SUBSTRATE PROCESSING METHOD
20230343551 · 2023-10-26
Inventors
Cpc classification
C23C16/045
CHEMISTRY; METALLURGY
C23C16/45536
CHEMISTRY; METALLURGY
International classification
C23C16/455
CHEMISTRY; METALLURGY
Abstract
Provided is a substrate processing method in which a liner layer is formed on the photo resist underlayer, followed by forming SiO.sub.2 patterning layer thereon. According to the embodiment, the liner layer is formed by providing a silicon-containing layer, followed by inert gas activated by providing a high frequency RF power and a low frequency RF power together simultaneously. Thus, a loss of photo resist underlayer may be minimized within the range that does not affect the device performance and the wet etch properties and the width between fine patterns may be kept constant while the thickness of the liner layer is thin.
Claims
1. A substrate processing method, comprising, a first phase of forming a liner layer on a patterned structure; and a second phase of forming a deposition layer on the liner layer; wherein the first phase of forming a liner layer is carried out by providing a dual frequency RF power.
2. The substrate processing method of claim 1, wherein, the first phase for forming the liner layer comprises, a first step of providing the substrate with a patterned structure to a reactor; a second step of providing a first reactant to the substrate and forming a first source layer on the patterned structure; a third step of providing a dual frequency RF power to the first source layer; a fourth step of converting the first source layer into a second source layer; wherein a third reactant is continuously provided throughout the second step to the fourth step.
3. The substrate processing method of claim 2, wherein, the third step of providing a dual frequency RF power provides a low frequency RF power and a high frequency RF power simultaneously.
4. The substrate processing method of claim 3, wherein, the low frequency of RF power ranges between 300 kHz to and 500 kHz; and the high frequency of RF power ranges between 5 MHz and 60 MHz.
5. The substrate processing method of claim 2, wherein, the first reactant comprises silicon, nitrogen, and carbon.
6. The substrate processing method of claim 5, wherein, the first reactant comprises at least one of TSA, (SiH.sub.3).sub.3N; DSO, (SiH.sub.3).sub.2; DSMA, (SiH.sub.3).sub.2NMe; DSEA, (SiH.sub.3).sub.2NEt; DSIPA, (SiH.sub.3).sub.2N(iPr); DSTBA, (SiH.sub.3).sub.2N(tBu); DEAS, SiH.sub.3NEt.sub.2; DTBAS, SiH.sub.3N(tBu).sub.2; BDEAS, SiH.sub.2(NEt.sub.2).sub.2; BDMAS, SiH.sub.2(NMe.sub.2).sub.2; BTBAS, SiH.sub.2(NHtBu).sub.2; BITS, SiH.sub.2(NHSiMe.sub.3).sub.2; DIPAS, SiH.sub.3N(iPr).sub.2; TEOS, Si(OEt).sub.4; SiCl.sub.4; HCD, Si.sub.2Cl.sub.6; 3DMAS, SiH(N(Me).sub.2).sub.3; BEMAS, SiH.sub.2[N(Et)(Me)].sub.2; AHEAD, Si.sub.2(NHEt).sub.6; TEAS, Si(NHEt).sub.4; Si.sub.3Hs ; DCS, SiH.sub.2Cl.sub.2; SiHl.sub.3; SiH.sub.2l.sub.2; or the mixture or derivatives thereof.
7. The substrate processing method of claim 2, wherein, the first source layer is dissociated by the third reactant activated by the dual frequency RF power and is converted into the second source layer.
8. The substrate processing method of claim 7, wherein the second source layer comprises: individual silicon elements, nitrogen element, carbon elements, or a mixture thereof.
9. The substrate processing method of claim 7, wherein, the second source layer comprises a SiCN layer.
10. The substrate processing method of claim 2, wherein, the third reactant comprises at least one of Ar, He, or N.sub.2, or the mixture thereof.
11. The substrate processing method of claim 1, wherein, the second phase of forming the deposition layer on the liner layer comprises, a fifth step of providing a first reactant and forming a third source layer on the liner layer formed on the patterned structure; a sixth step of providing a second reactant to the third source layer; a seventh step of providing a high frequency RF power to the reactor and activating the second reactant; and an eighth step for forming a compound by reacting the third source layer with the second reactant.
12. The substrate processing method of claim 11, wherein, the third source layer is the same material as the first source layer.
