Method for manufacturing member having recessed structure

Abstract

Disclosed is a method with which it is possible to relatively easily manufacture a member having a recessed structure that is close to a vertical structure. This method for manufacturing a member having a recessed structure includes: (1) installing a catalyst material (130) on a part of a first surface (112) of a workpiece (110), wherein the first surface (112) contains silicon (Si), and oxygen (O) and / or nitrogen (N), and the catalyst material (130) contains an organic molecule; and (2) exposing the workpiece (110) to a fluorine-containing gas at 80°C or higher. After the step (2), a recessed structure (150) is formed in a part of the first surface (112). With respect to the organic molecule, the value of the distance dHF between the hydrogen atom and the fluorine atom in a hydrogen fluoride molecule when an adsorption structure is assumed is 0.965 (Å) or more as calculated using the 6-31 + G(d) basis function and the B3LYP correlation-exchange functional.

Description

Method for manufacturing a member having a recessed structure

[0001] The present invention relates to a method for manufacturing a member having a recessed portion structure.

[0002] There is a need in various fields for microfabrication techniques that can form minute recessed structures such as bottomed structures or through-hole structures on the surface of a sample. Various microfabrication techniques have been proposed and put to practical use.

[0003] One microfabrication technique is dry etching, in which reactants such as reactive gases, ions, and / or radicals are used to etch the surface of a sample.

[0004] For example, in reactive ion etching (RIE) methods, such as inductive coupled plasma-RIE (ICP-RIE), etching is performed by converting an etching gas into plasma and colliding it with a sample. It has been reported that such RIE methods enable extremely fine processing of samples (for example, Non-Patent Document 1).

[0005] Xiao Li, King Yuk Chan and Rodica Ramer, "Fabrication of Through via Holes in Ultra-Thin Fused SilicaWafers for "Microwave and Millimeter-Wave Applications", Micromachines, 2018, 9, 138

[0006] However, when forming a recess structure on the surface of a sample, the RIE method has the problem that the etching rate is slow, the processing takes time, and the resulting recess structure has a tapered shape and is not very perpendicular.

[0007] The present invention has been made in view of the above background, and an object of the present invention is to provide a method that can relatively quickly manufacture a member having a recessed portion structure that is close to a vertical structure.

[0008] The present invention provides a method for producing a member having a recessed portion structure, the method comprising: (1) applying a catalyst material to a portion of a first surface of a workpiece, the first surface containing silicon (Si) and oxygen (O) and / or nitrogen (N), and the catalyst material containing an organic molecule; and (2) exposing the workpiece to a fluorine-containing gas at 80°C or higher, wherein after (2), a recessed portion structure is formed on the portion of the first surface, and the organic molecule has a distance dHF between a hydrogen atom and a fluorine atom in a hydrogen fluoride molecule, calculated using 6-31+G(d) basis set and a B3LYP correlation-exchange functional, of 0.965 (Å) or greater when assuming an adsorption structure.

[0009] The present invention can provide a method that allows a member having a recessed portion structure to be manufactured relatively easily.

[0010] FIG. 1 is a diagram schematically illustrating a reaction mechanism that may occur on the first surface of a workpiece when no catalytic material is used. FIG. 2 is a diagram schematically illustrating a reaction mechanism that may occur on the first surface of a workpiece when an organic molecule is used in which the value of the distance dHF between the hydrogen atom and the fluorine atom in the hydrogen fluoride molecule is less than 0.965 (Å). FIG. 3 is a diagram schematically illustrating a reaction mechanism that may occur on the first surface of a workpiece when an organic molecule is used in which the value of the distance dHF between the hydrogen atom and the fluorine atom in the hydrogen fluoride molecule is 0.965 (Å) or more. FIG. 4 is a diagram schematically illustrating an optimized three-dimensional structure of molecule X obtained by the ETKDG method and atoms with negative Gasteiger charges. FIG. 5 is a diagram schematically illustrating a three-dimensional structure of a structure obtained by the ETKDG method in which a hydrogen atom is added to molecule X. FIG. 6 is a diagram schematically illustrating a state in which a fluorine atom is added to molecule Y to form a complex compound. FIG. 7 is a diagram schematically illustrating a structure of molecule Z optimized by DFT calculation. 1 is a diagram showing the relationship between the processing temperature and the etching reaction rate during hydrogen fluoride (HF) gas etching of glass. FIG. 1 is a cross-sectional view schematically showing a process of a process according to one embodiment of the present invention. FIG. 2 is a cross-sectional view schematically showing a process of a process according to one embodiment of the present invention. FIG. 3 is a diagram showing a flow of a method for manufacturing a member having a recessed structure according to one embodiment of the present invention. FIG. 4 is a perspective view schematically showing a state in which a catalyst material is placed on a processing object in a method for manufacturing a member having a recessed structure according to one embodiment of the present invention. FIG. 5 is a cross-sectional view schematically showing an example of a processing object 110 after etching processing in a method for manufacturing a member having a recessed structure according to one embodiment of the present invention. FIG. 6 is a schematic cross-sectional view of a member according to one embodiment of the present invention. FIG. 7 is a diagram schematically showing the surface morphology of a sidewall of a recessed structure in a member according to one embodiment of the present invention. FIG. 8 is a schematic view for explaining the taper angle θ of the recessed structure. FIG. 9 is a graph showing the relationship between the dHF of organic molecules and the etching rate of a quartz glass substrate obtained from the evaluation results of various samples prepared using a cross-linking agent. FIG. 10 is a graph showing the relationship between the dHF of organic molecules and the etching rate of a quartz glass substrate obtained from the evaluation results of various samples prepared without using a cross-linking agent.

[0011] An embodiment of the present invention will be described below.

[0012] As mentioned above, conventional methods have the problem that the etching rate is slow and the processing time is long. In order to address these conventional problems, the inventors of the present application have conducted extensive research and development and discovered a microfabrication technology that can more quickly form components having a recessed structure such as a bottomed structure or a through structure.

[0013] That is, one embodiment of the present invention provides a method for producing a member having a recessed portion structure, the method comprising: (1) applying a catalyst material to a portion of a first surface of a workpiece, the first surface containing silicon (Si) and oxygen (O) and / or nitrogen (N), and the catalyst material containing an organic molecule; and (2) exposing the workpiece to a fluorine-containing gas at 80°C or higher, wherein after (2), a recessed portion structure is formed on the portion of the first surface, and the organic molecule has a distance dHF between a hydrogen atom and a fluorine atom in a hydrogen fluoride molecule, calculated using 6-31+G(d) basis set and a B3LYP correlation-exchange functional, of 0.965 (Å) or greater when assuming an adsorption structure.

[0014] A method according to one embodiment of the present invention includes a process of exposing a workpiece having a catalytic material disposed on a first surface thereof to hydrogen fluoride gas (hereinafter, this process will be referred to as the "etching process of the present invention"). By carrying out such an etching process of the present invention, the method according to one embodiment of the present invention can selectively etch the region on the first surface of the workpiece where the catalytic material is disposed (hereinafter, referred to as the "covered region"). The currently considered reasons why such etching is possible will be explained below with reference to the drawings.

[0015] First, the role of the catalytic material in the etching process of the present invention will be explained.

[0016] (Role of Organic Molecules Increasing the Bond Distance Between Hydrogen Fluoride Molecules) In the etching process of the present invention, the catalytic material contains organic molecules that increase the distance between the hydrogen atom and the fluorine atom in a hydrogen fluoride molecule (hereinafter referred to as "dHF") to 0.965 (Å) or more. The partial structure of the organic molecule having such characteristics is thought to play a role in lowering the activation energy for fluoride formation on the surface of the workpiece.

[0017] This role will be explained below with reference to Figures 1 to 3. Figure 1 shows a schematic diagram of the reaction on the surface of the workpiece when no catalytic material is installed, and Figures 2 and 3 show a schematic diagram of the reaction on the surface of the workpiece when a catalytic material is installed.

[0018] In the following description, the object to be treated is, for example, SiO ２ It is assumed that the first surface is hydrogen-terminated, where Si atoms are bonded to H atoms to stabilize the surface, forming a hydrophobic surface.

[0019] First, FIG. 1 shows a schematic diagram of an etching mechanism that is assumed to occur on the first surface of a processing target when no catalytic material is used.

[0020] SiO as the object to be treated ２ When hydrogen fluoride (HF) gas is supplied to a region on the surface where no catalytic material is provided (hereinafter referred to as the "uncoated region"), HF molecules (a) undergo nucleophilic attack on Si atoms (b), as shown in (i).

[0021] However, in order for the Si atoms (b) to react with the F atoms on the surface of the workpiece, the OH groups (c) on the surface must interact with the H atoms of the HF molecules (a) to weaken the H-F bonds, as shown in (ii). In other words, unless energy is provided to break the H-F bonds in the HF molecules (a), the H ２ The Si—F bond (d) does not occur with the elimination of O (g).

[0022] However, in this reaction system, there is no substance that contributes to lowering the activation energy of the Si—F bond (d), so no significant etching reaction occurs in the coated region.

[0023] In this system, as in ordinary mask pattern processing, the etching rate tends to be higher in the portion of the object to be processed that comes into direct contact with the HF gas, that is, in the uncoated area of ​​the surface.

[0024] Next, FIG. 2 schematically shows a reaction mechanism on the first surface of the object to be treated when organic molecules having a dHF value of less than 0.965 (Å) are used.

[0025] In this case, when HF gas is supplied to the coated region from the environment, HF molecules (a) undergo nucleophilic attack on Si atoms (b), as shown in (i).

[0026] In this case, in addition to this, the catalytic material interacts with the H of the HF molecule (a), thus weakening the H—F bond of the HF molecule (a), as shown in (ii).

