Method for adjusting a film stress

Abstract

The provided method is for adjusting membrane stress. In one embodiment, a first membrane is formed on a substrate by sequentially and alternately supplying a first reactant and a second reactant in a first step, and the first membrane is transformed into a second membrane by supplying a third reactant to the first membrane in a second step. The membrane stress of the second membrane is adjusted by controlling the ratio of the first step to the second step.

Description

[Technical Field]

[0001] This disclosure provides a method for processing a substrate, and more specifically, a method for adjusting the stress of a film formed on a substrate. [Previous Technology]

[0002] The substrate and the film formed thereon may be subjected to heat treatment during high-temperature processes, which can generate stress. This can lead to substrate deformation (such as warpage or cracking), film peeling, or device degradation. Figure 1 shows how film stress can lead to film peeling or substrate breakage or deformation. [Summary of the Invention]

[0003] This disclosure provides a method for processing a substrate. More specifically, this disclosure provides a method for adjusting a stress in a film.

[0004] According to one embodiment, a first film can be formed on a substrate by sequentially and alternately supplying a first reactant and a second reactant in a first step. The first film can be transformed into a second film by supplying a third reactant in a second step. The second reactant can be activated. The third reactant can be activated and reactive to the first film. The stress of the second film can be adjusted by controlling the cycle ratio of the first step to the second step.

[0005] According to another embodiment, a first film can be formed on a substrate having a pattern as a hard mask by sequentially and alternately supplying a first reactant and a second reactant in a first step. The first film can be transformed into a second film by supplying a third reactant in a second step. The second reactant can be activated. The third reactant can be activated and reactive to the first film. The wet etching rate of the hard mask formed at 50°C can be almost the same as that of the silicon oxide hard mask formed at 300°C or higher.

[0006] According to another embodiment, a first film can be formed on the back side of a substrate by sequentially and alternately supplying a first reactant and a second reactant in a first step, and can be converted into a second film by supplying a third reactant in a second step. The second reactant can be activated. The third reactant can be activated and reactive to the first film. A third film can be formed on the front side of the substrate at a high temperature. The second film can be etched away after processing the substrate.

[0007] According to another embodiment, a substrate having a gap to be filled is provided, and the gap can be filled by a first film. A second film can be formed on the first film by sequentially and alternately supplying a first reactant and a second reactant in a first step, and can be transformed into a third film by supplying a third reactant in a second step. The second reactant can be activated. The third reactant is activated and reactive to the second film.

Implementation Method

[0008] The substrate processing method disclosed herein provides a method for adjusting film stress and preventing and / or suppressing substrate deformation or film peeling caused by stress of the film or substrate.

[0009] Figure 2 is a process flow according to an embodiment, and the details of Figure 2 are described below.

[0010] - Loading substrate (101): The substrate can be loaded onto the substrate support in the reaction space. The substrate support supports the substrate and provides heat energy to the substrate to maintain the substrate temperature at a specified temperature.

[0011] - Formation of a first film (201): A first film can be formed on a substrate by alternately and sequentially supplying a first reactant and a second reactant to the substrate. The first reactant can be a precursor containing Si, and the second reactant can be activated by radio frequency power. The second reactant may not chemically react with the first reactant. For example, the first reactant may be an aminosilane precursor. The second reactant may be an inert gas (such as Ar, or He, or combinations thereof). In this step, the first reactant can be dissociated and broken by plasma and adsorbed onto the substrate. Since there may be no chemical reaction between the first reactant and the second reactant, the film adsorbed onto the substrate may contain fragments of the dissociated or broken first reactant molecules (e.g., silicon (Si), carbon (C), nitrogen (N), chlorine (Cl), iodine (I), alkyl ligands (e.g., CnH2n+1), and hydrogen (H) fragments, and / or mixtures thereof). The first layer of the first film may be chemically adsorbed onto the substrate. The second layer may be deposited on top of the first membrane and may contain a stack of those fragments. The first membrane may be densified by an activated second gas. Similarly, the activated second gas may facilitate the dissociation of the first gas. This first step may be repeated "M" times.

[0012] - Converting the first film into a second film (301): A third reactant may be supplied to the first film formed on the substrate. The third reactant may be activated by radio frequency power and react chemically with the first film. The third reactant may be an oxygen-containing gas, more preferably, oxygen. In this step, the first film may be converted into a second film. The first film may be converted into a second film because the activated third reactant reacts chemically with the first film. For example, the second film may be a SiO2 film. This second step may be repeated "N" times.

