Laminate for chamber inner wall of semiconductor manufacturing apparatus and method for producing the same

Abstract

To provide a means which can form a side YF3 film on the inside wall, etc., of the chamber of a semiconductor-manufacturing device without causing film unevenness.SOLUTION: A laminate for an inner wall of a chamber of a semiconductor manufacturing apparatus, comprising a base material, an amorphous layer disposed on a surface of the base material, and a crystalline layer disposed on a surface of the amorphous layer, wherein the amorphous layer has a thickness of 1 nm or more and 10 nm or less, the crystalline layer consists essentially of yttrium and fluorine, and the crystalline layer has a density of 4.7g / cm3 or more and 5.3g / cm3 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate for the inner wall of a chamber of a semiconductor manufacturing device and a method for manufacturing the same. [Background technology]

[0002] In semiconductor manufacturing equipment, the manufacturing process using corrosive gases corrodes the inside of the equipment, generating dust particles and metal contamination. Internal components made of aluminum (Al) alloys are particularly susceptible to corrosion by halogen gases, such as fluorine. Because dust particles and metal contamination reduce the yield of semiconductor products, corrosion-resistant coatings, typically aluminum oxide (Al2O3) and yttrium oxide (Y2O3), have traditionally been formed on the inner walls of semiconductor manufacturing equipment chambers using techniques such as thermal spraying, physical vapor deposition (PVD), aerosol deposition (AD), and atomic layer deposition (ALD). There is a particular demand for highly corrosion-resistant coatings, such as those made using ALD, which can produce conformal, dense films.

[0003] In cutting-edge semiconductor devices, the demands for dust generation and metal contamination are becoming stricter as devices become smaller, and the corrosion resistance of conventional thermally sprayed Al2O3 or YO3 films on the inner walls of chambers in semiconductor manufacturing equipment is insufficient. For this reason, a technology using YOF materials as coating films has been proposed (see, for example, Patent Document 1). A technology using oxygen-free YF3 films has also been proposed (see, for example, Patent Document 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2023-014880 [Patent Document 2] Special Publication No. 2022-510278 Summary of the Invention [Problem to be solved by the invention]

[0005] However, when forming YF3 films using ALD, the vapor pressure of the yttrium-containing raw materials is low, making film formation difficult. For example, compared to trimethylaluminum (TMA), which is used to form Al2O3 films, commercially available yttrium-containing raw materials have vapor pressures that are three orders of magnitude lower (see Figure 1). Therefore, due to a shortage of yttrium-containing raw materials, it is difficult to form a uniformly thick and conformal YF3 film.

[0006] In addition, Al alloys are corroded by the fluorine used in forming the YF3 film, and differences in surface conditions such as crystal orientation and particle size cause differences in the surface adsorption efficiency of raw materials containing yttrium, making it difficult to form a YF3 film without causing film unevenness.

[0007] Therefore, an object of the present invention is to provide a means for forming a YF3 film without causing film unevenness on the inner walls of the chamber of a semiconductor manufacturing device. [Means for solving the problem]

[0008] The above-mentioned problems of the present invention can be solved by the following means.

[0009] That is, the present invention is a laminate for an inner wall of a chamber of a semiconductor manufacturing apparatus, A substrate; an amorphous layer disposed on a surface of the substrate; a crystalline layer disposed on a surface of the amorphous layer, the amorphous layer has a thickness of 1 nm or more and 10 nm or less; the crystalline layer consists essentially of yttrium and fluorine; The density of the crystalline layer is 4.7 g / cm 3 More than 5.3g / cm 3 The laminate is as follows: [Effects of the Invention]

[0010] According to the present invention, a means is provided for forming a YF3 film without causing film irregularities on the inner walls of the chamber of a semiconductor manufacturing device. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a graph showing the vapor pressure versus temperature for trimethylaluminum (TMA), Ybeta-prime, tris(methylcyclopentadienyl)yttrium (Y(MeCp)3), and tris(isopropylcyclopentadienyl)yttrium (Y(i-PrCp)3). [Figure 2] FIG. 2 is a schematic diagram of a laminate according to one embodiment of the present invention. [Figure 3] FIG. 3 is a schematic diagram of a cross-sectional SEM image of the laminate of Comparative Example 1. [Figure 4] FIG. 4 is a graph showing the X-ray diffraction pattern of the laminate of Example 1. [Figure 5] FIG. 5 is a graph showing the X-ray diffraction patterns of the crystalline layer (YF3 film) of the laminate of Example 9 and the amorphous layer (YF3 film) of Comparative Example 2. [Figure 6] FIG. 6 shows the results of visual sensory evaluation of the laminates of Examples 2, 4, 6 and 8 and Comparative Example 1. [Figure 7] FIG. 7 shows the results of evaluation of film peeling and film cracking for the laminates of Examples 1 and 7 and Comparative Examples 3 and 4. [Figure 8] FIG. 8 shows the results of evaluation of film peeling and film cracking for the laminates of Examples 1, 3, 5 and 7 and Comparative Example 3. [Figure 9] FIG. 9 shows the results of evaluation of film peeling and film cracking for the laminates of Examples 2, 4, 6 and 8. [Figure 10] FIG. 10 is a graph showing the relationship between the Al2O3 normalized etching depth and the film density for the crystalline layers (YF3 films) of the laminates of Examples 1 to 9 and Comparative Example 1, and the amorphous layers (YF3 films and Al2O3 films) of the laminates of Comparative Examples 2 and 4. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be modified in various ways within the scope of the claims. The embodiments described in this specification can be combined in any way to form other embodiments. Unless otherwise specified, in this specification, operations and measurements of physical properties, etc. are performed under conditions of room temperature (20°C or higher and 25°C or lower) and a relative humidity of 40% RH or higher and 50% RH or lower.