[0027] As a result, as shown in (iii), the atoms of the catalyst material take away the H atoms of the HF molecule (a) and move to the OH group side of the surface, resulting in the formation of H ２ Desorption of O(g) occurs.

[0028] This causes the Si atom (b) to bond with the fluorine atom. Finally, SiF is formed according to the following reaction formula (2): ４ and H ２ O is formed. SiO ２ +4HF → SiF ４ ↑ + 2H ２ O↑ (2) SiF produced by the reaction ４ and H ２ O is in a gaseous state at the treatment temperature and quickly dissipates outside the system.

[0029] By the above reaction mechanism, the area immediately below the area coated with the catalytic material in the object to be treated is selectively etched.

[0030] 3 is a schematic diagram showing the reaction mechanism on the first surface of the workpiece when an organic molecule having a dHF value of 0.965 (Å) or more is used. Here, an organic molecule containing a secondary amine is assumed.

[0031] In this case as well, when HF gas is supplied from the environment to the region coated with the catalytic material, HF molecules (a) undergo nucleophilic attack on Si atoms (b), as shown in (i).

[0032] However, in this case, in addition to this, the atom in the -δ part (e) interacts with the H atom (+δ part) of the HF molecule (a), increasing the HF bond distance in (a). Therefore, as shown in (ii), the H-F bond in the HF molecule (a) is weakened. This increases the basicity of F, significantly reducing the activation energy required for the bonding reaction between the Si atom and the F atom.

[0033] As a result, as shown in (iii), the atoms in the -δ portion (e) take away the H atoms (+δ portion) of the HF molecule (a) and move to the OH group side of the surface, resulting in the formation of H ２ Desorption of O(g) occurs.

[0034] This causes the Si atom (b) to bond with the fluorine atom. Finally, according to the above reaction formula (2), SiF ４ and H ２ O is formed.

[0035] SiF produced by the reaction ４ and H ２ O is in a gaseous state at the treatment temperature and quickly dissipates outside the system.

[0036] Due to the above reaction mechanism, the area of ​​the workpiece directly below the region coated with the catalytic material is selectively and more quickly etched.

[0037] The above reaction is not limited to the case where a secondary amine is included, but a similar reaction can also occur with, for example, an organic molecule capable of forming a hydrogen bond and capable of acting as a hydrogen bond acceptor, specifically, with at least one heterocyclic structure or a tertiary amine.

[0038] Thus, in the etching process of the present invention, the presence of organic molecules contained in the catalytic material and having a dHF value of 0.965 (Å) or more promotes the fluoride production reaction in the coated region of the workpiece, making it possible to selectively etch the area immediately below the coated region.

[0039] Here, dHF is calculated by the following method.

[0040] (Method of calculating dHF) First, structural information of the target organic molecule (hereinafter referred to as "molecule X") is obtained from SMILES using the RDKit library, and a three-dimensional structure is generated using the ETKDG method. The RDKit version used was 2023.9.4, developed by GitHub and SourceForge, running on Python 3.10.13, and available as open source, with the open source being released in June 2006.

[0041] Next, the Gasteiger charge is calculated to determine atoms with negative Gasteiger charge (hereinafter referred to as "site atoms P").

[0042] As an example, Figure 4 shows a schematic diagram of the optimized structure of molecule X obtained by the above method and the site atom P determined for molecule X. In this example, molecule X is a primary amine whose general formula is represented by formula (10) described below, and there is only one site atom P. In Figure 4, the large gray sphere represents a carbon atom, the black sphere represents a nitrogen atom, and the smallest white sphere represents a hydrogen atom.

[0043] Next, a conjugate acid compound (hereinafter referred to as "compound Y") is formed by adding an H atom to molecule X according to the following procedure, and the three-dimensional coordinates of compound Y are generated.

[0044] First, add 1 to the formal charge of the site atom P and bond a hydrogen atom to the site atom.

[0045] Next, the structure is optimized by the ETKDG method to generate the three-dimensional structure of the conjugate acid.

[0046] 5 shows a schematic representation of the three-dimensional structure of compound Y, the site atom P, and the added hydrogen atom H. The three-dimensional structure of compound Y thus generated is converted into an sdf file to obtain three-dimensional coordinates.

[0047] Next, a fluorine atom is placed at a position 1.0 (Å) away from the hydrogen atom that has been bonded to the site atom P to form a composite compound (hereinafter referred to as "compound Z"), and a three-dimensional structure is generated by the ETKDG method.

[0048] In this case, the site atom P, the hydrogen atom, and the fluorine atom must be arranged on a straight line.

[0049] 6 shows a schematic representation of the three-dimensional structure of compound Z, site atoms P, hydrogen atoms H, and fluorine atoms F. The dashed arrows indicate the lines they share.

[0050] The three-dimensional structure of compound Z generated by the above procedure is used as the initial structure, and structural optimization is performed by DFT calculation. Figure 7 shows the structure of compound Z structurally optimized by DFT calculation.

[0051] From the obtained optimized structure, the distance dHF between the fluorine atom and the hydrogen atom in the added hydrogen fluoride molecule is calculated.

[0052] When the target compound has a plurality of site atoms, the above procedure is repeated with each atom as a site atom, and the distance between the fluorine atom and the hydrogen atom in the largest hydrogen fluoride molecule is defined as dHF.

[0053] All DFT calculations are performed using the Gaussian package, and structural optimization is preferably performed using the DFT method, 6-31+G(d) basis set, B3LYP correlation-exchange functional, default spin, charge ±0, and singlet state. The version of Gaussian used is Gaussian 16, developed by Carnegie Mellon University, available through a paid license agreement, and first available in 1970.

[0054] Here, for atomic species with atomic numbers greater than Kr, LanL2DZ is used as the basis function.

[0055] The dHF can be calculated similarly for different basis functions and correlation-exchange functionals other than the 6-31+g(d) basis function and the B3LYP correlation-exchange functional.

[0056] The requirements for the basis functions include having outer shell orbitals at the DZ level or higher or the TZ level or higher, plus a diffuse function.

[0057] Although the absolute value of dHF defined in the present invention does not coincide with the calculated value using other basis functions and correlation-exchange functionals, the tendency coincides with good precision.

[0058] In addition, the organic molecules used in the etching process of the present invention have an adsorption energy E ａｄｓ The compound may contain a primary amine having a valence of 0.35 eV or more.

[0059] Adsorption energy E ａｄｓ is calculated in the following way: ａｄｓ (eV) = E １ (eV) + E ＨＦ -E ２ (eV) (A1) where E １ is the energy obtained when the three-dimensional structure of the target organic molecule X (see Figure 1) used in the calculation of dHF described above is optimized by DFT calculation, and E ＨＦ is the energy (constant value) of the optimal structure of the HF molecule, and E ２ is the energy of the target organic molecule (see "Compound Y") in which HF molecules are arranged and the structure is optimized, which was used in the calculation of the maximum dHF described above.

[0060] (Influence of Processing Temperature) Next, the influence of processing temperature will be described.

[0061] In the etching process of the present invention, the processing temperature is 80° C. or higher because, at temperatures below 80° C., proper etching selectivity between the coated and uncoated regions on the first surface of the workpiece is not achieved.

[0062] The effect of the processing temperature will be described in more detail below with reference to Fig. 8. Fig. 8 shows the relationship between the processing temperature and the etching reaction rate when etching glass with hydrogen fluoride (HF) gas, as obtained by the inventors of the present application.

[0063] 8, the etching rate of glass gradually increases with temperature up to a processing temperature of 80° C. However, once the processing temperature reaches 80° C. or higher, the etching rate decreases rapidly. As a result, the etching rate peaks at temperatures below 80° C.

[0064] This phenomenon is thought to correspond to the association / non-association state of HF gas. That is, HF gas is in an association state below 80°C, but becomes non-associated (single molecule) at 80°C or higher. Furthermore, when HF gas is in an association state, the bonding strength of the H-F bond is relatively weak when viewed as a single molecule. Therefore, the F atom of the HF molecule is more likely to bond with the surface of the workpiece and form fluoride. It is thought that this behavior is why a high etching rate can be obtained at temperatures below 80°C.

[0065] In the etching process of the present invention, if the processing temperature is set to less than 80° C., the association state of the HF gas will have an effect, and the object will be etched in the uncoated area of ​​the catalytic material, resulting in a decrease in the etching selectivity in the coated area due to the reaction mechanism described above.

[0066] In contrast, when the processing temperature is set to 80°C or higher, the high etching power of the associated HF gas can be suppressed in the non-coated region of the catalytic material. Furthermore, based on the reaction mechanism described above, etching of the workpiece is possible directly below the coated region. As a result, the etching process of the present invention (processing temperature of 80°C or higher) can achieve high etching selectivity between the coated region and the non-coated region of the catalytic material. This also allows the etching process of the present invention to selectively etch the coated region.

[0067] The processing temperature is preferably 150°C to 500°C, more preferably 200°C to 450°C, and even more preferably 250°C to 400°C. By setting the processing temperature to 150°C or higher, the etching reaction rate can be improved. Furthermore, by setting the processing temperature to 450°C or lower, deterioration of the organic molecules contained in the catalyst material 130 can be suppressed.

[0068] (Formed Recess Structure) In conventional RIE methods, a "tapered shape" is likely to form on the sidewall of the recess structure, making it difficult to form a recess structure that is nearly vertical.

[0069] Here, the term "tapered shape" refers to a form in which the side walls that define the recessed structure are inclined with respect to the extension axis in the depth direction of the recessed structure.

