Semiconductor element forming method and substrate processing apparatus

Abstract

A semiconductor element forming method includes a step of forming a cover layer (Ps), and a step of performing etching. In the step of forming the cover layer (Ps), the cover layer (Ps) is formed to selectively cover a portion on a surface side in a recess (R) provided in a layered structure (L) supported by a base material (S). In the step of performing etching, a deep portion (Rf) of the recess (R) is etched with a chemical liquid (C) in a manner of enlarging a diameter of the deep portion (Rf) of the recess (R) compared with the cover layer (Ps).

Description

Technical Field

[0001] This invention relates to a method for forming semiconductor devices and an apparatus for processing substrates. Background Technology

[0002] Substrate processing apparatuses for processing substrates are used, for example, for the formation of semiconductor elements. In recent years, in order to precisely fabricate memory elements, memory elements formed by stacking memory elements on a semiconductor substrate are being developed (see Patent Document 1). In the semiconductor memory element of Patent Document 1, in the stacked structure of the semiconductor substrate, a hole with a large aspect ratio, referred to as a memory hole, is formed in the vertical direction relative to the substrate. A large number of memory elements are arranged within this hole.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2019-117894 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] In the semiconductor memory element of Patent Document 1, the diameter of the lower part of the memory hole is smaller than the diameter of the upper part. This is because the etching solution is less likely to reach the lower part of the memory hole compared to the upper part. In this case, the electrical characteristics of the memory element formed within the memory hole may deviate. The aspect ratio (the ratio of the height to the width of the memory hole) of memory holes has been increasing year by year, and in recent years, memory holes with aspect ratios exceeding 50 have appeared. For such high aspect ratio memory holes, it is not easy to unify the diameter of the upper part and the diameter of the lower part of the memory hole.

[0008] Furthermore, with the increasing refinement of components and the three-dimensionalization of component structures in recent years, the same problem has arisen not only in memory holes mentioned above, but also in recesses such as holes or trenches with large aspect ratios. Specifically, compared to the area above the recess, the etching solution has difficulty penetrating to the area below the recess, making liquid displacement difficult. Therefore, the area below the recess is etched to different degrees than the area above it. Consequently, in recesses such as holes and trenches with relatively large aspect ratios (hereinafter referred to as grooves), the diameter of the recess within the recess is sometimes not constant.

[0009] The present invention was made in view of the above-mentioned problems, and its object is to provide a semiconductor device forming method and a substrate processing apparatus by selectively etching the grooves provided in the laminated structure of the substrate to adjust the diameter of the grooves.

[0010] Methods for solving problems

[0011] According to one aspect of the present invention, a method for forming a semiconductor element includes: a step of forming a cover layer that selectively covers a portion of a groove located on the surface side in a laminated structure supported by a substrate; and a step of etching the depth of the groove with a chemical solution in such a way as to increase the diameter of the groove being deeper than the cover layer.

[0012] In one embodiment, the process of forming the covering layer includes: forming a partial filling layer that partially fills the depth of the groove; supplying a waterproofing agent after forming the partial filling layer; and removing the partial filling layer and the waterproofing agent after supplying the waterproofing agent and forming the coating layer on the surface side of the groove.

[0013] In one embodiment, the process of removing the aforementioned partial filler layer includes a process of supplying a removal liquid to dissolve the aforementioned partial filler layer.

[0014] In one embodiment, the aforementioned partial filler layer contains a sublimable substance, and the process of removing the aforementioned partial filler layer includes a process of heating the aforementioned partial filler layer.

[0015] In one embodiment, the process of forming the partial filler layer includes: forming a filler layer that fills the groove; and after forming the filler layer, partially removing the filler layer.

[0016] In one embodiment, the process of partially removing the filler layer includes the process of supplying a removal liquid to remove the filler layer.

[0017] In one embodiment, the etching solution described above contains any one of hydrofluoric acid, water, and phosphoric acid.

[0018] In one embodiment, a plurality of storage elements are formed in the aforementioned groove.

[0019] In one embodiment, the above-described stacked structure is provided with a plurality of the above-described grooves, and the difference in the top diameter of the grooves is less than 5%.

[0020] In one embodiment, the groove has a regular structure.

[0021] In one embodiment, an etch stop layer is disposed between the substrate and the laminated structure.

[0022] According to another aspect of the present invention, a substrate processing apparatus includes a processing liquid supply unit, a removal liquid supply unit, a waterproofing agent supply unit, a chemical solution supply unit, and a control unit. The processing liquid supply unit supplies processing liquid. The removal liquid supply unit supplies removal liquid for removing the filler layer formed by the processing liquid. The waterproofing agent supply unit supplies waterproofing agent. The chemical solution supply unit supplies chemical solution. The control unit controls the processing liquid supply unit, the removal liquid supply unit, the waterproofing agent supply unit, and the chemical solution supply unit. The control unit controls the processing liquid supply unit, the removal liquid supply unit, the waterproofing agent supply unit, and the chemical solution supply unit in the following manner: (1) supplies the processing liquid to form a filler layer that fills a groove provided in a laminated structure supported by a substrate; (2) supplies the removal liquid to partially remove the filler layer in the groove; (3) supplies the waterproofing agent to form a covering layer that selectively covers the portion of the groove located on the surface side not covered by the filler layer; (4) supplies the chemical solution to increase the diameter of the groove that is deeper than the covering layer.

[0023] The effects of the invention

[0024] According to the present invention, the diameter of the groove provided in the laminated structure of the substrate can be adjusted. Attached Figure Description

[0025] [ Figure 1 [This is a schematic diagram of the substrate processing apparatus of this embodiment.]

[0026] [ Figure 2 [This is a schematic diagram of the substrate processing apparatus of this embodiment.]

[0027] [ Figure 3 [This is a block diagram of the substrate processing apparatus of this embodiment.]

[0028] [ Figure 4 ] Figure 4 (a) is a schematic side view of a semiconductor device manufactured using the substrate processing apparatus of this embodiment. Figure 4 (b) is a schematic top view of a semiconductor device. Figure 4 (c) is Figure 4 A magnified view of (b).

[0029] [ Figure 5 ] Figure 5 (a)~ Figure 5 (e) is a schematic diagram used to illustrate the semiconductor element formation method of this embodiment.

[0030] [ Figure 6 ] Figure 6 (a)~ Figure 6(g) is a schematic diagram used to illustrate the semiconductor element formation method of this embodiment.

[0031] [ Figure 7 [This is a flowchart of the semiconductor device formation method of this embodiment.]

[0032] [ Figure 8 [This is a flowchart of the semiconductor device formation method of this embodiment.]

[0033] [ Figure 9 [This is a schematic diagram of the substrate processing apparatus of this embodiment.]

[0034] [ Figure 10 [This is a flowchart of the semiconductor device formation method of this embodiment.]

[0035] [ Figure 11 [This is a schematic diagram of the substrate processing apparatus of this embodiment.]

[0036] [ Figure 12 [This is a flowchart of the semiconductor device formation method of this embodiment.]

[0037] [ Figure 13 [This is a schematic diagram of the substrate processing apparatus of this embodiment.]

[0038] [ Figure 14 [This is a flowchart of the semiconductor device formation method of this embodiment.]

[0039] [ Figure 15 [This is a schematic diagram of the substrate processing apparatus of this embodiment.]

[0040] [ Figure 16 [This is a flowchart of the semiconductor device formation method of this embodiment.]

[0041] [ Figure 17 [This is a schematic diagram of the substrate processing apparatus of this embodiment.]

[0042] [ Figure 18 [This is a schematic diagram of a semiconductor element formed by the semiconductor element formation method of this embodiment.] Detailed Implementation

[0043] Hereinafter, embodiments of the semiconductor element formation method and substrate processing apparatus of the present invention will be described with reference to the accompanying drawings. It should be noted that identical or equivalent parts are indicated by the same reference numerals in the drawings and will not be described again. It should be noted that, for ease of understanding the invention, this application specification describes mutually orthogonal X-axis, Y-axis, and Z-axis. Typically, the X-axis and Y-axis are parallel to the horizontal direction, and the Z-axis is parallel to the vertical direction. Furthermore, in this application specification, for ease of understanding the invention, mutually orthogonal x-axis, y-axis, and z-axis are described. Typically, the x-axis and y-axis extend parallel to the main surface of the substrate or base material, and the z-axis extends in a direction perpendicular to the main surface of the substrate or base material.

[0044] First, refer to Figure 1 An embodiment of the substrate processing apparatus 100 of the present invention will be described. Figure 1 This is a schematic top view of the substrate processing apparatus 100 of this embodiment.

[0045] The substrate processing apparatus 100 processes the substrate W. The substrate processing apparatus 100 processes the substrate W by at least one of the following methods: etching, surface treatment, property application, forming a processing film, removing and cleaning the film.

[0046] Substrate W is used as a semiconductor substrate. Substrate W includes a semiconductor wafer. For example, substrate W is generally circular. Here, substrate processing apparatus 100 processes substrate W one by one.

[0047] like Figure 1 As shown, the substrate processing apparatus 100 includes: multiple chambers 110, a fluid cabinet 100A, a fluid tank 100B, multiple loading ports LP, an indexing robot IR, a central robot CR, and a control device 101. The control device 101 controls the loading ports LP, the indexing robot IR, and the central robot CR. The control device 101 includes a control unit 102 and a storage unit 104.

[0048] Each loading port LP is stacked and houses multiple substrates W. A sorting robot IR transports substrates W between the loading ports LP and the central robot CR. The central robot CR transports substrates W between the sorting robot IR and chamber 110. Each chamber 110 sprays liquid onto the substrates W to process them. The liquid includes processing liquid, removal liquid, waterproofing agent, and / or chemical solution. A fluid cabinet 100A houses the liquid. It should be noted that the fluid cabinet 100A can also house gas.

[0049] Specifically, multiple chambers 110, viewed from above, form multiple towers TWs arranged to surround the central robotic arm CR. Figure 1 The four towers (TW) in the middle. Each tower (TW) includes multiple chambers 110 stacked vertically. Figure 1The three chambers 110 in the fluid tank 100A correspond to multiple towers TW. The liquid in the fluid tank 100A is supplied to all chambers 110 in the tower TW corresponding to any one of the fluid tanks 100B. In addition, the gas in the fluid tank 100A is supplied to all chambers 110 in the tower TW corresponding to any one of the fluid tanks 100B.

[0050] The control device 101 controls various operations of the substrate processing device 100.

[0051] The control device 101 includes a control unit 102 and a storage unit 104. The control unit 102 has a processor. The control unit 102 may have, for example, a central processing unit (CPU). Alternatively, the control unit 102 may also have a general-purpose processor.

[0052] Storage unit 104 stores data and computer programs. The data includes process data. The process data includes a large amount of information representing the process. Each of the numerous processes specifies the processing content and steps for the substrate W.

[0053] The storage unit 104 includes a main storage device and an auxiliary storage device. The main storage device is, for example, a semiconductor memory. The auxiliary storage device is, for example, a semiconductor memory and / or a hard disk drive. The storage unit 104 may also include a removable medium. The control unit 102 executes the computer program stored in the storage unit 104 to perform board processing operations.

