Pattern formation method and plasma processing method

Abstract

In this pattern forming method for forming a pattern film on a substrate, the pattern film contains a triptycene derivative having a triptycene skeleton. The triptycene skeleton has a first plane on which the 1-position, 8-position, and 13-position of the triptycene skeleton are located, and a second plane on which the 4-position, 5-position, and 16-position of the triptycene skeleton are located. The triptycene derivative has a first side chain on one plane-side among the first plane and the second plane, and a second side chain on the other plane-side among the first plane and the second plane or on said one plane-side, the second side chain having a different etch selectivity than the first side chain.

Description

[Technical Field]

[0001] This disclosure relates to a pattern formation method and a plasma processing method. [Background technology]

[0002] Patent Document 1 describes a base resin whose alkali solubility is improved by an acid, and CF3-C(OR 2 )-R 3 A method for forming a pattern using a resist material containing a polymer additive having repeating units derived from styrene, which have ester groups bonded to a base, is disclosed.

[0003] Patent Document 2 discloses a pattern-forming method in which a polymer material having a first segment and a second segment is embedded in the recesses of a guide having an uneven pattern, and the polymer material is subjected to microphase separation. In this technique, a self-assembled pattern is formed having a cylindrical first polymer portion including the first segment, and a second polymer portion including the second segment surrounding the side of the first polymer portion, and the first polymer portion is selectively removed.

[0004] Patent Document 3 discloses a technique for forming a pattern by coating a substrate with an induced self-assembly (DSA) composition containing a block copolymer (BCP). In this technique, the BCP is selected to contain at least two blocks and have a high interaction parameter (Chi), and the BCP forms vertical lamellae by simple thermal annealing on a neutralized substrate without a topcoat. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2014-126623 [Patent Document 2] Japanese Patent Publication No. 2014-241374 [Patent Document 3] Special Publication No. 2017-505709 [Overview of the project] [Problems that the invention aims to solve]

[0006] This disclosure provides a pattern formation method capable of forming a fine pattern structure that is resistant to etching. [Means for solving the problem]

[0007] A pattern formation method according to one aspect of the present disclosure is a pattern formation method for forming a pattern film on a substrate, wherein the pattern film contains a triptycene derivative having a triptycene skeleton, the triptycene skeleton having a first face where positions 1, 8 and 13 of the triptycene skeleton are aligned, and a second face where positions 4, 5 and 16 of the triptycene skeleton are aligned, the triptycene derivative having a first side chain on either the first face or the second face, and having a second side chain on either the other face of the first face or the second face, having an etching selectivity different from that of the first side chain. [Effects of the Invention]

[0008] According to one aspect of this disclosure, it is possible to form a fine pattern structure that is resistant to etching. [Brief explanation of the drawing]

[0009] [Figure 1] A diagram showing the chemical structure of triptycene. [Figure 2] A schematic diagram showing the molecular assembly structure in a conventional patterned film. [Figure 3] A diagram showing the two-dimensional aggregate structure of triptycene. [Figure 4] A diagram showing the three-dimensional aggregate structure of triptycene. [Figure 5] A diagram showing the side chains of the triptycene skeleton. [Figure 6] A diagram showing the chemical structure of an example of a trypsetin derivative having a configuration in which the first and second side chains are bonded in series from the triptycene skeleton. [Figure 7] A diagram showing the general formula of a tripcene derivative having a structure in which a first side chain and a second side chain are serially bonded in this order from the tripcene skeleton. [Figure 8] A diagram showing the chemical structure of a specific example of a tripcene derivative represented by the general formula in FIG. 7. [Figure 9] A diagram showing the chemical structure of an example of a tripcene derivative having a structure in which a first side chain and a second side chain extend in opposite directions with respect to the tripcene skeleton. [Figure 10] A diagram showing the general formula of a tripcene derivative having a structure in which a first side chain and a second side chain extend in opposite directions with respect to the tripcene skeleton. [Figure 11] A diagram showing the chemical structure of a specific example of a tripcene derivative represented by the general formula in FIG. 7. [Figure 12] A diagram showing the chemical structure of a specific example of a tripcene derivative represented by the general formula in FIG. 7. [Figure 13] A diagram showing a process of forming a pattern using a tripcene derivative. [Figure 14] A diagram showing the state of a film formed by the three-dimensional aggregation of a tripcene derivative. [Figure 15] A diagram showing an example of the aggregation structure of the tripcene derivative in FIG. ID=26]] [Figure 16] A diagram showing an example of the aggregation structure of the tripcene derivative in FIG. ID=29]]<0000##100> [Figure 17] A diagram showing an example of the aggregation structure of the tripcene derivative in FIG. ID=32]] [[ID=##33]] [Figure 18] A diagram showing an example of the aggregation structure of the tripcene derivative in FIG. ID=35]] [Figure 19] A diagram showing the result of structural analysis of a tripcene derivative by X-ray diffraction (diffraction in the in-plane direction). [Figure 20] A diagram showing the result of structural analysis of a tripcene derivative by X-ray diffraction (diffraction in the out-of-plane direction). [Figure 21] A diagram showing a plasma processing system for implementing a plasma processing method which is an example of a pattern forming method. [Figure 22] A diagram showing a process of forming a pattern by plasma etching using a tripcene derivative. [Figure 23] Figure 22 shows the relationship between etching time and etching amount of the side chain of the triptycene derivative when CF-based etching is performed. [Figure 24] Figure 22 shows the relationship between etching time and etching amount of the side chain of the triptycene derivative when oxygen-based etching is performed. [Figure 25] A table showing the etching resistance of the side chains of triptycene derivatives. [Figure 26] A graph showing the results of elemental analysis after etching on the surface of a triptycene derivative film. [Figure 27] This graph shows the results of elemental analysis when the surface of a triptycene derivative film was etched by 10 nm using argon ion etching. [Figure 28] This graph shows the results of elemental analysis when the surface of a triptycene derivative film was etched by 20 nm using argon ion etching. [Figure 29] A diagram illustrating the process of forming a wiring pattern using a triptycene derivative. [Figure 30] A diagram illustrating the process of forming a wiring mask pattern using a triptycene derivative. [Figure 31] A diagram showing the spherical aggregate structure of triptycene derivatives. [Modes for carrying out the invention]

[0010] The embodiments of this disclosure will be described below with reference to the drawings. Note that parts common to each drawing may be denoted by the same or corresponding reference numerals, and their descriptions may be omitted.

[0011] Figure 1 shows the chemical structure of triptycene. Figure 2 shows the molecular assembly structure in a conventional patterned film. Figure 3 shows the two-dimensional assembly structure of triptycene. Figure 4 shows the three-dimensional assembly structure of triptycene.