[0013] <Laminate> One aspect of the present invention is a laminate for a chamber inner wall of a semiconductor manufacturing apparatus, comprising: A substrate; an amorphous layer disposed on a surface of the substrate; a crystalline layer disposed on a surface of the amorphous layer, the amorphous layer has a thickness of 1 nm or more and 10 nm or less; the crystalline layer consists essentially of yttrium and fluorine; The density of the crystalline layer is 4.7 g / cm 3 More than 5.3g / cm 3 The laminate is as follows: The laminate having the above configuration can suppress the occurrence of film irregularities in the crystalline layer (YF3 film).

[0014] FIG. 2 is a schematic diagram of a laminate according to one embodiment of the present invention. As shown in FIG. 2, the laminate 10 includes a substrate 1, an amorphous layer 2 disposed on the surface of the substrate 1, and a crystalline layer 3 disposed on the surface of the amorphous layer 2. The laminate 10 is used as the inner wall of a chamber of a semiconductor manufacturing device. The laminate 10 is disposed so that the crystalline layer 3 comes into contact with a corrosive gas. The amorphous layer 2 and the crystalline layer 3 can be formed to match the shape of the chamber inner wall, i.e., the shape of the substrate 1. For example, the amorphous layer 2 and the crystalline layer 3 may be formed on only one surface (one side) of the substrate 1, or on both surfaces (both sides) of the substrate 1.

[0015] In this specification, the laminate for the inner wall of a chamber of a semiconductor manufacturing apparatus according to the present invention is also simply referred to as the "laminate according to the present invention."

[0016] The present inventors presume that the mechanism by which the above configuration solves the problem is as follows.

[0017] FIG. 3 is a schematic diagram of a cross-sectional SEM image of the laminate of Comparative Example 1. The Al alloy used as the substrate is an aggregate of crystals with a grain size of several tens of micrometers and has various crystal orientations. This results in different surface adsorption efficiencies for the Al alloy, making it difficult to form a crystalline layer (YF3 film) with a uniform thickness. As shown in FIG. 6, the laminate of Comparative Example 1 exhibits film irregularities due to the absence of an amorphous layer. On the other hand, the laminate of Example 8 exhibits suppressed film irregularities due to the presence of an amorphous layer (thickness: 7 nm) between the substrate and the crystalline layer. The amorphous layer in the laminate of Example 8, even though it is only 7 nm thick, acts as a buffer and can suppress the effects of differences in surface adsorption efficiencies for the Al alloy, thereby suppressing the occurrence of film irregularities in the crystalline layer (YF3 film). The crystalline layer with suppressed film irregularities is smooth, thereby reducing its surface area and reducing the effects of plasma etching.

[0018] The above mechanism is based on speculation, and its correctness does not affect the technical scope of the present invention. Similarly, the correctness of other speculations in this specification does not affect the technical scope of the present invention.

[0019] (base material) The laminate according to the present invention has a substrate.

[0020] In the laminate according to the present invention, the substrate is not particularly limited. Examples of the substrate include a silicon substrate, a metal substrate, and a ceramic substrate. The substrate preferably includes at least one of silicon, a metal, and a ceramic. Specific examples of metals include aluminum (Al), aluminum alloys (Al alloys), stainless steel (SUS), titanium (Ti), and nickel (Ni). Examples of Al alloys include aluminum 6000-series alloys such as A6061, A6063, and A6101. Examples of SUS include SUS304, SUS316, SUS316L, SUS420J2, and SUS630. Specific examples of ceramics include aluminum oxide (Al2O3), aluminum nitride (AlN), silicon carbide (SiC), and silicon nitride (Si3N4).

[0021] In one embodiment, the substrate comprises at least one selected from the group consisting of silicon, metal, and ceramic.

[0022] In one embodiment, the metal in the substrate is at least one selected from the group consisting of Al, Al alloy, SUS, Ti, and Ni, and the ceramic in the substrate is at least one selected from the group consisting of Al2O3, AlN, SiC, and Si3N4.

[0023] The thickness of the substrate can be set appropriately, for example, to 1 mm or more and 10 mm or less.

[0024] (amorphous layer) The laminate according to the present invention has an amorphous layer disposed on the surface of a substrate, and the thickness of the amorphous layer is 1 nm or more and 10 nm or less.

[0025] When an amorphous layer is formed by ALD, the crystalline state of the amorphous layer can be controlled by adjusting the chamber temperature.

[0026] The amorphous layer may be a single layer or may be a laminate of two or more layers.

[0027] The amorphous layer can be confirmed to be amorphous by the absence of peaks observed in X-ray diffraction measurement. For example, when the amorphous layer contains aluminum oxide or is composed of aluminum oxide, the amorphous layer does not have peaks at 2θ=25.57°±1°, 35.14°±1°, and 37.76°±1° in X-ray diffraction measurement using CuKα radiation. When the amorphous layer contains yttrium oxide or is composed of yttrium oxide, the amorphous layer does not have peaks at 2θ=16.70°±1°, 20.49°±1°, 23.70°±1°, 29.13°±1°, 31.52°±1°, 33.76°±1°, 35.88°±1°, 37.89°±1°, and 39.82°±1° in X-ray diffraction measurement using CuKα radiation. Details of the X-ray diffraction measurement are described in the Examples.

[0028] The material constituting the amorphous layer is not particularly limited, and examples thereof include aluminum oxide (Al2O3), yttrium oxide (Y2O3), etc. In one embodiment, the amorphous layer contains Al2O3 or Y2O3, and preferably consists essentially of Al2O3 or Y2O3.

[0029] In this specification, the term "an amorphous layer substantially consisting of Al2O3 or YO3" means that the concentration of components (impurities) other than Al2O3 or YO3 in the amorphous layer is 5 atomic % or less. Impurities include hydrogen and carbon derived from raw materials used in the manufacturing process. The impurity concentration can be measured by photoelectron spectroscopy (XPS) and elastic recoil scattering analysis (ERDA).