[0070] In contrast, the etching process of the present invention can relatively easily form a recess structure (hereinafter referred to as a "vertical recess structure") that does not have a "tapered shape" (a taper angle θ described below is 0° to 2°) and has sidewalls that extend substantially parallel to the extension axis in the depth direction.

[0071] The reason for this will be explained below with reference to FIGS.

[0072] 9 and 10 are schematic diagrams showing one step of the etching process of the present invention.

[0073] Fig. 9 shows a schematic diagram of a state in which a catalyst material 3 is placed on the surface of a workpiece 1. In Fig. 9 and Fig. 10, for convenience of illustration, the workpiece 1 and the catalyst material 3 are shown as being spaced apart from each other, but in reality, they are in contact with each other.

[0074] As described above, the object to be processed 1 is made of SiO ２ and the surface is assumed to be hydrogen-terminated.

[0075] The catalyst material 3 is an organic molecule having a dHF value of 0.965 (Å) or more, and is assumed to be an organic molecule containing a primary amine. By applying the catalyst material 3 to the surface of the treatment object 1, a coated region 8 a and an uncoated region 8 b are formed on the treatment object 1.

[0076] As described above, by exposing the workpiece 1 heated to 80° C. or higher to HF gas, etching proceeds selectively directly below the coating region 8 a where the catalytic material 3 is disposed, thereby forming a recessed structure directly below the coating region 8 a.

[0077] FIG. 10 shows a state in which etching of the object 1 has progressed to a certain extent and a recess structure 5 of a certain depth has been formed.

[0078] As described above, the catalytic material 3 is provided in the covering region 8a. Therefore, even if the etching reaction progresses, the catalytic material 3 remains on the bottom surface 6 of the recessed structure 5. That is, as long as the etching process continues, the bottom surface 6 of the recessed structure 5 continues to be in contact with the catalytic material 3. As a result, the bottom surface 6 of the recessed structure 5 continues to be etched by the above-described reaction mechanism, and the etching of the bottom surface 6 continues to progress in the depth direction.

[0079] On the other hand, when attention is focused on the sidewall 7 of the recess structure 5, once etching begins, the etching reaction proceeds in accordance with the mechanism described above in the portion of the sidewall 7 in contact with the catalytic material 3. More precisely, the portion of the workpiece 1 in contact with the side surface of the catalytic material 3 is preferentially etched. As a result, a recess structure 5 defined by the sidewall 7 is formed in the portion in contact with the side surface of the catalytic material 3.

[0080] However, as the catalytic material 3 continues to descend deeper, after a certain point, the upper portion of the sidewall 7 no longer comes into contact with the side surface of the catalytic material 3. Hereinafter, such a sidewall 7 that is no longer in contact with the side surface of the catalytic material 3 will be referred to as the "first sidewall portion 7a."

[0081] As described above, etching does not substantially proceed in areas such as the uncoated region 8b where the catalytic material 3 is not present. In other words, the etching reaction in the workpiece 1 proceeds preferentially when the workpiece 1 is in contact with the catalytic material 3, and does not occur in other states. Therefore, once a portion of the sidewall 7, such as the first sidewall portion 7a, comes out of contact with the catalytic material 3, etching virtually stops thereafter.

[0082] This is a crucial feature that distinguishes this method from conventional dry etching methods such as RIE. In RIE, even areas where etching has already been completed, such as areas near openings on the surface of the workpiece, continue to be exposed to the reactive gas during the etching process. Therefore, as the etching process continues, there is a high possibility that a tapered recess structure will be formed.

[0083] In the etching process of the present invention, as a result of the etching stopping action at the first sidewall portion 7a that does not come into contact with the catalytic material 3, etching of the workpiece 1 proceeds selectively directly below the catalytic material 3, ultimately forming a vertical recess structure.

[0084] Due to the above effects, the etching process of the present invention makes it possible to form a characteristic vertical recess structure as the recess structure 5 .

[0085] The etching process of the present invention further has the following additional effects: (I) Rapid etching is possible. The processing speed of the conventional RIE method is about 1 μm / min or less, which is hardly a sufficiently fast micro-processing technique.

[0086] In contrast, the etching process of the present invention enables etching at a rate of, for example, 13.0 μm / min or more by increasing the amount of catalyst material provided and / or the supply rate of fluorine-containing gas, etc. Therefore, the etching process of the present invention can be used as a rapid recess structure formation technique.

[0087] (II) Deep recessed structures can be formed. Conventional RIE methods use SiO ２ For example, when a photoresist is used as a mask material, it is difficult to form a deep recessed structure of 20 μm.

[0088] However, in the etching process of the present invention, the etching reaction continues as long as the supply of fluorine-containing gas to the coated region is continued, and therefore, a recess structure with a high aspect ratio can be formed. For example, an aspect ratio of 10 or more can be realized.

[0089] The "aspect ratio" means the dimension in the depth direction relative to the minimum dimension of the opening of the recess structure.

[0090] As mentioned above, the processing speed is faster than that of conventional methods, making it possible to form deep recessed structures in a short time.

[0091] (Method for manufacturing a member having a recessed portion structure according to one embodiment of the present invention) Next, with reference to FIGS. 11 to 13, a method for manufacturing a member having a recessed portion structure according to one embodiment of the present invention will be described in more detail.

[0092] FIG. 11 shows a schematic flow of a method for manufacturing a member having a recessed portion structure according to one embodiment of the present invention (hereinafter simply referred to as "first method").

[0093] As shown in FIG. 11 , the first method includes: (1) providing a workpiece having a first surface (S110), the first surface including silicon (Si), oxygen (O) and / or nitrogen (N); (2) placing a catalytic material on a portion of the first surface of the workpiece, the catalytic material including organic molecules having a dHF value of 0.965 (Å) or more (S120); and (3) exposing the workpiece to a fluorine-containing gas at 80° C. or more (S130).

[0094] Each step will be explained below.

[0095] (Step S110) First, an object to be processed is prepared.

[0096] The object to be treated may contain at least one element selected from the group consisting of B, C, Si, P, S, Ti, V, Cr, Ga, Ge, As, Se, Nb, Mo, Tc, Ru, Rh, Sn, Sb, Te, Zr, Hf, I, Ta, W, Re, Os, Ir, Pt, and Au.

[0097] The object to be processed may further contain at least one element selected from the group consisting of H, N, Cl, Br, and O.

[0098] In particular, the object to be treated preferably contains at least one element selected from the group consisting of Si, C, and B, and O and / or N, and more preferably contains Si, O, and / or N.

[0099] The object to be processed may be made up of a single member or multiple members.

[0100] When the object to be treated is made up of a single member, the object to be treated is preferably made up of an element that forms a fluoride having a boiling point of 550° C. or less by reacting with fluorine (F).

[0101] In particular, it is more preferable that the object to be treated be made of an element that reacts with fluorine to form a fluoride having a boiling point of 200° C. or less.

[0102] For example, BF ３ (boiling point -100℃), CF ４ (boiling point -127°C), PF ５ (boiling point -84℃), SF ６ (boiling point -63℃), VF ５ (boiling point 48°C), GeF ４ (boiling point -36°C), NbF ５ (boiling point 236°C), MoF ６ (boiling point 38°C), TaF ５ (boiling point 230°C) and the like.

[0103] For example, silicon (Si) is converted into the fluoride SiF ４ The boiling point of the silicon-containing substance is −86° C., and the silicon-containing substance can be suitably used as the substance to be treated in the first method.

[0104] Note that Al and Ca are fluorides (AlF ３ ) and (CaF ２ ) has a boiling point exceeding 550° C. Therefore, Al and Ca cannot be said to be elements that react with fluorine (F) to form fluorides having a boiling point of 550° C. or lower.

[0105] The object to be processed may be, for example, a quartz glass substrate, a boron-containing quartz glass substrate, a phosphorus-containing quartz glass substrate, a quartz substrate, or a silicon substrate.

[0106] On the other hand, when the workpiece is composed of a laminate of multiple components, the workpiece preferably contains at least one element selected from the group consisting of Si, C, B, O, and N on the outermost surface (hereinafter referred to as the "first surface"), and more preferably contains Si and O and / or N.

[0107] For example, the object to be processed may have one or more films disposed on a substrate, and the outermost film may satisfy the above-described characteristics. Alternatively, the entirety of the multiple films may satisfy the above-described characteristics.

[0108] Such a film may be, for example, SiO ｘ , SiN ｙ , and at least one of SiON, SiOC, SiCN, and SiC. ｘ The x in the formula is a number that satisfies 0<x, and preferably 1.2≦x≦2. ｙ The y in the formula is a number satisfying 0<y, and preferably 0.8≦y≦4 / 3.

[0109] Alternatively, the substrate may have the above-described characteristics in addition to the film. In this case, a member having a recessed structure formed even inside the substrate can be manufactured by the first method. The substrate may be, for example, a quartz glass substrate, a boron-containing quartz glass substrate, a phosphorus-containing quartz glass substrate, a quartz substrate, or a silicon substrate.

[0110] In the following description, to avoid complication, it is assumed that the object to be processed is made of a single piece of quartz glass, and that a recess structure is formed on a first surface of the quartz glass.

[0111] (Step S120) Next, a catalytic material is applied to a first surface of the object to be processed in a predetermined area of ​​the first surface.

[0112] The catalyst material includes an organic molecule that increases the value of the distance dHF between the fluorine atom and the hydrogen atom of a hydrogen fluoride molecule to 0.965 (Å) or more.

[0113] Here, when the distance between the fluorine atom and the hydrogen atom increases, the bond between the fluorine atom and the hydrogen atom weakens, and when the distance between the fluorine atom and the hydrogen atom decreases, the bond between the fluorine atom and the hydrogen atom strengthens.

