A Y2O3 thin film with plasma etching resistance and a method for manufacturing the same.

Abstract

To provide a method for manufacturing a Y2O3 thin film that exhibits excellent resistance to fluorocarbon-based high-density plasma. [Solution] The method is characterized by using Bis(methylcyclopentadienyl)(N'-isopropyl-Nn-propylacetamidinate)Yttrium(Y(MeCp)2(iPr-nPrAMD)) as a precursor and producing a Y2O3 thin film by atomic layer deposition (ALD).

Description

[Technical Field]

[0001] This invention relates to a Y2O3 thin film having plasma etching resistance and a method for producing the same. [Background technology]

[0002] Oxide ceramics such as Al2O3 and SiO2 are commonly used to protect semiconductor components from plasma erosion and particle contamination. However, with the increasing power output of fluorine-based plasma systems, the performance of Al2O3 and SiO2 coatings is becoming increasingly problematic. Furthermore, these materials have been shown to be vulnerable to fluorine-based plasma etching processes when exposed to repetitive cycles in a chamber. To address these issues, yttrium oxide (Y2O3) is being proposed in recent years as a widely used protective coating material due to its low etching rate and low chemical reactivity.

[0003] Patent Document 1: Korean Published Patent No. 10-2017-0006807 proposes a technique for depositing yttria on component parts by chemical vapor deposition, using Tris[N,N-bis(trimethylsilyl)amide]yttrium (YTDTMSA) as a precursor. However, this publication does not mention at all whether the yttria (Y2O3) thin film deposited by this method is resistant to chemical etching reactions by fluorinated plasma. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Korean Published Patent No. 10-2017-0006807 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a method for producing a Y2O3 thin film that can exhibit resistance to fluorocarbon-based high-density plasma.

[0006] This invention investigates the precursors used in the production of Y2O3 thin films, examines the ALD growth dynamics of the thin films associated with them, and systematically analyzes the dependence of the growth rate and physical properties of Y2O3 thin films on growth temperature. Furthermore, the etching resistance characteristics of ALD-Y2O3 thin films in fluorine-based plasmas were investigated in detail. [Means for solving the problem]

[0007] In accordance with the above objective, the present invention uses Bis(methylcyclopentadienyl)(N'-isopropyl-Nn-propylacetamidinate) Yttrium(Y(MeCp)2(iPr-nPrAMD)) as a precursor to produce an ALD-Y2O3 thin film.

[0008] In other words, the present invention provides a method for producing a Y2O3 thin film, characterized by using Bis(methylcyclopentadienyl)(N'-isopropyl-Nn-propylacetamidinate)Yttrium(Y(MeCp)2(iPr-nPrAMD)) as a precursor and using ALD (Atomic Layer Deposition).

[0009] The above is characterized by using one or more of H2O, O3, O2, and H2O2 as reactants along with the Y(MeCp)2(iPr-nPrAMD) precursor.

[0010] In other words, the present invention provides a method for producing a Y2O3 thin film, characterized by using Bis(methylcyclopentadienyl)(N'-isopropyl-Nn-propylacetamidinate) Yttrium(Y(MeCp)2(iPr-nPrAMD)) as a precursor, using ALD (Atomic Layer Deposition), and using one or more of H2O, O3, O2, and H2O2 as reactants.

[0011] The present invention provides a method for producing a Y2O3 thin film, characterized in that one ALD cycle includes the steps of introducing Y(MeCp)2(iPr-nPrAMD) with an inert gas at a flow rate of 30 to 100 sccm for a predetermined time t1, purging with an inert gas at a flow rate of 30 to 100 sccm for t2, introducing 30 to 100 sccm of H2O reactant for t3, and further purging with an inert gas at a flow rate of 30 to 100 sccm for t4.

[0012] The present invention provides a method for manufacturing a Y2O3 thin film, characterized in that the thin film growth temperature can be controlled between 150°C and 350°C.

[0013] The present invention provides a method for manufacturing a Y2O3 thin film, characterized in that t1 is 3 seconds or less.

[0014] The present invention provides a method for manufacturing a Y2O3 thin film, characterized in that t2 and t4 are 18 to 22 seconds, and t3 is 2 to 22 seconds.

[0015] The present invention provides a method for manufacturing a Y2O3 thin film, characterized in that Y(MeCp)2(iPr-nPrAMD) is chemically adsorbed in a self-limiting manner, and the thickness of the formed Y2O3 thin film can be linearly increased in accordance with the increase in the ALD cycle.