[0054] Next, refer to Figure 2 The substrate processing apparatus 100 of this embodiment will be described. Figure 2 This is a schematic diagram of the substrate processing apparatus 100.

[0055] The substrate processing apparatus 100 includes: a chamber 110, a substrate holding section 120, and a liquid supply section 130. The chamber 110 houses the substrate W. The substrate holding section 120 holds the substrate W.

[0056] The chamber 110 is generally rectangular with an internal space. The chamber 110 houses the substrate W. Here, the substrate processing apparatus 100 is a monolithic type that processes substrates W one by one, and the chamber 110 houses the substrates W one by one. The substrate W is housed within the chamber 110 and processed within the chamber 110. At least a portion of the substrate holding section 120 and the liquid supply section 130 are respectively housed within the chamber 110.

[0057] The substrate holding portion 120 holds the substrate W. The substrate holding portion 120 holds the substrate W horizontally such that the upper surface (surface) Wa of the substrate W faces upward and the back surface (lower surface) Wb of the substrate W faces vertically downward. Furthermore, the substrate holding portion 120 rotates the substrate W while holding it. The upper surface Wa of the substrate W is provided with a laminated structure in which grooves are formed, details of which will be described later. The substrate holding portion 120 rotates the substrate W while holding it.

[0058] For example, the substrate holding portion 120 may be a clamping type that clamps the end of the substrate W. Alternatively, the substrate holding portion 120 may have any mechanism for holding the substrate W from the back surface Wb. For example, the substrate holding portion 120 may also be a vacuum type. In this case, the substrate holding portion 120 holds the substrate W horizontally by adsorbing the central portion of the back surface Wb of the substrate W, which is a non-device forming surface, onto the upper surface. Alternatively, the substrate holding portion 120 may combine a clamping type that contacts the peripheral end face of the substrate W with multiple chuck pins and a vacuum type.

[0059] For example, the substrate holding part 120 includes a rotating base 121, a chuck member 122, a shaft 123, a motor 124, and a housing 125. The chuck member 122 is disposed on the rotating base 121. The chuck member 122 holds the substrate W. Typically, a plurality of chuck members 122 are disposed on the rotating base 121.

[0060] Shaft 123 is a hollow shaft. Shaft 123 extends vertically along the rotation axis Ax. A rotating base 121 is attached to the upper end of shaft 123. The substrate W is placed above the rotating base 121.

[0061] The rotating base 121 is a circular plate that horizontally supports the substrate W. A shaft 123 extends downward from the center of the rotating base 121. A motor 124 applies a rotational force to the shaft 123. By rotating the shaft 123 in the rotational direction, the motor 124 causes the substrate W and the rotating base 121 to rotate about the rotation axis Ax. A housing 125 surrounds the shaft 123 and the motor 124.

[0062] The liquid supply unit 130 supplies liquid to the substrate W. Typically, the liquid supply unit 130 supplies liquid to the upper surface Wa of the substrate W.

[0063] The liquid supply unit 130 includes: a treatment liquid supply unit 132, a removal liquid supply unit 134, a waterproofing agent supply unit 136, and a medicine supply unit 138. At least a portion of the treatment liquid supply unit 132, the removal liquid supply unit 134, the waterproofing agent supply unit 136, and the medicine supply unit 138 are housed within the chamber 110.

[0064] The processing liquid supply unit 132 supplies processing liquid to the upper surface Wa of the substrate W. For example, the processing liquid includes a solute and a volatile solvent. After the processing liquid is supplied to the upper surface Wa of the substrate W, the solvent evaporates, thereby forming a filling layer from the solute. The filling layer is a solid film formed from the solute components. The filling layer can retain particles remaining in the grooves of the substrate W. During the formation of the filling layer, particles attached to the upper surface Wa of the substrate W detach from the substrate W and remain in the filling layer.

[0065] Here, "coagulation" refers to the hardening of the solute due to forces acting between molecules and atoms, for example, along with the evaporation of the solvent. "Curement" refers to the hardening of the solute through chemical changes such as polymerization or cross-linking. Therefore, "coagulation or curing" indicates that the solute "hardens" due to various reasons. It should be noted that the treatment solution only needs to coagulate or cure to a degree that can maintain the particles; complete evaporation of the solvent is not required. Furthermore, the "solute component" forming the filler layer can be the solute itself contained in the treatment solution, or components derived from the solute, such as components obtained as a result of chemical changes.

[0066] As a solute, various resins that are soluble in any solvent and can detach and retain particles adhering to the upper surface of the substrate W from the substrate W during solidification or curing can be used to form the filler layer. For example, as a solute, a resin that is sparingly soluble or even insoluble in water before being heated to a specified modification temperature and then modified to become water-soluble by heating to a modification temperature or above (hereinafter sometimes referred to as "thermosensitive water-soluble resin") can also be used.

[0067] As a heat-sensitive water-soluble resin, for example, a resin that can be decomposed by heating to a specified modification temperature (e.g., 200°C or higher), thereby exposing polar functional groups and becoming water-soluble. The heat-sensitive water-soluble resin is modified to be water-soluble when heated to a modification temperature or higher.

[0068] Alternatively, the temperature of the thermosensitive water-soluble resin can be maintained below the modification temperature to form a filler layer that remains sparingly soluble or even insoluble in aqueous liquids. When forming the filler layer, the temperature of the processing solution is set below the modification temperature of the thermosensitive water-soluble resin, thus preventing the resin from becoming water-soluble and allowing a filler layer that is sparingly soluble or even insoluble in aqueous liquids to be formed on the upper surface of the substrate W. In this case, particles will not detach from the filler layer, and the filler layer, maintained in a blocky state, can be removed from the substrate W. Therefore, particles can be removed with a high removal rate.

[0069] It should be noted that, in addition to heat-sensitive water-soluble resins, other solutes contained in the treatment solution can include, for example, acrylic resins, phenolic resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, alkyd resins, polyurethanes, polyimides, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polytetrafluoroethylene, acrylonitrile butadiene styrene resin, acrylonitrile styrene resin, polyamide, polyacetal, polycarbonate, polyvinyl alcohol, modified polyphenylene ether, polybutylene terephthalate, polyethylene terephthalate, polyphenylene sulfide, polysulfone, polyetheretherketone, polyamide-imide, etc.

[0070] The preferred solvent has higher volatility than water. PGEE (propylene glycol monoethyl ether) is preferably used as the solvent.

[0071] In addition, the treatment solution may also contain sublimable substances. As sublimable substances, various substances with high vapor pressure at temperatures ranging from 5°C to 35°C that transform from a solid phase to a gaseous phase without passing through a liquid phase can be used. Examples of sublimable substances include hexamethylenetetramine, 1,3,5-trioxane, ammonium 1-pyrrolidinedithiocarbamate, metaldehyde, paraffin wax with approximately 20 to 48 carbon atoms, tert-butanol, p-dichlorobenzene, naphthalene, L-menthol, and fluorinated hydrocarbon compounds. In particular, fluorinated hydrocarbon compounds can be used as sublimable substances.

[0072] As a fluorinated hydrocarbon compound, one or more of the following compounds (A) to (E) can be used, for example.

[0073] Compound (A): A fluoroalkane or its derivative having 3 to 6 carbon atoms.

[0074] Compound (B): Fluorinated cycloalkanes with 3 to 6 carbon atoms, or their derivatives.

[0075] Compound (C): A fluorobicycloalkane with 10 carbon atoms, or a derivative thereof.

[0076] Compound (D): Fluorotetracyanoquinone dimethane or its derivatives

[0077] Compound (E): Fluorocyclic triphosphazene or its derivatives

[0078] It should be noted that, as compound (A), examples include fluoroalkanes with 3 to 6 carbon atoms represented by formula (1) or their derivatives.

[0079] C m H n F2 m+2－n (1)

[0080] [In the formula, m represents a number from 3 to 6, and n represents a number from 0 to n to 2m+1.]

[0081] 1,1,2,2,3,3,4-heptafluorocyclopentane is particularly preferred as the sublimable substance. This compound has a vapor pressure of approximately 8266 Pa at 20°C, a melting point (freezing point) of 20.5°C, and a boiling point of 82.5°C. Furthermore, when mixing the sublimable substances in their molten state, a solvent that exhibits compatibility with the molten sublimable substances is preferred as the solvent. Additionally, when dissolving the sublimable substance as a solute, a solvent that exhibits solubility in that sublimable substance is preferred.

[0082] Furthermore, when mixing sublimed substances in their molten state, a solvent that exhibits compatibility with the sublimed substances in their molten state is preferred as the solvent. Additionally, when dissolving the sublimed substance as a solute, a solvent that exhibits solubility in the sublimed substance is preferred.

[0083] As a solvent, examples include at least one selected from the group consisting of DIW, pure water, aliphatic hydrocarbons, aromatic hydrocarbons, esters, alcohols, ethers, etc. Specifically, examples include DIW, pure water, methanol, ethanol, IPA, butanol, ethylene glycol, propylene glycol, NMP (N-methyl-2-pyrrolidone), DMF (N,N-dimethylformamide), DMA (dimethylacetamide), DMSO (dimethyl sulfoxide), hexane, toluene, PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), PGPE (propylene glycol monopropyl ether), PGEE (propylene glycol monoethyl ether), GBL (gamma-butyrolactone), acetylacetone, 3-pentanone, 2-heptanone, ethyl lactate, cyclohexanone, dibutyl ether, HFE (hydrofluoroether), ethyl perfluoroisobutyl ether, ethyl nonafluorobutyl ether, and m-xylenehexafluoride.

[0084] The processing fluid supply unit 132 includes: a pipe 132a, a valve 132b, and a nozzle 132n. The nozzle 132n sprays processing fluid onto the upper surface Wa of the substrate W. The nozzle 132n is connected to the pipe 132a. Processing fluid is supplied to the pipe 132a from a supply source. The valve 132b opens and closes the flow path within the pipe 132a. Preferably, the nozzle 132n is configured to be movable toward the substrate W.

[0085] The removal liquid supply unit 134 supplies removal liquid to the upper surface Wa of the substrate W. The removal liquid can remove the filler layer formed by the solute in the processing liquid. By controlling the supply time of the removal liquid, the filler layer can be selectively removed from the substrate W.

[0086] As the removal liquid, any solvent that is soluble in any resin can be used. Examples of suitable removal liquids include diluents, toluene, ethyl acetate, alcohols, ethylene glycol, and other organic solvents, as well as acidic liquids such as acetic acid, formic acid, and glycolic acid. Solvents compatible with aqueous liquids are particularly preferred. For example, isopropyl alcohol (IPA) is preferably used as the removal liquid.

[0087] The removal liquid supply unit 134 includes: a pipe 134a, a valve 134b, and a nozzle 134n. The nozzle 134n sprays the removal liquid onto the upper surface Wa of the substrate W. The nozzle 134n is connected to the pipe 134a. The removal liquid is supplied to the pipe 134a from a supply source. The valve 134b opens and closes the flow path within the pipe 134a. Preferably, the nozzle 134n is configured to be movable toward the substrate W.