[0114] The dHF value is preferably 0.97 (Å) or more, and more preferably 0.975 (Å) or more.

[0115] For example, the organic molecule may have at least one of: (i) a phosphorus-containing structural moiety (e.g., a phosphorus-containing linear or cyclic structural moiety); (ii) a nitrogen- and / or oxygen-containing cyclic structural moiety; (iii) a secondary amine structural moiety; and (iv) a tertiary amine structural moiety.

[0116] Representative examples of organic molecules of type (i) include tris(dimethylamino)phosphine and tris(dimethylamino)phosphine oxide, triallylphosphine oxide, triallylphosphate, triallylphosphine, and alkylphosphonic acid. Representative examples of organic molecules of type (ii) include pyridine, imidazole, pyrrole, and oxazoline. Here, the ring structure moiety containing nitrogen and / or oxygen, i.e., the heterocyclic structure, includes a pyridine ring, lactone ring, imidazole ring, benzimidazole ring, benzoxazole ring, porphyrin ring, and graphitic carbon nitride. Representative examples of organic molecules of type (iii) include morpholine. Representative examples of organic molecules of type (iv) include trimethylamine and triethanolamine.

[0117] Alternatively, the organic molecule has the following adsorption energy with hydrogen fluoride: ａｄｓ The primary amine may be characterized by a valence energy of 0.35 eV or greater.

[0118] Representative examples of such primary amines include, for example, benzylamine, phenylamine, phenylenediamine, and the like.

[0119] An example of an organic molecule having the structure (i) is a compound represented by the following chemical formula (1):

[0120] The dHF of this organic molecule of chemical formula (1) is 0.9916 (Å).

[0121] Other examples include compounds of the formula:

[0122] The dHF of this organic molecule of chemical formula (1-1) is 0.9759 (Å).

[0123] An example of triallylphosphine oxide is the compound of the following chemical formula (1-2): The dHF of this organic molecule is 0.9753 (Å).

[0124]

[0125] An example of triallyl phosphate is the compound (1-3) of the following chemical formula: The dHF of this organic molecule is 0.9684 (Å).

[0126]

[0127] Examples of alkylphosphonic acids include the following compounds (1-4) to (1-6).

[0128] The dHF of this organic molecule of chemical formula (1-4) is 0.9840 (Å).

[0129] The dHF of this organic molecule of chemical formula (1-5) is 0.9811 (Å).

[0130] The dHF of this organic molecule of chemical formula (1-6) is 0.9746 (Å).

[0131] Examples of organic molecules having the structure (ii) include compounds of the following chemical formulas (2) to (4-4):

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138] The dHF of the organic molecules of chemical formulas (2) to (4-4) are 0.9688 (Å), 0.9787 (Å), 0.9824 (Å), 0.987 (Å), 0.996 (Å), 0.9824 (Å), and 0.9787 (Å), respectively. Of these materials, the materials of chemical formulas (2) to (4-1) are independently crosslinkable. On the other hand, the materials of chemical formulas (4-2) to (4-4) are not independently crosslinkable.

[0139] The materials of the chemical formulas (3) and (4-4) are imidazole, and the materials of the chemical formulas (4) to (4-3) are pyridine.

[0140] Compounds having a benzimidazole ring include compounds of the following chemical formulas (4-5) and (4-6):

[0141] The dHF of this compound of chemical formula (4-5) is 0.9851 (Å).

[0142] The dHF of this compound of chemical formula (4-6) is 0.9844 (Å).

[0143] Examples of compounds having a benzoxazole ring include compounds of the following chemical formula (4-7).

[0144] The dHF of this compound of chemical formula (4-7) is 0.9738 (Å).

[0145] Examples of compounds having a porphyrin ring include tetraphenylporphyrin (dHF: 0.9745 Å) represented by the chemical formula (4-8) and tetrapyridylporphyrin (dHF: 0.9809 Å) represented by the chemical formula (4-9).

[0146]

[0147]

[0148] The compound having graphite carbon nitride in its partial structure is g-C represented by the following structural formula (4-10): ３ N ４ (Graphitic carbon nitride) (dHF: 0.9734 Å).

[0149]

[0150] Furthermore, examples of the organic molecules of (iii) include compounds of the following chemical formulas (5) and (6):

[0151]

[0152] The dHF of the organic molecules of chemical formulas (5) and (6) is 1.0024 (Å) and 0.9994 (Å). The material of chemical formula (5) is independently crosslinkable, but the material of chemical formula (6) is not independently crosslinkable.

[0153] Examples of the organic molecules of (iv) include compounds of the following chemical formulas (7) to (9):

[0154]

[0155]

[0156] The dHF of the organic molecules of chemical formulas (7) to (9) are 0.9994 (Å), 1.0040, and 1.0041 (Å), respectively. These materials are independently crosslinkable. The material of chemical formula (7) is morpholine.

[0157] Furthermore, examples of the organic molecules of (v) include compounds of the following chemical formulas (10) to (11-2):

[0158]

[0159]

[0160]

[0161] The dHF of the organic molecules of chemical formulas (10) to (11-2) are 0.975 (Å), 0.995 (Å), 1.007 (Å), and 0.9746 (Å), respectively. Of these materials, the organic molecules of chemical formulas (10) to (11) are independently crosslinkable. On the other hand, the organic molecules of chemical formulas (11-1) and (11-2) are not independently crosslinkable.

[0162] The organic molecules of the chemical formulas (10) to (11-2) each have an adsorption energy E calculated by the above-mentioned formula (A1) ａｄｓ are 0.51 eV, 0.71 eV, 0.73 eV and 0.55 eV.

[0163] The organic molecules described above may be monomers or polymers as long as they have a dHF value of 0.965 (Å) or more. Polymers can be obtained by polymerizing organic molecules having a dHF value of 0.965 (Å) or more with organic molecules having reactive functional groups such as (meth)acryloyl groups, vinyl groups, epoxy groups, oxetane groups, thiol groups, carbonyl groups, and amino groups through radical, cationic, or condensation polymerization. Polymers can also be obtained by copolymerizing a monomer having an organic molecule having a dHF value of 0.965 (Å) or more with a monomer not having such an organic molecule.

[0164] The catalyst material may consist solely of the aforementioned organic molecules or may contain a cross-linking agent.

[0165] If the catalyst material is composed solely of the aforementioned organic molecules, faster etching is possible.

[0166] When the catalyst material contains a cross-linking agent, it is possible to directly pattern the object to be processed.

[0167] Examples of crosslinking agents include, but are not limited to, TADT (N,N',N''-triacryloydiethylenetriamine; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), MT3041 (manufactured by Toagosei Co., Ltd.), EX512 (manufactured by Nagase ChemteX Corporation), PETA (Pentaerythritol triacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.), and TAAA (N-[Tris(3-acrylamidopropoxymethyl)methyl]acrylamide; manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).

[0168] TADT and PETA are represented by the following structural formulas (12) and (13), respectively.

[0169]

[0170] It may also be provided as a mixture with other additives.

[0171] The additive may be, but is not limited to, a photoradical initiator, a photoacid generator, a photobase generator, a thermal acid generator, or a thermal base generator.

[0172] The amount of the additive added may be, for example, in the range of 0.1 mol % to 40 mol %, and preferably in the range of 0.1 mol % to 30 mol %, based on the total amount of the organic material according to one embodiment of the present invention. Alternatively, the amount of the additive added may be, for example, in the range of 0.1 wt % to 30 wt %, and preferably in the range of 0.1 wt % to 20 wt %, based on the total amount of the organic material according to one embodiment of the present invention.

[0173] In order to increase the etching rate, it is preferable that the organic molecules are present in the catalyst material at 10 mol % or more.

[0174] In the latter case, the catalyst material may contain a solvent, a binder, and / or fine particles, etc. The method for applying the catalyst material is not particularly limited.

[0175] The catalyst material may be applied to the first surface of the object to be processed by, for example, a coating method, a printing method, a spin coating method, or a spray method.

[0176] FIG. 12 is a schematic diagram showing the state in which the catalyst material is placed on the object to be treated.

[0177] 12, the workpiece 110 has a first surface 112 and a second surface 114. The catalytic material 130 is disposed on a portion of the first surface 112 of the workpiece 110.

[0178] 12, the catalytic material 130 is disposed as a pattern 131 of multiple parallel lines. However, this is merely an example, and the catalytic material 130 may be disposed in any manner depending on the required recess structure. The catalytic material 130 may be disposed, for example, as a single straight line. Alternatively, the catalytic material 130 may be disposed, for example, as a pattern of circular dots or as a single circular dot.

[0179] Examples of methods for forming a pattern of the catalyst material 130 include, but are not limited to, a method of directly applying a solution containing the catalyst material by inkjet, dispenser, screen printing, gravure printing, or the like; a method of applying a solution containing the catalyst material onto a pattern formed by metal vapor deposition using a photoresist or a mask pattern; a method of forming a film of a photosensitive resin composition containing the catalyst material by spin coating, bar coating, dip coating, or the like, and then imparting a shape to the film by photolithography or UV imprinting; and a method of forming a film of a resin containing a catalyst structure by spin coating, bar coating, dip coating, or the like, and then forming a pattern by thermal imprinting.

[0180] Preferably, the method is coating onto a pattern formed with a photoresist, photolithography, or UV or thermal imprinting.

[0181] Photolithography is more preferred.

[0182] The thickness of the catalytic material 130 is not particularly limited, but may be, for example, in the range of 0.01 μm to 4 μm. According to the above definition, the region of the first surface 112 where the catalytic material 130 is provided is referred to as the coated region 140 a, and the other region is referred to as the uncoated region 140 b.