13. The substrate processing method of claims 11, wherein, the first reactant comprises at least one of TSA, (SiH.sub.3).sub.3N; DSO, (SiH.sub.3).sub.2; DSMA, (SiH.sub.3).sub.2NMe; DSEA, (SiH.sub.3).sub.2NEt; DSIPA, (SiH.sub.3).sub.2N(iPr); DSTBA, (SiH.sub.3).sub.2N(tBu); DEAS, SiH.sub.3NEt.sub.2; DTBAS, SiH.sub.3N(tBu).sub.2; BDEAS, SiH.sub.2(NEt.sub.2).sub.2; BDMAS, SiH.sub.2(NMe.sub.2).sub.2; BTBAS, SiH.sub.2(NHtBu).sub.2; BITS, SiH.sub.2(NHSiMe.sub.3).sub.2; DIPAS, SiH.sub.3N(iPr).sub.2; TEOS, Si(OEt).sub.4; SiCl.sub.4; HCD, Si.sub.2Cl.sub.6; 3DMAS, SiH(N(Me).sub.2).sub.3; BEMAS, SiH.sub.2[N(Et)(Me)].sub.2; AHEAD, Si.sub.2(NHEt).sub.6; TEAS, Si(NHEt).sub.4; Si.sub.3Hs ; DCS, SiH.sub.2Cl.sub.2; SiHl.sub.3; SiH.sub.2l.sub.2; or the mixture or derivatives thereof.
14. The substrate processing method of claim 11, wherein, the second reactant comprises at least one of O.sub.2, O.sub.3, CO.sub.2, H.sub.2O, NO.sub.2, N.sub.2O, or the mixture thereof.
15. The substrate processing method of claim 11, wherein, the second reactant comprises at least one of N2, N.sub.2O, NO.sub.2, NH3, N2H2, N2H4, or the mixture thereof.
16. The substrate processing method of claim 11, wherein, the compound comprises at least one of silicon oxide or silicon nitride.
17. The substrate processing method of claim 11, wherein, at least a part of the liner layer is converted into a compound by activated second reactant.
18. The substrate processing method of claim 17, wherein, the whole liner layer is converted into a compound by activated second reactant.
19. The substrate processing method of claim 1, wherein, the thickness of the liner layer is 10 Å or greater than 10 Å.
20. The substrate processing method of claim 11, wherein, a loss of the patterned structure is below 5 Å.
21. The substrate processing method of claim 1, wherein, the patterned structure comprises at least one of: a photo resist, carbon material, or amorphous silicon.
22. The substrate processing method of claim 11, wherein, the widths of the patterned structures are almost the same.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
[0015]
[0016]
[0017]
[0018]
[0019]
[0020]
[0021]
[0022]
DETAILED DESCRIPTION OF THE DISCLOSURE
[0023] The disclosure relates to a method to solve the above-mentioned problems, and more specifically relates to a method of forming a liner layer having a thin thickness as a protective layer to minimize damage to an underlayer.
[0024] In the embodiment of the disclosure, dual frequency RF power may be provided to form a liner layer on a carbon-containing photo resist layer. More specifically, the liner layer may be formed by simultaneously providing a low frequency RF power and a high frequency RF power. The supply of low frequency RF power may have a technical advantage in that the density and the hardness of the liner layer may be improved, while minimizing the underlayer damage. The supply of high frequency RF power may have a technical advantage of promoting radical generation and achieving a high uniformity and a high film growth rate.
[0025]
[0026] A first step S1: a substrate is loaded into a reactor. The substrate may include a patterned structure formed thereon and the patterned structure may comprise a carbon-containing photo resist.
[0027] A second step S2: a first source layer may be formed by supplying a first reactant. The first reactant may be a silicon-containing gas. For instance, the first reactant may comprise at least one of aminosilane, iodosilane, or halide. The first source layer may be formed by adsorbing the first reactant on the photo resist. And a third reactant may be continuously provided together throughout the process, that is, throughout the second step to the eighth step. The third reactant may comprise an inert gas such as Ar, He, or N.sub.2. The third reactant may carry the first reactant to the substrate or facilitate the uniform supply of the first reactant to the reaction space.
[0028] A third step S3: a low frequency RF power and a high frequency RF power are provided simultaneously, resulting in activation of the third reactant.
[0029] A fourth step S4: The activated third reactant may dissociate the first source layer adsorbed on the photo resist. The dissociated first source layer may then be converted into a second source layer. The second source layer may consist of fragments of molecules of the first reactant. For instance, when an aminosilane source gas (as a first reactant) is provided and adsorbed on the photo resist as the first source layer, the second source layer may contain individual silicon elements, carbon elements, nitrogen elements, hydrogen elements, and fragments of ligands (such as alkyl group). The first source layer may be dissociated and converted into the second source layer, and the second source layer may be densified on the photo resist due to the ion bombardment effect of the activated third reactant.