[0012] In the pattern formation method according to this disclosure, a pattern film is formed on a substrate.

[0013] The substrate is not particularly limited; for example, a wafer made of single-crystal silicon (Si) processed by a semiconductor device manufacturing process can be used. Alternatively, the substrate may be a patterned substrate with an insulating layer such as a silicon oxide film formed on the silicon. Furthermore, the substrate is not limited to wafers; glass substrates for flat panel display manufacturing can also be used.

[0014] The pattern film is not particularly limited and includes, for example, interlayer insulating films, spacers, protective films, and colored pattern films for semiconductor devices. The thickness of the pattern film is, for example, 0.1 to 10 μm, preferably 0.1 to 5 μm, and more preferably 0.1 to 3 μm.

[0015] The method for manufacturing patterned films is not particularly limited and includes various film deposition methods such as vapor deposition, chemical vapor deposition (CVD), sputtering, and spin coating. CVD methods include thermal CVD, plasma CVD, and photo-CVD.

[0016] The patterned film contains a triptycene derivative having a triptycene skeleton. As shown in Figure 1, triptycene has three benzene rings arranged in a three-bladed propeller shape. 3h It is an aromatic hydrocarbon having a symmetrical structure. In this disclosure, the positional numbers of triptycene are indicated as positions 1 to 16 according to the CAS nomenclature (Figure 1).

[0017] In this disclosure, the triptycene skeleton corresponds to the triptycene TS shown in Figure 1. In this disclosure, triptycene (hereinafter sometimes referred to as the triptycene skeleton) is defined as having a first virtual plane where positions 1, 8, and 13 are aligned, and a second virtual plane where positions 4, 5, and 16 are aligned (see Figure 1).

[0018] Here, we will explain the properties of triptycene. In conventional patterned films using polymer compounds, there is a tendency for misalignment to occur within the aggregate structure M1 of the molecules constituting the patterned film. For example, molecules with a triangular chemical structure and molecules with a quadrilateral chemical structure are prone to misalignment in the translational direction. Also, molecules with a hexagonal chemical structure are prone to misalignment in the rotational direction (see Figure 2).

[0019] In contrast, because triptycene has a three-fold symmetric propeller-like chemical structure, the two-dimensional aggregate structure M2 of triptycene TS is arranged in a nested manner, and displacement is suppressed in both the translational and rotational directions (see Figure 3).

[0020] Furthermore, the three-dimensional aggregate structure M3 of triptycene TS is an aggregate structure in which two-dimensional aggregate structures M2 are stacked in the height direction or thickness direction. The three-dimensional aggregate structure M3 of triptycene TS can form a self-organized laminate in the height direction or thickness direction by stacking while maintaining the nested orientation of the two-dimensional aggregates M2 of triptycene TS.

[0021] Such a three-dimensional aggregate structure M3 of triptycene TS constitutes a lamellar structure (a structure in which thin layered or plate-like structures are stacked), forming a dense nanophase separation structure as an aggregate of organic molecules that can precisely define the size and geometric structure of triptycene derivatives at the single-molecule level (Figure 4).

[0022] The pattern formation method of this disclosure forms a pattern film containing a trypsetin derivative having such a trypsetin (trypsetin skeleton) TS. The trypsetin derivative can be selected from trypsetin derivatives reported by one of the inventors of this disclosure in Japanese Patent Publication No. 6219314, Japanese Patent Publication No. 6272242, Japanese Patent Publication No. 6793946, etc.

[0023] In this disclosure, among these triptycene derivatives, those having a first side chain on either the first or second face of the triptycene skeleton, and a second side chain on either the other face or one of the two faces are used. Furthermore, the first and second side chains are used which have different etching selectivity ratios.

[0024] Here, the first and second side chains are not particularly limited, but examples include side chains with organic compositions such as alkyl chains, tetraethylene glycol chains (hereinafter referred to as TEG chains), and aryl chains, and side chains with inorganic compositions such as siloxane compounds including dimethylsiloxane chains (hereinafter referred to as DMS chains). Of these, alkyl chains, TEG chains, and DMS chains are shown in Figure 5. The side chains may also constitute alkoxy chains that are bonded to the triptycene skeleton via oxygen.

[0025] Furthermore, if the first or second side chain has an organic composition, it is preferable that the end of the first or second side chain having the organic composition is hydroxy-terminated. Here, hydroxy-termination refers to a state in which a hydroxyl group (OH group) is bonded to the carbon atom at the end of the side chain having an organic composition. For example, the side chains of the TEG chain represented by chemical formulas (3-1) to (3-4) in Figure 12, which will be described later, that are terminated with OH groups fall under this category.

[0026] The combination of the first and second side chains, which have different etching selectivity ratios, is arbitrary and can be determined by the conditions for forming the patterned film. For example, in the etching process described later, if an alkyl chain or TEG chain is used for the first side chain and a DMS chain for the second side chain, the first side chain is easily etched and the second side chain is not. In this disclosure, the first and second side chains can be selected by utilizing this ease of etching.

[0027] In the present disclosure, when having a first side chain on one side of either the first surface or the second surface and a second side chain on one side of either the first surface or the second surface, specifically, it is the case where the first side chain is bonded to the triphenylene skeleton on one side of either the first surface or the second surface, and further the second side chain is bonded to the end of the first side chain. That is, the first side chain and the second side chain are bonded in series in the order of the first side chain and the second side chain from the triphenylene skeleton and extend in the same direction.

[0028] The tripcene derivative having a structure in which the first side chain and the second side chain are bonded in series in this order from the triphenylene skeleton is not particularly limited. For example, such a tripcene derivative can use a tripcene derivative in which an alkyl chain is bonded to the first surface or the second surface of the triphenylene skeleton via oxygen (an alkoxy group), and a TEG chain is bonded in series to the end of the alkyl chain (see Fig. 6).

[0029] In addition, the tripcene derivative having a structure in which the first side chain and the second side chain are bonded in series in the order from the triphenylene skeleton is represented by the general formula shown in Fig. 7. In the general formula of Fig. 7, R 11 , R 21 , R 31 correspond to the first side chain, and R 12 , R 22 , R 32 correspond to the second side chain.

