii) as a necessary step. (ii).

In certain embodiments, the pulsed plasma assisted deposition method is a pulsed plasma enhanced CVD deposition method, wherein the precursor is continuously supplied to the reaction space in steps (i) and (ii), that is, step (ii) The plasma pulse treatment is performed intermittently, while step (i) is performed continuously.

In some embodiments, the pulsed plasma-assisted deposition method is a plasma-enhanced ALD-like deposition that follows a layout of plasma-enhanced ALD deposition process conditions through repeated deposition cycles. Each cycle includes: step (i), wherein the precursor is supplied in the form of pulses; and step (ii), in which the RF power is applied in the form of pulses without overlapping precursors, that is, step (ii) is performed intermittently by means of plasma pulse processing, and the step (i) performed intermittently without overlapping step (ii) as a necessary step.

In certain embodiments, each cycle of PEALD-like deposition includes: step (i), followed by a blowout; and step (ii), wherein after step (ii), no blowout is performed in each cycle, The duration of the blowing is less than half the duration of step (i), and the duration of step (ii) is more than twice the duration of step (i).

In some embodiments, the second process conditions include a plasma ignition gas flow rate of 0.8 slm or less, a pressure of 900 Pa or greater, and a temperature of 85°C or greater.

In certain embodiments, all gases supplied to the reaction space in steps (i) and (ii) are: precursors; N ₂, Ar, and/or He selective carrier gas; and Ar, He, or N ₂, or a plasma ignition gas of a mixture thereof, wherein the plasma ignition gas contains hydrogen in the range of 0% to 30%. In certain embodiments, a carrier gas is used and is He, N ₂or Ar, and the plasma ignition gas is He, N ₂Or Ar. In certain embodiments, the flow rates (slm) of these selective drying gases are 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, 3.0, 4.0, 5.0, and In PEALD-like processes and PECVD processes using pulsed plasma, the range is between any two of the aforementioned values and also depends on the aforementioned factors. In certain embodiments, Ar or He plasma is used for polymerization without H; however, H addition (e.g., from about 1% to about 30% relative to the total flow rate of the dry gas) does not have a negative impact on the filling properties. . Moreover, O ₂, Ar, and N ₂Additives (eg, from about 1% to about 30% relative to the total flow rate of dry gas) are not detrimental to filling performance.

In some embodiments, the first process conditions include a first process temperature, a first process pressure, a first flow rate of a precursor, a first flow rate of a carrier gas, and a first flow rate of a plasma ignition gas, wherein in step ( In ii), setting the second process by reducing the first process temperature to the second process temperature, increasing the first process pressure to the second process pressure, and/or reducing the first flow rate of the plasma ignition gas conditions without changing the first flow rate of the precursor.

In certain embodiments, steps (i) and (ii) are continued until the patterned recesses are completely filled with the fill-capable film, wherein substantially no holes are formed in the filled recesses (which are visible in the cross-sectional view of the trench). Empty spaces with dimensions of approximately 5 nm or larger can be observed in STEM photographs.

In certain embodiments, when a film with filling capability is deposited on the bottom and side walls of a patterned recess, steps (i) and (ii) are stopped such that the cross-section of the deposited film in the recess has a downward parabola. shaped top surface, wherein the thickness of the deposited film in the recess at the center of the bottom of the recess is at least twice the thickness of the deposited film on the top surface of the substrate, and substantially no holes are formed in the filled recess.

In some embodiments, the method further includes exposing the substrate to Ar or He plasma as a post-deposition treatment after depositing the thin film with filling capability. Periodic H (or O) plasma treatment can be beneficially applied from the standpoint of post-anneal reduction (e.g., 450°C for 30 minutes in a nitrogen environment), RI, dry etch rate properties, and O content. H ₂The effect of the treatment is to form a higher degree of cross-linking in the polymer and stabilize the polymer structure and properties. On the other hand, O ₂The treatment effect is only to oxidize the carbon polymer. In some embodiments of performing a PEALD-like process, periodic plasma treatment may be performed at RF power (W) of 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 10000, and as For measurements on 300 mm wafers, the range is between any two of the aforementioned values, which can be converted into units of W/cm for wafers of different sizes. ², duration (in seconds) 1, 5, 10, 20, 30, 40, 50, 60, and range between any two of the aforementioned values, and in ALD-like cycle/process ratio 1/1, 2/1 , 3/1, 4/1, 5/1, 6/1, 7/1, 8/1, 9/1, 10/1, 20/1, 30/1, 40/1, 50/1.