[0013] In Figure 2, the cycle ratio of the first step 201 to the second step 301 can be greater than 5, preferably greater than 20, or more preferably greater than 50. For example, the first step 201 can be repeated 50 times, and the second step 301 can be repeated once. Further, the first step 201 and the second step 301 can be repeated as a group cycle or supercycle "X" times (at least once) to further promote the conversion of the first membrane into the second membrane as the thickness of the first membrane increases.

[0014] Figure 3 is a schematic diagram of the process flow of Figure 2. The first step and the second step in Figure 3 correspond to the first step 201 and the second step 301 in Figure 2, respectively. In the first step of Figure 3, the first layer can be formed by sequentially and alternately supplying a first reactant and a second reactant. For example, the second reactant can be activated by radio frequency power.

[0015] In another embodiment, the second reactant may be supplied continuously as shown in Figure 3. In Figure 3, the first step may be repeated "M" times (at least once), followed by the second step. In the second step of Figure 3, a third reactant may be supplied and activated by plasma, and the second step may be repeated "N" times (at least once). The cycle ratio of the first step to the second step (i.e., M / N) may be greater than 5, preferably greater than 20, or more preferably greater than 50. The activated third reactant may convert the first film into the second film. For example, the first reactant may be a Si-containing precursor, the second reactant may be Ar, and the third reactant may be oxygen. The silicon-containing precursor as the first reactant can be at least one of the following: DIPAS (SiH3N(iPr)2), TSA ((SiH3)3N), DSO ((SiH3)2), DSMA ((SiH3)2NMe), DSEA ((SiH3)2NEt), DSIPA ((SiH3)2N(iPr)), DSTBA ((SiH3)2N(tBu)). The reactants may be: DEAS (SiH3NEt2), DTBAS (SiH3N(tBu)2), BDEAS (SiH2(NEt2)2), BDMAS (SiH2(NMe2)2), BTBAS (SiH2(NHtBu)2), BITS (SiH2(NHSiMe3)2), TEOS (Si(OEt)4), SiCl4, HCD (Si2Cl6), 3DMAS (SiH(N(Me)2)3), BEMAS (SiH2[N(Et)(Me)]2), AHEAD (Si2(NHEt)6), TEAS (Si(NHEt)4), Si3H8, DCS (SiH2Cl2), SiHI3, SiH2I2, or mixtures thereof. Oxygen as the third reactant may be at least one of O2, O3, CO2, H2O, NO2, and N2O, or mixtures thereof.

[0016] The first film can be a stack of fragments of plasma-densified Si precursor molecules, which can be converted into SiO2 as the second film by oxygen plasma. In other words, step 1 can be a source coating step, and step 2 can be an oxygen treatment step. In Figure 3, the plasma conditions of step 2 can be changed. For example, the radio frequency power can be provided as a pulse with a certain duty cycle to reduce damage to the substrate or sublayer.

[0017] As shown in Figure 4, when RF power is provided in pulses, the ratio of the actual RF power supply time b to the unit cycle time a of the RF pulse (i.e., b / a) is defined as the duty cycle. In another embodiment according to the concept disclosed herein, the RF power can be provided as pulses having a duty cycle range of 10% to 75%.

[0018] Figure 5 illustrates another embodiment based on the concept disclosed herein. In the first step, plasma can be supplied in a continuous mode, but in the second step, plasma can be supplied in a pulsed mode with a certain duty cycle. However, supplying plasma in a pulsed mode is not limited to this. In another embodiment, plasma can be pulsed to at least one of the first and second steps.