[0016] A method for forming a protective coating material for a semiconductor manufacturing component is provided, wherein a Y2O3 thin film is formed on a semiconductor manufacturing component as a protective coating against chemical etching by fluorinated plasma according to the method for manufacturing the above Y2O3 thin film.

[0017] A semiconductor manufacturing component is provided, which comprises a Y2O3 protective coating material having resistance to chemical etching by fluorinated plasma according to the method for forming a protective coating material for the semiconductor manufacturing component.

Advantages of the Invention

[0018] According to the present invention, the ALD-Y2O3 thin film manufactured using Bis(methylcyclopentadienyl)(N'-isopropyl-N-n-propylacetamidinate) Yttrium (Y(MeCp)2(iPr-nPrAMD)) as a precursor has excellent etching resistance in fluorine-based plasma.

[0019] According to the present invention, the ALD-Y2O3 thin film manufactured using Y(MeCp)2(iPr-nPrAMD) as a precursor is of high purity and high density, has a wide ALD temperature window, and exhibits properties similar to those of Y2O3 bulk. Therefore, it is a promising thin film in various application fields including protective coatings against CF4-based plasma.

[0020] According to the present invention, the formation process of the ALD-Y2O3 thin film manufactured using Y(MeCp)2(iPr-nPrAMD) as a precursor shows a self-limiting reaction mechanism, and the growth of the ALD-Y2O3 thin film shows linearity with respect to the number of ALD cycles. Therefore, the thin film thickness can be digitally controlled with high precision.

Brief Description of the Drawings

[0021] [Figure 1](a) shows the growth rate of the ALD-Y2O3 thin film at 260 °C according to the pulse time of Y(MeCp)2(iPr-nPrAMD) and the pulse time of H2O. (b) shows the growth rate of the ALD-Y2O3 thin film according to the H2O pulse time at the growth temperature of 260 °C. (c) shows the film thickness of the ALD-Y2O3 thin film according to the number of ALD cycles at the growth temperature of 260 °C. (d) shows the growth rate and refractive index (in the range of 150 °C to 290 °C) of the ALD-Y2O3 thin film according to the growth temperature. [Figure 2] (a) shows the XRD pattern of the ALD-Y2O3 thin film according to the film formation temperature in the range of 150 °C to 290 °C. (b) shows the XRR pattern. [Figure 3] (a) shows the AES depth profile of the ALD-Y2O3 thin film fabricated at the film formation temperature of 150 °C, and (b) shows the AES depth profile of the ALD-Y2O3 thin film fabricated at the film formation temperature of 290 °C. [Figure 4] Shows the plasma etching rates of the ALD-Al2O3 thin film and the ALD-Y2O3 thin film, which are calculated based on the film thickness difference before and after 15 minutes of RIE treatment.

Mode for Carrying Out the Invention

[0022] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0023] Atomic layer deposition (ALD) of Y2O3 thin films using Y(MeCp)2(iPr-nPrAMD) precursors and H2O reactants was investigated. At a growth temperature of 260°C, the self-limiting reaction mechanism of the ALD-Y2O3 thin film was confirmed. Furthermore, a saturation growth rate of approximately 0.11 nm / cycle was confirmed. In addition, a consistent growth rate was maintained across a wide ALD temperature window of 150°C to 290°C. The ALD-Y2O3 thin film was found to have a typical cubic polycrystalline structure, independent of the growth temperature, which is thought to be due to the stoichiometric composition of Y2O3, negligible carbon impurities, and high thin film density. Moreover, even at a low growth temperature of 150°C, ALD-Y2O3 exhibited a significantly lower plasma etching rate (approximately 0.77 nm / min) compared to the etching rate of ALD-Al2O3 (approximately 4.6 nm / min) when using a mixed gas Ar / CF4 / O2 and a plasma power of 400 W with RIE. Furthermore, it was confirmed that the growth temperature of the Y2O3 thin film has almost no effect on the etching rate.