In some embodiments, the second process conditions include a second process pressure and a second process temperature, wherein the second process temperature is higher than the melting point of the Si-free C-containing film with filling capability, but under the second partial pressure lower than its boiling point.

The embodiments will be explained with reference to the drawings. However, the present invention is not limited to the illustrated drawings.

The continuous flow of carrier gas can be achieved using a flow-pass system (FPS), in which the carrier gas pipeline has a branch pipeline containing a precursor storage tank (storage bottle), and the main line and branch pipeline are switched. When only the carrier gas When the gas is fed into the reaction chamber, the branch line is closed, however when both the carrier gas and the precursor gas are fed into the reaction chamber, the main line is closed and the carrier gas flows through the branch line and out of the storage bottle along with the precursor gas. . In this way, the carrier gas can continuously flow into the reaction chamber, and the precursor gas can be carried in pulses by switching between the main line and the branch line. Figure 1B schematically illustrates a precursor supply system using a flow-through system (FPS) according to one embodiment of the present invention (black valve indicates closed valve). As shown in (a) in Figure 1B, when the precursor is fed to the reaction chamber (not shown), first, a carrier gas such as Ar (or He) flows through the gas line with valves b and c, and then enters Storage bottle (storage tank) 20. The carrier gas flows out from the storage bottle 20, carrying a relative amount of precursor gas corresponding to the internal vapor pressure of the storage bottle 20, and flows through the gas line with valves f and e, and then is fed into the reaction chamber together with the precursor. In the foregoing, valves a and d are closed. When only the carrier gas (inert gas) is fed to the reaction chamber, as shown in (b) in FIG. 1B , the carrier gas flows through the gas line through the valve a while bypassing the storage bottle 20 . In the foregoing, valves b, c, d, e, and f are closed.

Those skilled in the art will appreciate that the apparatus includes one or more controllers (not shown) programmed or configured to perform the deposition and reactor cleaning processes described elsewhere herein. Those familiar with the art will understand that the controller communicates with various power supplies, heating systems, pumps, automated machinery, and gas flow controllers or reactor valves.

For example, any suitable device may be used to perform the process cycle, including the device shown in Figure 1A. Figure 1A is a schematic diagram of a PEALD device that may be used in certain embodiments of the invention and is programmed to perform the following sequence. In this figure, HRF power (13.56MHz or 27MHz) 25 is applied by providing pairs of conductive plate electrodes 4, 2 parallel and facing each other in the interior 11 (reaction zone) of the reaction chamber 3. One side and 12 on the other side are electrically connected to ground, exciting a plasma between the electrodes. A temperature regulator is provided in the lower layer 2 (lower electrode), and the temperature of the substrate 1 placed thereon is kept constant at a specific temperature. The upper electrode 4 also serves as a spray plate. Reactive gas and/or diluent gas (if any exists) and precursor gas are introduced into the reaction chamber 3 through the gas line 21 and the gas line 22 respectively, and pass through the spray plate 4 . In addition, in the reaction chamber 3, a circular pipe 13 having an exhaust pipe 7 is provided through which the gas in the interior 11 of the reaction chamber 3 can be discharged. In addition, the transfer chamber 5 disposed below the reaction chamber 3 has a sealing gas line 24 to introduce the sealing gas into the interior 11 of the reaction chamber 3 via the interior 16 (transfer area) of the transfer chamber 5, in which a separation is provided. Separation plate 14 for reaction zone and transfer zone (This figure omits the gate valve through which wafers can be transferred into and out of the transfer chamber 5). The transfer chamber also has an exhaust pipe 6 . In certain embodiments, deposition of the multi-element film and surface treatment are performed in the same reaction space so that all steps can be performed continuously without exposing the substrate to air or other oxygen-containing atmosphere.

In some embodiments, in the apparatus shown in Figure 1A, a system for switching the flow of the inert gas shown in Figure 1B and the flow of the precursor gas (as described above) can be used to introduce the precursor gas in the form of pulses, In essence, the pressure of the reaction chamber will not fluctuate.