[0030] In the formula of Fig. 7, R 11 , R 21 , R 31 are the same group and represent a saturated or unsaturated divalent hydrocarbon group having 5 to 30 carbon atoms, and the hydrocarbon group may have one or more substituents. Also, one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a silicon atom, or -NR7- (where R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

[0031] In addition, in the formula of Fig. 7, R 12 , R 22 , R 32 are the same group, and R11 , R 21 , R 31 This is a different group from the above, representing a saturated or unsaturated divalent hydrocarbon group having 5 to 30 carbon atoms, and the hydrocarbon group may have one or more substituents. Furthermore, one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a silicon atom, or -NR8- (where R8 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

[0032] In the formula in Figure 7, X1, X2, and X3 are the same group, and are a linking group (or linker group) consisting of a divalent group of atoms selected from the group consisting of nitrogen, oxygen, sulfur, carbon, and silicon atoms, and hydrogen atoms.

[0033] Furthermore, in the formula in Figure 7, Z1, Z2, and Z3 are the same group and are terminal groups (or terminating groups) consisting of a hydrogen atom, or a monovalent group of atoms consisting of 1 to 15 atoms selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, carbon atoms, phosphorus atoms, halogen atoms, and silicon atoms, and a hydrogen atom.

[0034] Examples of triptycene derivatives represented by the general formula in Figure 7 include the triptycene derivatives represented by chemical formulas (1-1) to (1-3) shown in Figure 8, as well as the trypsetin derivatives shown in Figure 6 above.

[0035] Furthermore, in this disclosure, when a first side chain is present on one of the first and second faces and a second side chain is present on the other face, specifically, the first side chain is bonded to the triptycene skeleton on one of the first and second faces, and the second side chain is bonded to the triptycene skeleton on the other face. That is, the first and second side chains extend in opposite directions relative to the triptycene skeleton.

[0036] The trypsetin derivative having a configuration in which the first and second side chains extend in opposite directions relative to the triptycene skeleton is not particularly limited. For example, such a trypsetin derivative can be used in which an alkyl chain is bonded to the first or second face of the triptycene skeleton via oxygen (alkoxy group), as shown in the chemical structure of Figure 9, and a TEG chain is bonded to the first or second face opposite to the face to which the alkyl chain is bonded (see Figure 9).

[0037] The trypsetin derivative having the chemical structure shown in the lower part of Figure 9 is a monomolecule TD represented by the schematic diagram shown in the upper part of Figure 9. The monomolecule TD of the triptycene derivative has a triptycene skeleton TS, a first side chain S1 bonded to the first face of the triptycene skeleton TS, and a second side chain S2 bonded to the second face of the triptycene skeleton TS (see Figure 9).

[0038] Trypsetin derivatives having a structure in which the first and second side chains extend in opposite directions relative to the triptycene skeleton are represented by the general formula shown in Figure 10. In the general formula in Figure 10, R1, R2, and R3 correspond to the first side chain, and R4, R5, and R6 correspond to the second side chain.

[0039] In the formula in Figure 10, R1, R2, and R3 represent the same group, which is a saturated or unsaturated divalent hydrocarbon group having 5 to 30 carbon atoms, and the hydrocarbon group may have one or more substituents. Furthermore, one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a silicon atom, or -NR7- (where R7 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

[0040] Furthermore, in the formula in Figure 10, R4, R5, and R6 are the same group, but different from R1, R2, and R3, and represent a saturated or unsaturated divalent hydrocarbon group having 5 to 30 carbon atoms, and the hydrocarbon group may have one or more substituents. In addition, one or more carbon atoms in the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a silicon atom, or -NR8- (where R8 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms).

[0041] In the formula in Figure 10, X1, X2, and X3 are the same group, and are a linking group (or linker group) consisting of a divalent group of atoms selected from the group consisting of nitrogen, oxygen, sulfur, carbon, and silicon atoms, and hydrogen atoms.

[0042] Furthermore, in the formula in Figure 10, Z1, Z2, and Z3 are the same group and are terminal groups (or terminating groups) consisting of a hydrogen atom, or a monovalent group of atoms consisting of 1 to 15 atoms selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, carbon atoms, phosphorus atoms, halogen atoms, and silicon atoms, and a hydrogen atom.

[0043] Furthermore, in the formula in Figure 10, Z4, Z5, and Z6 are the same group and are terminal groups (or terminating groups) consisting of a hydrogen atom, or a monovalent group of atoms consisting of 1 to 15 atoms selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, carbon atoms, phosphorus atoms, halogen atoms, and silicon atoms, and a hydrogen atom.

[0044] Examples of triptycene derivatives represented by the general formula in Figure 10 include the triptycene derivatives shown in Figure 9 above, as well as the triptycene derivatives represented by chemical formulas (2-1) to (2-7) shown in Figure 11. Additionally, examples of triptycene derivatives represented by the general formula in Figure 10 include the triptycene derivatives represented by chemical formulas (3-1) to (3-5) shown in Figure 12.

[0045] Figure 13 shows the process of forming a resist pattern using a triptycene derivative. In Figure 13(A), two opposing sidewalls (sidewalls 300, 400) are laminated as etching stop layers, such as a silicon nitride film, on a laminate in which an insulating layer 200, such as a silicon oxide film, is laminated on a substrate 100, such as a single crystal silicon.

[0046] Space G (sometimes referred to as a pattern groove) is formed inside the side walls 300 and 400 that constitute the etching stop layer. The distance (width) between the side walls 300 and 400 of space G is adjusted to approximately 40 nm, and the height of the side walls 300 and 400 is adjusted to approximately 150 nm.

[0047] In Figure 13(B), when the above-mentioned triptycene derivative is supplied to the space G inside the side walls 300 and 400 and subjected to film formation treatment such as vapor deposition or CVD, a layer (three-dimensional aggregate structure) M3 of triptycene derivative molecules is formed, as shown in Figure 13(C).

[0048] In this embodiment, a triptycene derivative is supplied onto a pattern substrate provided with side walls 300 and 400, and when the pattern substrate is heated, the molten triptycene derivative spreads onto the pattern substrate by capillary action. When the pattern substrate is further slowly cooled in this state, the triptycene derivative recrystallizes.

[0049] The method of supplying the triptycene derivative onto the pattern substrate is not limited. For example, the triptycene derivative may be placed on a pattern substrate made of silicon dioxide (SiO2) and melted. Alternatively, the triptycene derivative may be deposited onto a heated pattern substrate.

[0050] Furthermore, the conditions for heating the pattern substrate are not particularly limited. For example, the heating temperature can be about 10 to 50°C higher than the melting point of the triptycene derivative. The heating time can be 30 minutes to 5 hours. In this embodiment, the pattern substrate supplied with the triptycene derivative is heated at a temperature about 30°C higher than the melting point of the triptycene derivative for about 3 hours.