[0183] (Step S130) Next, the object 110 to be processed on which the catalytic material 130 is placed is placed in a processing chamber. Thereafter, the processing chamber is heated to a predetermined temperature and a processing gas is supplied to perform an etching process on the object.

[0184] The processing gas contains hydrogen fluoride gas. For example, the processing gas may be adjusted to a predetermined concentration using a carrier gas such as argon gas or nitrogen gas. In this case, the concentration of hydrogen fluoride gas or fluorine gas may be in the range of 0.1 vol % to 100 vol %.

[0185] As mentioned above, the processing temperature is 80° C. or higher. The actual processing temperature varies depending on the elements contained in the object 110 (particularly the first surface 112) and the type and depth of the recessed structure, but is typically in the range of 200° C. to 450° C., and preferably in the range of 250° C. to 400° C. Setting the processing temperature to 450° C. or lower can suppress the deterioration of organic molecules contained in the catalyst material 130.

[0186] As described above, when the workpiece 110 is etched under such an environment, the reaction represented by the above-mentioned formula (2) occurs in the coated region 140a. The fluoride and water produced by the reaction are vaporized and dissipated outside the system. As a result, a recessed structure is formed in the coated region 140a of the first surface 112.

[0187] The recessed structure may be a bottomed structure or a through structure. The bottomed structure may be, for example, a bottomed hole and / or a bottomed groove. The through structure may be a through hole or a through groove.

[0188] FIG. 13 shows a schematic cross section of an example of the object 110 after etching.

[0189] 13, the recess structure 150 is composed of a plurality of grooves, which extend parallel to each other in a top view. In this example, each groove extends in the depth direction from the first surface 112 but does not reach the second surface 114, and therefore is a bottomed groove.

[0190] After step S130, a step of removing the catalyst material 130 remaining on the bottom surface of the recess structure 150 may be performed. For example, the catalyst material 130 may be removed by cleaning the workpiece 110 with an acid solution, an alkaline solution, an organic solvent, a corrosive gas, or plasma.

[0191] Through the above steps, it is possible to manufacture the member 100 having the recess structure 150 on the first surface 112. (Member having a recess structure according to one embodiment of the present invention) Next, a member having a recess structure according to one embodiment of the present invention will be described with reference to Figures 14 to 16 .

[0192] FIG. 14 shows a schematic cross-sectional view of a member having a recessed portion structure according to one embodiment of the present invention (hereinafter referred to as a "first member 200").

[0193] 14 , the recessed structure 250 has an opening 252 in the first surface 202. The recessed structure 250 also has a bottom surface 256 and a sidewall 257. In other words, the recessed structure 250 is defined by the opening 252, the bottom surface 256, and the sidewall 257. Here, the first member 200 is characterized in that the sidewall 257 has a streak pattern that runs along the depth direction.

[0194] This feature will be described below with reference to FIG.

[0195] Fig. 15 schematically shows the surface morphology of a sidewall 257 of the recessed portion structure 250. Fig. 15 also schematically shows a portion of the sidewall 257 obtained when the recessed portion structure 250 is cut along the extension axis in the direction along the first surface 202 of the first member 200 and the extension axis in the depth direction.

[0196] As shown in FIG. 15 , in the first member 200, a continuous, uninterrupted streak (hereinafter referred to as a “continuous streak”) 280 is formed on the side wall 257 of the recess structure 250, extending from the first opening 252 to the bottom surface 256.

[0197] 15 shows three continuous streaks 280. However, this is merely an example, and the number of continuous streaks 280 is not particularly limited.

[0198] The pattern of the continuous streaks 280 is significant and not observed in conventionally etched members, that is, the continuous streaks 280 are a unique feature observed in the first member 200 manufactured by the first method described above.

[0199] Such a pattern of continuous streaks 280 is believed to be formed for the following reason.

[0200] As described above with reference to the figures, in the first method, the covered region 8a is selectively etched by the catalytic material 3 placed on the covered region 8a. As long as the relationship between the catalytic material 3 and the covered region 8a continues, the recess structure 5 continues to grow in the depth direction.

[0201] In the case of such an etching mechanism, the sidewalls 7 of the recessed structure 5 formed by etching are affected by the state of the side surfaces of the catalyst material 3 with which the sidewalls 7 come into contact.

[0202] That is, when the side surface of the catalyst material 3 has irregularities, the side wall 7 of the recessed structure 5 is considered to have a surface state having corresponding irregularities, reflecting the influence of the irregularities on the side surface of the catalyst material 3 .

[0203] Furthermore, in the first method, the catalyst material 3 having such irregularities on the side surface advances along the depth direction of the recess structure 5 to the bottom surface 6 of the recess structure 5. Therefore, it is considered that a pattern of continuous stripes 280 corresponding to such irregularities is also formed on the side wall 7 of the recess structure 5 that is finally obtained.

[0204] In addition to or alternatively to the above-mentioned characteristics, the first member 200 may have a characteristic in which the minimum taper angle θ of the recessed structure 5 is in the range of 0° to 2°.

[0205] This feature will be described below with reference to FIG.

[0206] FIG. 16 shows a schematic cross section of a recess along the extension axis L.

[0207] The recess 50 has an opening 52 in a first surface of the member, and has a bottom surface 56 and sidewalls 57.

[0208] Although it is not clear from Fig. 16, the recess 50 may have a round hole shape or a rectangular groove shape when viewed from above. The recess 50 may also have a through structure. In this case, the recess 50 may have a second opening instead of the bottom surface 56.

[0209] For such a recess 50, the taper angle θ is defined as follows:

[0210] Here, a is the minimum dimension of the opening 52, b is the minimum dimension of the bottom surface 56, and c is the distance between the first opening 52 and the bottom surface 56, i.e., the depth of the recess 50.

[0211] The taper angle θ expressed by equation (1) is an index of the "perpendicularity" of the recess 50. That is, a smaller taper angle θ indicates that the inclination of the sidewall 57 of the recess 50 with respect to the extension axis L is suppressed, and such a recess 50 can be said to be closer to a "vertical recess structure." In particular, when the taper angle θ of the recess structure 250 in the first member 200 is in the range of 0° to 2°, the recess structure 250 can be said to have a vertical recess structure. Note that when the recess structure is composed of a plurality of grooves, the taper angle θ is calculated for each groove, and if the taper angle θ of the groove with the smallest taper angle θ is 0° to 2°, the first member 200 can be said to have a vertical recess structure.

[0212] In the first member 200, the taper angle θ of the recessed portion structure 250 may be 1° or less.

[0213] Furthermore, the depth of the recessed structure 250 in the first member 200 may be 1 μm or more. In particular, the depth of the recessed structure 250 in the first member 200 is, for example, 2 μm or more, and preferably 3 μm or more.

[0214] Examples of the present invention will be described below.

[0215] In the following description, Examples 1 to 20 and Examples 25 to 27 are working examples, and Examples 21 to 24 and Example 28 are comparative examples.

[0216] Examples 1 to 20 Example 1 A recessed structure was formed on one surface (first surface) of a processing body by the following method.

[0217] First, a coating solution containing a catalyst material was prepared. The catalyst material was an organic substance (dHF0.9916 (Å)) represented by the aforementioned chemical formula (1), and a crosslinking agent EX512 was added to the catalyst material in an amount of 1.0 g. The resulting composition was mixed with 1.0 g of methyl ethyl ketone as a solvent and 0.03 g of a photoradical initiator, Omnirad 651 (manufactured by IGM Resins B.V.).

[0218] Next, a quartz glass substrate was prepared as a processing body, with dimensions of 50 mm length x 50 mm width x 0.5 mm thickness.

[0219] The coating liquid was applied to the first surface of the substrate by spin coating at a rotation speed of 1250 rpm for 30 seconds, and then the substrate was baked at 80° C. for 60 seconds.

[0220] Furthermore, the substrate was irradiated with 3000 mJ / cm using a light source with a wavelength of 365 nm. ２ to provide a pattern of catalytic material on the first surface of the substrate.

[0221] Next, the substrate on which the catalytic material pattern was formed was cut into a size of about 50 mm x about 10 mm, and the cut sample was placed in a processing chamber. The sample was then subjected to a gas etching process in the processing chamber. The processing gas was a mixture of hydrogen fluoride gas and nitrogen gas (HF / N ２ = 20 / 80 vol%) was used, and the processing temperature was 250° C. The etching time was 300 seconds.

[0222] The processed body obtained after the etching process is referred to as "Sample 1."

[0223] (Evaluation) After the etching treatment, the sample was removed from the reactor, and the etching rate of the substrate was evaluated. The etching rate was calculated from the weight loss per unit area of ​​the substrate. Specifically, the etching rate v (μm / min) of the substrate was calculated from the following formula: v (μm / min) = (ΔW) / {(ρ × S) / t)} × 104, where ΔW is the weight loss (g) of the substrate before and after treatment, and ρ is the density of the substrate (g / cm ３ ), and S is the area of ​​the substrate coverage (cm ２ ) and t is the etching time (minutes).

[0224] The weight of the coating film placed on the substrate was extremely small compared to the total weight, and therefore the weight of the coating film was not taken into consideration in the calculation of ΔW.

[0225] Furthermore, when a similar etching treatment was carried out without providing a coating film on the surface of the quartz glass substrate, almost no weight loss was observed, and therefore, it was found that the etching rate was zero.

[0226] The etching rate of sample 1 was 4.02 μmin －１ It was.

[0227] Example 2: A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 2, the catalyst material used was an organic substance (dHF 0.9688 (Å)) represented by the aforementioned chemical formula (2). Furthermore, methanol was used as the solvent, and MT3041 was mixed in as the cross-linking agent. The treated body obtained after the etching process is referred to as "Sample 2."