Those skilled in the art will appreciate that the apparatus includes one or more controllers (not shown) programmed or configured to perform the deposition and reactor cleaning processes described elsewhere herein. Those skilled in the art will appreciate that the controller communicates with various power supplies, heating systems, pumps, automated machinery, and gas flow controllers or reactor valves.

In certain embodiments, a dual-chamber reactor (for processing two parts or compartments of a wafer located close to each other) may be used, in which the reactive gases and inert gases may be supplied through a common line, whereas the precursor gases may pass through Supply through non-shared pipelines.

Thin films with filling capabilities can be applied to various semiconductor components, including but not limited to cell isolation, self-aligned holes, pseudo gates (replacing current polysilicon), Reverse tone patterning, PC RAM isolation, cut hard mask, and DRAM storage node contact (SNC) isolation. &lt;br/&gt;<b>Example</b>

In the following examples in which conditions and/or structures are not specified, those skilled in the art can easily provide such conditions and/or structures from the perspective of this specification based on traditional experiments. Those skilled in the art will appreciate that the apparatus used in the embodiments includes one or more controllers (not shown) programmed or configured to perform the deposition and reactor cleaning processes described in this specification. Those skilled in the art will appreciate that the controller communicates with various power supplies, heating systems, pumps, automated machinery, and gas flow controllers or reactor valves. &lt;br/&gt;Example 1

The Si-free C-containing film is deposited on a Si substrate (with a diameter of 300 mm and a thickness of 0.7 mm) through a PEALD-like process. It has a narrow/deep trench with an opening of about 20 nm and a depth of about 200 nm (aspect ratio of about 10). trenches, and narrow/shallow trenches with openings of about 20 to 35 nm and a depth of about 90 nm, to use the device shown in Figure 1A and the gas supply system (FPS) shown in Figure 1B, under the conditions shown in Table 5 below Determines the filling capacity of the film. The precursor was fed to the reaction chamber using carrier gas (its flow rate was 0.1 slm). However, due to the high vapor pressure of the precursor, a carrier gas is not required. In this example, a low mass flow carrier is used as a precaution against condensation of the precursor in the line. If the lines are sufficiently heated, carrier gas does not need to be used. In addition, although the use of dry He flow can make plasma ignition easier and more stable, as long as the plasma is ignited, the dry He flow can be eliminated. The film is deposited to completely fill the trench and further builds up on it, forming a flat top surface. Cross-sectional images of each substrate filling the trench were taken using STEM.

Table 5 (Values are approximate) <tables><table><table border="1" borderColor="#000000" width="85%"><tbody><tr><td>temperature setting &lt;br/&gt;</td><td>SUS temperature(°C) &lt;br/&gt;</td><td>75 &lt;br/&gt;</td></tr><tr><td>SHD temperature(°C) &lt;br/&gt;</td><td>50 &lt;br/&gt;</td></tr><tr><td>Wall temperature(°C) &lt;br/&gt;</td><td>75 &lt;br/&gt;</td></tr><tr><td>BLT temperature(°C) &lt;br/&gt;</td><td>RT &lt;br/&gt;</td></tr><tr><td>deposition &lt;br/&gt;</td><td>Pressure(Pa) &lt;br/&gt;</td><td>1160 &lt;br/&gt;</td></tr><tr><td>Gap(mm) &lt;br/&gt;</td><td>16.5 &lt;br/&gt;</td></tr><tr><td>Feed time(s) &lt;br/&gt;</td><td>0.4 &lt;br/&gt;</td></tr><tr><td>blow drive(s) &lt;br/&gt;</td><td>0.1 &lt;br/&gt;</td></tr><tr><td>RF power(W) &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td></tr><tr><td>blow drive(s) &lt;br/&gt;</td><td>0.1 &lt;br/&gt;</td></tr><tr><td>RF power(W) &lt;br/&gt;</td><td>230 &lt;br/&gt;</td></tr><tr><td>Precursor &lt;br/&gt;</td><td>Cyclopentene &lt;br/&gt;</td></tr><tr><td>carrier &lt;br/&gt;</td><td>He &lt;br/&gt;</td></tr><tr><td>Carrier flow (slm) &lt;br/&gt;</td><td>0.1 &lt;br/&gt;</td></tr><tr><td>DryHe(slm) &lt;br/&gt;</td><td>0.2 &lt;br/&gt;</td></tr><tr><td>N2 (slm) &lt;br/&gt;</td><td>0 &lt;br/&gt;</td></tr><tr><td>He (slm) &lt;br/&gt;</td><td>0 &lt;br/&gt;</td></tr><tr><td>Ar(slm) &lt;br/&gt;</td><td>0 &lt;br/&gt;</td></tr><tr><td>H2 (slm) &lt;br/&gt;</td><td>0 &lt;br/&gt;</td></tr><tr><td>O2 (slm) &lt;br/&gt;</td><td>0 &lt;br/&gt;</td></tr><tr><td>Seal He (slm) &lt;br/&gt;</td><td>0.1 &lt;br/&gt;</td></tr></tbody></table></table></tables>