[0024] 1. Introduction In the semiconductor industry, miniaturized semiconductor devices are sensitive to particle and metallic contamination, making this a significant concern. For example, three-dimensional vertical NAND (3D V NAND) technology is used to directly reduce the linewidth of integrated circuits on a wafer and stack circuits in multiple layers. Therefore, dry etching processes using fluorocarbon-based high-density plasma are repeatedly performed in a chamber, while ceramic equipment components are exposed to the plasma atmosphere. Furthermore, the fluorocarbon plasma impacts and erodes the inner wall material of the equipment components. In particular, showerheads positioned facing the wafer can undergo significant etching under harsh high-density plasma flux. Such erosion of equipment components and generation of contaminating particles cause serious problems that reduce yield during mass production. Therefore, in recent years, the development of advanced protective coating materials and appropriate film deposition techniques has been intensively studied to minimize erosion of equipment components and reduce the generation of contaminating particles. The main requirements for coatings for equipment components are that the coating itself does not emit particles and does not contain metallic contaminants. Therefore, it is necessary to exhibit high corrosion and erosion resistance under various chemical and plasma conditions. To reduce corrosion, a ceramic coating with excellent resistance to fluorine plasma can be used.

[0025] To protect semiconductor components from plasma erosion and particle contamination, oxide ceramics such as Al2O3 and SiO2 are commonly used. However, with the increasing power output of fluorine-based plasma devices, the performance of Al2O3 and SiO2 coatings is becoming increasingly problematic. Furthermore, these materials have been shown to be vulnerable to fluorine-based plasma etching processes when exposed to repetitive cycles in a chamber. To address these issues, yttrium oxide (Y2O3) has been increasingly proposed as a widely used protective coating material due to its low etching rate and low chemical reactivity. Y2O3 possesses many excellent properties that make it highly attractive in multiple industrial applications. These properties include a wide energy bandgap (5.5 eV~5.8 eV) and band offset (2.3 eV), a relatively high dielectric constant (14~18), a high refractive index (1.9), a high melting point (2430°C) that ensures excellent thermal stability, and good thermal conductivity (κ=0.33 W cm⁻¹). -1 K -1 These include, among others. In particular, Y2O3 has excellent wear resistance, high mechanical and dielectric strength, as well as excellent corrosion and chemical resistance, making it an ideal choice as a protective coating for fluorine-based plasma equipment components.

[0026] To date, Y2O3 protective coatings have been extensively studied using various deposition techniques, including atmospheric pressure plasma spraying (APS), vacuum plasma spraying (VPS), physical vapor deposition (PVD), and chemical vapor deposition (CVD). However, to improve protective performance and reduce coating thickness, it is necessary to address defects such as pore formation, impurities, and insufficient adhesion. In this context, atomic layer deposition (ALD) technology has recently attracted attention as a practical method for forming Y2O3 protective coatings. In this process, precursor molecules in a gaseous state are introduced into a chamber and react with the substrate surface to grow thin films layer by layer. The main advantages of ALD lie in its atomic-scale deposition and inherently self-limiting growth mechanism, which provides numerous benefits such as precise film thickness control at the atomic level, perfectly adhering pinhole-free coatings, and excellent step coverage in very complex structures. Furthermore, recent developments in batch-type ALD equipment have accelerated the application of ALD protective layers to large components. ALD-Y2O3 has been demonstrated using various precursors such as Y(MeCp)3, Y(EtCp)3, Y(iPrCp)3, Y(thd)3, and Y(EtCp)2(iPr2-amd) with oxidizing agents such as H2O and O3. However, most of the research on ALD-Y2O3 to date has focused on high dielectric constant applications, and there are very few studies reporting on its corrosion resistance properties to fluorine-based plasmas. Furthermore, the relatively narrow ALD temperature window of some precursors may limit its potential in diverse industrial applications, and further improvements are needed. For example, the ALD temperature window of Y(MeCp)3 is 250-300°C, and Y(EtCp)3 and Y(iPrCp)3 also exhibited similarly narrow ALD temperature windows (250-280°C for Y(EtCp)3 and 245-300°C for Y(iPrCp)3). For the Y(EtCp)2(iPr2-amd) precursor, the ALD temperature window is 300–450°C, which may limit low-temperature applications. On the other hand, Y(thd)3 showed a relatively wide ALD temperature window of 250–375°C, but the presence of high carbon and hydrogen impurities has also been reported.

[0027] Therefore, in this invention, we investigated ALD-Y2O3 thin films using Bis(methylcyclopentadienyl)(N'-isopropyl-Nn-propylacetamidinate) Yttrium(Y(MeCp)2(iPr-nPrAMD)). The ALD growth dynamics of Y(MeCp)2(iPr-nPrAMD) were investigated in detail. Furthermore, the dependence of the growth rate and physical properties of the Y2O3 thin film on the growth temperature was systematically analyzed. Finally, the etching resistance characteristics of the ALD-Y2O3 thin film in fluorine-based plasmas were discussed in detail.