[0019] Table 1 shows the experimental conditions according to one embodiment of Figure 3, wherein plasma can be supplied in a continuous mode, and plasma can be supplied without pulses. Table 1: Experimental conditions of one embodiment project condition Process temperature (°C) Room temperature to 150°C (ideally 50 to 150°C) Process pressure Torr 1.0 to 5.0 (preferably 2.0 to 3.0 tors) Si precursor DIPAS (diisopropylaminosilane) reactants O2 purge gas Ar The first step in forming the first membrane Process time (seconds) Source feed (S1) 0.05 to 2.0 seconds (preferably 0.1 to 1.0 seconds) Source purging (S2) 0.05 to 2.0 seconds (preferably 0.1 to 1.0 seconds) Plasma activation (S3) 0.05 to 2.0 seconds (preferably 0.1 to 1.0 seconds) Purge (S4) 0.05 to 2.0 seconds (preferably 0.1 to 1.0 seconds) S1 to S4 cycle 50 to 200 cycles (ideally 100 to 150 cycles) Gas flow rate (standard milliliters per unit time (sccm)) Source carrier Ar 100 to 10,000 standard milliliters per unit time (preferably 600 to 1,200 standard milliliters per unit time) Sweep Ar 1,000 to 10,000 standard milliliters per unit time (preferably 3,000 to 6,000 standard milliliters per unit time) Plasma conditions Radio frequency (RF) power (watts (W)) 100 to 1,000 watts (ideally 200 to 400 watts) Radio frequency 13 to 100 megahertz (MHz) (preferably 27 to 60 megahertz) The second step in converting the first membrane into the second membrane Process time (seconds) Pre-purge (S5) 0.05 to 5.0 seconds (preferably 0.5 to 5.0 seconds) Plasma activation (S6) 0.05 to 3.0 seconds (preferably 0.1 to 2.0 seconds) Purge (S7) 0.05 to 2.0 seconds (preferably 0.1 to 1.0 seconds) S5 to S7 cycle 1 to 10 cycles (preferably 1 to 5 cycles) Gas flow rate (standard milliliters per unit time) Reactant (O2) 50 to 1000 standard milliliters per unit time (preferably 200 to 500 standard milliliters per unit time) Sweep Ar 1,000 to 10,000 standard milliliters per unit time (preferably 3,000 to 6,000 standard milliliters per unit time) plasma Conditional RF power (watts) 100 to 1,000 watts (ideally 200 to 500 watts) Radio frequency 13 to 100 megahertz (ideally 27 to 60 megahertz)

[0020] Figure 6 shows the film stress according to the cycle ratio of the first step to the second step. In Figure 6, the SiO2 film formed at room temperature by a normal process in which silicon-containing precursors and oxygen plasma are alternately and sequentially provided to form a SiO2 film can have a tensile stress of 109.8 MPa, but the stress of the SiO2 film according to the concept disclosed herein can be changed according to the cycle ratio of the first step to the second step.

[0021] In the first step, the Si-containing precursor as the first reactant and the Ar plasma as the second reactant may be alternately and sequentially provided to the substrate to form a first film composed of elements and fragments of ligands of the dissociated Si precursor.

[0022] In the second step, oxygen plasma, as a third reactant, may be provided to the first membrane to convert the first membrane into a SiO2 membrane, which serves as the second membrane. In one embodiment, the cycle ratio of the first step to the second step may be 50. For example, the first step may be 50 cycles, and the second step may be one cycle. In another embodiment, the cycle ratio of the first step to the second step may be 100. For example, the first step may be 100 cycles, and the second step may be one cycle.

[0023] Figure 7 shows the membrane composition after performing the first and second steps. As shown in Figure 7, the SiO2 membranes formed under the cycling ratios of 50:1 and 100:1 in Figure 6 have, for example, a stoichiometric SiO2 membrane composition, without any other elements from nitrogen, carbon, and hydrogen, or fragments of mixtures thereof. This means that the first membrane can be substantially converted into the second membrane by oxygen plasma as the third reactant.

[0024] As shown in Figure 6, the first film has a compressive stress of -74.8 MPa, but as the oxygen plasma is supplied and the first film is transformed into the second film, the film stress becomes tensile stress. Similarly, the higher the cycle ratio of step 1 to step 2, the higher the tensile stress of the SiO2 film. That is to say, the stress of the SiO2 film can be appropriately adjusted by controlling the cycle ratio of the first step to the second step. Therefore, optimal process conditions or cycle ratios can be set to prevent substrate deformation and film peeling (e.g., warping, cracking, etc.). Therefore, a film with a target stress can be formed by controlling the cycle ratio.

[0025] In another embodiment, this process can be implemented to introduce a stress control film. For example, if a substrate is treated at high temperature in a reactor, subjecting it to compressive or tensile stress, the substrate may deform or break, or film peeling or cracking may occur therein. In this case, a stress control film can be introduced onto the back side of the substrate to counteract the compressive or tensile stress on the substrate. The stress control film can be a film with compressive or tensile stress formed prior to substrate treatment by the methods described in Figures 2 and 3 above. That is, the stress of the stress control film can be counteracted by adjusting the cycle ratio of the source coating step to the plasma treatment step. Therefore, the stress control film can suppress substrate deformation and cracking in the film on the substrate during high-temperature treatment of the substrate. Figure 8 shows the process flow for introducing a stress control film.