[0030] The thickness of the amorphous layer is 1 nm or more and 10 nm or less. If the thickness of the amorphous layer is less than 1 nm, a uniform crystalline layer (YF3 film) cannot be obtained. If the thickness of the amorphous layer exceeds 10 nm, the film formation time increases, which is undesirable as it increases costs. The thickness of the amorphous layer is preferably 3 nm or more and 9 nm or less, and more preferably 5 nm or more and 8 nm or less. When the amorphous layer is formed by ALD, the thickness of the amorphous layer can be controlled by the ALD conditions (e.g., the number of cycles).

[0031] The thickness of the amorphous layer can be measured by ellipsometry, film thickness measurement using a cross-sectional SEM image, X-ray reflectometry (XRR), etc. In the present invention, the thickness of the amorphous layer is a value measured by ellipsometry.

[0032] (crystalline layer) The laminate according to the present invention has a crystalline layer disposed on a surface of an amorphous layer, the crystalline layer consisting essentially of yttrium and fluorine, and the density of the crystalline layer is 4.7 g / cm 3 More than 5.3g / cm 3 The following is the result.

[0033] When a crystalline layer is formed by ALD, the crystalline state of the crystalline layer can be controlled by adjusting the chamber temperature.

[0034] The crystalline layer may be a single layer or a laminate of two or more layers.

[0035] The crystalline nature of the crystalline layer can be confirmed by observing peaks in X-ray diffraction measurement. In one embodiment, the crystalline layer has peaks at at least one of 2θ=24.03°±1°, 24.61°±1°, 25.98°±1°, 27.88°±1°, 31.00°±1°, and 36.08°±1° in X-ray diffraction measurement using CuKα radiation. Details of the X-ray diffraction measurement are described in the Examples.

[0036] In this specification, the crystalline layer being substantially composed of yttrium and fluorine means that the concentration of components (impurities) other than yttrium and fluorine in the crystalline layer is 5 atomic % or less. Examples of impurities include hydrogen, carbon, oxygen, nitrogen, sulfur, and the like derived from the raw materials used in the production. The impurity concentration is the sum of the concentrations of these atoms. The concentrations of carbon, oxygen, nitrogen, and sulfur can be measured by photoelectron spectroscopy (XPS), and the hydrogen concentration can be measured by elastic recoil scattering analysis (ERDA).

[0037] The density of the crystalline layer is 4.7 g / cm 3 More than 5.3g / cm 3 The density of the crystalline layer is 4.7 g / cm 3 If the density is less than 5.3 g / cm3, the corrosion resistance will be low, which is not preferable. The density of the crystalline layer is preferably high, and the upper limit of the measured value is 5.3 g / cm3. 3 The density of the crystalline layer is preferably 5.0 g / cm3 from the viewpoint of being able to more effectively exhibit the effects of the present invention. 3 More than 5.3g / cm 3 or less, more preferably 5.1 g / cm 3 More than 5.3g / cm 3 The density of the crystalline layer can be measured by X-ray reflectometry (XRR).

[0038] The thickness of the crystalline layer is not particularly limited and is, for example, 20 nm or more. The thickness of the crystalline layer is preferably 20 nm or more and 200 nm or less, more preferably 80 nm or more and 180 nm or less, even more preferably 100 nm or more and 160 nm or less, and particularly preferably 120 nm or more and 150 nm or less. When the crystalline layer is formed by ALD, the thickness of the crystalline layer can be controlled by the ALD conditions (e.g., the number of cycles).

[0039] The thickness of the crystalline layer can be measured using ellipsometry, film thickness measurement using a cross-sectional SEM image, X-ray reflectometry (XRR), etc. In the present invention, the thickness of the crystalline layer is a value measured by ellipsometry.

[0040] The refractive index of the crystalline layer is, for example, 1.40 or more and 1.60 or less. In the present invention, the refractive index of the crystalline layer is a value measured by polarized light analysis (ellipsometry).

[0041] <Method of manufacturing laminate> One aspect of the present invention is a method for producing the above-mentioned laminate, a crystalline layer forming step of forming a crystalline layer on a surface of the amorphous layer by atomic layer deposition (ALD); the crystalline layer forming step includes supplying a source material 1 containing yttrium and a source material 2 containing fluorine; The supply amount of the raw material 1 is 1.0 × 10 15 pieces / cm 3 -A manufacturing method that is adjusted to have more than one cycle.

[0042] One aspect of the present invention is a method for producing the above-mentioned laminate, a crystalline layer forming step of forming the crystalline layer on a surface of the amorphous layer by atomic layer deposition (ALD), the crystalline layer forming step includes supplying a source material 1 containing yttrium and fluorine, and a source material 2 containing oxygen; The supply amount of the raw material 1 is 1.0 × 10 15 pieces / cm 3 -A manufacturing method that is adjusted to have more than one cycle.

[0043] The manufacturing method of the laminate having the above configuration allows for the formation of a uniform crystalline layer (YF3 film). Furthermore, since the manufacturing method of the present invention does not require stress relaxation or adhesion improvement, it is possible to suppress film cracking and film peeling of the crystalline layer (YF3 film) even in an amorphous layer having a thickness of 10 nm or less. On the other hand, in conventional technology, stress due to the difference in linear expansion coefficient between the crystalline layer and the substrate can cause film cracking and film peeling of the crystalline layer, so an amorphous layer having a thickness of more than 10 nm is typically formed to relieve stress to the crystalline layer and improve adhesion.

[0044] The method for manufacturing a laminate according to the present invention includes a crystalline layer formation step of forming a crystalline layer by atomic layer deposition (ALD), which includes supplying a source material 1 containing yttrium and a source material 2 containing fluorine, or supplying a source material 1 containing yttrium and fluorine and a source material 2 containing oxygen.