[0088] The waterproofing agent supply unit 136 supplies liquid waterproofing agent to the upper surface Wa of the substrate W. Through the supply of the waterproofing agent, a waterproof layer is formed on the upper surface Wa of the substrate W.

[0089] For example, the waterproofing agent contains compounds with methyl or silyl groups at the end. Typically, the surface of the groove has hydroxyl groups (OH groups), but with the waterproofing agent, the hydroxyl groups on the surface of the substrate W are replaced with methyl or silyl groups. It should be noted that the waterproofing agent preferably does not change the properties of the filler layer.

[0090] For example, a waterproofing agent is one that hydrophobizes silicon (Si) itself and silicon-containing compounds. Typically, the waterproofing agent is a silane coupling agent. In one example, the silane coupling agent includes at least one of HMDS (hexamethyldisilazane), TMS (tetramethylsilane), fluorinated alkylchlorosilanes, alkyldisilazanes, and non-chlorinated waterproofing agents. Non-chlorinated waterproofing agents include, for example, at least one of dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis(dimethylamino)dimethylsilane, N,N-dimethyltrimethylsilane, N-(trimethylsilyl)dimethylamine, and organosilane compounds.

[0091] The waterproofing agent supply unit 136 includes: a pipe 136a, a valve 136b, and a nozzle 136n. The nozzle 136n sprays waterproofing agent onto the upper surface Wa of the substrate W. The nozzle 136n is connected to the pipe 136a. Waterproofing agent is supplied to the pipe 136a from a supply source. The valve 136b opens and closes the flow path within the pipe 136a. Preferably, the nozzle 136n is configured to be movable toward the substrate W.

[0092] The solution supply unit 138 supplies a solution to the upper surface Wa of the substrate W. Through solution treatment, the upper surface Wa of the substrate W can be treated. Solution treatment allows for at least one of the following: etching, surface treatment, property assignment, formation of a treated film, and removal of a film. Typically, the solution is an etching solution used for etching the substrate W.

[0093] The solution contains hydrofluoric acid. For example, hydrofluoric acid can be heated to a temperature between 40°C and 70°C, or between 50°C and 60°C. Alternatively, hydrofluoric acid can be heated without heating. The solution may also contain water or phosphoric acid.

[0094] Furthermore, the solution may also contain hydrogen peroxide. In addition, the solution may also contain SC1 (ammonia-hydrogen peroxide mixture), SC2 (hydrochloric acid-hydrogen peroxide mixture), or aqua regia (a mixture of concentrated hydrochloric acid and concentrated nitric acid).

[0095] The liquid medicine supply unit 138 includes: a pipe 138a, a valve 138b, and a nozzle 138n. The nozzle 138n sprays liquid medicine onto the upper surface Wa of the substrate W. The nozzle 138n is connected to the pipe 138a. Liquid medicine is supplied to the pipe 138a from a supply source. The valve 138b opens and closes the flow path within the pipe 138a. Preferably, the nozzle 138n is configured to be movable toward the substrate W.

[0096] It should be noted that, as described above, the nozzles 132n, 134n, 136n, and 138n of the treatment fluid supply unit 132, the removal fluid supply unit 134, the waterproofing agent supply unit 136, and the medicine supply unit 138 can also be movable. The nozzles 132n, 134n, 136n, and 138n can move horizontally and / or vertically following the moving mechanism controlled by the control unit 102. It should be noted that, to avoid making the drawings overly complex, the moving mechanism has been omitted in this specification.

[0097] The substrate processing apparatus 100 also includes a cup 180. The cup 180 collects liquid splashed from the substrate W. The cup 180 is movable. For example, during the period when the liquid supply section 130 supplies liquid to the substrate W, the cup 180 rises vertically upward to the side of the substrate W. At this time, the cup 180 collects liquid splashed from the substrate W due to the rotation of the substrate W. In addition, when the period when the liquid supply section 130 supplies liquid to the substrate W ends, the cup 180 descends vertically downward from the side of the substrate W.

[0098] As described above, the control device 101 includes a control unit 102 and a storage unit 104. The control unit 102 controls the substrate holding unit 120, the processing liquid supply unit 132, the removal liquid supply unit 134, the waterproofing agent supply unit 136, and / or the cover 180. In one example, the control unit 102 controls the motor 124 and valves 132b, 134b, 136b, and / or 138b.

[0099] The substrate processing apparatus 100 of this embodiment is applicable to the fabrication of semiconductor devices in which semiconductors are disposed. Typically, in a semiconductor device, a conductive layer and an insulating layer are stacked on a substrate. The substrate processing apparatus 100 is suitable for cleaning and / or processing (e.g., etching, property modification, etc.) of the conductive layer and / or insulating layer during the fabrication of semiconductor devices.

[0100] Next, refer to Figures 1-3 The substrate processing apparatus 100 of this embodiment will be described. Figure 3 This is a block diagram of the substrate processing apparatus 100.

[0101] like Figure 3 As shown, the control device 101 controls various operations of the substrate processing apparatus 100. The control device 101 controls the indexing robot IR, the central robot CR, the substrate holding section 120, and the liquid supply section 130. Specifically, the control device 101 controls the indexing robot IR, the central robot CR, the substrate holding section 120, and the liquid supply section 130 by sending control signals to them.

[0102] Specifically, the control unit 102 controls the indexing robot IR to receive the substrate W.

[0103] The control unit 102 controls the central robot arm CR to receive the substrate W. For example, the central robot arm CR receives the unprocessed substrate W and moves it into any one of the multiple chambers 110. Alternatively, the central robot arm CR receives the processed substrate W from the chamber 110 and moves it out.

[0104] The control unit 102 controls the substrate holding unit 120 to start the rotation of the substrate W, change the rotation speed, and stop the rotation of the substrate W. For example, the control unit 102 can control the substrate holding unit 120 to change the rotation speed of the substrate holding unit 120. Specifically, the control unit 102 can change the rotation speed of the substrate W by changing the rotation speed of the motor 124 of the substrate holding unit 120.

[0105] The control unit 102 can individually control the valves 132b, 134b, 136b, and 138b of the liquid supply unit 130, enabling the valves 132b, 134b, 136b, and 138b to switch between open and closed states. Specifically, the control unit 102 controls the valves 132b, 134b, 136b, and 138b of the liquid supply unit 130 to be in the open state, thereby allowing the processing liquid, removal liquid, waterproofing agent, and chemical solution flowing in the pipes 132a, 134a, 136a, and 138a to pass through the nozzles 132n, 134n, 136n, and 138n. In addition, the control unit 102 controls the valves 132b, 134b, 136b, and 138b of the liquid supply unit 130 to close the valves 132b, 134b, 136b, and 138b, thereby stopping the supply of the treatment liquid, removal liquid, waterproofing agent, and chemical solution flowing in the pipes 132a, 134a, 136a, and 138a to the nozzles 132n, 134n, 136n, and 138n, respectively.

[0106] The substrate processing apparatus 100 of this embodiment is suitable for forming semiconductor elements. For example, the substrate processing apparatus 100 is suitable for processing a substrate W used as a semiconductor element with a stacked structure. The semiconductor element is a so-called 3D structure memory (storage device). As an example, the substrate W is suitable for use as a NAND flash memory.

[0107] Next, refer to Figure 4 The substrate W used to fabricate a semiconductor element 300 using the substrate processing apparatus 100 of this embodiment will be described. Figure 4 (a) is a schematic side view of a semiconductor element 300 manufactured by processing a substrate W using a substrate processing apparatus 100. Figure 4 (b) is a schematic top view of semiconductor element 300. Figure 4 (c) is Figure 4 A magnified view of (b). It should be noted that... Figure 4 In the diagram, the direction orthogonal to the main surface of the substrate S of the substrate W is represented as the z-direction, and the directions orthogonal to the z-direction are represented as the x-direction and y-direction.

[0108] like Figure 4 As shown in (a), the substrate W has a substrate S and a laminated structure L. The substrate S is a thin film unfolded in the xy plane. The laminated structure L is formed on the upper surface of the substrate S. The substrate S supports the laminated structure L. The laminated structure L is formed such that it extends from the upper surface of the substrate S along the z-direction.

[0109] It should be noted that, Figure 4The substrate W shown in (a) also has an etch stop layer Es between the substrate S and the laminated structure L. The etch stop layer Es is formed, for example, by aluminum oxide (Al2O3). The laminated structure L is partially removed by etching, thereby forming a groove R, as described in detail below. The etching is stopped by the etch stop layer Es.

[0110] The stacked structure L has an insulating layer N and a conductive layer M. The insulating layer N and the conductive layer M are stacked alternately. For example, the insulating layer N is formed of a silicon oxide film. The conductive layer M is formed of a metal. For example, the conductive layer M contains tungsten (W).

[0111] Each of the multiple insulating layers N extends parallel to the upper surface of the substrate S. Multiple conductive layers M are disposed between two adjacent insulating layers N. The two adjacent insulating layers N are supported by the conductive layers M.

[0112] For example, the thickness (length along the z-direction) of the insulating layer N is 1 nm or more and 50 nm or less. Similarly, the thickness (length along the z-direction) of the conductive layer M is 1 nm or more and 50 nm or less.

[0113] The combined thickness of one insulating layer N and one conductive layer M is 20 nm to 100 nm. The stacked structure L has 10 to 100 insulating layers N and 10 to 100 conductive layers M.

[0114] A groove R is provided in the laminated structure L. The groove R extends in a direction perpendicular to the main surface of the substrate S. The groove R extends within the range between the surface La of the laminated structure L and the etch stop layer Es.

[0115] The aperture (diameter) of the groove R is in the nanometer range. For example, the diameter of the groove R is between 20 nm and 300 nm. The diameter of the groove R can also be between 50 nm and 200 nm.

[0116] Ideally, the groove R is formed perpendicular to the main surface of the substrate S. The diameter of the surface portion of the groove R (top diameter Wt) is between 20 nm and 300 nm, and between 50 nm and 200 nm.

[0117] For example, the aspect ratio of the groove R is 10 or higher. Furthermore, it has been reported to date that memory holes with a height of approximately 1 μm have been formed with an aspect ratio of 40 to 50, and it is believed that the aspect ratio will further increase in the future. For example, the upper limit of the aspect ratio of the groove R can be 100 or 200.

[0118] Figure 4In the semiconductor device 300 shown in (a), a cylindrical charge retention layer H is disposed within a groove R of the substrate W. A cylindrical channel layer Ch is disposed inside the charge retention layer H. For example, the channel layer Ch is formed of polysilicon. A cylindrical dielectric layer D is disposed inside the channel layer Ch. The dielectric layer D is formed of a silicon oxide film.