[0030] The second step S2 to the fourth step S4 may be repeated a plurality of times, for instance, M times, and the third reactant may be continuously provided throughout the second step S2 to the fourth step S4. The second step S2 to the fourth step S4 may be referred to as the phase for forming a liner layer. The liner layer may be a protective layer to protect the photo resist underlayer from active species in the following phase for forming a deposition layer. In an exemplary embodiment, a purge step may be provided between the second step S2 and the third step S3, and between the third step S3 and the fourth step S4.
[0031] A fifth step S5: a third source layer may be formed on the second source layer by supplying the first reactant thereto. The first reactant may be a silicon-containing gas and may comprise at least one of aminosilane, iodosilane, or halide. The third source layer may be formed by adsorbing the first reactant on the second source layer. The third source layer may be the same material as the first source layer and the third reactant may be supplied together. The third reactant may be an inert gas such as Ar or N.sub.2, and may carry the first reactant to the substrate and facilitate the uniform supply of the first reactant in the reaction space.
[0032] A sixth step S6: a second reactant may be provided to the reactor. The second reactant may not chemically react with the third source layer, but may chemically react with the third source layer when it is activated. Thus, the second reactant may be referred to as a reactive purge gas.
[0033] In one embodiment of the disclosure, the second reactant may contain oxygen. For instance, the second reactant may comprise least one of O.sub.2, CO.sub.2, N.sub.2O, NO.sub.2, O.sub.3, H.sub.2O, or the mixture thereof.
[0034] In another embodiment of the disclosure, the second reactant may contain nitrogen. For instance, the second reactant may comprise at least one of N.sub.2, N.sub.2O,NO.sub.2, NH.sub.3, N.sub.2H.sub.2, N.sub.2H.sub.4, or the mixture thereof. The third reactant may be continuously provided from the sixth step S6 to the seventh step S7.
[0035] A seventh step S7: high frequency RF power may be provided to the reactor. The high RF power may activate the second reactant. In alternative embodiment, a low frequency RF power and a high frequency RF power may be provided together.
[0036] An eight step S8: the activated second reactant and the third source layer chemically react with each other and form a deposition layer on the second source layer. In one embodiment, the deposition layer may be a patterning layer such as silicon oxide (SiO.sub.x) layer or silicon nitride (Si.sub.xN.sub.y) or any insulating material layer. In another embodiment, the sixth step S6 to the eight step S8 may be carried out simultaneously.
[0037] The fifth step S5 and the eight step S8 may be repeated a plurality of times, for instance, N times, and the third reactant may be continuously provided throughout the second step S5 to the fourth step S8. The fifth step S5 to the eight step S8 may be referred to as the phase for forming a deposition layer. In a selective embodiment, a purge step may be provided between the fourth step S4 and the fifth step S5, and between the fifth step S5 and the sixth step S6, and between the sixth step S6 and the seventh step S7, and between seventh step S7 and the eight step S8, and after the eight step S8. In another embodiment, the second reactant and the third reactant may be continuously provided throughout the fifth step S5 to the eight step S8.
[0038] A ninth step S9: after the first step S1 to S4, that is, a phase for forming a liner layer, and the fifth step S5 to the eight step S8, that is, a phase for forming a deposition layer are completed, the substrate processing process may end.
[0039] According to the embodiment of the disclosure described in
[0040]
[0041] A first phase of
[0042] A second phase of
[0043] The first reactant provided during the timing steps T1 and T5 may contain silicon (Si) such as aminosilane, iodosilane, or halide. For instance, the first reactant may comprise: at least one of TSA, (SiH.sub.3).sub.3N; DSO, (SiH.sub.3).sub.2; DSMA, (SiH.sub.3).sub.2NMe; DSEA, (SiH.sub.3).sub.2NEt; DSIPA, (SiH.sub.3).sub.2N(iPr); DSTBA, (SiH.sub.3).sub.2N(tBu); DEAS, SiH.sub.3NEt.sub.2; DTBAS, SiH.sub.3N(tBu).sub.2; BDEAS, SiH.sub.2(NEt.sub.2).sub.2; BDMAS, SiH.sub.2(NMe.sub.2).sub.2; BTBAS, SiH.sub.2(NHtBu).sub.2; BITS, SiH.sub.2(NHSiMe.sub.3).sub.2; DIPAS, SiH.sub.3N(iPr).sub.2; TEOS, Si(OEt).sub.4; SiCl.sub.4; HCD, Si.sub.2Cl.sub.6; 3DMAS, SiH(N(Me).sub.2).sub.3; BEMAS, SiH.sub.2[N(Et)(Me)].sub.2; AHEAD, Si.sub.2(NHEt).sub.6; TEAS, Si(NHEt).sub.4; Si.sub.3H.sub.8 ; DCS, SiH.sub.2Cl.sub.2; SiHl.sub.3; SiH.sub.2l.sub.2; or the mixture or derivatives thereof.