[0228] The etching rate of sample 2 is 1.38 μm min －１ It was.

[0229] Example 3 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 3, an organic substance (dHF0.9746 (Å)) represented by the aforementioned chemical formula (10) was used as the catalyst material. Methanol was used as the solvent, and the cross-linking agent TADT represented by the aforementioned chemical formula (11) was mixed in.

[0230] The processed body obtained after the etching process is referred to as "Sample 3."

[0231] The etching rate of sample 3 was 1.23 μm min －１ It was.

[0232] Example 4 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 4, the catalyst material was an organic substance (dHF0.9787 (Å)) represented by the aforementioned chemical formula (3). Furthermore, methanol was used as the solvent, and the cross-linking agent TADT was mixed in.

[0233] The processed body obtained after the etching process is referred to as "Sample 4."

[0234] The etching rate of sample 4 was 1.21 μm min －１ It was.

[0235] Example 5 A recessed structure was formed on the first surface of the substrate by the same method as in Example 4. However, in Example 5, MT3041 was mixed as a crosslinking agent.

[0236] The processed body obtained after the etching process is referred to as "Sample 5."

[0237] The etching rate of sample 5 was 1.52 μm min －１ It was.

[0238] Example 6 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 6, the catalyst material was an organic substance (dHF 0.9824 (Å)) represented by the aforementioned chemical formula (4). Furthermore, methanol was used as the solvent, and a crosslinking agent, PETA, was mixed in.

[0239] The processed body obtained after the etching process is referred to as "Sample 6."

[0240] The etching rate of sample 6 was 2.64 μm min －１ It was.

[0241] Example 7 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 7, the catalyst material was an organic substance (dHF0.9954 (Å)) represented by the aforementioned chemical formula (11). Furthermore, methanol was used as the solvent, and the cross-linking agent TADT was mixed in.

[0242] The processed body obtained after the etching process is referred to as "Sample 7."

[0243] The etching rate of sample 7 was 3.48 μm min －１ It was.

[0244] Example 8: A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 8, the catalyst material was an organic substance (dHF 0.9994 (Å)) represented by the aforementioned chemical formula (7). Furthermore, methanol was used as the solvent, and a crosslinking agent, PETA, was mixed in. The treated body obtained after the etching process is referred to as "Sample 8."

[0245] The etching rate of sample 8 was 4.73 μm min－１ It was.

[0246] Example 9 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 9, the catalyst material was an organic substance (dHF 1.0024 (Å)) represented by the aforementioned chemical formula (5). Furthermore, methanol was used as the solvent, and the cross-linking agent TADT was mixed in.

[0247] The processed body obtained after the etching process is referred to as "Sample 9."

[0248] The etching rate of sample 9 was 7.97 μm min －１ It was.

[0249] Example 10 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 10, the catalyst material was an organic substance (dHF 1.0040 (Å)) represented by the above-mentioned chemical formula (8). Furthermore, methanol was used as the solvent, and a crosslinking agent, PETA, was mixed in.

[0250] The processed body obtained after the etching process is referred to as "Sample 10."

[0251] The etching rate of sample 10 was 13.39 μm min －１ It was.

[0252] Example 11 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 11, the catalyst material was an organic substance (dHF 1.0041 (Å)) represented by the above-mentioned chemical formula (9). Furthermore, methanol was used as the solvent, and a cross-linking agent, PETA, was mixed in.

[0253] The processed body obtained after the etching process is referred to as "Sample 11."

[0254] The etching rate of sample 11 was 5.87 μm min －１ It was.

[0255] Example 12 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 12, the catalyst material was an organic substance (dHF0.987 (Å)) represented by the above-mentioned chemical formula (4-1). Furthermore, methanol was used as the solvent, and no crosslinking agent was used.

[0256] The processed body obtained after the etching process is referred to as "Sample 12."

[0257] The etching rate is 10.20 μm min －１ It was.

[0258] Example 13 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 13, the catalyst material used was an organic substance (dHF 1.007 (Å)) represented by the aforementioned chemical formula (11-1). Furthermore, methanol was used as the solvent, and a crosslinking agent EX512 was mixed into it.

[0259] The processed body obtained after the etching process is referred to as "Sample 13."

[0260] The etching rate of sample 13 was 4.72 μm min －１ It was.

[0261] Example 14 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 14, the catalyst material was an organic substance (dHF0.996 (Å)) represented by the above-mentioned chemical formula (4-2). Furthermore, methanol was used as the solvent, and a crosslinking agent EX512 was mixed in.

[0262] The processed body obtained after the etching process is referred to as "Sample 14."

[0263] The etching rate of sample 14 was 2.00 μm min －１ It was.

[0264] Example 15 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 15, the catalyst material was an organic substance (dHF0.9824 (Å)) represented by the aforementioned chemical formula (4). Furthermore, methanol was used as the solvent, and a crosslinking agent, TAAA, was mixed in.

[0265] The processed body obtained after the etching process is referred to as "Sample 15."

[0266] The etching rate of sample 15 was 2.40 μm min －１ It was.

[0267] To calculate the taper angle θ, the recess structure of the sample substrate was fractured along the extension axis in the depth direction so that the bottom surface, sidewalls, and fractured surface of the recess opening were exposed, as shown in FIG. 16 . The fractured surface was imaged using a scanning electron microscope (SEM, SU8030) in secondary electron image mode (SE mode) with an upper detector to observe and analyze the recess structure. The acceleration voltage was 1.5 kV. Various dimensions (a, b, c) were measured from the recess structure imaged with the SEM, and the taper angle θ was calculated using equation (1). a is the minimum dimension of the recess opening, b is the minimum dimension of the bottom surface of the recess structure, and c is the depth of the recess structure.

[0268] The minimum taper angle θ of Sample 15 was 0.22°.

[0269] Example 16 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 16, the organic substance (dHF0.9746 (Å)) represented by the above-mentioned chemical formula (11-2) was used as the catalyst material, and no crosslinking agent was used.

[0270] The processed body obtained after the etching process is referred to as "Sample 16."

[0271] The etching rate of sample 16 was 24.62 μm min －１ It was.

[0272] Example 17 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 17, the catalyst material was an organic substance (dHF 0.9824 (Å)) represented by the above-mentioned chemical formula (4-3), and the solvent was 1-methoxy-2-propanol. No crosslinking agent was used.

[0273] The processed body obtained after the etching process is referred to as "Sample 17."

[0274] The etching rate of sample 17 was 31.42 μm min －１It was.

[0275] Example 18 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 18, the catalyst material was an organic substance (dHF 0.9787 (Å)) represented by the above-mentioned chemical formula (4-4), and the solvent was N,N-dimethylformamide. No crosslinking agent was used.

[0276] The processed body obtained after the etching process is referred to as "Sample 18."

[0277] The etching rate of sample 18 was 19.02 μm min －１ It was.

[0278] Example 19 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 19, the catalyst material was an organic substance (dHF 0.9688 (Å)) represented by the above-mentioned chemical formula (10), and the solvent was water. No crosslinking agent was used.

[0279] The processed body obtained after the etching process is referred to as "Sample 19."

[0280] The etching rate of sample 18 was 14.84 μm min －１ It was.

[0281] Example 20 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 20, the catalyst material was an organic substance (dHF 0.9994 (Å)) represented by the above-mentioned chemical formula (6), and the solvent was methyl ethyl ketone. No crosslinking agent was used.

[0282] The processed body obtained after the etching process is referred to as "sample 20."

[0283] The etching rate of sample 20 was 68.24 μm min －１ It was.

[0284] (Examples 21 to 24) Recessed structures were formed on the first surface of a substrate by the same method as in Example 1. However, in Examples 21 to 24, the type of catalyst material was changed from that in Examples 1 to 20, respectively, to organic molecules having a dHF of less than 0.965, and the recessed structures were formed.

[0285] Example 21 The catalyst material was an organic substance (dHF0.9559 (Å)) represented by the following chemical formula (14): butyl acetate was used as the solvent, and diazonaphthoquinone, a crosslinking agent, was mixed therewith.

[0286] The processed body obtained after the etching process is referred to as "Sample 21."

[0287] The etching rate of sample 21 was 0.85 μm min －１ It was.

[0288] Example 22 The catalyst material was an organic substance (dHF0.9612 (Å)) represented by the following chemical formula (15): Methanol was used as the solvent, and a crosslinking agent MT3041 was mixed in.

[0289] The processed body obtained after the etching process is referred to as "Sample 22."

[0290] The etching rate of sample 22 was 0.85 μm min －１ It was.

[0291] Example 23 The catalyst material was an organic substance (dHF0.9617 (Å)) represented by the following chemical formula (16): Methanol was used as the solvent, and a crosslinking agent MT3041 was mixed in.

[0292] The processed body obtained after the etching process is referred to as "Sample 23."

[0293] The etching rate of sample 23 was 0.96 μm min －１ It was.

[0294] Example 24 The catalyst material was an organic substance (dHF0.9617 (Å)) represented by the following chemical formula (17): Methanol was used as the solvent, and PETA, a cross-linking agent, was mixed into the solvent.

[0295] The processed body obtained after the etching process is referred to as "Sample 24."

[0296] The etching rate of sample 24 was 1.03 μm min－１ It was.

[0297] Table 1 below summarizes the organic molecules, additives, dHF and etching rates of the organic molecules used in each example.

[0298]

[0299] 17 and 18 show the relationship between the dHF of the organic molecules and the etching rate obtained from the evaluation results of each sample. In each of these figures, the horizontal axis represents the dHF of the organic molecules contained in the organic material, and the vertical axis represents the etching rate of the substrate (expressed as a natural logarithm).