[0119] The charge retention layer H also has a three-layer structure. For example, the charge retention layer H includes: a cylindrical inner layer H1, a cylindrical middle layer H2, and a cylindrical outer layer H3. The outer layer H3 is in contact with the stacked structure L. The middle layer H2 is disposed inside the outer layer H3. The inner layer H1 is disposed inside the middle layer H2. The inner layer H1 is in contact with the channel layer Ch. Therefore, starting from the center of the groove R of the stacked structure L, the dielectric layer D, the channel layer Ch, the inner layer H1, the middle layer H2, and the outer layer H3 are disposed.

[0120] For example, the inner layer H1 is formed of a silicon oxide film. The inner layer H1 is also called the tunnel layer.

[0121] For example, the intermediate layer H2 is formed from a silicon nitride film. The intermediate layer H2 stores electrical charge. The intermediate layer H2 is also called a charge storage layer.

[0122] For example, the outer layer H3 is formed of a silicon oxide film. The outer layer H3 is also called a barrier layer.

[0123] By applying a voltage to the conductive layer M and the channel layer Ch, charge accumulates in the corresponding intermediate layer H2. For example... Figure 4 As shown in (a), memory elements Se are formed corresponding to the conductive layers M. Therefore, a number of memory elements Se corresponding to the number of conductive layers M are formed in one groove R.

[0124] It should be noted that, as Figure 4 As shown in (b), a plurality of grooves R are formed in the substrate W, and the grooves R are regularly arranged in the substrate W. A charge holding layer H, a channel layer Ch, and a dielectric layer D are respectively disposed in the grooves R. The plurality of grooves R are designed to have the same diameter and height. For example, the difference in the top diameter Wt of each groove R is less than 5%, or less than 3%.

[0125] Typically, the groove R is formed by dry etching the laminated structure L. When forming the groove R by dry etching the laminated structure L, sometimes the diameter of the deep portion of the groove R is smaller than the diameter of the surface portion. In particular, as the height of the laminated structure and / or the number of layers increases, the diameter of the deep portion of the groove R is more likely to be smaller than the diameter of the surface portion. Furthermore, the more efforts are made to shorten the dry etching processing time to improve throughput, the more likely the diameter of the deep portion of the groove R is to be smaller than the diameter of the surface portion.

[0126] like Figure 4 As shown in (a), a plurality of storage elements Se are formed within the groove R. Therefore, it is preferable that the diameter of the groove R is constant from the surface side portion to the depth portion. However, when the groove R is formed in the stacked structure L, sometimes the diameter of the groove R is not constant. When the diameter of the groove R is different, if storage elements are formed within the groove R, the electrical characteristics of the storage elements are sometimes not constant, making it impossible to homogenize the characteristics of the storage elements.

[0127] Furthermore, generally, the smaller the diameter of the groove R, the more memory elements can be formed on the substrate. Therefore, to increase memory capacity, a small diameter of the groove R is preferred. However, if the diameter of the groove R is small, the flow of the etching fluid used to etch the groove R can easily become insufficient. Therefore, when etching the groove R, etching is prone to bias depending on the location of the groove R. Specifically, the surface portion of the groove R is relatively easy to etch, while the deeper part of the groove R is relatively difficult to etch.

[0128] According to this embodiment, even if the diameter of the groove R is small, the deeper portion Rf of the groove R can be selectively etched, as detailed below. This suppresses the non-uniformity of the diameter of the groove R.

[0129] Next, refer to Figure 5 The semiconductor device formation method of this embodiment will be described below. A portion of the semiconductor device formation method of this embodiment is based on... Figures 1-3 This is performed using the substrate processing apparatus 100 described above.

[0130] like Figure 5 As shown in (a), the substrate W has a substrate S and a laminated structure L. The substrate S is a thin film unfolded in the xy plane. The laminated structure L is formed on the upper surface of the substrate S. The laminated structure L is formed such that it extends from the upper surface of the substrate S along the z-direction. For example, the laminated structure L is formed of a silicon oxide film and a silicon nitride film. The laminated structure L has a surface La.

[0131] The stacked structure L has an insulating layer N and a sacrificial layer Sa. The insulating layer N and the sacrificial layer Sa are stacked alternately. Multiple insulating layers N extend parallel to the upper surface of the substrate S. Multiple sacrificial layers Sa are disposed between two adjacent insulating layers N. The two adjacent insulating layers N are supported by the sacrificial layers Sa. It should be noted that during the fabrication of the semiconductor device 300, the sacrificial layer Sa is... Figure 4 The conductive layer M shown is replaced.

[0132] For example, the thickness (length along the z-direction) of insulating layer N is more than 1 nm and less than 50 nm. Insulating layer N is formed of silicon oxide film.

[0133] Additionally, for example, the thickness (length along the z-direction) of the sacrificial layer Sa is between 1 nm and 50 nm. For example, the sacrificial layer Sa is formed from a material that will be etched when using an etchant that does not substantially etch the insulating layer N. In one example, the sacrificial layer Sa is formed from a silicon nitride film. For example, when phosphoric acid is used as the etchant, the insulating layer N is not substantially etched, but the sacrificial layer Sa can be etched.

[0134] like Figure 5 As shown in (b), a groove R is formed in the laminated structure L. Typically, the groove R is formed by dry etching. Ideally, the diameter (length in the xy plane) of the groove R formed by dry etching is constant from the surface side to the depth. However, in reality, the diameter of the groove R is sometimes not constant from the surface side to the depth. Especially when the processing time of dry etching is shortened to increase the throughput of the substrate W, it is difficult to keep the diameter of the groove R constant from the surface side to the depth. In this case, the diameter of the deep portion Rf of the groove R is smaller than the diameter of the surface portion Rn of the groove R.

[0135] like Figure 5 As shown in (c), the groove R of the substrate W is deformed. For example, the diameter of the deep portion Rf of the groove R is selectively made larger than the diameter of the deep portion Rf of the groove R after dry etching. In one example, the diameter of the deep portion Rf of the groove R is spread over a length of less than 10 nm along the xy plane. Thus, the diameter of the groove R of the substrate W can be made uniform from the surface side to the depth.

[0136] like Figure 5 As shown in (d), a charge-retaining layer H is formed inside the groove R of the stacked structure L.

[0137] like Figure 5 As shown in (e), a channel layer Ch and a dielectric layer D are formed inside the charge-retaining layer H. Then, the sacrificial layer Sa is replaced with a conductive layer M. In this manner, a [structure / structure] can be formed. Figure 4 The semiconductor element 300 shown.

[0138] It should be noted that, Figure 5 In (b), to avoid making the explanation too complicated, the diameter of the groove R is shown to change linearly from the surface side to the depth, but this embodiment is not limited to this. Due to the bowing phenomenon, the diameter of the groove R may sometimes be largest near the center.

[0139] Next, refer to Figures 1-3 and Figure 6 The method for forming a semiconductor device according to this embodiment will be described. Figure 6 (a)~ Figure 6 (g) is a schematic diagram used to illustrate the semiconductor element formation method of this embodiment. Figure 6 (a)~ Figure 6 The semiconductor device formation method shown in (g) is suitable for use as a reference. Figure 5 This is part of the semiconductor device formation method. For example, Figure 6 (a)~ Figure 6 The semiconductor device formation method shown in (g) is for Figure 5 The groove R shown in (c) has been deformed. The semiconductor device formation method of this embodiment uses a reference... Figures 1-3 The substrate processing apparatus 100 performs the process.

[0140] like Figure 6 As shown in (a), a groove R is provided in the laminated structure L. For example, the groove R is formed in the laminated structure L by etching the substrate W. Here, the groove R is formed in the insulating layer N and the sacrificial layer Sa. The groove R can reach the etch stop layer Es.

[0141] like Figure 6 As shown in (b), a filler layer F is filled in the groove R. The filler layer F is, for example, an organic material (carbon-based material). In one example, the filler layer F is a polymer. The filler layer F may also be formed from a photoresist. For example, if the solvent is allowed to evaporate from the process liquid after the process liquid supply section 132 supplies the process liquid to the substrate W, the filler layer F is formed from the solute of the process liquid. Here, the filler layer F is filled in the range from the depth Rf of the groove R to the surface side portion Rn.

[0142] The preferred processing solution becomes solid after being applied to the substrate W. The processing solution itself is liquid, but after being coated on the substrate W, the solvent evaporates, thereby the solute becomes solid and forms the filler layer F.

[0143] like Figure 6 As shown in (c), a removal liquid Ds is applied to the substrate W. The removal liquid Ds dissolves the filler layer F. Here, the removal liquid Ds partially dissolves the filler layer F filling the groove R. As a result, while the deep portion Rf of the groove R is filled with the filler layer F, the surface portion Rn of the groove R is replaced by the removal liquid Ds. Consequently, a partial filler layer Fp is formed by the filler layer F, partially filling the deep portion Rf of the groove R.

[0144] For example, the removal liquid supply unit 134 supplies removal liquid Ds to the substrate W. The removal liquid supply unit 134 supplies removal liquid Ds in a manner that causes the filler layer F to partially dissolve rather than completely dissolve, with a set time and amount. For example, the removal liquid Ds contains isopropyl alcohol (IPA).

[0145] Typically, more than half of the depth of the groove R is replaced by the removal fluid Ds, leaving less than half of the filler layer F in the groove R, which becomes the partial filler layer Fp. For example, the depth (length in the z-axis direction) of the partial filler layer Fp is less than 1 / 3 of the depth of the groove R.

[0146] like Figure 6 As shown in (d), a waterproofing agent P is supplied. For example, the waterproofing agent supply unit 136 supplies the waterproofing agent P to the substrate W. Partially the filler layer Fp is unaffected by the waterproofing agent P, and the removal liquid Ds is replaced by the waterproofing agent P. Thus, in the state where the deep portion Rf of the groove R is filled with a portion of the filler layer Fp, the removal liquid Ds on the surface side portion Rn of the groove R is replaced by the waterproofing agent P.

[0147] It should be noted that although the deep portion Rf of the groove R is partially covered by the filling layer Fp, the surface portion Rn of the groove R is not covered by the filling layer Fp. Therefore, when the waterproofing agent P is supplied, the surface of the laminated structure L reacts with the waterproofing agent P in the surface portion Rn of the groove R to form a covering layer Ps.

[0148] like Figure 6 As shown in (e), a portion of the filler layer Fp and the waterproofing agent P are removed. At this time, a portion of the waterproofing agent P on the surface side of the groove R is removed along with a portion of the filler layer Fp in the deeper part Rf of the groove R. Particles that are preferably residues left during the formation of the groove R (e.g., during dry etching) are also removed. With the removal of the portion of the filler layer Fp, the insulating layer N and the sacrificial layer Sa in the deeper part Rf of the groove R are exposed. On the other hand, the surface side portion Rn of the groove R remains covered by the capping layer Ps.

[0149] For example, a removal liquid can be applied to remove part of the filler layer Fp and the waterproofing agent P. In one example, the removal liquid contains IPA. For example, the removal liquid supply unit 134 supplies removal liquid Ds to the substrate W. The removal liquid supply unit 134 supplies removal liquid in a manner that allows for complete dissolution of part of the filler layer Fp within a set time and amount.

[0150] Alternatively, the substrate W can be heated to remove part of the filler layer Fp and the waterproofing agent P. For example, if part of the filler layer Fp is formed of a sublimable material, heating can also sublimate part of the filler layer Fp.