[0028] 2. Materials and Methods The Y2O3 thin film was deposited on a p-type Si(100) wafer by ALD in the growth temperature range of 150°C to 290°C. Bis(methylcyclopentadienyl)(N'-isopropyl-Nn-propylacetamidinate)yttrium(Y(MeCp)2(iPr-nPrAMD), iChems Co. Ltd.) was used as the precursor, and H2O was used as the reactant. Y(MeCp)2(iPr-nPrAMD) and H2O were housed in separate containers maintained at 120°C and room temperature, respectively, and sufficient vapor pressure was supplied. In addition to H2O, the present invention allows the use of various oxidizing agents such as O3, O2, and H2O2 as reactants. That is, it is possible to substitute O3, O2, H2O2, etc., as reactants in the examples using H2O while keeping other conditions the same.

[0029] One ALD cycle includes the steps of introducing Y(MeCp)2(iPr-nPrAMD) with an inert gas at a flow rate of 30-100 sccm, preferably 45-55 sccm, for a predetermined time t1, purging with an inert gas at a flow rate of 30-100 sccm, preferably 45-55 sccm, for t2, introducing the H2O reactant at a flow rate of 30-100 sccm, preferably 45-55 sccm, for t3, and further purging with an inert gas at a flow rate of 30-100 sccm, preferably 45-55 sccm, for t4. The operating pressure of the chamber is 1.08 × 10⁻⁶ -1 Torr~1.32×10 -1 It can be maintained in Torr.

[0030] In a preferred embodiment, a single ALD cycle of Y2O3 consisted of introducing Y(MeCp)2(iPr-nPrAMD) with 50 sccm of Ar for 3 seconds, followed by purging with 50 sccm of Ar for 20 seconds, then introducing 50 sccm of H2O reactant for 2 seconds, and finally purging with 50 sccm of Ar for another 20 seconds. The operating pressure of the chamber was 1.2 × 10⁻⁶. -1 It was maintained by Torr.

[0031] In the above, t2 and t4 can be set to 18-22 seconds, and t3 can be set to 2-22 seconds. The ALD-Y2O3 thin film sets were deposited by varying the growth temperature within the range of 100 to 350°C, preferably **150 to 290°C**. The Y2O3 thin films deposited at 150°C, 180°C, 220°C, 260°C, and 290°C were denoted as Y2O3-150, Y2O3-180, Y2O3-220, Y2O3-260, and Y2O3-290, respectively. The number of repeated ALD cycles was intentionally adjusted to obtain nearly identical film thicknesses of **approximately 30 nm (27 to 33 nm)**, independent of the growth temperature, thereby minimizing the influence of film thickness on the physical and chemical properties of the Y2O3 thin films.

[0032] The film thickness and corresponding refractive index were evaluated using spectroscopic ellipsometry (α-SE, JA Woollam Co., Inc.). The crystal structure and density of the thin film were analyzed by X-ray diffraction (XRD) and X-ray reflectivity (XRR) measurements using a Rigaku SmartLab diffractometer (D / MAX-2500V) with Cu-Kα1 emission. Furthermore, the depth profile of the composition was investigated using Auger electron spectroscopy (AES, PHI-710, ULVAC-PHI). Surface morphology was observed using an atomic force microscope (AFM). High-density plasma resistance was evaluated by reactive ion etching (RIE, LABStar, TTL), where etching was performed for 15 minutes using a mixed gas of Ar (50 sccm), CF4 (45 sccm), and O2 (5 sccm) under conditions of plasma power of 400 W and pressure of 50 mTorr.