[0051] Furthermore, the conditions for slowly cooling the pattern substrate are not particularly limited. For example, the slow cooling rate can be 0.1 to 3°C / minute. The slow cooling time can be 30 minutes to 5 hours. In this embodiment, the pattern substrate, in which the triptycene derivative is molten, is cooled to room temperature at 3°C / minute over approximately 2 hours.

[0052] Note that the schematic diagram in the upper part of Figure 13(C) and Figure 14 are magnified views of a portion of the triptycene derivative molecular assembly. Layer M3 of the triptycene derivative molecular assembly has an aggregate structure in which multiple single molecules TD of triptycene derivatives are assembled in the horizontal and vertical directions. Here, horizontal and vertical include approximately horizontal and approximately vertical arrangements.

[0053] Layer M3 of the triptycene derivative molecular assembly has a structure in which, for example, the triptycene skeletons TS of single-molecule triptycene derivatives TD are aligned vertically. Here, Figures 15 to 18 show specific examples of aggregate structures of triptycene derivatives in which the triptycene skeletons TS of single-molecule triptycene derivatives TD are aligned vertically.

[0054] Figures 15 and 16 show specific examples of the aggregate structure of the triptycene derivative represented by the general formula in Figure 7. Figures 15 and 16 show aggregates of single molecules TD of a trypsetin derivative, in which the first side chain S1 of an alkyl chain is bonded to the first or second face of the triptycene skeleton TS via an alkoxy linking group, and the second side chain S2 of a TEG chain is bonded in series to the end of the alkyl chain.

[0055] In the example shown in Figure 15, in layer M3 of the molecular assembly of trypsetin derivatives, the single molecules TD of the trypsetin derivatives are arranged such that the triptycene skeletons TS are aligned vertically and adjacent to each other horizontally. Furthermore, the single molecules TD of the trypsetin derivatives are arranged such that the alkyl chains of the first side chain S1 are aligned vertically, and the TEG chains of the second side chain S2 are aligned vertically and adjacent to each other horizontally.

[0056] In the example shown in Figure 16, in layer M3 of the molecular assembly of trypsetin derivatives, the single molecules TD of the trypsetin derivative are arranged such that the triptycene skeleton TS is aligned vertically and adjacent to the TEG chain of the second side chain S2 horizontally. Additionally, the single molecules TD of the trypsetin derivative are arranged such that the alkyl chain of the first side chain S1 is aligned vertically and the TEG chain of the second side chain S2 is aligned vertically.

[0057] Figures 17 and 18 show specific examples of aggregate structures of triptycene derivatives represented by the general formula in Figure 10. Figures 17 and 18 show aggregates of single molecules TD of a trypsetin derivative, in which the first side chain S1 of an alkyl chain is bonded to the first face of the triptycene skeleton TS via an alkoxy linking group, and the second side chain S2 of a DMS chain is bonded to the second face via an alkoxy linking group.

[0058] In the example shown in Figure 17, in layer M3 of the molecular assembly of the trypsetin derivative, the single molecules TD of the trypsetin derivative are arranged such that the alkyl chains of the first side chain S1, which are bound to the trypsetine skeleton TS, are aligned vertically and adjacent horizontally. Furthermore, the single molecules TD of the trypsetine derivative are arranged such that the DMS chains of the second side chain S2 are aligned vertically and adjacent horizontally.

[0059] In the example shown in Figure 18, in layer M3 of the molecular assembly of the trypsetin derivative, each single molecule TD of the triptycene derivative is positioned such that the alkyl chain of the bonded first side chain S1 is aligned vertically and adjacent to the DMS chain of the second side chain S2 horizontally.

[0060] Furthermore, the horizontal length of the single molecule TD of the triptycene derivative constituting layer M3 of the trypsetin derivative molecular assembly shown in Figures 15 to 18 is approximately 2 to 3 nm.

[0061] As a result, a layer M3 of triptycene derivative molecular assemblies is formed as a pattern film inside the side walls 300 and 400 in Figure 13(C). The layer M3 of triptycene derivative molecular assemblies has a structure in which, for example, aggregates A1 of the first side chain S1 stacked vertically and aggregates A2 of the second side chain S2 stacked vertically are alternately arranged horizontally.

[0062] In layer M3 of the triptycene derivative molecular aggregate, the horizontal thickness of aggregate A1 of the first side chain S1 is 100 nm or more, and the horizontal thickness of aggregate A2 of the second side chain S2 is also 100 nm or more.

[0063] Furthermore, in this embodiment, the aspect ratio of the inside of the side walls 300 and 400 in Figure 13(C) is adjusted to 2 or more. Here, the aspect ratio of the inside of the side walls 300 and 400 represents the ratio of the vertical dimension (depth) to the horizontal dimension (width) in the space G formed inside the side walls 300 and 400.

[0064] In this embodiment, the ratio of the height of the side walls 300 and 400 to the distance between the side walls 300 and 400 is 2 or more, and the aspect ratio of the pattern film formed on the inside of the side walls 300 and 400 as layer M3 of triptycene derivative molecular aggregates is also 2 or more.

[0065] Specifically, in layer M3 of the triptycene derivative molecular aggregate, aggregates A1 of the first side chain S1 and aggregates A2 of the second side chain S2, which are arranged alternately in the horizontal direction, are stacked such that the vertical dimension (stacking direction) is at least twice the horizontal dimension.

[0066] In this embodiment, with the first side chain S1 aggregate A1 and the second side chain S2 aggregate A2 stacked horizontally, a layer M3 of triptycene derivative molecular aggregates is formed inside the side walls 300 and 400. This layer M3 of triptycene derivative molecular aggregates is adjusted to have a vertical dimension (height) of 150 nm (height of side walls 300 and 400) and a horizontal dimension (width) of 40 nm (distance between side walls 300 and 400) corresponding to space G.

[0067] In Figure 13(D), the layer M3 of triptycene derivative molecular aggregates formed inside the side walls 300 and 400 is etched, leaving behind the aggregate A1 of the first side chain S1 and the etching-resistant aggregate A2 of the second side chain S2. Spaces G1 are formed between the aggregates A2 of the second side chain S2. The aggregates A2 of the second side chain S2 have a horizontal thickness of 10 nm or less and can become a fine patterned film (e.g., a protective film) that is etching-resistant.

[0068] In Figure 13(D), the aggregate A2 of the second side chain S2 acts as a protective film. After further etching of the portion of the insulating layer 200 directly beneath the space G1, the aggregate A2 of the second side chain S2 is removed, forming an insulating layer 200' on the substrate 100, and a space G2 is formed between the insulating layers 200'. Each insulating layer 200' and the space G2 between the insulating layers 200' have a horizontal thickness of 10 nm or less, making it possible to form a fine pattern on the substrate 100.