[0151] like Figure 6 As shown in (f), the groove R is etched using solution C. Typically, solution C contains hydrofluoric acid. For example, solution C contains hydrofluoric acid diluted in the range of 1:100 to 1:2000. Alternatively, solution C may also contain water or deionized water (DIW). Alternatively, solution C may also contain phosphoric acid.

[0152] The deep portion Rf of the groove R is exposed due to the insulating layer N and the sacrificial layer Sa, and is therefore etched by the chemical solution C. On the other hand, the surface portion Rn of the groove R is covered by the capping layer Ps and is therefore not etched by the chemical solution C. Therefore, as Figure 6 As shown in (f), the region Re located in the deep Rf of the groove R is removed by the drug solution C, thereby widening the diameter of the groove R. Alternatively, the diameter of the deep Rf of the groove R can be widened to be equal to the diameter of the groove R in front (top diameter).

[0153] like Figure 6 As shown in (g), the chemical solution C and the capping layer Ps are removed. The removal of chemical solution C and the capping layer Ps can also be performed by ultraviolet irradiation or heating. Additionally, residues from the dry etching process are preferably removed at this time. The removal of chemical solution C and the capping layer Ps can also be performed using an apparatus different from the substrate processing apparatus 100.

[0154] The diameter of the groove R in the stacked structure L can be adjusted in the manner described above. It should be noted that... Figure 6 of (e) Figure 6 (f) and Figure 6 In (g), to facilitate understanding of the shape change of the groove R, it is illustrated such that the diameter of the deep portion Rf of the groove R is equal to the diameter of the top portion (aperture) of the groove R, and the diameter of the deep portion Rf of the groove R is greater than the diameter of the central portion of the groove R. However, this is merely an example. For the groove R, the diameter of the deep portion Rf of the groove R can also be increased so that the diameter of the deep portion Rf of the groove R is equal to the diameter of the central portion of the groove R. Alternatively, the groove R can be deformed so that the diameter of the deep portion Rf of the groove R is equal to both the diameter of the top portion and the diameter of the central portion of the groove R.

[0155] It should be noted that, Figure 6 In (c), by applying the removal liquid Ds, a portion of the filler layer F is replaced by the removal liquid Ds. When the diameter of the groove R is small, it takes a long time for the removal liquid Ds to remove the entire filler layer F. Therefore, by interrupting the removal process of the filler layer F based on the removal liquid Ds midway through the removal process of the entire filler layer F by the removal liquid Ds, the filler layer F can be partially removed. Additionally, as... Figure 6 As shown in (c), by adjusting the amount of the removal liquid Ds and the treatment time, a partial filling layer Fp covering an appropriate portion can be left.

[0156] in addition, Figure 6In (c), a partial filler layer Fp is formed from the filler layer F using the removal liquid Ds, but this embodiment is not limited to this. When the filler layer F is formed from a sublimable substance, a partial filler layer Fp can also be formed from the filler layer F by heating. In this case, a partial filler layer Fp that partially fills the depth Rf of the groove R can also be formed from the filler layer F by adjusting the heating time and temperature.

[0157] It should be noted that the substrate W is preferably used as a memory having multiple storage elements Se. Typically, when the substrate W is used as a memory, it has multiple recesses R with a constant diameter and height. Therefore, multiple recesses used in large-capacity memories can be deformed simultaneously through the same process.

[0158] It should be noted that when forming the groove R in the stacked structure L, due to the curling phenomenon, the diameter of the groove R may sometimes become largest near the center. In this case, it is preferable to cover the area near the center with a capping layer Ps. Alternatively, the diameter of the depth Rf of the groove R can be enlarged by etching in a manner equal to the diameter of the largest central portion of the groove R.

[0159] It should be noted that this was referenced. Figure 6 In the above description, the covering layer Ps is formed by supplying a liquid waterproofing agent P to a groove R that is partially filled with the filler layer Fp, but this embodiment is not limited to this. The covering layer Ps can also be formed by gas.

[0160] Next, refer to Figures 1-3 , Figure 6 and Figure 7 The semiconductor device formation method of this embodiment will be described. Figure 7 This is a flowchart of a semiconductor device formation method. The semiconductor device formation method of this embodiment is described by referring to... Figures 1-3 The substrate processing apparatus 100 is used appropriately.

[0161] First, in step S10, the groove R is partially covered in the stacked structure L. Typically, the surface side portion Rn of the groove R is selectively covered. For example, a covering layer Ps is formed on the surface side portion Rn of the groove R. The covering layer Ps selectively covers the surface side portion Rn of the groove R, but does not cover the deep portion Rf of the groove R. Therefore, the deep portion Rf of the groove R is exposed in the stacked structure L.

[0162] In step S20, the diameter of the depth Rf of the groove R is increased. By applying the drug solution C to the groove R, the diameter of the depth Rf of the groove R can be increased. Since the groove R is partially covered by the covering layer Ps, the diameter of the depth Rf in the groove R not covered by the covering layer Ps can be partially increased. Therefore, since the diameter of the depth Rf of the groove R can be increased, the diameter of the groove R can be adjusted.

[0163] Next, refer to Figures 1-3 , Figures 6-8 The semiconductor device formation method of this embodiment will be described. Figure 8 This is a flowchart of a semiconductor device formation method. The semiconductor device formation method of this embodiment uses reference [reference needed]. Figures 1-3 The substrate processing apparatus 100 is used appropriately.

[0164] First, in step Sa, the substrate W is moved into the substrate processing apparatus 100. Here, the substrate W has a substrate S and a laminated structure L, and a groove R is provided in the laminated structure L.

[0165] In step S10, the groove R is partially covered in the laminated structure L. Here, the partial coverage of the groove R in step S10 can be achieved by forming the filling layer F in step S12, partially removing the filling layer F in step S14 (forming a partial filling layer Fp), supplying the waterproofing agent in step S16, and removing the partial filling layer Fp in step S18.

[0166] In step S12, a filler layer F is filled into the groove R. The processing liquid supply unit 132 supplies processing liquid to the substrate W. As a result, the groove R of the substrate W is filled with the filler layer F. It should be noted that, typically, after the processing liquid is supplied, the substrate holding unit 120 increases the rotation speed of the substrate W to throw the processing liquid remaining on the surface of the substrate W to the outside of the substrate W.

[0167] In step S14, a portion of the filler layer F is removed. For example, the remover supply unit 134 supplies remover to the substrate W for a predetermined time. By applying remover Ds to the filler layer F in the groove R, the filler layer F is partially dissolved, forming a partial filler layer Fp within the groove R. The time for applying remover Ds is set such that the filler layer F in the groove R is partially removed. At this time, the filler layer F in the surface portion Rn of the groove R is removed, while the partial filler layer Fp in the deeper portion Rf of the groove R is retained.

[0168] Alternatively, a partial filling layer Fp can be formed in the groove R by heating the filling layer F for a specified time. For example, when the filling layer F contains a sublimable substance, heating the filling layer F for a specified time can cause a portion of the filling layer F to sublimate, thereby forming a partial filling layer Fp in the groove R.

[0169] In step S16, a waterproofing agent is supplied to the substrate W. The waterproofing agent supply unit 136 supplies waterproofing agent to the substrate W. By applying the waterproofing agent to the groove R where a partial filling layer Fp is formed in the deep Rf, the waterproofing agent can be filled into the surface side portion Rn in the groove R where the partial filling layer Fp is not formed, thus forming a waterproof layer. At this time, the characteristics of the surface side portion Rn of the groove R change due to the waterproofing agent, and a cover layer Ps is formed on the surface side portion Rn of the groove R. Thus, by supplying the waterproofing agent, a cover layer Ps is formed on the surface side portion Rn of the groove R as part of the waterproof layer.

[0170] In step S18, a portion of the filler layer Fp is removed. Here, the portion of the waterproof layer formed by the waterproofing agent, excluding the cover layer Ps, is removed, and a portion of the filler layer Fp is also removed simultaneously. For example, the removal liquid supply unit 134 supplies removal liquid to the substrate W, thereby dissolving a portion of the filler layer Fp and replacing the portion of the waterproof layer excluding the cover layer Ps. At this time, the surface side portion Rn of the groove R is covered by the cover layer Ps, while the deep portion Rf of the groove R exposes the laminated structure L.

[0171] Alternatively, a portion of the filler layer Fp can be removed by heating it for a specified time. For example, if the filler layer F contains a sublimable substance, heating the filler layer F will cause a portion of it to sublimate, thus removing a portion of the filler layer Fp from the groove R.

[0172] Next, in step S20, the diameter of the deep portion Rf of the groove is increased. For example, the solution supply unit 138 supplies solution to the substrate W. As a result, the deep portion Rf in the groove R that is not covered by the cover layer Ps is partially etched, and the groove diameter becomes wider.

[0173] In step Sb, the substrate W is removed from the substrate processing apparatus 100. Then, the capping layer Ps is removed as needed. The capping layer Ps can also be removed by ashing through ultraviolet irradiation or heat treatment. In the above manner, a substrate W in which variations in the groove diameter are suppressed can be formed.

[0174] It should be noted that, in reference Figure 8 In the above description, although the etching in step S20 is performed using a single etching solution, this embodiment is not limited to this. The etching in step S20 can also be performed using multiple etching solutions. For example, with a single etching solution, it is sometimes impossible to make the etching amount of the insulating layer N equal to the etching amount of the sacrificial layer Sa. In this case, the etching in step S20 is preferably performed using multiple etching solutions.

[0175] Next, refer to Figures 1-3 , Figure 6 , Figure 9 and Figure 10 The semiconductor device formation method of this embodiment will be described. Figure 9 This is a schematic diagram of the substrate processing apparatus 100 according to this embodiment. The liquid supply unit 130 further includes a rinsing liquid supply unit 137, and the medicine supply unit 138 includes a first medicine supply unit 138A and a second medicine supply unit 138B. In addition, Figure 9 The substrate processing apparatus 100 has a common feature with Figure 2 The substrate processing apparatus 100 shown has the same configuration, so a repeated description is omitted to avoid redundancy.

[0176] In the substrate processing apparatus 100, the liquid supply unit 130 further includes a rinsing liquid supply unit 137. The rinsing liquid supply unit 137 supplies rinsing liquid to the substrate W.

[0177] The rinsing solution supply unit 137 supplies rinsing solution to the upper surface Wa of the substrate W. By rinsing with the rinsing solution, the chemicals and impurities adhering to the upper surface Wa of the substrate W can be washed away. The rinsing solution supplied by the rinsing solution supply unit 137 may contain any one of deionized water (DIW), carbonated water, electrolyzed ionized water, ozone water, ammonia water, hydrochloric acid water with a dilution concentration (e.g., 10ppm to 100ppm), or reduced water (hydrogen-rich water).