[0045] The atomic layer deposition (ALD) method may be plasma ALD or thermal ALD.

[0046] The raw material 1 containing yttrium includes tris(methylcyclopentadienyl)yttrium (Y(MeCp)3), tris(isopropylcyclopentadienyl)yttrium (Y(i-PrCp)3), tris(butylcyclopentadienyl)yttrium (Y(CpBu)3), tris(ethylcyclopentadienyl)yttrium (Y(EtCp)3), tris(N,N'-diisopropyl-2-dimethylamido-guanidinato)yttrium (Y(DPDMG)3), Y(EtCp)2(iPr2 AMD), tris(N,N'-diisopropylacetamidinate) yttrium (Y(iPr2AMD)3), Y(iPrCp)2(iPr2AMD), Y(iPrFMD)3, tris(sec-butylcyclopentadienyl) yttrium (Y(sBuCp)3), tris(N,N'-di-tert-butyl-formamidinate) yttrium (Y(tBu2FMD)3), tris(2,2,6,6-tetramethyl-3,5-heptanedionate) yttrium (Y(thd)3), and the like.

[0047] Examples of the raw material 1 containing yttrium and fluorine include Ybeta-prime (Kamimura, S. et al. Y2O3 and YF3 thermal ALD for anti-corrosion coating, EUROCVD / Baltic ALD 2023).

[0048] Examples of the fluorine-containing raw material 2 include sulfur hexafluoride (SF6), hydrogen fluoride-pyridine (HF-pyridine), titanium tetrafluoride (TiF4), carbon tetrafluoride (CF4), ammonium fluoride (NH4F), tantalum pentafluoride (TaF5), tungsten hexafluoride (WF6), and fluorine molecules (F2).

[0049] Examples of the raw material 2 containing oxygen include ozone (O3), water (H2O), and oxygen plasma.

[0050] An embodiment of the crystalline layer forming step will be described below.

[0051] A substrate having an amorphous layer on its surface is placed in the chamber of an ALD apparatus, and the temperature and pressure are adjusted appropriately. The chamber temperature can be adjusted appropriately depending on the raw materials used. The substrate is heated to the desired chamber temperature. When the ALD is plasma ALD, the yttrium-containing raw material 1 is Y(MeCp)3, and the fluorine-containing raw material 2 is SF6, the chamber temperature is preferably 150°C or higher and 250°C or lower. When the ALD is thermal ALD, the yttrium- and fluorine-containing raw material 1 is Ybeta-prime, and the oxygen-containing raw material 2 is O3, the chamber temperature is preferably 300°C or higher and 350°C or lower. The pressure in the chamber is, for example, 50 Pa or lower.

[0052] When heating the substrate, an inert gas such as nitrogen gas, argon gas, helium gas, neon gas, krypton gas, or xenon gas is supplied.

[0053] After adjusting the temperature and pressure, raw material 1 is supplied. Raw material 1 is supplied in a gaseous state. The supply temperature and supply time of raw material 1 can be appropriately set depending on the raw material 1 used. For example, when raw material 1 is Y(MeCp)3, the supply temperature is about 130°C and the supply time is about 2 seconds. When raw material 1 is Ybeta-prime, the supply temperature is about 120°C and the supply time is about 2 seconds.

[0054] The supply amount of raw material 1 is 1.0 × 10 15 pieces / cm 3 The supply of yttrium is adjusted to be 1.0 × 10 cycles or more. 15 pieces / cm 3 If the number of cycles is less than 1, cracking and peeling of the YF3 film may occur. The upper limit of the number of yttrium supplied is not particularly limited, but from the viewpoint of cost, it is preferably 1.0 × 10 16 pieces / cm 3 cycles or less, preferably 5.5 x 10 15 pieces / cm3 · Less than a cycle.

[0055] The number of atoms supplied is calculated from the mass loss of the raw material using the following formula: Number of atoms supplied [number / cm 3 Cycle]= Amount of raw material supplied [g / cycle] ÷ Mass of raw material [g / mol] × 6.02 × 10 23 [mol / mol] ÷ chamber volume [cm 3 ].

[0056] After the supply of the raw material 1, an inert gas is passed through to perform purging. The purging time can be set arbitrarily.

[0057] After purging, raw material 2 is supplied. Raw material 2 is supplied in a gaseous state. The supply temperature and supply time of raw material 2 can be set appropriately depending on the raw material 2 used. For example, when raw material 2 is SF6 or O3, the supply temperature is room temperature (e.g., 23°C ± 2°C) and the supply time is about 9 seconds. When raw material 2 is HF-pyridine, the supply temperature is about 50°C and the supply time is about 1 second.

[0058] After the supply of the raw material 2, an inert gas is passed through to perform purging. The purging time can be set arbitrarily.

[0059] One cycle consists of supplying and purging raw material 1, and then supplying and purging raw material 2. The number of cycles can be appropriately set so as to obtain a crystalline layer having a desired thickness.

[0060] In this manner, a crystalline layer can be formed.

[0061] In one embodiment, the method for producing a laminate according to the present invention includes, before the crystalline layer forming step, an amorphous layer forming step of forming an amorphous layer on the surface of the substrate by atomic layer deposition (ALD), where the amorphous layer and the crystalline layer can be formed in the same chamber.

[0062] The crystalline layer forming step when the amorphous layer contains Al2O3 will be described below.

[0063] In the amorphous layer formation process, similar to the crystalline layer formation process described above, one cycle consists of supplying raw material 1, purging, and supplying raw material 2, and purging. The number of cycles can be appropriately set to obtain a crystalline layer with the desired film thickness. Hereinafter, in the amorphous layer formation process, raw material 1 will also be referred to as raw material a, and raw material 2 will also be referred to as raw material b.

[0064] The substrate is placed in the chamber of the ALD apparatus, and the temperature and pressure are appropriately adjusted. The chamber temperature and pressure can be the same as those described in the crystalline layer formation step.