[0069] Figure 19 shows the results of a structural analysis (in-plane diffraction) performed by X-ray diffraction on a molecular assembly of the triptycene derivative represented by Figure 9 (chemical formula (2-3) in Figure 11). In this structural analysis, diffraction originating from the lamellar structure constituting the molecular assembly of the triptycene derivative appears in the in-plane (horizontal) direction.

[0070] The diffraction results shown in Figure 19 show that by using the triptycene derivative shown in chemical formula (2-3) of Figure 11, a patterned film can be obtained having a structure in which aggregates of vertically stacked first side chains and aggregates of vertically stacked second side chains are alternately arranged in the horizontal direction.

[0071] Furthermore, Figure 20 shows the results of a structural analysis (out-of-plane diffraction) performed by X-ray diffraction on the molecular assembly of the triptycene derivative represented by chemical formula (2-1) in Figure 11. In this structural analysis, diffraction originating from the lamellar structure constituting the triptycene derivative molecular assembly appears in the out-of-plane (perpendicular) direction.

[0072] The diffraction results shown in Figure 20 show that by using the triptycene derivative shown in chemical formula (2-1) in Figure 11, a patterned film can be obtained having a structure in which aggregates of first side chains stacked horizontally and aggregates of second side chains stacked horizontally are alternately stacked vertically.

[0073] Thus, the structural analysis in Figures 19 and 20 shows that by appropriately selecting the type of triptycene derivative, the stacking direction of the lamellar structure constituting the triptycene derivative molecular assembly can be controlled.

[0074] In the pattern formation method of the present disclosure, a pattern film containing a triptycene derivative is formed as described above. The triptycene derivative has a triptycene skeleton, a first side chain on either the first or second face of the triptycene skeleton, and a second side chain having a different etching selectivity from the first side chain on either the other face or either of the first and second faces.

[0075] As a result, in the pattern-forming method of the present disclosure, a lamellar structure can be formed in which aggregates of first side chains stacked vertically or horizontally and aggregates of second side chains stacked vertically or horizontally are alternately stacked horizontally or vertically in the resulting layer of triptycene derivative molecular aggregates.

[0076] Furthermore, in such a lamellar structure, the horizontal or vertical thickness of the aggregate of the first side chains can be reduced to 10 nm or less, and the horizontal thickness of the aggregate of the second side chains can also be reduced to 10 nm or less. Therefore, in this disclosure, a fine pattern structure with etching resistance can be formed.

[0077] In the pattern formation method of this disclosure, as described above, the first side chain is bound to the triptycene skeleton and the second side chain is bound to the end of the first side chain (Figures 6 to 8). As a result, the obtained pattern film can form a dense pattern structure in which aggregates of the first side chains stacked vertically and aggregates of the second side chains stacked vertically are alternately arranged horizontally with a thickness of 10 nm or less (Figures 15 and 16).

[0078] In the pattern formation method of this disclosure, as described above, the first side chain is bound to the triptycene skeleton on one of the face sides, and the second side chain is bound to the triptycene skeleton on the other of the face sides (Figures 9 to 12). As a result, the resulting pattern film can form a dense pattern structure in which aggregates of the first side chains stacked vertically and aggregates of the second side chains stacked vertically are alternately arranged horizontally with a thickness of 10 nm or less (Figures 17 and 18).

[0079] In the pattern formation method of this disclosure, as described above, the pattern film is formed on the inside of two opposing side walls. As a result, in this disclosure, a dense pattern structure in which aggregates of first side chains stacked vertically and aggregates of second side chains stacked vertically are alternately arranged horizontally with a thickness of 10 nm or less can be constructed within a limited area (see Figure 13).

[0080] Furthermore, as described above, by heating and slowly cooling the pattern substrate to which the triptycene derivative is supplied, the recrystallized triptycene derivative on the pattern substrate can form a densely self-organized molecular aggregate layer (three-dimensional aggregate structure) M3.

[0081] As mentioned above, when triptycene derivatives are deposited onto a patterned substrate, voids tend to form on the substrate. In contrast, in this embodiment, by depositing the trypsetin derivative onto a heated patterned substrate, the triptycene derivative melts and deposits in the pattern grooves. Subsequent heating and slow cooling then form a layer of self-assembled, dense molecular aggregates, thus suppressing the formation of voids.

[0082] As described above, in the pattern formation method of this disclosure, by making the aspect ratio of the pattern film 2 or more, it is possible to form multiple fine, elongated pattern structures in the vertical direction within a limited area on the inside of the side wall.

[0083] In the pattern formation method of this disclosure, as described above, by having either the first side chain or the second side chain have an inorganic composition, the pattern film, which is composed of an aggregate of side chains having an inorganic composition stacked vertically, can function as a protective film with etching resistance.

[0084] Furthermore, in the pattern formation method of this disclosure, as described above, the boiling point of the triptycene derivative can be lowered even when the side chains of the triptycene skeleton have an inorganic composition, because the inorganic composition constituting either the first side chain or the second side chain includes a siloxane compound. Therefore, the temperature at which the film is formed can be lowered according to the pattern formation method of this disclosure.

[0085] In the pattern formation method of this disclosure, as described above, by having either the first side chain or the second side chain have an organic composition, a fine pattern film composed of an aggregate of side chains having an organic composition stacked vertically can be made to function as an etching film.

[0086] In the pattern-forming method of this disclosure, as described above, hydrogen bonds can be formed at the ends of the first or second side chains by hydroxy-terminating the ends of the first or second side chains having an organic composition. This increases the melting point of the triptycene derivative in which the ends of the first or second side chains having an organic composition are hydroxy-terminated. Therefore, the pattern-forming method of this disclosure can improve the thermal stability of the resulting pattern film.

[0087] The pattern formation method of this disclosure can be applied to a plasma processing method by utilizing such configuration and effects. Figure 21 shows a plasma processing system for carrying out a plasma processing method as an example of the pattern formation method according to this disclosure. Embodiments of the plasma processing system will be described below.

[0088] The plasma processing system includes a capacitively coupled plasma processing apparatus 1 and a control unit 2.

[0089] The capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply 30, and an exhaust system 40. The plasma processing apparatus 1 also includes a substrate support unit 11 and a gas introduction unit. The gas introduction unit is configured to introduce processing gas into the plasma processing chamber 10. The gas introduction unit includes a shower head 13.

[0090] Here, the processing gas includes various gases. For example, when a pattern film is deposited on the substrate W described later, the deposition gas containing the trypsetin derivative mentioned above is included. When etching the pattern film, the etching gas, such as an oxygen-based gas or a CF (fluorocarbon)-based gas, is included. Furthermore, an inert gas such as argon gas or nitrogen gas is included as a carrier gas when depositing or etching the pattern film.