[0178] The rinsing fluid supply unit 137 includes: a pipe 137a, a valve 137b, and a nozzle 137n. The nozzle 137n sprays rinsing fluid onto the upper surface Wa of the substrate W. The nozzle 137n is connected to the pipe 137a. Rinsing fluid is supplied to the pipe 137a from a supply source. The valve 137b opens and closes the flow path within the pipe 137a. Preferably, the nozzle 137n is configured to be movable toward the substrate W.

[0179] In the substrate processing apparatus 100, the solution supply unit 138 includes a first solution supply unit 138A and a second solution supply unit 138B. The first solution supply unit 138A supplies a first solution to the substrate W. The second solution supply unit 138B supplies a second solution to the substrate W.

[0180] The first solution supply unit 138A supplies a first solution to the upper surface Wa of the substrate W. By using the first solution for treatment, the upper surface Wa of the substrate W can be treated with the solution. The first solution supply unit 138A includes a pipe 138a, a valve 138b, and a nozzle 138n. The nozzle 138n sprays the first solution onto the upper surface Wa of the substrate W. The nozzle 138n is connected to the pipe 138a. The first solution is supplied to the pipe 138a from a supply source. The valve 138b opens and closes the flow path within the pipe 138a. Preferably, the nozzle 138n is configured to be movable toward the substrate W.

[0181] The second chemical solution supply unit 138B supplies a second chemical solution to the upper surface Wa of the substrate W. By using the second chemical solution for chemical treatment, the upper surface Wa of the substrate W can be treated with the chemical solution. The second chemical solution supply unit 138B includes: a pipe 138c, a valve 138d, and a nozzle 138m. The nozzle 138m sprays the second chemical solution onto the upper surface Wa of the substrate W. The nozzle 138m is connected to the pipe 138c. The second chemical solution is supplied to the pipe 138c from a supply source. The valve 138d opens and closes the flow path within the pipe 138c. Preferably, the nozzle 138m is configured to be movable toward the substrate W.

[0182] The etch selectivity of the sacrificial layer Sa in the first solution relative to the insulating layer N differs from that of the sacrificial layer Sa in the second solution relative to the insulating layer N. For example, if the etch ratio of the sacrificial layer Sa in the first solution relative to the insulating layer N is high, the etch ratio of the sacrificial layer Sa in the second solution relative to the insulating layer N is low. In one example, if the first solution contains hydrofluoric acid, the second solution preferably contains water or phosphoric acid. Thus, by using the first and second solutions with different etch selectivity of the sacrificial layer Sa relative to the insulating layer N, the etch amount of the insulating layer N can be made equal to the etch amount of the sacrificial layer Sa.

[0183] The control unit 102 individually controls valves 137b, 138b, and 138d of the liquid supply unit 130, enabling the valves 137b, 138b, and 138d to switch between open and closed states. Specifically, the control unit 102 controls valves 137b, 138b, and 138d of the liquid supply unit 130 to be in the open state, thereby allowing the flushing fluid, the first medicinal solution, and the second medicinal solution flowing in the pipes 137a, 138a, and 138c to pass through nozzles 137n, 138n, and 138m. In addition, the control unit 102 controls the valves 137b, 138b, and 138d of the liquid supply unit 130 to close the valves 137b, 138b, and 138d, thereby stopping the supply of flushing fluid, first medicine, and second medicine to the nozzles 137n, 138n, and 138m respectively.

[0184] Figure 10 This is a flowchart of the semiconductor device formation method according to this embodiment. Besides the aspect of etching the deep portion Rf of the groove R using various etchants, Figure 10 Flowcharts and Figure 8 Similarly, the flowchart is omitted to avoid redundancy.

[0185] In this embodiment, the etching in step S20 includes the first etching in step S20a, the rinsing solution supply in step S20b, and the second etching in step S20c. The etch selectivity of the sacrificial layer Sa relative to the insulating layer N differs for the first and second etchings. For example, if the etch ratio of the sacrificial layer Sa relative to the insulating layer N is high in the first etching, it is preferable that the etch ratio of the sacrificial layer Sa relative to the insulating layer N is low in the second etching.

[0186] In step S20a, the first etching is a selective etching of either the insulating layer N or the sacrificial layer Sa. For example, the first solution supply unit 138A supplies a first solution to the upper surface Wa of the substrate W. It should be noted that when selectively etching the insulating layer N of the insulating layer N and the sacrificial layer Sa, hydrofluoric acid is preferably used as the first solution. Furthermore, when selectively etching the sacrificial layer Sa of the insulating layer N and the sacrificial layer Sa, warm water or phosphoric acid is preferably used as the first solution.

[0187] Then, in step S20b, a rinsing process is performed. The rinsing fluid supply unit 137 supplies rinsing fluid to the upper surface Wa of the substrate W.

[0188] In step S20c, the second etching selectively etches the other of the insulating layer N and the sacrificial layer Sa. For example, the second solution supply unit 138B supplies the second solution to the upper surface Wa of the substrate W. When the first etching selectively etched one of the insulating layer N and the sacrificial layer Sa, the second etching selectively etched the other of the insulating layer N and the sacrificial layer Sa. As described above, by performing two etching operations with different selection ratios, the etching amount of the insulating layer N and the etching amount of the sacrificial layer Sa can be made equal.

[0189] It should be noted that the reference Figure 2 , Figure 6 and Figure 7 As described above, the processing liquid supply unit 132 supplies processing liquid to the substrate W, thereby forming the filler layer F. It should be noted that when the processing liquid contains a solute and a volatile solvent, it is preferable to heat the processing liquid after the processing liquid supply unit 132 supplies it to the substrate W. By heating the processing liquid, the filler layer F can be formed quickly.

[0190] Next, refer to Figure 11 and Figure 12 The semiconductor device formation method of this embodiment will be described. Figure 11 This is a schematic diagram of the substrate processing apparatus 100 according to this embodiment. In addition to including a heat supply unit 140, a gas supply unit 142, and a shielding member 150, Figure 11 The substrate processing apparatus 100 has a common feature with Figure 2The substrate processing apparatus 100 shown has the same configuration, so a repeated description is omitted to avoid redundancy.

[0191] The substrate processing apparatus 100 further includes a heat supply unit 140, a gas supply unit 142, and a shielding member 150. The heat supply unit 140 supplies heat to the substrate W. The gas supply unit 142 supplies gas to the substrate W. The shielding member 150 shields the substrate W from the vertically above side.

[0192] The processing liquid supply unit 132 supplies a processing liquid containing solute and volatile solvent. The packing layer F is formed from the solute component.

[0193] The heat medium supplied by the heat medium supply unit 140 can be either a liquid or a gas. For example, the heat medium is warm water. In the middle or after the processing liquid supply unit 132 supplies processing liquid to the upper surface Wa of the substrate W, the heat medium supply unit 140 heats the substrate W held on the rotating base 121 and the chuck member 122 from the back side Wb side of the substrate W, forming a filling layer on the upper surface Wa of the substrate W.

[0194] When the substrate W rotates, the heat supply unit 140 supplies heat medium to the center of the back surface Wb of the substrate W. The supplied heat medium is distributed throughout almost the entire back surface Wb of the substrate W by centrifugal force. As a result, the processing liquid on the substrate W and the upper surface Wa of the substrate W is heated, causing the solvent to evaporate from the processing liquid and rapidly forming a filling layer.

[0195] The heat transfer medium supply unit 140 includes: a pipe 140a, a valve 140b, and a nozzle 140n. The nozzle 140n faces the back surface Wb of the substrate W. The nozzle 140n sprays heat transfer medium onto the back surface Wb of the substrate W. The nozzle 140n is connected to the pipe 140a. Heat transfer medium is supplied to the pipe 140a from a supply source. The valve 140b opens and closes the flow path within the pipe 140a.

[0196] The gas supply unit 142 supplies gas to the upper surface Wa of the substrate W. Preferably, the gas supplied by the gas supply unit 142 contains an inactive gas. The inactive gas contains nitrogen.

[0197] The gas supply unit 142 includes a pipe 142a and a valve 142b. Gas is supplied from a supply source to the pipe 142a. The valve 142b opens and closes the flow path within the pipe 142a.

[0198] The shielding member 150 is located above the substrate holding portion 120. The shielding member 150 faces the substrate W. Here, at least a portion of the outer diameter of the shielding member 150 in the horizontal direction is almost equal to the outer diameter of the substrate W.

[0199] The shielding member 150 moves toward the substrate W between an approaching position and a retracted position. When the shielding member 150 is in the approaching position, it descends and approaches the upper surface of the substrate W at a predetermined interval. In the approaching position, the shielding member 150 covers the surface of the substrate W, shielding the upper part of the substrate W. When the shielding member 150 is in the retracted position, it is located in a space vertically above the substrate W, away from the approaching position. When the shielding member 150 changes from the approaching position to the retracted position, it rises and detaches from the substrate W.

[0200] The shielding member 150 includes a shielding plate 152, a support shaft 154, and a nozzle 156. The support shaft 154 is located on the rotation axis Ax of the shaft 123. The shielding plate 152 extends horizontally from the support shaft 154. Here, the shielding plate 152 has a shape that extends horizontally. For example, the shielding plate 152 is generally circular.

[0201] The nozzle 156 is connected to the pipe 134a of the removal liquid supply unit 134 and the pipe 142a of the gas supply unit 142. The nozzle 156 functions as a nozzle for both the removal liquid supply unit 134 and the gas supply unit 142.

[0202] The control unit 102 independently controls valves 140b and 142b, enabling the valves 140b and 142b to switch between open and closed states. Specifically, the control unit 102 controls valves 140b and 142b, setting them to the open state, thereby allowing the heat medium and gas flowing in pipes 140a and 142a to pass through nozzles 140n and 156. Conversely, the control unit 102 controls valves 140b and 142b, setting them to the closed state, thereby stopping the supply of heat medium and gas flowing in pipes 140a and 142a to nozzles 140n and 156.

[0203] In addition, the control unit 102 controls the shielding member 150 to move the shielding member 150 toward the substrate W between the approach position and the retraction position.

[0204] Figure 12 This is a flowchart of the semiconductor device formation method according to this embodiment. Besides the aspect of forming the fill layer F through multiple steps, Figure 12 Flowcharts and Figure 8 Similarly, the flowchart is omitted to avoid redundancy.

[0205] The formation of the filling layer F in step S12 includes: the supply of processing liquid in step S12a, the spin-off in step S12b, and the heating in step S12c.

[0206] In step S12a, a processing liquid is supplied. The processing liquid supply unit 132 supplies processing liquid to the upper surface Wa of the substrate W. At this time, the rotational speed of the substrate W is 10 rpm to 100 rpm.

[0207] In step S12b, after the substrate holding section 120 supplies the processing liquid, the rotation speed of the substrate W is increased to spin-off the processing liquid on the upper surface Wa of the substrate W. For example, the rotation speed of the substrate W is increased to 300 rpm to 1500 rpm.

[0208] In step S12c, the heat supply unit 140 supplies heat medium to the back surface Wb of the substrate W. For example, after the processing liquid is spun, the rotation speed of the substrate W is reduced to 100 rpm to 1000 rpm. By heating the processing liquid on the upper surface Wa of the substrate W, the filling layer F can be rapidly formed from the processing liquid.