10 shows a deep trench undergoing a gap filling cycle repeated 242 times in (a) and a trench with different opening sizes (widths) undergoing a gap filling cycle repeated 242 times in (b) according to one embodiment of the present invention. STEM photo of the cross-section of the trough. As shown in the STEM photos, the film deposited by the PEALD-like deposition method has excellent filling ability, showing narrow/shallow trenches ((b) in Figure 10) and also showing that no holes are formed in the trenches and there are substantial Narrow/deep trench with flat top surface. &lt;br/&gt;Comparative Example 1

The Si-free C-containing film was deposited on the Si substrate in a manner substantially similar to Example 1, except that the total He flow rate was 1.5 slm, the gap (between the capacitive coupling electrodes) was 16 mm, and the total pressure was 800 Pa. The duration of the RF applied pulse was 1.2 seconds and the number of cycles was 93. In addition, the substrate has a narrow trench with an opening of about 30 nm and a depth of about 90 nm (aspect ratio of about 3); a middle trench with an opening of about 70 nm and a depth of about 90 nm (aspect ratio of about 1.3); and A wide trench with an opening of about 100 nm and a depth of about 90 nm (aspect ratio of about 0.9).

11 shows a wide trench undergoing a gap fill cycle in (a), a wide and narrow trench undergoing a gap fill cycle in (b), and a narrow trench undergoing a gap fill cycle in (c) according to this comparative example. STEM photo of a cross-sectional view of the trench. As shown in the STEM images, the deposited film is quite conformal and has no filling ability (B/T ratio is 1.28), and narrow trenches appear to form holes, and gaps and irregularities are expected on the top surface. Compared to Example 1, this is mainly because the He flow rate is too high and the pressure is too low without significant filling ability, that is, the partial pressure of the precursor is not maintained during the entire period of exposing the trench of the substrate to the plasma. Above the precursor partial pressure required for void filling. Therefore, the polymer solidifies immediately without passing through a sufficient flowable state. &lt;br/&gt;Example 2

A Si-free C-containing film was deposited on the Si substrate in a manner substantially similar to that of Example 1, and the properties of the film were evaluated. The results are shown in Table 6 below.

Table 6 (Values are approximate) <img file="TWI828582B_D0001.tif" />

In the above, RBS stands for Rutherford backscattering spectrometry, SIMS stands for Secondary-ion mass spectrometry, AR stands for aspect ratio, DR stands for deposition rate, and CD stands for critical dimension (nm). RI stands for reflective index. As shown in Table 6, the film is essentially composed of carbon and hydrogen, which is considered to be an amorphous carbon polymer and has excellent properties. Typically, the flowable film is essentially composed of carbon and hydrogen, containing 50 to 80% carbon and 20 to 50% hydrogen, and has a density of 0.4 to 1 g/cm ³, RI is 1.4 to 1.6, and the contact angle is 50 to 80°. &lt;br/&gt;Examples and comparative examples using different parameters