[0065] When heating the substrate, an inert gas is supplied, which may be nitrogen gas, argon gas, helium gas, neon gas, krypton gas, xenon gas, or the like, as described above.

[0066] After adjusting the temperature and pressure, raw material a is supplied. Raw material a is supplied in a gaseous state. Examples of raw material a for the crystalline layer formation step include trimethylaluminum (TMA), triethylaluminum (TEA), and trichloroaluminum.

[0067] The supply temperature and supply time of the raw material a can be appropriately set depending on the raw material a used. For example, when the raw material a is TMA, the supply temperature is room temperature (e.g., 23°C ± 2°C), and the supply time is about 0.15 seconds.

[0068] After the supply of the raw material a, an inert gas is passed through to perform purging. The purging time can be set arbitrarily.

[0069] After purging, raw material b is supplied. Raw material b is supplied in a gaseous state. Examples of raw material b for the crystalline layer formation process include oxygen (O2), ozone (O3), water (H2O), and oxygen plasma.

[0070] The supply temperature and supply time of raw material b can be set appropriately depending on the raw material b used. For example, when raw material b is O2, the supply temperature is room temperature (e.g., 23°C ± 2°C) and the supply time is about 3 seconds.

[0071] After the supply of raw material b, an inert gas is passed through to perform purging. The purging time can be set arbitrarily.

[0072] In this manner, an amorphous layer can be formed.

[0073] <Semiconductor manufacturing equipment> One aspect of the present invention is a semiconductor manufacturing apparatus having the above-described stacked structure on the inner wall of a chamber.

[0074] The laminate according to the present invention has a crystalline layer (YF3 film) on its surface, and the YF3 film is uniformly formed and is inhibited from cracking and peeling, so that it can be used as the inner wall of a chamber in a semiconductor manufacturing device. The semiconductor manufacturing device is not particularly limited, and any conventionally known device can be used.

[0075] Although the embodiments of the present invention have been described in detail, it is clear that this is by way of illustration and example only and not of limitation, and that the scope of the present invention should be interpreted by the appended claims.

[0076] The present invention encompasses the following aspects and configurations: 1. A laminate for the inner wall of a chamber of a semiconductor manufacturing device, A substrate; an amorphous layer disposed on a surface of the substrate; a crystalline layer disposed on a surface of the amorphous layer, the amorphous layer has a thickness of 1 nm or more and 10 nm or less; the crystalline layer consists essentially of yttrium and fluorine; The density of the crystalline layer is 4.7 g / cm 3 More than 5.3g / cm 3 The laminate is as follows: 2. The laminate described in 1 above, wherein the crystalline layer has a peak at at least one of 2θ=24.03°±1°, 24.61°±1°, 25.98°±1°, 27.88°±1°, 31.00°±1°, and 36.08°±1° in X-ray diffraction measurement using CuKα radiation. 3. The laminate according to 1. or 2. above, wherein the amorphous layer contains aluminum oxide or yttrium oxide. 4. The laminate according to any one of 1. to 3. above, wherein the substrate contains at least one of silicon, metal, and ceramic. 5. The laminate described in 4 above, wherein the metal is at least one selected from the group consisting of aluminum alloy, stainless steel (SUS), titanium and nickel, and the ceramic is at least one selected from the group consisting of aluminum oxide, aluminum nitride, silicon carbide and silicon nitride. 6. A method for producing the laminate according to any one of 1. to 5. above, a crystalline layer forming step of forming the crystalline layer on a surface of the amorphous layer by atomic layer deposition (ALD), the crystalline layer forming step includes supplying a source material 1 containing yttrium and a source material 2 containing fluorine; The supply amount of the raw material 1 is 1.0 × 10 15 pieces / cm 3 - A manufacturing method that is adjusted to be more than one cycle. 7. A method for producing a laminate according to any one of 1. to 5. above, a crystalline layer forming step of forming the crystalline layer on a surface of the amorphous layer by atomic layer deposition (ALD), the crystalline layer forming step includes supplying a source material 1 containing yttrium and fluorine, and a source material 2 containing oxygen; The supply amount of the raw material 1 is 1.0 × 10 15 pieces / cm 3 - A manufacturing method that is adjusted to be more than one cycle. [Example]

[0077] The present invention will be described in more detail using the following examples and comparative examples, but the technical scope of the present invention is not limited to the following examples.

[0078] Example 1 A substrate (silicon substrate, A / R 10, thickness 2 mm) was placed in the chamber of the ALD device and evacuated to 50 Pa or less. The substrate was heated at 250°C for 10 minutes. During heating, nitrogen gas, an inert gas, was flowed.

[0079] Next, an amorphous layer was formed on the substrate, and then a crystalline layer was formed on the amorphous layer. The amorphous layer and the crystalline layer were formed in the same chamber (chamber temperature: 250°C).

[0080] In forming the amorphous layer (Al2O3 film), trimethylaluminum (TMA) was used as source a, O2 was used as source b, and the Al2O3 film was formed using the plasma-assisted ALD (PEALD) method. The supply temperatures for source a and source b were 23°C ± 2°C. The supply time for source a was 0.15 seconds, and the supply time for source b was 3 seconds, with an optional purge time between each supply. The above process constitutes one cycle, and 60 cycles were repeated to form an Al2O3 film with a film thickness of 7 nm. Discharge was performed while source b was being supplied. A CCP type electrode was used, and discharge was performed at RF 100 W. The supply amount of source a was 1.0 x 10 Al. 15 pieces / cm 3 The supply amount of raw material b is adjusted so that the number of O supplied is 1.5 × 10 15 pieces / cm 3 -Adjusted to create a cycle.