[0209] It should be noted that the reference Figure 11 and Figure 12 In the description, the processing liquid is heated by a heat medium supplied by the heat medium supply unit 140, but this embodiment is not limited to this. A heat source such as a lamp or an electric heater may also be provided in the substrate processing apparatus 100 to heat the processing liquid using heat from the heat source.

[0210] It should be noted that, preferably, a stripping solution is supplied to the substrate W before the removal solution for removing the filler layer F and / or part of the filler layer Fp is supplied.

[0211] Next, refer to Figure 6 , Figure 13 and Figure 14 The semiconductor device formation method of this embodiment will be described. Figure 13 This is a schematic diagram of the substrate processing apparatus 100 according to this embodiment. In addition to the liquid supply unit 130, it also includes a rinsing liquid supply unit 137 and a stripping liquid supply unit 160. Figure 13 The substrate processing apparatus 100 has a common feature with Figure 11 The substrate processing apparatus 100 shown has the same configuration, so a repeated description is omitted to avoid redundancy.

[0212] In the substrate processing apparatus 100 of this embodiment, the liquid supply unit 130 further includes a rinsing liquid supply unit 137 and a stripping liquid supply unit 160. The rinsing liquid supply unit 137 supplies rinsing liquid to the substrate W. The stripping liquid supply unit 160 supplies stripping liquid to the substrate W.

[0213] The rinsing fluid supply unit 137 supplies rinsing fluid to the substrate W. The rinsing fluid supply unit 137 includes a pipe 137a and a valve 137b. Rinsing fluid is supplied from a supply source to the pipe 137a. The valve 137b opens and closes the flow path within the pipe 137a.

[0214] A pipe 137a of a flushing fluid supply unit 137 is connected to the nozzle 156 of the shielding member 150. The nozzle 156 functions as the nozzle of the flushing fluid supply unit 137.

[0215] The stripping liquid supply unit 160 supplies stripping liquid to the upper surface Wa of the substrate W. The stripping liquid has the property of peeling off the filler layer F. By supplying the stripping liquid, the filler layer F can be easily removed. For example, the stripping liquid contains at least one of DIW and SC1. By controlling the concentration of the stripping liquid supplied by the stripping liquid supply unit 160 and the processing time, a partial filler layer Fp can be appropriately formed from the filler layer F.

[0216] Here, the stripping fluid supply unit 160 includes a first stripping fluid supply unit 162 and a second stripping fluid supply unit 164. The first stripping fluid supply unit 162 supplies a first stripping fluid to the upper surface Wa of the substrate W. The second stripping fluid supply unit 164 supplies a second stripping fluid to the upper surface Wa of the substrate W. The first stripping fluid supply unit 162 supplies a stripping fluid different from that supplied by the second stripping fluid supply unit 164 to the upper surface Wa of the substrate W.

[0217] The first stripping fluid supply unit 162 includes a pipe 162a and a valve 162b. The first stripping fluid is supplied to the pipe 162a from a supply source. The valve 162b opens and closes the flow path within the pipe 162a.

[0218] The second stripping fluid supply unit 164 includes a pipe 164a and a valve 164b. The second stripping fluid is supplied to the pipe 164a from a supply source. The valve 164b opens and closes the flow path within the pipe 164a.

[0219] The stripping fluid supply unit 160 also includes a pipe 160a and a nozzle 160n. The pipe 160a is connected to pipes 162a and 164a. The nozzle 160n sprays stripping fluid onto the upper surface Wa of the substrate W. The nozzle 160n is connected to the pipe 160a. Preferably, the nozzle 160n is configured to be movable toward the substrate W.

[0220] The control unit 102 individually controls valves 162b and 164b of the stripping fluid supply unit 160, enabling the valves 162b and 164b to switch between open and closed states. Specifically, the control unit 102 controls valves 162b and 164b of the stripping fluid supply unit 160, setting either valve 162b or 164b to the open state, thereby allowing the first and second stripping fluids flowing in pipes 160a and 162a or 164a to pass through nozzle 160n. Conversely, the control unit 102 controls valves 162b and 164b of the stripping fluid supply unit 160, setting them to the closed state, thereby stopping the supply of the first and second stripping fluids flowing in pipes 160a and 162a or 164a to nozzle 160n.

[0221] When the processing solution contains a heat-sensitive water-soluble resin as a solute, and the processing solution is heated, in order to set the temperature of the heat-sensitive water-soluble resin below the modification temperature, a heat transfer medium with a boiling point lower than the modification temperature is preferably used as the heat transfer medium. For example, in the case of a heat-sensitive water-soluble resin with a modification temperature of 180°C, DIW (boiling point: 100°C) or the like can be used as the heat transfer medium. It should be noted that it is even more preferable to set the temperature of the heat transfer medium below the boiling point of the solvent. By setting the temperature of the processing solution below the boiling point of the solvent, the solvent can remain in the filler layer. Furthermore, through the interaction between the solvent remaining in the filler layer and the stripping liquid, the filler layer can be easily peeled off from the upper surface of the substrate W.

[0222] Figure 14 This is a flowchart of the semiconductor device formation method according to this embodiment. In addition to supplying a removal liquid to remove the filler layer and portions thereof, and supplying a stripping liquid before supplying the removal liquid, Figure 14 Flowcharts and Figure 12 Similarly, the flowchart is omitted to avoid redundancy.

[0223] After heating the substrate W in step S12c, a first stripping liquid is supplied in step S13a. The first stripping liquid supply unit 162 supplies the first stripping liquid to the substrate W. For example, the first stripping liquid supply unit 162 supplies DIW as the first stripping liquid.

[0224] In step S13b, a second release agent is supplied. The second release agent supply unit 164 supplies the second release agent to the substrate W. For example, the second release agent supply unit 164 supplies SC1 as the second release agent.

[0225] In step S13c, rinsing fluid is supplied. For example, the rinsing fluid supply unit 137 supplies rinsing fluid to the upper surface Wa of the substrate W.

[0226] Then, in step S14a, the filler layer F is partially dissolved by the removal liquid to form a partial filler layer Fp. The removal liquid supply unit 134 supplies the removal liquid to the substrate W after a predetermined time. By applying the removal liquid Ds to the filler layer F in the groove R, the filler layer F can be partially dissolved, forming a partial filler layer Fp in the groove R. By controlling the concentration and processing time of the first stripping liquid, the second stripping liquid, and the removal liquid supplied by the first stripping liquid supply unit 162, the second stripping liquid supply unit 164, and the removal liquid supply unit 134, the partial filler layer Fp can be appropriately formed from the filler layer F.

[0227] In addition, after the waterproofing agent is supplied in step S16, a removal liquid is supplied in step S18a to remove the waterproofing agent P (excluding the covering layer Ps) and part of the filler layer Fp. Subsequent processing is the same as described above.

[0228] It should be noted that, Figure 14 In the flowchart shown, the first stripping liquid and the second stripping liquid are supplied before the filler layer F is partially dissolved by the stripping liquid, but this embodiment is not limited to this. The first stripping liquid and the second stripping liquid may be supplied not only before the partial dissolution of the filler layer F, but also before the partial dissolution of the filler layer Fp. Alternatively, the first stripping liquid and the second stripping liquid may be supplied before the partial dissolution of the filler layer F, but before the partial dissolution of the filler layer Fp.

[0229] in addition, Figure 14 The flowchart shown provides both a first stripping solution and a second stripping solution, but this embodiment is not limited to this. Alternatively, only one of the first and second stripping solutions may be supplied before dissolving the filler layer F and / or part of the filler layer Fp.

[0230] It should be noted that the reference Figure 13 and Figure 14 In the above description, the filler layer F and / or part of the filler layer Fp are removed by stripping liquid and removal liquid, but this embodiment is not limited to this. The filler layer F and / or part of the filler layer Fp can also be removed by heating.

[0231] Next, refer to Figure 6 , Figure 15 and Figure 16 The semiconductor device formation method of this embodiment will be described. Figure 15 This is a schematic diagram of the substrate processing apparatus 100 according to this embodiment. Besides the aspect of the processing liquid containing a sublimable substance and cooling the filler layer formed by the processing liquid, Figure 15 The substrate processing apparatus 100 has a common feature with Figure 11 The substrate processing apparatus 100 shown has the same configuration, so a repeated description is omitted to avoid redundancy.

[0232] In this embodiment, the processing liquid supply unit 132 supplies a processing liquid containing a sublimable substance to the upper surface Wa of the substrate W. Furthermore, when mixing the sublimable substance in its molten state, a solvent that exhibits compatibility with the sublimable substance in its molten state is preferred as the solvent. Additionally, when dissolving the sublimable substance as a solute, a solvent that exhibits solubility in the sublimable substance is preferred.

[0233] The substrate processing apparatus 100 also includes a refrigerant supply unit 144. The refrigerant supply unit 144 supplies a refrigerant below room temperature to the substrate W. The refrigerant is, for example, DIW cooled to below room temperature.

[0234] The refrigerant supplied by the refrigerant supply unit 144 can be any liquid or gas. After the processing liquid supply unit 132 supplies processing liquid to the upper surface Wa of the substrate W, the refrigerant supply unit 144 cools the substrate W held on the rotating base 121 and the chuck member 122 from the back side Wb side of the substrate W.

[0235] When the substrate W rotates, the refrigerant supply unit 144 supplies refrigerant to the center of the back surface Wb of the substrate W. The supplied refrigerant is distributed across almost the entire back surface Wb of the substrate W by centrifugal force. As a result, the processing liquid on the substrate W and its upper surface Wa is cooled and solidified, and a filling layer can be quickly formed from the processing liquid.

[0236] The refrigerant supply unit 144 includes a pipe 144a and a valve 144b. Refrigerant is supplied to the pipe 144a from a supply source. The valve 144b opens and closes the flow path within the pipe 144a. The pipe 144a is connected to the pipe 140a of the heat supply unit 140. Refrigerant is supplied from the nozzle 140n of the heat supply unit 140 to the back surface Wb of the substrate W.

[0237] It should be noted that, in addition to the refrigerant supply unit 144, the substrate processing apparatus 100 also includes a heat supply unit 140. The heat supply unit 140 supplies heat to the back surface Wb of the substrate W until the refrigerant supply unit 144 supplies refrigerant to the back surface Wb of the substrate W, thereby enabling the filling layer F to be formed thinner. Therefore, the internal stress generated within the filling layer F can be reduced.

[0238] Figure 16 This is a flowchart of the semiconductor device formation method according to this embodiment. Aside from the fact that the processing solution contains a sublimable substance and heating is performed during the removal of part of the filler layer, Figure 16 Flowcharts and Figure 8 Similarly, the flowchart is omitted to avoid redundancy.

[0239] In step S12, a filler layer F is formed. The processing liquid supply unit 132 supplies processing liquid to the substrate W. Here, the processing liquid contains a sublimable substance. The processing liquid supply unit 132 supplies the processing liquid containing the sublimable substance to the upper surface Wa of the substrate W.