Each Si-free C-containing film was deposited on a Si substrate (with an opening of 70 nm and a depth of 90 nm) in a manner substantially similar to that in Example 1 under the common conditions shown in Table 7 below and the specific conditions shown in Table 8 below. middle trench, and a wide trench with an opening of 100 nm and a depth of 90 nm). The B/T ratio of each resulting film is also shown in Table 8, where films with a B/T ratio of 1.5 or higher but less than 2.0 are considered fairly flowable, and films with a B/T ratio of 2.0 or higher but less than 2.5 are considered fairly flowable. Films with a B/T ratio of 2.5 or higher but less than 3.0 are considered very flowable, and films with a B/T ratio of 3.5 or higher are considered extremely flowable, and films with a B/T ratio of Films with a T ratio below 1.5 are considered poor or difficult to flow. Table 8 also shows the figure numbers (Figures 13 to 28), if STEM photos of the trench cross-sections are available, where Figure 27 shows a B/T ratio of 3.0 or higher; Figure 28 shows a B/T ratio of 2.5 or higher but Below 3.0; Figures 13 and 24 show a B/T ratio of 2.0 or higher but lower than 2.5; Figures 14, 15, 16, and 25 show a B/T ratio of 1.5 or higher but lower than 2.0; and Figures 17 to 23 and 26 shows a B/T ratio lower than 1.5 (comparative example).

Table 7 (Values are approximate) <tables><table><table border="1" borderColor="#000000" width="85%"><tbody><tr><td>Common conditions &lt;br/&gt;</td><td>Feed(s) &lt;br/&gt;</td><td>0.4 &lt;br/&gt;</td></tr><tr><td>blow drive(s) &lt;br/&gt;</td><td>0.1 &lt;br/&gt;</td></tr><tr><td>Rear RF blow drive(s) &lt;br/&gt;</td><td>0 &lt;br/&gt;</td></tr><tr><td>Carrier flow (slm) &lt;br/&gt;</td><td>0.1 &lt;br/&gt;</td></tr><tr><td>H2 (slm) &lt;br/&gt;</td><td>0 &lt;br/&gt;</td></tr></tbody></table></table></tables>