[0026] In Figure 8, a first film can be formed on the back side of the substrate by supplying a first reactant and a second reactant in a first step. Next, the first film can be transformed into a second film by supplying a third reactant in a second step. The stress of the second film can be adjusted by controlling the cycle ratio of the first step to the second step, and the second film can act as a stress control film. The process sequence is described in more detail in Figures 2 and 3, and therefore its detailed description is omitted herein. Subsequently, a third film can be formed on the front side of the substrate. After the process is completed, the stress control film (i.e., the second film) can be removed by using a fluorinated etchant (such as CF4). By performing this process, deformation or breakage of the substrate and cracking or damage in the third film can be suppressed.

[0027] The process in Figure 8 can be performed ex-situ. For example, this process can be carried out in a chamber having multiple reactors. For example, the substrate can be processed by sequentially transferring it from one reactor to another to perform the steps in Figure 8.

[0028] Figure 9 shows the embodiment of Figure 8. In Figure 9A, the second film or stress control film 2 can be formed on the back side of the substrate 1 at a low temperature (e.g., room temperature). Then, the target third film 3 can be formed on the front side of the substrate 1 at a high temperature. The stress of the substrate can be offset by introducing a stress control film with compressive or tensile stress to the back side of the substrate 1.

[0029] In Figure 9A, the tensile stress of the substrate can be counteracted by forming a stress control film 2 with compressive stress on the back side of the substrate 1, thereby suppressing the deformation or breakage of the substrate or the cracking of the third film 3 on the substrate.

[0030] In Figure 9B, the compressive stress of the substrate can be counteracted by forming a stress control film 2 with tensile stress on the back side of the substrate 1, thereby suppressing the deformation or breakage of the substrate or the cracking in the third film 3 on the substrate.

[0031] Controlling film stress by transforming one film into another at low temperatures provides another technological advantage. SiO2 hardmasks can be used in patterning processes in semiconductor device manufacturing. However, as devices shrink, the film thickness on the device becomes thinner, and the thermal budget becomes a serious problem because it leads to sublayer damage, abnormal electron migration across the device structure, and device failure. Therefore, it may be necessary for low-temperature SiO2 hardmask processes to have the same film properties as those formed under existing high-temperature processes. Therefore, the inventive concept disclosed herein provides a solution to this problem.

[0032] Figure 10 shows a process flow for forming a hard mask on a substrate pattern according to another embodiment.

[0033] In the first step 101 of Figure 10, a substrate with a patterned structure can be loaded onto a substrate support. In the second step 301 of Figure 10, a first film can be formed on the substrate pattern. The first film can be formed according to the methods in Figures 2 and 3 above, therefore, a detailed description will be omitted herein. After the second step 301, the first film can be converted into a second film in the third step 501. The conversion from the first film to the second film can be performed according to the methods in Figures 2 and 3 above, therefore, a detailed description will be omitted herein.

[0034] Figure 11 shows the wet etch ratio (WER) of the SiO2 film formed according to Figure 10 and the existing method. The wet etch ratio is performed in hydrofluoric acid (HF) diluted in deionized water (DIW) at a ratio of 100:1.

[0035] In Figure 11, the details of each process condition are described as follows.

[0036] -A: A SiO2 film is formed at 50°C by a conventional plasma-enhanced atomic layer deposition (PEALD) method, wherein a diisopropylaminosilane precursor and oxygen plasma are provided alternately and sequentially.

[0037] -B: Precursor deposition. Si-containing films can be formed at 50°C by alternating and sequentially supplying diisopropylaminosilane silicon precursor and Ar plasma.

[0038] -C: A SiO2 film is formed at 50°C by performing 50 cycles of alternating and sequential supply of diisopropylaminosilane precursor and Ar plasma and one cycle of oxygen plasma to convert it into a SiO2 film.

[0039] -D: A SiO2 film for hard masking applications is formed at 300°C by a conventional plasma-enhanced atomic layer deposition method, wherein a diisopropylaminosilane precursor and oxygen plasma are provided alternately and sequentially.