[0240] During the formation of the filler layer F, the coolant supply unit 144 supplies coolant to the back surface Wb of the substrate W. As a result, the processing liquid solidifies to form the filler layer F. The coolant supplied to the back surface Wb of the substrate W is distributed across approximately the entire back surface Wb of the substrate W by centrifugal force. This initiates the cooling of the processing liquid on the upper surface Wa of the substrate W.

[0241] Furthermore, during the removal of a portion of the filler layer Fp in step S18b, the supply of refrigerant based on the refrigerant supply unit 144 is stopped, and the supply of heat medium based on the heat medium supply unit 140 is started. As a result, the portion of the filler layer Fp sublimates, thereby enabling the removal of the portion of the filler layer Fp.

[0242] It should be noted that the reference Figures 1 to 16 In the above description, the substrate processing apparatus 100 is a single-piece type, and the substrate processing apparatus 100 processes substrates W one by one, but the present invention is not limited to this. The substrate processing apparatus can be a batch type.

[0243] Next, refer to Figure 17 The substrate processing apparatus 100 of this embodiment will be described. Figure 17 This is a schematic diagram of a substrate processing apparatus 100. The substrate processing apparatus 100 is capable of processing multiple substrates W together.

[0244] The substrate processing apparatus 100 includes a substrate holding section 120 and a liquid supply section 130. The liquid supply section 130 includes a processing liquid supply section 132, a removal liquid supply section 134, a waterproofing agent supply section 136, and a chemical liquid supply section 138. The processing liquid supply section 132, the removal liquid supply section 134, the waterproofing agent supply section 136, and the chemical liquid supply section 138 respectively store liquids.

[0245] The processing fluid supply unit 132 includes a processing fluid storage tank 132t. The processing fluid is stored in the processing fluid storage tank 132t. A packing layer is formed by the processing fluid. For example, the processing fluid contains a solute and a volatile solvent. Alternatively, the processing fluid contains a sublimable substance.

[0246] The removal liquid supply unit 134 includes a removal liquid storage tank 134t. The removal liquid storage tank 134t stores removal liquid. The filler layer formed by the processing liquid can be removed by the removal liquid. By controlling the timing of the removal liquid supply, the filler layer can be selectively removed from the substrate W.

[0247] As the removal liquid, any solvent that is soluble in any resin can be used. Examples of removal liquids include diluents, toluene, ethyl acetate, alcohols, ethylene glycol, and other organic solvents, as well as acidic solutions such as acetic acid, formic acid, and glycolic acid.

[0248] The waterproofing agent supply unit 136 includes a waterproofing agent storage tank 136t. The waterproofing agent storage tank 136t stores liquid waterproofing agent. A waterproof layer is formed on the substrate W using the waterproofing agent. The waterproofing agent is a waterproofing agent that hydrophobizes silicon (Si) itself and silicon-containing compounds. The waterproofing agent is, for example, a silane coupling agent. Silane coupling agents include, for example, at least one of HMDS (hexamethyldisilazane), TMS (tetramethylsilane), fluoroalkylchlorosilane, alkyldisilazane, and non-chlorinated waterproofing agents. Non-chlorinated waterproofing agents include, for example, at least one of dimethylsilyldimethylamine, dimethylsilyldiethylamine, hexamethyldisilazane, tetramethyldisilazane, bis(dimethylamino)dimethylsilane, N,N-dimethyltrimethylsilane, N-(trimethylsilyl)dimethylamine, and organosilane compounds.

[0249] The chemical supply unit 138 includes a chemical storage tank 138t. The chemical storage tank 138t stores chemical solutions. By using the chemical solution for treatment, the substrate W can be treated. Through chemical treatment, the substrate W can be etched, surface-treated, property-imparted, formed with a treatment film, or at least a portion thereof removed. Typically, the chemical solution is an etching solution used for etching treatment of the substrate W.

[0250] The solution contains hydrofluoric acid. For example, hydrofluoric acid can be heated to a temperature between 40°C and 70°C, or between 50°C and 60°C. Alternatively, hydrofluoric acid can be heated without heating. The solution may also contain water or phosphoric acid.

[0251] Furthermore, the solution may also contain hydrogen peroxide. In addition, the solution may also contain SC1 (ammonia-hydrogen peroxide mixture), SC2 (hydrochloric acid-hydrogen peroxide mixture), or aqua regia (a mixture of concentrated hydrochloric acid and concentrated nitric acid).

[0252] The substrate holding portion 120 holds the substrate W. The normal direction of the main surface of the substrate W held by the substrate holding portion 120 is parallel to the Y direction. The substrate holding portion 120 moves the substrate W while holding multiple substrates W. For example, the substrate holding portion 120 moves vertically upward or downward while holding the substrate W. Alternatively, the substrate holding portion 120 may move horizontally while holding the substrate W.

[0253] The substrate holding section 120 includes a main body plate 122b and holding rods 124b. The main body plate 122b is a plate extending in the vertical direction (Z direction). The holding rods 124b extend from one main surface of the main body plate 122b in the horizontal direction (Y direction). Here, two holding rods 124b extend from one main surface of the main body plate 122b in the Y direction. When the plurality of substrates W are arranged in a state where the plurality of substrates W are in the inward and forward direction along the paper surface, the lower edge of each substrate W abuts against the plurality of holding rods 124b and is held in an upright posture (vertical posture).

[0254] The substrate processing apparatus 100 also includes a control device 101. The control device 101 includes a control unit 102 and a storage unit 104. The control unit 102 controls the substrate holding unit 120.

[0255] In the substrate processing apparatus 100 of this embodiment, the control unit 102, similar to that of the monolithic type, processes the substrate W held on the substrate holding unit 120 with a different liquid, thereby enabling it to be processed with the reference in the monolithic type. Figures 6 to 16 Similarly, the diameter of the groove in the laminated structure L on the substrate W is adjusted.

[0256] It should be noted that, after referring to Figures 1 to 17 In the description, a storage element Se is disposed in a groove R of the substrate W, but this embodiment is not limited to this. A pseudo-storage element having the same structure as the storage element Se but which cannot be used as a storage element may also be formed in the groove R of the substrate W. Alternatively, a contact plug for electrical connection with the storage element Se may also be formed in the groove R of the substrate W.

[0257] Next, refer to Figure 18 The semiconductor element 300 formed by the semiconductor element formation method of this embodiment will be described. Figure 18 This is a schematic diagram of semiconductor element 300.

[0258] The semiconductor device 300 has multiple recesses R. In addition to the memory recesses Rs on which the memory element Se is disposed, the multiple recesses R also include contact recesses Rc on which contact plugs Cp are disposed. The contact recesses Rc are electrically connected to the conductive layer M.

[0259] According to the semiconductor device formation method of this embodiment, not only the memory groove Rs, but also the diameter of the contact groove Rc can be made uniform from the surface portion to the depth portion. Therefore, the strength of the contact groove Rc supporting the semiconductor device can be made uniform.

[0260] The embodiments of the present invention have been described above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments, and various methods can be implemented without departing from its spirit. Furthermore, various inventions can be formed by appropriately combining the multiple constituent elements disclosed in the above embodiments. For example, several constituent elements may be deleted from all the constituent elements shown in the embodiments. Furthermore, constituent elements from different embodiments may be appropriately combined. In the accompanying drawings, for ease of understanding, each constituent element is schematically represented. For ease of drawing, the thickness, length, number, spacing, etc., of each constituent element shown may sometimes differ from the actual dimensions. Additionally, the material, shape, size, etc., of each constituent element shown in the above embodiments are merely examples and are not particularly limited; various modifications can be made without substantially departing from the effects of the present invention.

[0261] Industrial availability

[0262] This invention is suitable for semiconductor device formation methods and substrate processing apparatus.

[0263] Explanation of reference numerals in the attached figures

[0264] 100 Substrate Processing Apparatus

[0265] 110 chambers

[0266] 120 Substrate Holding Section

[0267] 130 Liquid Supply Department

[0268] 132 Processing Fluid Supply Department

[0269] 134 De-icing Fluid Supply Section

[0270] 136 Waterproofing Agent Supply Department

[0271] 138 Pharmaceutical Supply Department

[0272] W substrate

Claims

1. A method for forming a semiconductor device, comprising: A process for forming a cover layer that selectively covers the surface-side portion of a groove in a laminated structure supported by a substrate; The process of etching the depth of the groove with a chemical solution in a way that increases the diameter of the groove relative to the depth of the cover layer. The process of forming the cover layer includes: The process of forming a partial filler layer that partially fills the depth of the groove; The process of supplying a waterproofing agent after the formation of the partial filler layer; and The process of supplying the waterproofing agent and forming the covering layer on the surface side of the groove, followed by removing the partial filler layer and the waterproofing agent.

2. The semiconductor device formation method as described in claim 1, wherein, The process of removing the partial filler layer includes the process of supplying a removal solution to dissolve the partial filler layer.

3. The semiconductor device formation method as described in claim 1, wherein, The filler layer contains a sublimable substance. The process of removing the partial filler layer includes a process of heating the partial filler layer.

4. The method for forming a semiconductor device according to any one of claims 1 to 3, wherein, The process of forming the partial filler layer includes: The process of forming a filling layer to fill the groove; and The process of partially removing the filler layer after its formation.

5. The semiconductor device formation method as described in claim 4, wherein, The process of partially removing the filler layer includes the process of supplying a removal solution to remove the filler layer.

6. The method for forming a semiconductor device as described in any one of claims 1 to 3, wherein, In the etching process, the solution contains any one of hydrofluoric acid, water, and phosphoric acid.

7. The method for forming a semiconductor device according to any one of claims 1 to 3, wherein, Multiple storage elements are formed in the groove.

8. The method for forming a semiconductor device as claimed in any one of claims 1 to 3, wherein, The stacked structure is provided with a plurality of the aforementioned grooves. The difference in the top diameter of the plurality of grooves is less than 5%.

9. The semiconductor device formation method as described in claim 8, wherein, From a top view of the stacked structure, the plurality of grooves are regularly arranged.

10. The method for forming a semiconductor device according to any one of claims 1 to 3, wherein, An etch stop layer is disposed between the substrate and the laminated structure.

11. A substrate processing apparatus, comprising: The processing fluid supply unit supplies processing fluid; A removal liquid supply unit supplies removal liquid for removing the filler layer formed by the treatment liquid; The waterproofing agent supply department supplies waterproofing agents. The pharmaceutical supply department supplies pharmaceutical solutions. and The control unit controls the treatment liquid supply unit, the removal liquid supply unit, the waterproofing agent supply unit, and the medicine supply unit, wherein... The control unit controls the treatment liquid supply unit, the removal liquid supply unit, the waterproofing agent supply unit, and the medicine supply unit in the following manner. (1) The processing liquid is supplied to form a filling layer that fills the grooves disposed in the laminated structure supported by the substrate; (2) Supply the removal liquid to partially remove the filling layer in the groove; (3) Supply the waterproofing agent to form a covering layer that selectively covers the portion of the surface side of the groove that is not covered by the filling layer; (4) Supply the liquid medicine to increase the diameter of the groove relative to the depth of the covering layer.

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