[0081] In forming the crystalline layer (YF3 film), tris(methylcyclopentadienyl)yttrium (Y(MeCp)3) was used as source material 1, and SF6 was used as source material 2. A YF3 film was formed by the PEALD method. The temperature at which source material 1 was supplied was 130°C, and the temperature at which source material 2 was supplied was 23°C ± 2°C. The supply time for source material 1 was 2 seconds, and the supply time for source material 2 was 9 seconds, with an optional purge time between each supply. This process constitutes one cycle, and 3000 cycles were repeated to form a YF3 film with a film thickness of 128 nm. Discharge was performed while source material 2 was being supplied. A CCP type electrode was used, and discharge was performed at 100 W RF. The supply amount of source material 1 was 1.5 x 10 15 pieces / cm 3 The supply amount of raw material 2 is adjusted so that the number of F supplies is 3.0 × 10 15 pieces / cm 3 -Adjusted to create a cycle.

[0082] After the crystalline layer was formed, the chamber was vented and the stack was removed.

[0083] The number of atoms supplied was calculated from the mass loss of the raw material using the following formula: Number of atoms supplied [number / cm 3 Cycle]= Amount of raw material supplied [g / cycle] ÷ Mass of raw material [g / mol] × 6.02 × 10 23 [mol / mol] ÷ chamber volume [cm 3 ].

[0084] Example 2 A laminate was produced in the same manner as in Example 1, except that an aluminum alloy (A6061) substrate (A / R 10, thickness 2 mm) was used as the base material instead of the silicon substrate.

[0085] Example 3 A laminate was produced in the same manner as in Example 1, except that the heating temperature of the substrate and the chamber temperature were changed from 250° C. to 200° C., and the film thickness of the crystalline layer was changed from 128 nm to 134 nm.

[0086] Example 4 A laminate was produced in the same manner as in Example 2, except that the heating temperature of the substrate and the chamber temperature were changed from 250° C. to 200° C., and the film thickness of the crystalline layer was changed from 128 nm to 134 nm.

[0087] Example 5 A laminate was produced in the same manner as in Example 1, except that the heating temperature of the substrate and the chamber temperature were changed from 250° C. to 150° C., and the film thickness of the crystalline layer was changed from 128 nm to 145 nm.

[0088] Example 6 A laminate was produced in the same manner as in Example 2, except that the heating temperature of the substrate and the chamber temperature were changed from 250° C. to 150° C., and the film thickness of the crystalline layer was changed from 128 nm to 145 nm.

[0089] Example 7 A substrate (silicon substrate, A / R 10, thickness 2 mm) was placed in the chamber of the ALD device and evacuated to 50 Pa or less. The substrate was heated at 350°C for 10 minutes. Nitrogen gas, an inert gas, was flowed during heating.

[0090] Next, an amorphous layer was formed on the substrate, and then a crystalline layer was formed on the amorphous layer. The amorphous layer and the crystalline layer were formed in the same chamber (chamber temperature: 350°C).

[0091] In forming the amorphous layer (Al2O3 film), TMA was used as source a, and H2O was used as source b, and the Al2O3 film was formed using the thermal ALD method. The supply temperatures of source a and source b were 23°C ± 2°C. The supply time of source a was 0.15 seconds, and the supply time of source b was 0.15 seconds, with an optional purge time between each supply. The above process constitutes one cycle, and 75 cycles were repeated to form an Al2O3 film with a film thickness of 7 nm. The supply amount of source a was 1.0 x 10 15 pieces / cm 3 The supply amount of raw material b is adjusted so that the number of O supplied is 1.5 × 1015 pieces / cm 3 -Adjusted to create a cycle.

[0092] In forming the crystalline layer (YF3 film), Ybeta-prime (Kamimura, S. et al. Y2O3 and YF3 thermal ALD for anti-corrosion coating, EUROCVD / Baltic ALD 2023) was used as source 1, and O3 was used as source 2. The YF3 film was formed using the thermal ALD method. The supply temperature of source 1 was 120°C, and the supply temperature of source 2 was 23°C ± 2°C. The supply time of source 1 was 2 seconds, and the supply time of source 2 was 5 seconds, with an optional purge time between each supply. The above process constitutes one cycle, and 1700 cycles were repeated to form a YF3 film with a film thickness of 127 nm. The supply amount of source 1 was 5.5 x 10 15 pieces / cm 3 The supply amount of raw material 2 was adjusted so that the number of O supplied was 1.7 × 10 16 pieces / cm 3 -Adjusted to create a cycle.

[0093] After the crystalline layer was formed, the chamber was vented and the stack was removed. Example 8 A laminate was produced in the same manner as in Example 7, except that an aluminum alloy (A6061) substrate (A / R 10, thickness 2 mm) was used as the base material instead of the silicon substrate.

[0094] Example 9 A laminate was produced in the same manner as in Example 7, except that the thickness of the crystalline layer was changed from 127 nm to 21 nm and the number of cycles in forming the crystalline layer was changed from 1,700 cycles to 300 cycles.

[0095] Comparative Example 1 A substrate (aluminum alloy (A6061) substrate (A / R 10, thickness 2 mm)) was placed in the chamber of the ALD device, and the chamber was evacuated to a pressure of 50 Pa or less. The substrate was heated at 350°C for 10 minutes. Nitrogen gas, an inert gas, was supplied during heating.

[0096] Next, a crystalline layer was formed on the substrate (chamber temperature: 350°C).

[0097] In forming the crystalline layer (YF3 film), Ybeta-prime was used as source 1, O3 was used as source 2 of the second gas, and a YF3 film was formed by thermal ALD. The supply temperature of source 1 was 120°C, and the supply temperature of source 2 was 23°C ± 2°C. The supply time of source 1 was 2 seconds, the supply time of source 2 was 5 seconds, and an optional purge time was provided between each supply. The above process constitutes one cycle, and 3000 cycles were repeated to form a YF3 film with a film thickness of 117 nm. The supply amount of source 1 was 5.5 x 10 15 pieces / cm 3 The supply amount of raw material 2 was adjusted so that the number of O supplied was 1.7 × 10 16 pieces / cm 3 -Adjusted to create a cycle.