[0300] 17, the black circle symbols are plots of Samples 1 to 15, and the white triangle symbols are plots of Samples 21 to 24. In FIG. 18, the black circle symbols are plots of Samples 16 to 20.

[0301] The results show that samples 1 to 14 (FIG. 17) and samples 15 to 19 (FIG. 15) have significantly improved etching rates for the quartz glass substrate compared to samples 21 to 24.

[0302] (Examples 25 to 28) A recessed portion structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Examples 24 to 27, the substrate was changed to a Si substrate on which a SiN film was formed to a thickness of 3 μm, and the recessed portion structure was formed.

[0303] Example 25 The catalyst material used was the organic material (dHF0.9824 (Å)) represented by the above-mentioned chemical formula (4-3), and was mixed with a crosslinking agent MT3041.

[0304] The processed body obtained after the etching process is referred to as "Sample 25."

[0305] The etching rate of sample 25 was 1.97 μm min －１ It was.

[0306] Example 26 The catalyst material used was an organic substance (dHF 1.0024 (Å)) represented by the above-mentioned chemical formula (5), and a crosslinking agent MT3041 was mixed therewith.

[0307] The processed body obtained after the etching process is referred to as "Sample 26."

[0308] The etching rate of sample 25 was 1.42 μm min －１ It was.

[0309] Example 27 The catalyst material used was the organic substance (dHF 0.9824 (Å)) represented by the above-mentioned chemical formula (4-3), and no crosslinking agent was used.

[0310] The processed body obtained after the etching process is referred to as "Sample 27."

[0311] The etching rate of sample 27 was 1.26 μm min －１ It was.

[0312] Example 28 The catalyst material used was the organic substance (dHF 0.9559 (Å)) represented by the above-mentioned chemical formula (14), and was mixed with a crosslinking agent, diazonaphthoquinone.

[0313] The processed body obtained after the etching process is referred to as "Sample 28."

[0314] The etching rate of sample 28 was 1.00 μm min －１ It was.

[0315] Table 2 below summarizes the organic molecules, additives, dHF and etching rates of the organic molecules used in each example.

[0316]

[0317] The above-mentioned evaluation was carried out using Samples 25 to 28. As a result, it was found that Samples 25 to 27 had significantly improved etching rates for the SiN substrate compared to Sample 28.

[0318] (Samples 29 to 42) (Example 29) A recessed structure was formed on the first surface of a quartz glass substrate by the same method as in Example 1. However, in Example 29, the organic substance (dHF 0.9759 (Å)) represented by the aforementioned chemical formula (1-1) was used as the catalyst material. Furthermore, methanol was used as the solvent, and crosslinking agent EX512 was mixed in. The ratio of the crosslinking agent to the total of the organic molecules and crosslinking agent was 27 mol %.

[0319] The processed body obtained after the etching process is referred to as "Sample 29."

[0320] The etching rate of sample 29 was 1.6 μm min －１ It was.

[0321] Example 30: A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 29, the catalyst material used was an organic substance (dHF0.9753 (Å)) represented by the aforementioned chemical formula (1-2). Furthermore, methanol was used as the solvent, and crosslinker EX512 was mixed in. The ratio of the crosslinker to the total of the organic molecules and crosslinker was 27 mol%.

[0322] The processed body obtained after the etching process is referred to as "sample 30."

[0323] The etching rate of sample 30 was 1.4 μm min －１ It was.

[0324] Example 31 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 31, the catalyst material used was an organic substance (dHF0.9684 (Å)) represented by the aforementioned chemical formula (1-3). Furthermore, methanol was used as the solvent, and crosslinker EX512 was mixed in. The ratio of the crosslinker to the total of the organic molecules and crosslinker was 27 mol %.

[0325] The processed body obtained after the etching process is referred to as "Sample 31."

[0326] The etching rate of sample 31 was 1.3 μm min －１ It was.

[0327] Example 32 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 32, the catalyst material used was an organic substance (dHF 0.9840 (Å)) represented by the above-mentioned chemical formula (1-4). Furthermore, methanol was used as the solvent, and no crosslinking agent was used.

[0328] The processed body obtained after the etching process is referred to as "sample 32."

[0329] The etching rate of sample 32 was 1.7 μm min －１ It was.

[0330] Example 33 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 33, the catalyst material used was an organic substance (dHF0.9811 (Å)) represented by the above-mentioned chemical formula (1-5). Furthermore, methanol was used as the solvent, and no crosslinking agent was used.

[0331] The processed body obtained after the etching process is referred to as "Sample 33."

[0332] The etching rate of sample 32 was 1.9 μm min －１ It was.

[0333] Example 34 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 34, the catalyst material used was an organic substance (dHF0.9746 (Å)) represented by the above-mentioned chemical formula (1-6). Furthermore, methanol was used as the solvent, and no crosslinking agent was used.

[0334] The processed body obtained after the etching process is referred to as "sample 34."

[0335] The etching rate of sample 34 was 1.7 μm min －１ It was.

[0336] Example 35: A recessed structure was formed on the first surface of a substrate using a method similar to that of Example 1. However, in Example 35, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and no crosslinker was used. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5-amino-2-(4-aminophenyl)benzimidazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. After dispersing the mixture in methanol, the precipitate was collected by filtration and dried in a vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (18), which has a monomer of the organic substance (dHF0.9851 (Å)) represented by chemical formula (4-5) in its partial structure.

[0337]

[0338] The processed body obtained after the etching process is referred to as "Sample 35."

[0339] The etching rate of sample 35 was 2.5 μm min －１ It was.

[0340] Example 36: A recessed structure was formed on the first surface of a substrate using a method similar to that of Example 1. However, in Example 36, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and no crosslinker was used. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5,3'-diamino-2-phenylbenzimidazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. The solution was dispersed in methanol, and the precipitate was collected by filtration and dried in vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (19), which has a monomer of the organic substance (dHF0.9844 (Å)) represented by chemical formula (4-6) in its partial structure.

[0341]

[0342] The processed body obtained after the etching process is referred to as "Sample 36."

[0343] The etching rate of sample 36 was 2.4 μm min－１ It was.

[0344] Example 37: A recessed structure was formed on the first surface of a substrate using a method similar to that of Example 1. However, in Example 37, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and no crosslinker was used. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5-amino-2-(4-aminophenyl)benzoxazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. The solution was dispersed in methanol, and the precipitate was collected by filtration and dried in vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (20), which has a monomer of the organic substance (dHF0.9738 (Å)) represented by chemical formula (4-7) in its partial structure.

[0345]

[0346] The processed body obtained after the etching process is referred to as "Sample 37."

[0347] The etching rate of sample 37 was 1.4 μm min －１ It was.

[0348] Example 38 Etching was carried out in the same manner as in Example 37, except that the treatment temperature was 300°C.

[0349] The processed body obtained after the etching process is referred to as "Sample 38."

[0350] The etching rate of sample 38 was 2.4 μm min －１ It was.

[0351] Example 39 Etching was carried out in the same manner as in Example 37, except that the treatment temperature was 300°C.

[0352] The processed body obtained after the etching process is referred to as "Sample 39."

[0353] The etching rate of sample 39 was 3.4 μm min －１ It was.

[0354] Example 40 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 40, the catalyst material used was an organic substance (dHF0.9745 (Å)) represented by the above-mentioned chemical formula (4-8). In addition, chloroform was used as the solvent, and no crosslinking agent was used.

[0355] The processed body obtained after the etching process is referred to as "sample 40."

[0356] The etching rate of sample 40 was 2.1 μm min －１ It was.

[0357] Example 41 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 41, the catalyst material was an organic substance (dHF0.9809 (Å)) represented by the above-mentioned chemical formula (4-9). In addition, chloroform was used as the solvent, and no crosslinking agent was used.

[0358] The processed body obtained after the etching process is referred to as "Sample 41."

[0359] The etching rate of sample 41 was 2.3 μm min －１ It was.

[0360] Example 42 A recessed structure was formed on the first surface of a substrate by the same method as in Example 1. However, in Example 42, the catalyst material used was an organic substance (dHF0.9734 (Å)) represented by the aforementioned chemical formula (4-10). Furthermore, methanol was used as the solvent, and no crosslinking agent was used.

[0361] The processed body obtained after the etching process is referred to as "sample 42."

[0362] The etching rate of sample 42 was 1.8 μm min －１ Table 3 below shows the organic molecules used in each example, the type and ratio of the crosslinking agent, the dHF of the organic molecules, and the etching rate.

[0363]

[0364] The results show that Samples 29 to 42 have significantly improved etching rates for the quartz glass substrate compared to Samples 21 to 24.

[0365] Example 43: A recessed structure was formed on the first surface of a quartz glass substrate by the same method as in Example 1. However, in Example 43, the organic substance (dHF0.9840 (Å)) represented by the aforementioned chemical formula (1-4) was used as the catalyst material. Methanol was used as the solvent, and crosslinker EX512 was mixed in. The ratio of the crosslinker to the total of the organic molecules and crosslinker was 27 mol%.

[0366] The processed body obtained after the etching process is referred to as "Sample 43."

[0367] The etching rate of sample 43 was 1.4 μm min －１ It was.

[0368] Example 44: A recessed structure was formed on the first surface of a quartz glass substrate by the same method as in Example 1. However, in Example 44, the catalyst material used was an organic substance (dHF0.9811 (Å)) represented by the aforementioned chemical formula (1-5). Furthermore, methanol was used as the solvent, and crosslinker EX512 was mixed in. The ratio of the crosslinker to the total of the organic molecules and the crosslinker was 27 mol %.