[0040] As shown in Figure 11, A, the SiO2 film formed at 50°C by a regular plasma-enhanced atomic layer deposition method has a high wet etch rate of 175.84 Å / min, in other words, low wet etch resistance. However, under condition B, by supplying a diisopropylaminosilane precursor and Ar plasma, a Si-containing film formed at 50°C has an extremely low wet etch rate, in other words, high wet etch resistance. But as shown in C, oxygen treatment and the resulting conversion from the Si-containing film to the SiO2 film at 50°C increase the wet etch rate to be closer to that of the SiO2 film formed at 300°C as shown in condition D. In another embodiment, by further controlling the cycle ratio of the first step to the second step, the wet etch rate of the SiO2 film formed at 50°C can be almost the same as that of the SiO2 film formed at 300°C or higher. In other words, by adjusting the cycle ratio of the precursor deposition step to the plasma processing step, film properties achievable at high temperatures (e.g., 300°C or higher) can be achieved at low temperatures, reducing the thermal budget of the device. Therefore, the inventive concept disclosed herein provides a solution for the needs of low-temperature processes. Figure 11 also shows that films with different wet etching rates can be achieved at low temperatures by adjusting the cycle ratio of the precursor deposition step to the plasma processing step, enabling a variety of applications.

[0041] Controlling membrane stress by transforming one membrane into another can provide another technical advantage in the gap filling process. In Figure 12, the membrane 1 covering the top surface can peel off due to membrane stress (e.g., tensile stress shown in Figure 12A). However, introducing a stress-control membrane to the top surface of the membrane can suppress membrane peeling, as shown in Figure 12B.

[0042] In Figure 12B, the gap is filled with a first membrane 1, and the second membrane or stress control membrane 2 can be formed by supplying a first reactant and a second reactant activated by plasma in the first step, and the second membrane can be transformed into a third membrane in the second step. The stress of the third membrane 3 can be adjusted by controlling the cycle ratio of the first step to the second cycle. The details of the process were previously described in Figures 2 and 3, and therefore their detailed description will be omitted herein.

[0043] Figure 13 shows the process flow of Figure 12, wherein a substrate with a gap structure may be loaded at step 101, and then the gap may be filled with a first film at step 301. A second film may be formed on the first film at step 501, and then converted into a third film at step 701. [Simplified Explanation of the Diagram]

[0045] The above and other features, characteristics, and advantages of certain embodiments of this disclosure will become more apparent from the following description taken in conjunction with the accompanying drawings, in which: Figure 1 is a view of stress-induced peeling of the film and substrate deformation. Figure 2 is a substrate processing flowchart according to an embodiment. Figure 3 is a process flow diagram according to an embodiment. Figure 4 is a schematic diagram defining the working ratio. Figure 5 is a process flow diagram according to another embodiment. Figure 6 is a graph showing the stress of the SiO2 film according to the cycle ratio of step 1 to step 2. Figure 7 is a view of the composition of the SiO2 film. Figure 8 is a view of the substrate processing flow according to another embodiment. Figure 9 is a process flow diagram according to another embodiment. Figure 10 is a substrate processing flowchart according to another embodiment. Figure 11 is a graph showing the wet etching rate of the SiO2 film under various conditions. Figure 12 is a process flow diagram according to another embodiment. Figure 13 is a substrate processing flowchart according to another embodiment.

Claims

1. A method for adjusting the stress of a membrane, comprising: A substrate is loaded onto a substrate support; In a first step, a first film is formed on the substrate. The first step includes: supplying a first reactant; and supplying a second reactant, wherein the first reactant and the second reactant are supplied sequentially and alternately; and in a second step, the first film is converted into a second film by supplying a third reactant to the first film, wherein the cycle ratio of the first step to the second step is greater than 5 to adjust the stress of the second film, wherein the third reactant is activated by a radio frequency power and chemically reacts with the first film, and wherein the second reactant is activated by a radio frequency power.

2. The method of claim 1, wherein the second reactant is at least one of Ar, He, or a mixture thereof.

3. The method of claim 2, wherein the second reactant densifies the first membrane, and the first membrane comprises a plurality of segments of the first reactant.

4. The method of request item 1, wherein the first step is repeated at least once, and the second step is repeated at least once, wherein the first step and the second step are repeated sequentially at least once.

5. The method of claim 1, wherein the first reactant is a silicon-containing gas.

6. The method of claim 1, wherein the second reactant is at least one of Ar, He, or a mixture thereof.

7. The method of claim 1, wherein the third reactant is an oxygen-containing gas.

8. As in claim 5, the silicon-containing system comprises at least one of the following: DIPAS (SiH3N(iPr)2), TSA ((SiH3)3N), DSO ((SiH3)2), DSMA ((SiH3)2NMe), DSEA ((SiH3)2NEt), DSIPA ((SiH3)2N(iPr)), DSTBA ((SiH3)2N(tBu)). ), DEAS (SiH3NEt2), DTBAS (SiH3N(tBu)2), BDEAS (SiH2(NEt2)2), BDMAS (SiH2(NMe2)2), BTBAS (SiH2(NHtBu)2), BITS (SiH2(NHSiMe3)2), TEOS (Si(OEt)4), Si Cl4, HCD (Si2Cl6), 3DMAS (SiH(N(Me)2)3), BEMAS (SiH2[N(Et)(Me)]2), AHEAD (Si2(NHEt)6), TEAS (Si(NHEt)4), Si3H8, DCS (SiH2Cl2), SiHI3, SiH2I2, or mixtures thereof.