[0098] After the crystalline layer was formed, the chamber was vented and the stack was removed.

[0099] Comparative Example 2 A substrate (silicon substrate, A / R 10, thickness 2 mm) was placed in the chamber of the ALD device and evacuated to 50 Pa or less. The substrate was heated at 250°C for 10 minutes. During heating, nitrogen gas, an inert gas, was flowed.

[0100] Next, an amorphous layer was formed on the substrate (chamber temperature: 250°C).

[0101] In forming the amorphous layer (YF3 film), Ybeta-prime was used as source a, O3 was used as source b, and a YF3 film was formed using the thermal ALD method. The supply temperature of source a was 120°C, and the supply temperature of source b was 23°C ± 2°C. The supply time of source a was 2 seconds, the supply time of source b was 5 seconds, and an optional purge time was provided between each supply. The above process constitutes one cycle, and 2200 cycles were repeated to form a YF3 film with a film thickness of 17 nm. The supply amount of source a was 5.5 x 10 15 pieces / cm 3 The supply amount of raw material b is adjusted so that the number of O supplied is 1.7 × 10 16 pieces / cm 3 -Adjusted to create a cycle.

[0102] After the amorphous layer was formed, the chamber was vented and the stack was removed.

[0103] Comparative Example 3 A substrate (silicon substrate, A / R 10, thickness 2 mm) was placed in the chamber of the ALD device and evacuated to 50 Pa or less. The substrate was heated at 300°C for 10 minutes. Nitrogen gas, an inert gas, was flowed during heating.

[0104] Next, a crystalline layer was formed on the substrate (chamber temperature: 300°C).

[0105] In forming the crystalline layer (YF3 film), tris(isopropylcyclopentadienyl)yttrium (Y(i-PrCp)3) was used as source 1, and hydrogen fluoride pyridine (HF-Pyridine) was used as source 2, and a YF3 film was formed using the thermal ALD method. The temperature at which source 1 was supplied was 160°C, and the temperature at which source 2 was supplied was 50°C. The supply time for source 1 was 30 seconds, and the supply time for source 2 was 1 second, with an optional purge time between each supply. The above process constitutes one cycle, and 1300 cycles were repeated to form a YF3 film with a film thickness of 79 nm. The supply amount of source 1 was 2.6 x 10 14 pieces / cm 3The supply amount of raw material 2 is adjusted so that the number of F supplies is 7.8 × 10 14 pieces / cm 3 -Adjusted to create a cycle.

[0106] After the crystalline layer was formed, the chamber was vented and the stack was removed.

[0107] Comparative Example 4 A substrate (silicon substrate, 2 mm thick) was placed in the chamber of the ALD device, and the chamber was evacuated to a vacuum of 50 Pa or less. The substrate was heated at 200°C for 10 minutes. Nitrogen gas, an inert gas, was supplied during heating.

[0108] Next, an amorphous layer was formed on the substrate (chamber temperature: 200°C).

[0109] In forming the amorphous layer (Al2O3 film), TMA was used as source a, and H2O was used as source b, and the Al2O3 film was formed using the thermal ALD method. The supply temperatures of source a and source b were 23°C ± 2°C. The supply time of source a was 0.15 seconds, and the supply time of source b was 0.15 seconds, with an optional purge time between each supply. The above process constitutes one cycle, and 1000 cycles were repeated to form an Al2O3 film with a film thickness of 111 nm. The supply amount of source a was 9.2 x 10 15 pieces / cm 3 The supply amount of raw material b is adjusted so that the number of O supplied is 1.4 × 10 16 pieces / cm 3 -Adjusted to create a cycle.

[0110] After the amorphous layer was formed, the chamber was vented and the stack was removed.

[0111] Table 1 summarizes the manufacturing conditions for the crystalline layers of the laminates of Examples 1 to 9 and Comparative Examples 1 and 3. Table 2 summarizes the manufacturing conditions for the amorphous layers of the laminates of Examples 1 to 9 and Comparative Examples 2 and 4.

[0112] [Table 1]

[0113] [Table 2]

[0114] evaluation The laminate produced above was evaluated as follows.

[0115] Film thickness and refractive index measurements The film thickness and refractive index were measured by ellipsometry for the laminates of Examples 1 to 9 and Comparative Examples 1 to 4. The results are shown in Table 3.

[0116] Film density measurement The film density of the crystalline layers of the laminates of Examples 1 to 9 and Comparative Examples 1 and 3, and the amorphous layers of the laminates of Comparative Examples 2 and 4 was measured by X-ray reflectometry (XRR) using a fully automatic horizontal sample multipurpose X-ray diffractometer (product name: SmartLab, manufactured by Rigaku Corporation). The results are shown in Table 3.

[0117] Crystallinity evaluation The crystallinity of the laminates of Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated by X-ray diffraction measurement (XRD). For the X-ray diffraction measurement, an automatic horizontal sample multipurpose X-ray diffractometer (product name: SmartLab, manufactured by Rigaku Corporation) was used. A Cu target was used for the X-ray tube, and measurements were performed from 2θ = 3° to 80° at 0.05° intervals. The results are shown in Table 3 and Figures 4 and 5.

[0118] As shown in Table 3, it was confirmed that the crystalline layer and the amorphous layer were crystalline and amorphous, respectively, in the laminates of Examples 1 to 9. It was confirmed that the crystalline layer was crystalline in the laminates of Comparative Examples 1 and 3, and the amorphous layer was amorphous in the laminates of Comparative Examples 2 and 4.

[0119] Figure 4 shows the measurement results for the laminate of Example 1. As shown in Figure 4, in the laminate of Example 1, the XRD peaks were only for YF3 and Si, confirming that the crystalline layer (YF3 film) was crystalline.