[0033] 3. Results and Discussion First, we investigated the self-limiting growth behavior of ALD-Y2O3 thin films. Figure 1a shows the growth rate of the Y2O3 thin film as a function of the Y(MeCp)2(iPr-nPrAMD) precursor pulse time, with the growth temperature fixed at a constant 260°C, in order to confirm the ALD reaction mechanism. In one ALD cycle, the steps other than the Y(MeCp)2(iPr-nPrAMD) precursor pulse were fixed to a 20-second purge, a 10-second H2O reactant pulse, and then another 20-second purge. It was confirmed that the growth rate increased as the Y(MeCp)2(iPr-nPrAMD) pulse time was increased from 2 seconds to 5 seconds, and saturation was reached at 0.11 nm / cycle at 3 seconds or more. This result indicates that the Y(MeCp)2(iPr-nPrAMD) precursor reacts by a self-limiting chemisorption mechanism. Figure 1b shows the growth rate of the Y2O3 thin film as a function of the H2O pulse time at a growth temperature of 260°C. In this case, the Y(MeCp)2(iPr-nPrAMD) precursor pulse, precursor purge, and reactant purge steps were fixed at 3 seconds, 20 seconds, and 20 seconds, respectively. As shown in Figure 1b, the growth rate of the Y2O3 thin film saturated at 0.11 nm / cycle when the H2O pulse time was 2 seconds or longer, confirming that a 2-second H2O pulse was sufficient for complete reaction with the chemiadsorbed Y(MeCp)2(iPr-nPrAMD) precursor. Therefore, it was confirmed that the saturated growth rate of the Y2O3 thin film at 260°C is approximately 0.11 nm / cycle. Another important feature of ALD is that the thin film thickness can be digitally controlled by the number of repeated ALD cycles. Therefore, as shown in Figure 1c, the dependence of the Y2O3 thin film thickness on the number of repeated ALD cycles was investigated. As is clear from Figure 1c, the thickness of the Y2O3 thin film increased linearly as the number of ALD-Y2O3 cycles increased from 300 to 900. Furthermore, the extrapolated line shows no growth delay, suggesting rapid nucleation of Y2O3 by ALD. Next, as shown in Figure 1d, the effect of growth temperature on the growth rate and refractive index of the Y2O3 thin film was investigated. Even when the growth temperature was increased from 150°C to 290°C, the growth rate of Y2O3 remained almost constant, and no CVD-like growth was observed. This result suggests that Y2O3 has a wide ALD temperature window.Also, within the ALD temperature window, a refractive index of approximately 1.87, which is close to that of the Y2O3 bulk (1.9), was obtained. Since the refractive index of a thin film generally depends on the thin film density, it is推测 that almost equivalent thin film densities were obtained in the temperature range of 150 °C to 290 °C. Furthermore, the self-decomposition temperature of the Y(MeCp)2(iPr-nPrAMD) precursor may be higher than 290 °C. In this study, although this could not be directly confirmed due to the temperature limitation of the ALD apparatus used, it is noteworthy that there is a possibility that the upper limit of the ALD temperature window can be further extended.

[0034] It was evaluated by X-ray diffraction (XRD). The XRD patterns shown in Fig. 2(a) were obtained from Y2O3 thin films fabricated by adjusting the number of ALD cycles considering the growth rate at each growth temperature so that the film thickness was approximately the same as about 30 nm. As shown in Fig. 2(a), all Y2O3 thin films showed the (222), (400), (431), and (440) planes of a typical cubic polycrystalline phase corresponding to Y2O3 (JCPDS 31-1105) regardless of the growth temperature. These characteristic diffraction peaks were also observed at a low growth temperature of 150 °C, which is considered to be due to the formation of a high-density and high-purity Y2O3 thin film. On the other hand, with an increase in the growth temperature, a tendency was confirmed that the orientation of the Y2O3 (222) plane becomes dominant due to the influence of higher thermal energy, and this behavior also agrees with the reports of previous studies. Therefore, the influence of the growth temperature on the film density was investigated by X-ray reflectivity (XRR) analysis. The film density was calculated from the position of the critical angle shown in Fig. 2(b). The film densities of the Y2O3-150, Y2O3-180, Y2O3-220, Y2O3-260, and Y2O3-290 samples were 4.88 g / cm 3 , 4.95 g / cm 3 , 5.00 g / cm 3 , 4.94 g / cm 3 , and 4.98 g / cm 3 , respectively. Regardless of the growth temperature, all Y2O3 thin films had a bulk Y2O3 (5.03 g / cm 3The film density is close to ), which supports the XRD observation results showing that a well-crystallized phase is formed even at a low temperature of 150°C. Similarly, the fact that the refractive index (approximately 1.87) is nearly constant within the ALD temperature window can also be explained by this high and stable film density.