[0091] The substrate support portion 11 is located inside the plasma processing chamber 10. The shower head 13 is located above the substrate support portion 11. In this embodiment, the shower head 13 constitutes at least a portion of the ceiling of the plasma processing chamber 10. The plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the side walls 10a of the plasma processing chamber 10, and the substrate support portion 11.

[0092] The plasma processing chamber 10 has at least one gas supply port for supplying processing gas to the plasma processing space 10s and at least one gas outlet for discharging gas from the plasma processing space. The side wall 10a is grounded. The shower head 13 and the substrate support portion 11 are electrically insulated from the housing of the plasma processing chamber 10.

[0093] The substrate support portion 11 includes a main body portion 111 and a ring assembly 112. The main body portion 111 has a central region (substrate support surface) 111a for supporting the substrate (wafer) W and an annular region (ring support surface) 111b for supporting the ring assembly 112.

[0094] Furthermore, as the substrate (wafer) W supported in the central region (substrate support surface) 111a, for example, a pattern substrate provided with the aforementioned side walls 300 and 400 is used.

[0095] The annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view. The substrate W is placed on the central region 111a of the main body 111. The ring assembly 112 is placed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111.

[0096] The substrate support portion 11 may also be provided with a heater (not shown) for heating the central region 111a of the main body portion 111. Such a heater can heat the substrate W placed on the central region 111a, thereby enabling heat treatment such as deposition or heating of the trypsetin derivative supplied to the substrate W.

[0097] In this embodiment, the main body 111 includes a base and an electrostatic chuck. The base includes a conductive member. The conductive member of the base functions as a lower electrode. The electrostatic chuck is positioned on the base. The upper surface of the electrostatic chuck has a substrate support surface 111a.

[0098] The ring assembly 112 includes one or more annular members, at least one of which is an edge ring. Although not shown in the figures, the substrate support 11 may also include a temperature control module configured to adjust at least one of the electrostatic chuck, the ring assembly 112, and the substrate to a target temperature.

[0099] The temperature control module may include a heater, a heat transfer medium, a flow path, or a combination thereof. A heat transfer fluid such as brine or gas flows through the flow path. The substrate support section 11 may also include a heat transfer gas supply section configured to supply heat transfer gas between the back surface of the substrate W and the substrate support surface 111a.

[0100] The showerhead 13 is configured to introduce the processing gas from the gas supply unit 20 into the plasma processing space 10s. The showerhead 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and a plurality of gas inlets 13c. The processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s through the plurality of gas inlets 13c.

[0101] Furthermore, the shower head 13 includes a conductive member. The conductive member of the shower head 13 functions as an upper electrode. In addition to the shower head 13, the gas introduction section may also include one or more side gas injectors (SGIs) attached to one or more openings formed in the side wall 10a.

[0102] The gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22. In this embodiment, the gas supply unit 20 is configured to supply the processing gas to the shower head 13 from the corresponding gas source 21 via the corresponding flow controller 22. Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller.

[0103] Furthermore, the gas supply unit 20 may include one or more flow modulation devices that modulate or pulse the flow rate of the processing gas.

[0104] The power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit. The RF power supply 31 is configured to supply at least one RF signal (RF power), such as a source RF signal and a bias RF signal, to the conductive members of the substrate support 11 and / or the showerhead 13. This causes plasma to be formed from the processing gas supplied to the plasma processing space 10s.

[0105] Therefore, the RF power supply 31 can function as at least part of a plasma generation unit configured to generate plasma from a processing gas in the plasma processing chamber 10. Furthermore, by supplying a bias RF signal to the conductive member of the substrate support unit 11, a bias potential is generated on the substrate W, and ionic components in the formed plasma can be drawn into the substrate W.

[0106] In this embodiment, the RF power supply 31 includes a first RF generation unit 31a and a second RF generation unit 31b. The first RF generation unit 31a is coupled to a conductive member of the substrate support unit 11 and / or a conductive member of the shower head 13 via at least one impedance matching circuit and is configured to generate a source RF signal (source RF power) for plasma generation.

[0107] In this embodiment, the source RF signal has a frequency in the range of 13 MHz to 150 MHz. In this embodiment, the first RF generation unit 31a may be configured to generate a plurality of source RF signals having different frequencies. The generated one or more source RF signals are supplied to the conductive member of the substrate support unit 11 and / or the conductive member of the shower head 13.

[0108] The second RF generation unit 31b is coupled to a conductive member of the substrate support unit 11 via at least one impedance matching circuit and is configured to generate a bias RF signal (bias RF power). In this embodiment, the bias RF signal has a lower frequency than the source RF signal. In this embodiment, the bias RF signal has a frequency in the range of 400 kHz to 13.56 MHz.

[0109] In this embodiment, the second RF generation unit 31b may be configured to generate a plurality of bias RF signals having different frequencies. The generated bias RF signals are supplied to the conductive member of the substrate support unit 11. In various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.

[0110] The power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10. The DC power supply 32 includes a first DC generation unit 32a and a second DC generation unit 32b.

[0111] In this embodiment, the first DC generation unit 32a is connected to a conductive member of the substrate support unit 11 and is configured to generate a first DC signal. The generated first bias DC signal is applied to the conductive member of the substrate support unit 11. In this embodiment, the first DC signal may also be applied to other electrodes, such as electrodes in an electrostatic chuck.

[0112] In this embodiment, the second DC generation unit 32b is connected to the conductive member of the shower head 13 and is configured to generate a second DC signal. The generated second DC signal is applied to the conductive member of the shower head 13.

[0113] In various embodiments, at least one of the first and second DC signals may be pulsed. The first and second DC generation units 32a and 32b may be provided in addition to the RF power supply 31, and the first DC generation unit 32a may be provided in place of the second RF generation unit 31b.

[0114] The exhaust system 40 may be connected to, for example, a gas outlet 10e located at the bottom of the plasma processing chamber 10. The exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure regulating valve regulates the pressure in the plasma processing space 10s. The vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.

[0115] The control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various processes described herein. The control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various processes described herein. In this embodiment, some or all of the control unit 2 may be included in the plasma processing apparatus 1.

[0116] The control unit 2 may include, for example, a computer 2a. The computer 2a may include, for example, a processing unit (CPU: Central Processing Unit) 2a1, a storage unit 2a2, and a communication interface 2a3. The processing unit 2a1 may be configured to perform various control operations based on a program stored in the storage unit 2a2.