[0120] Fig. 5 shows the measurement results of the crystalline layer (YF3 film) of the laminate of Example 9 and the amorphous layer (YF3 film) of the laminate of Comparative Example 2. As shown in Fig. 5, it was confirmed that the crystalline layer (YF3 film) of the laminate of Example 9 was crystalline, and the amorphous layer (YF3 film) of the laminate of Comparative Example 2 was amorphous.

[0121] Evaluation of film unevenness A visual sensory evaluation was carried out on the laminates of Examples 2, 4, 6 and 8, and Comparative Example 1. The results are shown in Table 3 and FIG.

[0122] As shown in Table 3 and Figure 6, the laminates of Examples 2, 4, 6, and 8 have an amorphous layer that suppresses the influence of the substrate, allowing the formation of a crystalline YF3 layer and enabling the formation of a more uniform film. Furthermore, the smooth film reduces the surface area, which has the advantage of reducing the influence of plasma etching.

[0123] Evaluation of film peeling and cracking Scanning electron microscope (SEM) images (5,000x, 10,000x, or 200,000x) of the cross sections of the laminates of Examples 1 to 9 and Comparative Examples 1 to 7 were taken. The presence or absence of film peeling was determined by the presence or absence of voids at the interface between the substrate and the film in the SEM images. The results are shown in Table 3, Figures 7, 8, and 9. In Figure 9, the laminate was cut along the line [1] and the cross section was photographed.

[0124] As shown in Table 3, Figs. 7, 8, and 9, in the laminates of Examples 1 to 9 and Comparative Examples 1 to 4, the number of yttrium supplied was 1.0 × 10 15 pieces / cm 3 On the other hand, in the laminate of Comparative Example 3, the number of yttrium supplied was 2.6 × 1014 pieces / cm 3 It is thought that the membrane peeling occurred because the supply of yttrium was insufficient during the cycle.

[0125] Measurement of impurity concentration Concentrations of carbon, oxygen, nitrogen, and sulfur were measured by photoelectron spectroscopy (XPS) for the crystalline layers (YF3 films) of the laminates of Examples 1, 5, 7, and 9, and Comparative Example 2, and the amorphous layer (YF3 film) of the laminate of Comparative Example 3. The concentrations of hydrogen were measured by elastic recoil scattering analysis (ERDA). The results are shown in Table 3. The results in Table 3 are the sum of the concentrations of each impurity.

[0126] As shown in Table 3, it can be seen that the impurity concentration is lower in the crystalline YF3 film than in the amorphous YF3 film.

[0127] Al2O3 normalized etching depth Etching was measured for the laminates of Examples 1 to 9 and Comparative Examples 1 to 4 using an ICP etching device. Measurements were performed under conditions of RF Power ICP 1500 W, Bias 30 W, CF 4 120 sccm, O 2 30 sccm, pressure 1 Pa, and etching time 5 hours. Etching depth was measured by measuring the film thickness using ellipsometry and cross-sectional SEM images, and the etching depth was normalized using an Al 2 O 3 film as a reference for comparison. The results are shown in Table 3 and Figure 10.

[0128] As shown in Table 3 and Fig. 10, the crystalline layers (YF3 films) of the laminates of Examples 1 to 9 and Comparative Example 1 have high corrosion resistance. On the other hand, the amorphous layers (YF3 films and Al2O3 films) of the laminates of Comparative Examples 2 and 4 have low corrosion resistance. The crystalline layer (YF3 film) of Comparative Example 3 is thought to have low corrosion resistance because film peeling occurred.

[0129] [Table 3] [Explanation of symbols]

[0130] 1 base material, 2 amorphous layer, 3 crystalline layers, 10 laminates.

Claims

1. A laminate for a chamber inner wall of a semiconductor manufacturing apparatus, comprising: A substrate; an amorphous layer disposed on a surface of the substrate; a crystalline layer disposed on a surface of the amorphous layer, the amorphous layer has a thickness of 1 nm or more and 10 nm or less; the crystalline layer consists essentially of yttrium and fluorine; The density of the crystalline layer is 4.7 g / cm ３ 5.3g / cm or more ３ The laminate is as follows:

2. 2. The laminate according to claim 1, wherein the crystalline layer has a peak at at least one of 2θ=24.03°±1°, 24.61°±1°, 25.98°±1°, 27.88°±1°, 31.00°±1°, and 36.08°±1° in X-ray diffraction measurement using CuKα radiation.

3. The stack of claim 1 , wherein the amorphous layer comprises aluminum oxide or yttrium oxide.

4. The laminate according to claim 1 , wherein the substrate comprises at least one of silicon, metal, and ceramic.

5. 5. The laminate according to claim 4, wherein the metal is at least one selected from the group consisting of an aluminum alloy, stainless steel (SUS), titanium, and nickel, and the ceramic is at least one selected from the group consisting of aluminum oxide, aluminum nitride, silicon carbide, and silicon nitride.

6. A method for producing the laminate according to any one of claims 1 to 5, a crystalline layer forming step of forming the crystalline layer on a surface of the amorphous layer by atomic layer deposition (ALD), the crystalline layer forming step includes supplying a source material 1 containing yttrium and a source material 2 containing fluorine; The supply amount of the raw material 1 is 1.0 × 10 １５ pieces / cm ３ - A manufacturing method that is adjusted to be more than one cycle.

7. A method for producing the laminate according to any one of claims 1 to 5, a crystalline layer forming step of forming the crystalline layer on a surface of the amorphous layer by atomic layer deposition (ALD), the crystalline layer forming step includes supplying a source material 1 containing yttrium and fluorine, and a source material 2 containing oxygen; The supply amount of the raw material 1 is 1.0 × 10 １５ pieces / cm ３ - A manufacturing method that is adjusted to be more than one cycle.

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