[0035] Furthermore, AES depth profile analysis was performed to investigate the effect of growth temperature on the composition and impurities of the Y2O3 thin film. For this purpose, ALD-Y2O3 thin films grown at 150°C and 290°C were selected. As shown in Figures 3(a) and 3(b), it was confirmed that stoichiometric Y2O3 thin films were well formed by ALD. In addition, carbon impurities were below the detection limit of AES, which means that the ligand of the Y(MeCp)2(iPr-nPrAMD) precursor was completely removed even at the low temperature of 150°C by the optimized ALD process. Therefore, the ALD-Y2O3 thin film has high purity and density and exhibits properties similar to bulk Y2O3, confirming that it is a promising thin film for various application fields, including protective coatings for CF4 substrate plasmas.

[0036] The plasma etching rate of ALD-Y2O3 thin films fabricated in the growth temperature range of 150°C to 290°C was evaluated using reactive ion etching (RIE) under conditions of plasma power of 400 W and pressure of 50 mTorr. A mixed gas of Ar (50 sccm), CF4 (45 sccm), and O2 (5 sccm) was used. Of the etching gases used, Ar is chemically stable and therefore induces only physical etching. CF4 is known to contribute to both chemical and physical etching, while O2 is used to remove carbon from the thin film or Si surface by converting the carbon produced by the decomposition of CF4 into CO2 gas. A Y2O3 thin film with a thickness of approximately 30 nm was used for the plasma etching test. For comparison, an Al2O3 thin film with a thickness of approximately 110 nm was fabricated by ALD under the same temperature conditions (150°C), and its etching behavior was compared with that of the ALD-Y2O3 thin film. After performing the RIE process for 15 minutes, the plasma etching rate was calculated based on the difference in film thickness before and after etching. As shown in Figure 4, the Y2O3 thin film fabricated at 150°C showed a low plasma etching rate of 0.77 nm / min, while the Al2O3 thin film fabricated at the same temperature showed a very high etching rate of 4.6 nm / min, which was approximately six times higher than that of the Y2O3 thin film.

[0037] The difference in plasma etching rates between the two materials indicates that the Y2O3 thin film exhibits higher resistance to Ar / CF4 / O2 plasma compared to the Al2O3 thin film. Furthermore, it is noteworthy that the growth temperature had little effect on the dry etching gas conditions for the Y2O3 thin film. This is likely due to the high purity and density of the ALD-Y2O3 thin film formed using the Y(MeCp)2(iPr-nPrAMD) precursor and H2O. These results can be explained by the differences in the chemical etching reactions by fluorinated plasma in the Y2O3 and Al2O3 thin films.

[0038] TIFF2026115024000002.tif39166

[0039] According to the fluorination reaction equation described above, Y2O3 and Al2O3 thin films are generally fluorinated at their surfaces, forming surface layers of YF3 and AlF3, and the CO2 produced in this process is removed by a vacuum system. In this reaction process, the standard enthalpy of formation and standard Gibbs free energy are negative, so the YF3 and AlF3 surface layers are formed spontaneously. Therefore, when Y2O3 and Al2O3 thin films are exposed to Ar / CF4 / O2 plasma, similar YF3 and AlF3 layers can be formed on the surfaces of both films. The formation of the YF3 surface layer can reduce the erosion rate of the Y2O3 thin film due to its high boiling point of 2230°C, and the AlF3 surface layer similarly has the effect of reducing the erosion rate of the Al2O3 thin film. However, the boiling point of AlF3 is low at 1291°C, which indicates that YF3 is more resistant to evaporation. Furthermore, it has been reported that the physical etching rate of AlF3 is much faster than that of YF3, while the physical etching rates of Y2O3 and Al2O3 itself are almost equivalent. Therefore, the difference in plasma etching rates between Y2O3 and Al2O3 can be explained by the continuous surface fluorination reaction and the difference in the physical etching rates of their respective fluoride layers. As a result, plasma erosion is suppressed in Y2O3 compared to Al2O3, suggesting that ALD-Y2O3 formed using the Y(MeCp)2(iPr-nPrAMD) precursor and H2O is a promising protective coating material compared to ALD-Al2O3.