[0117] The memory unit 2a2 may include RAM (Random Access Memory), ROM (Read Only Memory), HDD (Hard Disk Drive), SSD (Solid State Drive), or a combination thereof. The communication interface 2a3 may communicate with the plasma processing device 1 via a communication line such as a LAN (Local Area Network).

[0118] In this embodiment, the steps shown in Figures 22(A) to 22(G) are carried out by using such a plasma processing system. Specifically, a pattern film containing the above-mentioned trypsetin derivative is formed on the surface of the substrate W, and the pattern film is etched by plasma processing.

[0119] In Figure 22(A), an insulating layer 6 is laminated on the substrate 5.

[0120] In Figure 22(B), protective layers 7 and 8 are stacked on top of the insulating layer 6 in that order, and a pattern film 9 containing a triptycene derivative (layer M3 of triptycene derivative molecular aggregates) is formed on top of that.

[0121] In Figure 22(C), the aggregate A1 of the first side chain S1 in the pattern film 9 is etched, and a pattern film 9' is formed in which the aggregate A2 of the second side chain S2 remains.

[0122] In Figure 22(D), the pattern film 9' acts as a protective film, and the protective layer 8 is etched to form the protective layer 8'.

[0123] In Figure 22(E), the pattern film 9' is removed, and the protective layer 7 is etched while the protective layer 8' protects a portion of the protective layer 7, forming the protective layer 7'.

[0124] In Figure 22(F), the insulating layer 6 is etched while the protective layer 7' protects a portion of the insulating layer 6, thereby forming the insulating layer 6'.

[0125] In Figure 22(G), the protective layer 7' is removed, and a pattern of the insulating layer 6' is formed on the substrate 5. The resulting pattern can be used as a resist pattern.

[0126] Figure 23 shows the etching amount when CF (fluorocarbon) etching is performed using the process shown in Figure 22. In CF etching, after 50 seconds from the start of etching, the side chains become easier to etch in the order of DMS chain, TEG chain, and alkyl (C12) chain (Figure 25).

[0127] Figure 24 shows the amount of etching when oxygen-based etching is performed using the process shown in Figure 22. In oxygen-based etching, the side chains become easier to etch in the order of TEG chain, alkyl (C12) chain, and DMS chain after 5 seconds from the start of etching (Figure 25). Furthermore, in oxygen-based etching, the difference in etching resistance becomes more pronounced in a shorter time compared to CF-based etching.

[0128] Figure 26 shows the results of elemental analysis after etching on the surface of the triptycene derivative film. Figure 27 shows the results of elemental analysis when the surface of the triptycene derivative film was etched by 10 nm using argon ion etching. Figure 28 shows the results of elemental analysis when the surface of the triptycene derivative film was etched by 20 nm using argon ion etching.

[0129] As shown in Figure 26, the carbon content decreases on the etched surface in both CF-based etching and oxygen-based etching. Furthermore, as shown in Figures 27 and 28, when the surface is etched to 10 nm and 20 nm, the elemental ratio returns to its initial state. From this, it can be seen that alkyl chain aggregates have low etching resistance, while TEG chain and DMS chain aggregates have higher etching resistance compared to alkyl chain aggregates.

[0130] The plasma processing system of this embodiment can perform the pattern formation described herein. Furthermore, in this embodiment, by appropriately combining alkyl chains and TEG chains or DMS chains as side chains, first and second side chains with different etching selectivity ratios can be applied as side chains to the triptycene skeleton.

[0131] The pattern formation method of this disclosure can also be used for other applications by utilizing the above-described configuration and effects. Figure 29 shows the process of forming a wiring pattern using a triptycene derivative. Figure 30 shows the process of forming a wiring mask pattern using a triptycene derivative. In Figures 29 and 30, parts that are common with the resist pattern formation process in Figure 13 may be denoted by corresponding reference numerals and their explanation may be omitted.

[0132] In the wiring pattern formation process shown in Figure 29, first, a laminate is prepared as shown in Figure 29(A), which has an insulating layer 200 on a substrate 100, metal wiring 50 arranged within the insulating layer 200, and side walls 300 and 400 that constitute an etching stop layer.

[0133] When a gas containing a triptycene derivative is supplied to the space G inside the side walls 300 and 400, and a film formation process such as vapor deposition or CVD is performed, a layer M3 of triptycene derivative molecular aggregates (aggregate A1 of the first side chain S1, aggregate A2 of the second side chain S2) is formed inside the side walls 300 and 400, as shown in Figure 29(B).

[0134] In Figure 29(C), the layer M3 of triptycene derivative molecular aggregates formed inside the side walls 300 and 400 is etched by an etching process such as plasma treatment, resulting in the etching of aggregates A1 of the first side chain S1, leaving behind aggregates A2 of the second side chain S2, which are etch-resistant. Spaces G1 are formed between the aggregates A2 of the second side chain S2.

[0135] In Figure 29(D), metal wiring 60 is placed in the space G1 formed between the aggregates A2 of the second side chain S2. The resulting pattern constitutes a wiring pattern in which a portion of the metal wiring 60 connects with the metal wiring 50. In this example, the aggregates A2 of the second side chain S2 in layer M3 of the triptycene derivative molecular aggregate can function as part of the wiring pattern.

[0136] Furthermore, in the process of forming the wiring mask pattern (via mask) shown in Figure 30, first, a laminate is prepared as shown in Figure 30(A), which includes an insulating layer 200, metal wiring 70 arranged within the insulating layer 200, an insulating layer 600 laminated on top of the insulating layer 200, and a protective layer 80 having holes H1.

[0137] When a gas containing a triptycene derivative is supplied into the pores H1 of the protective layer 80 and a film formation process such as vapor deposition or CVD is performed, a layer M3 of the triptycene derivative is formed in the pores H1 of the protective layer 80. In this example, an aggregate A1 of the first side chain S1 is placed inside the layer M3 of the triptycene derivative, and an aggregate A2 of the second side chain S2 is placed outside.

[0138] Then, the layer M3 of triptycene derivative molecular aggregates formed in the pore H1 is etched by an etching process such as plasma treatment, and the aggregate A1 of the first side chain S1 is etched away, leaving behind the etching-resistant aggregate A2 of the second side chain S2, as shown in Figure 30(B). The aggregate A2 of the second side chain S2 is formed on the inner wall of the pore H1 of the protective layer 80.

[0139] In Figure 30(C), etching treatment such as plasma treatment causes the aggregate A2 of the second side chain S2 to protect the inner wall of the hole H1 in the protective layer 80, while an insulating layer 600' is formed in the insulating layer 600 with the hole H2 formed therein. After the insulating layer 600' is formed, the protective layer 80 is removed together with the aggregate A2 of the second side chain S2.