Table 8 (Values are approximate) <tables><table><table border="1" borderColor="#000000" width="85%"><tbody><tr><td>status number &lt;br/&gt;</td><td>He flow (slm) &lt;br/&gt;</td><td>Gap(mm) &lt;br/&gt;</td><td>Pressure(Pa) &lt;br/&gt;</td><td>RF(s) &lt;br/&gt;</td><td>N2 (slm) &lt;br/&gt;</td><td>Ar(slm) &lt;br/&gt;</td><td>temperature &lt;br/&gt;°C) &lt;br/&gt;</td><td>Electricity(W) &lt;br/&gt;</td><td>Bottom/Top Thickness Ratio &lt;br/&gt;</td><td>correspond &lt;br/&gt;No. # &lt;br/&gt;</td></tr><tr><td>#33 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>3.70 &lt;br/&gt;</td><td> &lt;br/&gt;</td></tr><tr><td>#35 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>16 &lt;br/&gt;</td><td>950 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>2.94 &lt;br/&gt;</td><td> &lt;br/&gt;</td></tr><tr><td>#46 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>16 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>100 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>2.04 &lt;br/&gt;</td><td> &lt;br/&gt;</td></tr><tr><td>#43 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>15 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>75 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>2.04 &lt;br/&gt;</td><td>Figure 13 &lt;br/&gt;</td></tr><tr><td>#37 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.82 &lt;br/&gt;</td><td>Figure 14 &lt;br/&gt;</td></tr><tr><td>#39 &lt;br/&gt;</td><td>1 &lt;br/&gt;</td><td>15 &lt;br/&gt;</td><td>950 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.61 &lt;br/&gt;</td><td>Figure 15 &lt;br/&gt;</td></tr><tr><td>#47 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>950 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>100 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.59 &lt;br/&gt;</td><td> &lt;br/&gt;</td></tr><tr><td>#40 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>16 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.56 &lt;br/&gt;</td><td>Figure 16 &lt;br/&gt;</td></tr><tr><td>#48 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>16 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>100 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.49 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr><tr><td>#41 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>950 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.43 &lt;br/&gt;</td><td>Figure 17 &lt;br/&gt;</td></tr><tr><td>#51 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>16 &lt;br/&gt;</td><td>950 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>100 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.35 &lt;br/&gt;</td><td>Figure 18 &lt;br/&gt;</td></tr><tr><td>#45 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>75 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.33 &lt;br/&gt;</td><td>Figure 19 &lt;br/&gt;</td></tr><tr><td>#42 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>16 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.28 &lt;br/&gt;</td><td>Figure 20 &lt;br/&gt;</td></tr><tr><td>#49 &lt;br/&gt;</td><td>1 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>100 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.25 &lt;br/&gt;</td><td>Figure 21 &lt;br/&gt;</td></tr><tr><td>#50 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>100 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.19 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr><tr><td>#44 &lt;br/&gt;</td><td>1 &lt;br/&gt;</td><td>16 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>75 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.18 &lt;br/&gt;</td><td>Figure 22 &lt;br/&gt;</td></tr><tr><td>#52 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>15 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>100 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.15 &lt;br/&gt;</td><td>Figure 23 &lt;br/&gt;</td></tr><tr><td>#74 &lt;br/&gt;</td><td>0.75 &lt;br/&gt;</td><td>15.6 &lt;br/&gt;</td><td>1120 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>2.00 &lt;br/&gt;</td><td>Figure 24 &lt;br/&gt;</td></tr><tr><td>#75 &lt;br/&gt;</td><td>0.9 &lt;br/&gt;</td><td>16.5 &lt;br/&gt;</td><td>1160 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>44 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.82 &lt;br/&gt;</td><td>Figure 25 &lt;br/&gt;</td></tr><tr><td>#76 &lt;br/&gt;</td><td>0.9 &lt;br/&gt;</td><td>15.2 &lt;br/&gt;</td><td>875 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>44 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>1.19 &lt;br/&gt;</td><td>Figure 26 &lt;br/&gt;</td></tr><tr><td>#72 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>3.45 &lt;br/&gt;</td><td>Figure 27 &lt;br/&gt;</td></tr><tr><td>#73 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>225 &lt;br/&gt;</td><td>2.70 &lt;br/&gt;</td><td>Figure 28 &lt;br/&gt;</td></tr><tr><td>#92 &lt;br/&gt;</td><td>0.45 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0.05 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>3.86 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr><tr><td>#93 &lt;br/&gt;</td><td>0.4 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0.1 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>3.47 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr><tr><td>#94 &lt;br/&gt;</td><td>0.4 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0.1 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>2.99 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr><tr><td>#101 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>35 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>2.68 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr><tr><td>#91 &lt;br/&gt;</td><td>0.5 &lt;br/&gt;</td><td>16 &lt;br/&gt;</td><td>1100 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>200 &lt;br/&gt;</td><td>3.76 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr><tr><td>#72 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>14 &lt;br/&gt;</td><td>800 &lt;br/&gt;</td><td>1.5 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>0.15 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr><tr><td>#76 &lt;br/&gt;</td><td>0.9 &lt;br/&gt;</td><td>15 &lt;br/&gt;</td><td>870 &lt;br/&gt;</td><td>1.2 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>0 &lt;br/&gt;</td><td>50 &lt;br/&gt;</td><td>175 &lt;br/&gt;</td><td>0.15 &lt;br/&gt;</td><td>- &lt;br/&gt;</td></tr></tbody></table></table></tables>

Table 8 shows how the process parameters can be manipulated to adjust the fluidity of the deposited film, as described below (see also Figure 12).

Just by increasing the pressure from 800 Pa (#48) to 1,100 Pa (#46), the B/T ratio increases from 1.49 (poor flow) to 3.70 (very easy flow). Mainly by lowering the temperature from 100°C (#48) to 75°C (#43), the B/T ratio increased from 1.49 (poor flow) to 2.04 (flowable). Mainly by increasing the pressure from 800 Pa (#48) to 950 Pa (#47), the B/T ratio increases from 1.49 (poor flow) to 1.59 (quite flowable).

Just by increasing the pressure from 950 Pa (#41) to 1,100 Pa (#40), the B/T ratio increased from 1.43 (poor flow) to 1.56 (fairly flowable).

Mainly by increasing the pressure from 800 Pa (#52) to 1,100 Pa (#50), the B/T ratio increased slightly from 1.15 (poor flow) to 1.19 (poor flow), but the increase was insufficient to render the film flowable. In addition, the B/T ratio slightly increased from 1.15 (poor flow) to 1.35 (poor flow) mainly by increasing the pressure from 800 Pa (#52) to 950 Pa (#51), but the increase was insufficient resulting in a flowable film. The above may be because the He flow rate in the above three cases is too high (1.5 slm), that is, the partial pressure of the precursor is too low.