9. The method of claim 7, wherein the oxygen-containing system comprises at least one of the following: O2, O3, CO2, H2O, NO2, and N2O, or a mixture thereof.

10. The method of claim 1, wherein the second film comprises silicon oxide.

11. The method of claim 3, wherein the fragments of the first reactant are at least one of silicon, carbon, nitrogen, chlorine, iodine, hydrogen, and alkyl, or mixtures thereof.

12. The method of claim 1, wherein as the cycle ratio of the first step to the second step increases, the tensile stress of one of the second membranes increases.

13. The method of claim 1, wherein as the cycle ratio of the first step to the second step decreases, the compressive stress of one of the second membranes increases.

14. The method of claim 1, wherein the radio frequency power is supplied in pulses using an operating ratio of 10% to 75%.

15. The method of claim 1, wherein the substrate includes a pattern and the second film is formed on the pattern as a hard mask, wherein the first step and the second step are performed at a temperature of 50°C or lower.

16. The method of claim 15, wherein the wet etching rate of the second film is adjusted by controlling the cycle ratio of the first step to the second step.

17. The method of claim 16, wherein the wet etch rate of the second film is substantially the same as the wet etch rate of a silicon oxide hard mask formed at 300°C or higher.

18. The method of claim 15, wherein the second film is a silicon monoxide hard mask.

19. A method for adjusting the stress of a membrane, comprising: A substrate is loaded onto a substrate support of a reactor; a first film is formed on a back side of the substrate by sequentially and alternately supplying a first reactant and a second reactant in a first step; the first film is converted into a second film by supplying a third reactant to the first film in a second step; a third film is formed on a front side of the substrate; the second film is removed from the back side of the substrate, wherein the cycle ratio of the first step to the second step is greater than 5 to adjust the stress of the second film, wherein the third reactant is activated by a radio frequency power and chemically reacts with the first film.

20. The method of claim 19, wherein the stress of the second film counteracts a stress of the substrate.

21. The method of claim 19, wherein the third film system is formed at a temperature of 300°C or higher.

22. The method of claim 19, wherein the substrate is processed by sequentially transferring it from one reactor to another in a system having a plurality of reactors.

23. The method of claim 19, wherein the second reactant is activated by a radio frequency power.

24. The method of claim 19, wherein the first reactant is a silicon-containing gas.

25. The method of claim 19, wherein the second reactant is at least one of Ar, He, or a mixture thereof.

26. The method of claim 19, wherein the third reactant is a gas comprising oxygen.

27. The method of claim 19, wherein the second film system is silicon oxide.

28. The method of claim 19, wherein the first step is repeated at least once, and the second step is repeated at least once, and the first step and the second step are repeated sequentially at least once as a group loop.

29. A method for adjusting the stress of a membrane, comprising: A substrate is loaded onto a substrate support; A first film is formed on the substrate; Forming a second membrane on the first membrane includes: alternately and sequentially supplying a first reactant and a second reactant in a first step; The second membrane is converted into a third membrane by supplying a third reactant to the second membrane in a second step, wherein the cycle ratio of the first step to the second step is greater than 5 to adjust a stress in the second membrane, wherein the third reactant is activated by a radio frequency power and reacts chemically with the second membrane, wherein the second reactant is activated by a radio frequency power.

30. The method of claim 29, wherein a stress in the third membrane counteracts a stress in the first membrane.

31. The method of claim 29, wherein the first reactant is a silicon-containing gas.

32. The method of claim 29, wherein the second reactant is at least one of Ar, He, or a mixture thereof.

33. The method of claim 29, wherein the third reactant is an oxygen-containing gas.

34. The method of claim 29, wherein the third film is silicon oxide.

35. The method of claim 29, wherein the first step is repeated at least once, and the second step is repeated at least once; and the first step and the second step are repeated sequentially at least once as a group loop.

36. The method of claim 29, wherein the substrate has a gap to be filled, and the gap is filled with the first film.

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