[0140] In Figure 30(D), the metal wiring 90 is embedded in the pore H2 of the insulating layer 600' and is electrically connected to a portion of the metal wiring 70. In the resulting pattern, the metal wiring 90 constitutes vias. In this example, the aggregate A2 of the second side chain S2 in layer M3 of the triptycene derivative molecular aggregate can function as a via mask.

[0141] In the pattern formation method of this disclosure, it is further possible to control the stacking direction of the lamellar structure in the layer of triptycene derivative molecular assemblies so that it is in the circumferential direction of a circle. For example, as shown in Figure 31, a layer M4 of triptycene derivative molecular assemblies can be obtained in which an assembly A1 of the first side chain S1, which is an alkyl chain, is arranged on the outside in the circumferential direction, and an assembly A2 of the second side chain S2, which is a DMS chain, is arranged on the inside in the circumferential direction.

[0142] In such a layer M4 of triptycene derivative molecular assemblies, a patterned film can be formed in which assemblies A1 of the first side chain S1 and A2 of the second side chain S2 are stacked radially in a tubular shape. A layer M4 of triptycene derivative molecular assemblies with this shape can be applied to applications such as via masks and tubular wiring patterns shown in Figure 30 above.

[0143] The embodiments disclosed above include, for example, the following aspects:

[0144] (Note 1) A pattern formation method for forming a pattern film on a substrate, The patterned film contains a triptycene derivative having a triptycene skeleton, The triptycene skeleton has a first surface where positions 1, 8 and 13 of the triptycene skeleton are aligned, and a second surface where positions 4, 5 and 16 of the triptycene skeleton are aligned. The triptycene derivative is The first side chain is located on either the first or second surface, and The other side of either the first or second surface has a second side chain having a different etching selectivity from the first side chain. Pattern formation method.

[0145] (Note 2) The first side chain is bonded to the triptycene skeleton, The second side chain is attached to the end of the first side chain. The pattern formation method described in Appendix 1.

[0146] (Note 3) The first side chain is bonded to the triptycene skeleton on either of the two sides, The second side chain is bonded to the triptycene skeleton on either the other side of the aforementioned surface. The pattern formation method described in Appendix 1.

[0147] (Note 4) The pattern film is formed on the inside of two opposing side walls. A pattern formation method as described in any one of the items in Appendix 1 to Appendix 3.

[0148] (Note 5) The aspect ratio of the inner side of the aforementioned side wall is 2 or more. The pattern formation method described in Appendix 4.

[0149] (Note 6) Either the first side chain or the second side chain has an inorganic composition. A pattern formation method described in any one of the items in Appendix 1 to Appendix 5.

[0150] (Note 7) The inorganic composition has a siloxane compound. The pattern formation method described in Appendix 6.

[0151] (Note 8) Either the first side chain or the second side chain has an organic composition. A pattern formation method as described in any one of the appendices 1 to 7.

[0152] (Note 9) The first or second side chain having the aforementioned organic composition is terminated at a hydroxyl terminator. The pattern formation method described in Appendix 8.

[0153] (Note 10) The method includes etching a pattern film formed by any one of the pattern formation methods described in Appendix 1 to Appendix 9 by plasma treatment. Plasma treatment method.

[0154] While embodiments of this disclosure have been described above, this disclosure is not limited to these embodiments, and various modifications and changes are possible within the scope of the disclosure described in the claims.

[0155] This application claims priority based on Japanese Patent Application No. 2021-114353, filed on 9 July 2021, which is incorporated herein by reference in its entirety. [Explanation of symbols]

[0156] TS Triptycene (Triptycene skeleton) Monomolecule of TD triptycene derivative M1 The molecular assembly structure that constitutes conventional patterned films Two-dimensional aggregate structure of M2 triptycenes Three-dimensional aggregate structure of M3 triptycenes S1 First side chain S2 Second side chain A1 Assembly of the first side chain A2 Assembly of the second side chain 40 Exhaust System 100 circuit boards 200, 200' insulating layer 300, 400 side wall G, G1, G2 space 1. Plasma processing equipment 10 Plasma processing chamber 10a side wall 10e Gas outlet 10s processing space 11. Substrate support section 111 Main body 111a Central area (board support surface) 111b Annular region (ring support surface) 112 Ring Assembly W wafer 13 Shower head 13a Gas supply port 13b Gas Diffusion Chamber 13c Gas inlet 2 Control Unit 2a Computer 2a1 Processing Unit 2a2 Storage section 2a3 communication interface 20 Gas Supply Department 21 Gas Source 22 Flow controller 30 power supply 31 RF power supply 31a First RF generation unit 31b Second RF generation unit 32 DC power supply 32a First DC generation unit 32b Second DC generation unit 5 circuit boards 6,600 insulating layer 7, 7´, 8, 8´, 80 protective layer 9, 9' Patterned film 50, 60, 70, 90 metal wiring H1, H2 hole

Claims

1. A pattern formation method for forming a pattern film on a substrate, The patterned film contains a triptycene derivative having a triptycene skeleton, The triptycene skeleton has a first surface where positions 1, 8 and 13 of the triptycene skeleton are aligned, and a second surface where positions 4, 5 and 16 of the triptycene skeleton are aligned. The triptycene derivative is The first side chain is located on either the first or second surface, and The other side of either the first or second surface, or the other side of either of the first surfaces, has a second side chain having a different etching selectivity ratio from the first side chain. Pattern formation method.

2. The first side chain is bonded to the triptycene skeleton, The second side chain is attached to the end of the first side chain. The pattern forming method according to claim 1.

3. The first side chain is bonded to the triptycene skeleton on either of the two sides, The second side chain is bonded to the triptycene skeleton on either the other side of the aforementioned surface. The pattern forming method according to claim 1.

4. The pattern film is formed on the inside of two opposing side walls. The pattern forming method according to claim 1.

5. The aspect ratio of the inner side of the aforementioned side wall is 2 or more. The pattern forming method according to claim 4.

6. Either the first side chain or the second side chain has an inorganic composition. The pattern forming method according to claim 1.

7. The inorganic composition has a siloxane compound. The pattern forming method according to claim 6.

8. Either the first side chain or the second side chain has an organic composition. The pattern forming method according to claim 1.

9. The first or second side chain having the aforementioned organic composition is terminated at a hydroxyl terminator. The pattern forming method according to claim 8.

10. The method includes etching a pattern film formed by any one of claims 1 to 9 by plasma treatment. Plasma treatment method.

Images