[0044] Thus, a SiCN liner layer as a protective layer may be formed on the photo resist during the first phase according to embodiments of
[0045] The second reactant provided during the timing steps T2 and T5 of
[0046] The third reactant provided during the timing steps T1 to T8 may be an inert gas. For instance, the third reactant may comprise at least one of Ar, He, or N.sub.2 or the mixture thereof.
[0047] The high frequency RF power provided during the phase for forming a liner layer may increase the ion density of the activated third reactant (such as Ar ions) and the low frequency RF power provided together may contribute to the film densification of the liner layer due to the ion bombardment effect. As a result, it contributes to minimizing damage to the underlying layer of the photoresist. Thus, the substrate processing method according to the disclosure may have a technical advantage in that: (1) the liner layer may be densified due to increased ion density; (2) the film conformality on the patterned structure may improve, and (3) the underlayer damage may decrease by providing the high frequency RF power and the low frequency RF power simultaneously.
[0048] According to the embodiment of
[0049]
[0050]
[0051] In
[0052] In
[0053] In
[0054]
[0055] In
[0056] In addition, when the SiCN liner layer is thicker, for instance, 20 Å, and the SiCN liner layer is formed by providing only a high frequency RF power or a high frequency RF power and a low frequency RF power together, followed by forming SiO.sub.2 patterning layer thereon by PEALD, the underlayer loss may be less than 5 Åand 1 Å,respectively. That is, below 5 Å, thus the underlayer loss may be controlled below the range that does not affect the device performance.
[0057]
[0058] In step 1 of
[0059] In step 2 of
[0060] In step 3 of
[0061] In step 4 of
[0062] Table 1 shows a process condition for SiCN liner layer and SiO.sub.2 deposition layer according to one embodiment of disclosure.
TABLE-US-00001 a process condition for SiCN liner layer and SiO.sub.2 deposition layer Process parameter Process condition SiCN liner layer SiO.sub.2 deposition layer Heating block temperature(°C) 50 to100 (preferably 60 to 80) 50 to 100 (preferably 60 to 80) Gas flow rate (sccm) Source carrier Ar 1,000 to 8,000 (preferably 3,000 to 5,000) 1,000 to 8,000 (preferably 3,000 to 5,000) Purge Ar 0 1,000 to 2,000 (preferably 1,300 to 1,500) Purge N.sub.2 1,000 to 2,000 (preferably 1,300 to 1,500) 0 Reactant O.sub.2 0 3,000 to 6,000 (preferably 4,000 to 5,000) Process time (second) Source feeding 0.05 to 0.4(preferably 0.1 to 0.3) 0.05 to 0.4(preferably 0.1 to 0.3) Source purge 0.1 to 0.5 (preferably 0.2 to 0.4) 0.1 to 0.5 (preferably 0.2 to 0.4) Reactant 0.05 to 0.4 (preferably 0.05 to 0.4 (preferably Plasma power (W) HRF (13.56 MHz) 150 to 300 (preferably 200 to 250) 150 to 500 (preferably 200 to 250) LRF (430 kHz) 100 to 200 (preferably 125 to 175) 0 to 500 (preferably 0 or 100 to 300) Process pressure (Pa) 200 to 400 (preferably 250 to 350) 200 to 500 (preferably 250 to 350) Silicon source aminosilane aminosilane
[0063]
[0064] In
[0065] The process gas is exhausted through an exhaust unit 80, which may be an exhaust pump. The gas supply unit 20 is connected to the RF power supply unit. The RF power supply unit may comprise: a matching network 50, a high frequency RF power generator 60, and/or a low frequency RF power generator 70. The RF power may be provided to the reactor and the intensity of RF power according to the disclosure may be controlled by step by programmable control unit such as PC controller (not shown).
[0066] It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the disclosure as defined by the following claims.