Similarly, when the He flow rate is too high (1.5 slm) and the pressure is too low (800 Pa), that is, the partial pressure of the precursor is too low, even if the temperature is reduced from 75°C (#45) to 50°C ( #42), the B/T ratio has not improved substantially (a slight decrease from 1.33 (bad flow) to 1.28 (bad flow)). In addition, when the He flow rate is too high (1.5 slm) and the pressure is too low (800 Pa), that is, the partial pressure of the precursor is too low, even if the temperature is reduced from 100°C (#49) to 75°C (# 44), the B/T ratio did not improve (a slight decrease from 1.25 (bad flow) to 1.18 (bad flow)). Furthermore, even when the temperature decreases from 50°C (#33) to 35°C (#101), the B/T ratio does not increase but decreases from 3.70 (very flowable) to 2.68 (very flowable). This may be because the temperature at #101 (35°C) is too low.

Mainly by increasing the pressure from 875 Pa (#76) to 1,160 Pa (#76), the B/T ratio increases from 1.19 (poor flow) to 1.82 (fairly flowable). Furthermore, the B/T ratio increased from 1.82 (quite flowable) to 2.00 (flowable) mainly by reducing the He flow rate from 0.9 slm (#75) to 0.75 slm (#74).

Mainly by reducing the He flow rate from 1 slm (#39) to 0.5 slm (#35), the B/T ratio increased from 1.61 (fairly flowable) to 2.94 (very flowable). Additionally, the B/T ratio increased from 2.94 (very flowable) to 3.70 (extremely flowable) primarily by increasing the pressure from 950 Pa (#35) to 1,100 Pa (#33).

Just by reducing the RF power from 225W (#73) to 175W (#33), the B/T ratio increases from 2.70 (very flowable) to 3.70 (extremely flowable). However, when the gap increases from 14 mm (#72) to 16 mm (#91), the B/T ratio changes from 3.45 (very easy) even when the RF power increases from 175W (#72) to 200W (#91). flow) increased to 3.76 (very easy to flow).

Just by adjusting the He/(He+Ar) ratio from 4/5 (#94) to 5/5 (#33), the B/T ratio increased from 2.99 (very flowable) to 3.70 (very flowable). Additionally, just by adjusting the He/(He+N2) ratio from 4/5 (#93) to 5/5 (#33), the B/T ratio increased from 3.47 (very easy to flow) to 3.70 (very easy to flow) ). Furthermore, just by adjusting the He/(He+N2) ratio from 40/50 (#93) to 45/55 (#92), the B/T ratio increased from 3.47 (very easy to flow) to 3.86 (very easy to flow) ). Additionally, just by adjusting the He/(He+N2) ratio from 50/50 (#33) to 45/55 (#92), the B/T ratio increased from 3.70 (very easy to flow) to 3.86 (very easy to flow) ).

Just by shortening the RF time from 1.5 seconds (#72) to 1.2 seconds (#33), the B/T ratio increased from 3.45 (very easy to flow) to 3.70 (very easy to flow).

Mainly by reducing the RF power from 200W (#91) to 175W (#72), the B/T ratio increases from 2.70 (very flowable) to 3.70 (extremely flowable).

Those skilled in the art will appreciate that many and various modifications may be made without departing from the spirit of the invention. Therefore, it should be clearly understood that the forms of the invention are illustrative only and do not limit the scope of the invention.