[0040] 4. Conclusion The ALD-Y2O3 process using Y(MeCp)2(iPr-nPrAMD) precursor and H2O as reactants exhibited a wide ALD temperature window ranging from 150°C to 290°C, and was confirmed to have a consistent growth rate and refractive index. Furthermore, because the ALD-Y2O3 thin films were highly pure and dense, they exhibited a typical cubic polycrystalline phase similar to bulk Y2O3, independent of the growth temperature. The plasma etching rates of ALD-Y2O3 thin films fabricated at different growth temperatures were evaluated by reactive ion etching (RIE) using an Ar / CF4 / O2 mixed gas under plasma power of 400 W. For comparison, the plasma etching rate of ALD-Al2O3 thin films was similarly investigated. When a growth temperature of 150°C was applied to both ALD-Al2O3 and Y2O3 thin films, ALD-Y2O3 showed a significantly lower plasma etching rate compared to ALD-Al2O3. The difference in plasma etching rates observed between Y2O3 and Al2O3 was explained in detail based on the differences in continuous surface fluorination reactions and physical etching rates. Furthermore, it was observed that the effect of growth temperature on the dry etching behavior of the Y2O3 thin film was minimal. These results suggest that ALD-Y2O3 formed using Y(MeCp)2(iPr-nPrAMD) precursor and H2O is a promising protective coating material for semiconductor manufacturing components, and in this respect, it is superior to ALD-Al2O3.

[0041] The ALD-Y2O3 of the present invention, which uses a Y(MeCp)2(iPr-nPrAMD) precursor and H2O, can be applied as a protective coating to a wide variety of semiconductor manufacturing components, such as plasma shower heads, bellons, various piping materials, back pressure device components, laser heads, various fixing jigs, etching masks, wafer holders, and chamber inner walls, which are applied in semiconductor manufacturing processes.

[0042] Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art in which the present invention pertains. Furthermore, terms defined in commonly used dictionaries should not be interpreted ideally or excessively unless explicitly specified otherwise. Throughout this specification, where any part is described as "containing" a component, unless otherwise specified, this does not exclude other components, but rather means that other components may be further included. Also, singular terms may take plural forms depending on the context.

[0043] The rights of the present invention are not limited to the embodiments described above, but are defined by the claims, and it will be obvious to a person skilled in the art to which the present invention belongs that various modifications and improvements can be made within the scope of the rights described in the claims.

Claims

1. As a precursor, Bis(methylcyclopentadienyl)(N'-isopropyl-Nn-propylacetamidinate) Yttrium (Y(MeCp) 2 Using (iPr-nPrAMD), the Atomic Layer Deposition (ALD) method is employed. H as a reactant 2 O, O 3 , O 2 , and H 2 O 2 Use at least one of the following: Y characterized by 2 O 3 A method for manufacturing thin films.

2. One ALD cycle is for a predetermined time t 1 and during this time, Y(MeCp) 2 (iPr-nPrAMD) is supplied together with an inert gas at a flow rate of 30 to 100 sccm. Subsequently, a purge with the inert gas is performed at a flow rate of 30 to 100 sccm for a predetermined time t 2 . Then, an H 3 O reactant is supplied at a flow rate of 30 to 100 sccm for a predetermined time t 2 . Further, a purge with the inert gas is performed at a flow rate of 30 to 100 sccm for a predetermined time t 4 , including the step of Y according to claim 1 2 O 3 A method for manufacturing thin films.

3. The thin film growth temperature is controlled within the range of 150°C to 350°C. Y according to claim 1 2 O 3 A method for manufacturing thin films.

4. said t 1 is less than 3 seconds Y according to claim 2 2 O 3 A method for manufacturing thin films.

5. said t 2 and t 4 The time is 18 to 22 seconds, and the aforementioned t 3 The time is 2 to 22 seconds. Y according to claim 2 2 O 3 A method for manufacturing thin films.

6. Y(MeCp) 2 (iPr-nPrAMD) is chemically adsorbed by a self-limiting mechanism, and Y is formed. 2 O 3 The film thickness can be increased linearly in response to an increase in the number of ALD cycles. Y according to claim 4 2 O 3 A method for manufacturing thin films.

7. Y according to any one of claims 1 to 6 2 O 3 By the method of manufacturing a thin film, Y 2 O 3 Thin films are formed on semiconductor manufacturing components as protective coatings against fluorinated plasma chemical etching. A method for forming a protective coating material for semiconductor manufacturing components, characterized by the features described herein.

8. Y formed by the method for forming a protective coating material for semiconductor manufacturing components described in claim 7, which has resistance to fluorinated plasma chemical etching. 2 O 3 Includes protective coating material A semiconductor manufacturing component characterized by the following features.

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