[0369] The processed body obtained after the etching process is referred to as "Sample 44."

[0370] The etching rate of sample 44 was 1.6 μm min －１ It was.

[0371] Example 45: A recessed structure was formed on the first surface of a quartz glass substrate by the same method as in Example 1. However, in Example 45, the catalyst material used was an organic substance (dHF0.9746 (Å)) represented by the aforementioned chemical formula (1-6). Furthermore, methanol was used as the solvent, and crosslinker EX512 was mixed in. The ratio of the crosslinker to the total of the organic molecules and the crosslinker was 27 mol%.

[0372] The processed body obtained after the etching process is referred to as "Sample 45."

[0373] The etching rate of sample 45 was 1.3 μm min －１ It was.

[0374] Example 46: A recessed structure was formed on the first surface of a quartz glass substrate using a method similar to that of Example 1. However, in Example 46, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and crosslinker EX512 was mixed. The ratio of crosslinker to the total of organic molecules and crosslinker was 10 wt %. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5-amino-2-(4-aminophenyl)benzimidazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. After dispersing the mixture in methanol, the precipitate was filtered and dried in vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (18), which has a monomer of the organic substance (dHF0.9851 (Å)) represented by chemical formula (4-5) as a partial structure.

[0375] The processed body obtained after the etching process is referred to as "Sample 46."

[0376] The etching rate of sample 46 was 2.1 μm min －１ It was.

[0377] Example 47: A recessed structure was formed on the first surface of a quartz glass substrate using a method similar to that of Example 1. However, in Example 47, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and crosslinker EX512 was mixed. The ratio of crosslinker to the total of organic molecules and crosslinker was 10 wt %. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5,3'-diamino-2-phenylbenzimidazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. The solution was dispersed in methanol, and the precipitate was filtered and dried in vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (19), which has a monomer of the organic substance (dHF0.9844 (Å)) represented by chemical formula (4-6) in its partial structure.

[0378] The processed body obtained after the etching process is referred to as "Sample 47."

[0379] The etching rate of sample 47 was 2.0 μm min －１ It was.

[0380] Example 48: A recessed structure was formed on the first surface of a quartz glass substrate using a method similar to that of Example 1. However, in Example 48, a polymer compound synthesized by the following method was used as the catalyst material, dimethylacetamide was used as the solvent, and crosslinker EX512 was mixed. The ratio of crosslinker to the total of organic molecules and crosslinker was 10 wt %. <Polymer Compound> First, isophthalic acid chloride, metaphenylenediamine, and 5-amino-2-(4-aminophenyl)benzoxazole were mixed with dimethylacetamide in a molar ratio of 2:1:1 and stirred at room temperature for 30 minutes. The solution was dispersed in methanol, and the precipitate was filtered and dried in vacuum at 150°C for one day. This resulted in a polymer compound represented by chemical formula (20), which has a monomer of the organic substance (dHF0.9738 (Å)) represented by chemical formula (4-7) as a partial structure.

[0381] The processed body obtained after the etching process is referred to as "Sample 48."

[0382] The etching rate of sample 48 was 1.3 μm min －１ It was.

[0383] Example 49: A recessed structure was formed on the first surface of a quartz glass substrate by the same method as in Example 1. However, in Example 49, the catalyst material used was an organic substance (dHF0.9745 (Å)) represented by the aforementioned chemical formula (4-8). Chloroform was used as the solvent, and crosslinker EX512 was mixed in. The ratio of the crosslinker to the total of the organic molecules and crosslinker was 30 mol %.

[0384] The processed body obtained after the etching process is referred to as "Sample 49."

[0385] The etching rate of sample 49 was 1.8 μm min －１ It was.

[0386] Example 50: A recessed structure was formed on the first surface of a quartz glass substrate by the same method as in Example 1. However, in Example 50, the catalyst material used was an organic substance (dHF0.9809 (Å)) represented by the aforementioned chemical formula (4-9). Chloroform was used as the solvent, and crosslinker EX512 was mixed in. The ratio of the crosslinker to the total of the organic molecules and crosslinker was 30 mol %.

[0387] The processed body obtained after the etching process is referred to as "sample 50."

[0388] The etching rate of sample 50 was 1.9 μm min －１ It was.

[0389] Example 51: A recessed structure was formed on the first surface of a quartz glass substrate by the same method as in Example 1. However, in Example 51, the catalyst material used was an organic substance (dHF0.9734 (Å)) represented by the aforementioned chemical formula (4-10). Furthermore, methanol was used as the solvent, and crosslinking agent EX512 was mixed in. The ratio of the crosslinking agent to the total of the organic molecules and crosslinking agent was 30 wt %.

[0390] The processed body obtained after the etching process is referred to as "Sample 51."

[0391] The etching rate of sample 51 was 1.6 μm min －１ Table 4 below shows the organic molecules used in each example, the type and ratio of the crosslinking agent, the dHF of the organic molecules, and the etching rate.

[0392]

[0393] The results show that Samples 43 to 51 also have significantly improved etching rates for the quartz glass substrate compared to Samples 21 to 24.

[0394] (Aspects of the Invention) The present invention may have the following aspects.

[0395] (Aspect 1) A method for producing a member having a recessed structure, the method comprising: (1) applying a catalyst material to a portion of a first surface of a workpiece, the first surface including silicon (Si) and oxygen (O) and / or nitrogen (N), the catalyst material including an organic molecule; and (2) exposing the workpiece to a fluorine-containing gas at 80°C or higher, wherein after (2), a recessed structure is formed on the portion of the first surface, and the organic molecule has a distance dHF between a hydrogen atom and a fluorine atom in a hydrogen fluoride molecule of 0.965 (Å) or greater, calculated using 6-31+G(d) basis set and a B3LYP correlation-exchange functional, assuming an adsorption structure.

[0396] (Aspect 2) The method according to aspect 1, wherein the organic molecule has at least one of: (i) a phosphorus-containing structural portion; (ii) a nitrogen- and / or oxygen-containing ring structural portion; (iii) a secondary amine structural portion; and (iv) a tertiary amine structural portion.

[0397] (Aspect 3) The organic molecule is a primary amine, and the primary amine has an adsorption energy E ａｄｓ is 0.35 eV or greater.

[0398] (Aspect 4) The method according to any one of Aspects 1 to 3, wherein the organic molecule includes at least one selected from the group consisting of pyridine, imidazole, pyrrole, morpholine, oxazoline, and organic phosphorus oxide.

[0399] (Aspect 5) The first surface is SiO ｘ or SiN ｙ 5. The method of any one of aspects 1 to 4, comprising:

[0400] (Aspect 6) The method according to any one of aspects 1 to 5, wherein the exposure in (2) is carried out at a temperature in the range of 80°C to 450°C.

[0401] (Aspect 7) The method according to aspect 6, wherein the exposure in (2) is carried out at a temperature in the range of 200°C to 450°C.

[0402] (Aspect 8) The method according to any one of aspects 1 to 7, wherein the object to be treated has one or more layers.

[0403] (Aspect 9) The method according to any one of Aspects 1 to 8, wherein the recessed portion structure is at least one of a blind hole, a through hole, a blind groove, and a through groove.

[0404] This application claims priority based on Japanese Patent Application No. 2024-105341, filed on June 28, 2024, the disclosure of which is incorporated herein in its entirety by reference.

[0405] 1 object to be processed 3 catalytic material 5 recessed portion structure 6 bottom surface 7 side wall 7a first side wall portion 8a coated region 8b uncoated region 50 recessed portion 52 opening 56 bottom surface 57 side wall 100 member 110 object to be processed 112 first surface 114 second surface 130 catalytic material 131 pattern 140a coated region 140b uncoated region 150 recessed portion structure 200 first member 202 first surface 250 recessed portion structure 252 opening 256 bottom surface 257 side wall 280 continuous stripe (a) HF molecule (b) Si atom (c) OH group (d) Si—F bond (g) H ２ O molecule

Claims

1. A method for producing a member having a recessed structure, comprising: (1) applying a catalyst material to a portion of a first surface of a workpiece, the first surface containing silicon (Si) and oxygen (O) and / or nitrogen (N), the catalyst material containing an organic molecule; and (2) exposing the workpiece to a fluorine-containing gas at 80°C or higher, wherein after (2), a recessed structure is formed on the portion of the first surface, and the organic molecule has a distance dHF between a hydrogen atom and a fluorine atom in a hydrogen fluoride molecule, calculated using 6-31+G(d) basis set and a B3LYP correlation-exchange functional, of 0.965 (Å) or greater when assuming an adsorption structure.

2. The method of claim 1, wherein the organic molecule has at least one of: (i) a phosphorus-containing structural portion; (ii) a nitrogen- and / or oxygen-containing ring structural portion; (iii) a secondary amine structural portion; and (iv) a tertiary amine structural portion.

3. The organic molecule is a primary amine, and the primary amine has an adsorption energy E ａｄｓ The method of claim 1 , wherein the Θ is 0.35 eV or more.

4. The method of claim 1, wherein the organic molecule comprises at least one selected from the group consisting of pyridine, imidazole, pyrrole, morpholine, oxazoline, and organic phosphorus oxide.

5. The first surface is SiO ｘ or SiN ｙ The method of claim 1 , comprising:

6. The method of claim 1, wherein the exposure in (2) is carried out at a temperature in the range of 80°C to 450°C.

7. The method of claim 1, wherein the exposure in (2) is carried out at a temperature in the range of 200°C to 450°C.

8. The method of claim 1, wherein the workpiece has one or more layers.

9. The method of claim 1, wherein the recessed structure is at least one of a blind hole, a through hole, a blind groove, and a through groove.

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