<p>1:Substrate &lt;br/&gt;:Conductive flat electrode/lower layer (lower electrode) &lt;br/&gt;:Reaction chamber &lt;br/&gt;:Conductive flat electrode/upper electrode/spray plate &lt;br/&gt;:Transfer chamber &lt;br/&gt;,7: Exhaust pipe &lt;br /&gt;1: Inside the reaction chamber &lt;br/&gt;2: The other side of HRF power &lt;br/&gt;3: Circular pipe &lt;br/&gt;4:Separation plate &lt;br /&gt;6: Inside the transfer chamber (transfer area) &lt;br/&gt;0: Storage bottle (storage tank) &lt;br/&gt;1: Gas pipeline &lt;br/&gt;2:Gas pipeline &lt;br/&gt;4:Seal gas pipeline &lt;br/&gt;5:HRF power &lt;br/&gt;1:Substrate &lt;br/&gt;2: Groove &lt;br/&gt;3: Gas phase precursor &lt;br/&gt;4: Thin layer &lt;br/&gt;5: Deposition &lt;br/&gt;6: Viscous material (polymer) &lt;br/&gt;01:Substrate &lt;br/&gt;02:Layer &lt;br/&gt;03:Trench &lt;br/&gt;04:Protrusion &lt;br/&gt;05:Next level &lt;br/&gt;06: Hole &lt;br/&gt;01:Trench &lt;br/&gt;02:Inhibitor &lt;br/&gt;03: Bottom growth filler &lt;br/&gt;01:Trench &lt;br/&gt;02, 303: Layer &lt;br /&gt;01: Narrow groove/gap &lt;br/&gt;02:Layer &lt;br/&gt;03:Wide groove &lt;br/&gt;04:Open your mouth &lt;br/&gt;05:Substrate &lt;br/&gt;01:Substrate &lt;br/&gt;02:Trench &lt;br/&gt;03: Bottom growth filling &lt;br/&gt;04: Flowable materials &lt;br/&gt;05:Clump &lt;br/&gt;, b, c, d, e, f: valve </p>

These and other features of the present invention will now be described with reference to the drawings, which are intended to illustrate but not to limit the preferred embodiments of the invention. The drawings have been significantly simplified for illustrative purposes and are not necessarily to scale.

[FIG. 1A] is a schematic diagram of a plasma-enhanced Atomic Layer Deposition (PEALD) apparatus used to deposit dielectric films that can be used in embodiments of the present invention.

[Fig. 1B] A schematic diagram schematically illustrating a precursor supply system using a flow-pass system (FPS) that can be used in embodiments of the present invention.

[Fig. 2] A schematic cross-sectional view schematically illustrating a trench in a conventional CVD process that undergoes gap filling in the order of (a) and (b).

[Fig. 3] A schematic cross-sectional view schematically illustrating a trench undergoing a conventional gap filling process in the order of (a), (b) and (c) using inhibitors.

[Fig. 4] A schematic cross-sectional view schematically illustrating a trench undergoing a conventional gap filling process in the order of (a) and (b) using a highly anisotropic process.

[Figure 5] Schematic cross-sectional view schematically illustrating a trench undergoing a conventional void filling process in the order of (a) and (b), or (c) and (d) using volume expansion processing ((d) shows the loading effect) .

[Figure 6] Shows the deposition used in (a), dry etching using different etchants in (b) to (d), and (e) to (g) corresponding to (b) to (d) respectively STEM image of a cross-sectional view of a trench undergoing a conventional gap-fill process for the second deposition combination.

[Fig. 7] A schematic cross-sectional view schematically illustrating a trench undergoing a conventional gap filling process in the order of (a) and (b) using a flowable material.

[Fig. 8] A schematic cross-sectional view schematically illustrating a trench undergoing a conventional gap filling process using flowable material.

[Fig. 9] A schematic cross-sectional view schematically illustrating a trench undergoing a gap filling process in the order of (a), (b) and (c) according to one embodiment of the present invention.

[Fig. 10] Shows a deep trench undergoing a gap filling cycle repeated 240 times in (a) and a deep trench having different opening sizes (width) undergoing a gap filling cycle repeated 240 times in (b) according to one embodiment of the present invention. ) of the cross-sectional view of the groove.

[Fig. 11] Shows a wide trench undergoing a gap filling period in (a), a wide and a narrow trench undergoing a gap filling period in (b), and a gap filling period in (c) according to a comparative example STEM image of a cross-sectional view of a periodic narrow trench.

[Fig. 12] shows a diagram showing a schematic relationship between process parameters and fluidity obtained using the data analysis software JMP® according to one embodiment of the present invention.

[Figures 13 to 28] STEM photos showing cross-sectional views of trenches undergoing gap-fill deposition through PEALD-like process conditions, where Figure 27 shows a B/T ratio of 3.0 or higher; Figure 28 shows a B/T ratio of 2.5 or higher but less than 3.0; Figures 13 and 24 show a B/T ratio of 2.0 or higher but less than 2.5; Figures 14, 15, 16 and 25 show a B/T ratio of 1.5 or higher but less than 2.0; Figures 17 to 23 and 26 shows a B/T ratio less than 1.5 (comparative example).