Substrate processing method

Abstract

The present invention relates to a substrate processing method, and more particularly, to a substrate processing method for removing impurities in a thin film of a substrate and improving the characteristics of the thin film, comprising: a pressure increasing step of increasing the pressure in a chamber to a first pressure higher than atmospheric pressure; a first pressure reducing step of reducing the pressure in the chamber from the first pressure to a second pressure after the pressure increasing step; and a second pressure reduction step of reducing the pressure in the chamber from the second pressure to a third pressure lower than normal pressure after the first pressure reduction step.

Description

Technical Field

[0001] The present invention relates to a substrate processing method and a substrate processing device, and more particularly to a substrate processing method for removing impurities in a thin film of a substrate and improving thin film properties. Background Art

[0002] Generally, a substrate processing method may include a process of forming a film by deposition.

[0003] However, there has been no particularly well-known technology that has been particularly favored by the industry and fully verified in order to remove impurities in a film and improve film properties after a thin film is formed on a substrate.

[0004] In particular, with the emergence of three-dimensional semiconductor devices and substrates with high aspect ratios, in order to meet step coverage specifications, the film deposition temperature must be lowered or a source with a high impurity content must be used, making it more difficult to remove impurities in the film.

[0005] Therefore, there is a demand for a substrate processing method that can remove impurities remaining in a film without special heating after film formation and improve film characteristics.

[0006] In addition, technology for reducing the plane space occupied by components has been further developed recently.

[0007] For example, instead of forming the channel region of the transistor in a planar manner on the substrate, a technology of forming a groove in the substrate to produce a two-dimensional channel shape, or a technology of using vertically stacked structures on the substrate is becoming increasingly common. In particular, in the case of NAND Flash, memory cell transistors that store binary information are also vertically stacked into hundreds of levels.

[0008] In order to manufacture integrated circuit components, various types of thin films must be repeatedly manufactured on a substrate.

[0009] The thin film is formed by supplying different raw material gases, reaction gases, carrier gases, etc. into a chamber where a chemical reaction can occur, depending on the type of thin film, and applying appropriate temperature and pressure to form a thin film of a desired thickness.

[0010] There is a tendency that the thin film formed on the element becomes thinner as the element size becomes smaller.

[0011] As described above, in order to form a thin film on the surface of the substrate, there are extremely small defects on the surface of the substrate, such as trace amounts of chlorine (Cl) remaining inside the chamber, nitrogen weakly bonded to silicon, and other elements remaining on the surface of the substrate, which can serve as a contamination source and cause defects.

[0012] There are various types of defects on the substrate surface. A small amount of silicon atoms existing in a dangling bond state or an incomplete covalent bond state are also defects.

[0013] This defect has a profound impact on the subsequent film formation. For example, in a silicon substrate, the position where the silicon atom should bond with the oxygen atom is occupied by defect impurities, and the element bonding to form a silicon oxide film (SiO2, Silicon Dioxide) cannot be achieved, thus ultimately affecting the film quality.

[0014] Another defect is a defect in the crystal structure of silicon, for example, when a defect such as a grain boundary is exposed on the surface of the substrate.

[0015] Other defects are caused by certain specific elements (eg, chlorine (Cl), etc.) that are caused by the residual gas in the chamber.

[0016] Even elements such as chlorine (Cl) gradually move between the lattices of an oxide film or a metal thin film such as TiN after forming these thin films, mainly to the interface with the silicon substrate, thereby causing defects on the substrate surface.

[0017] Ideally, all Ti elements constituting the thin film should be bonded to N elements without residue, but despite this reduction reaction, a portion of Cl (chlorine) elements remain at the interface between the oxide film and the TiN layer, becoming contaminating impurities.

[0018] These impurities will eventually cause the characteristics of the component to deteriorate rapidly.

[0019] For example, the following problems arise: the threshold voltage (Vt) characteristics of the transistor change, the capacitance value of the capacitor increases discretely, or the withstand voltage characteristics of the element deteriorate.

[0020] As the integration of components increases, the above-mentioned defects on the surface of the substrate and the like become a major problem, and therefore a substrate surface or a thin film surface with higher quality and cleaner surface is required to meet this trend.

[0021] For this purpose, special pretreatment technology is required before a thin film is formed on a substrate or before one thin film is covered with another thin film.

[0022] As is known to all, in most thin film forming processes, a so-called pretreatment process is performed to clean the surface on which the thin film is to be formed before film formation.

[0023] Pretreatment is the process of removing defects on the substrate surface before thin film formation to minimize the impact on the electrical and physical properties of the thin film.

[0024] This pretreatment method includes chemical method, mechanical method and mechanochemical method combining these two methods.

[0025] Even if the pretreatment process is performed, the effect of the pretreatment is gradually reduced due to the increasing refinement of the component structure, especially in the component structure of a three-dimensional structure, the phenomenon of halving the pretreatment effect as described above is more obvious.

[0026] For example, in the case of BCAT (Buried Channel Array Transistor), a groove with a large aspect ratio is set inside the substrate. When the inside of the groove is used as the channel region of the transistor, an insulating film, i.e., a gate oxide film, is first formed inside the groove, and then the gate material is filled.

[0027] At this time, in order to form a buried type groove, photosensitive masking and surface etching techniques are used as in most semiconductor manufacturing processes.

[0028] Since the surface of a semiconductor such as etched silicon is unstable, a process of performing surface oxidation and treatment using ozone (O 3 ) and hydrogen fluoride (HF) or the like is performed as a pretreatment process.

[0029] Even after this pretreatment process, when a high aspect ratio is formed on a silicon substrate, tiny defects still remain on the surface, which causes the film properties to deteriorate more rapidly.

[0030] In addition, in most thin film formation processes, various impurities remain after the reaction, and these residues may contain elements reduced from the raw material gas or organic matter of the photoresist.

[0031] In addition, since bonding of elements forming the thin film is incomplete during the thin film formation process, the thin film may be formed in a state where it is partially damaged.

[0032] Such impurities or damage adversely affect the physical and electrical properties of the components, ultimately reducing the reliability of the entire product.

[0033] For example, the presence of ion impurities or damage in the gate film may change the threshold voltage (Vt) of the transistor or widen the distribution of the capacitance value, resulting in a problem of deteriorating the withstand voltage characteristics of the element.

[0034] Conventional methods for removing thin films include chemical treatment of the film surface after film formation and mechanical grinding of a portion of the surface. Figure 1 As shown in the impurity concentration distribution of the film, these methods are only effective in removing impurities on the surface of the film, but are not very effective in removing impurities inside the film.

[0035] Therefore, the overall quality of the thin film formed on the substrate is more important than ever before. In particular, as the thickness of the film increases, there is a strong demand for the removal of impurities inside the film. Summary of the invention

[0036] (Problem to be solved)

[0037] The object of the present invention is to provide a substrate processing method for removing impurities in a thin film before, during and after thin film formation on the substrate and improving thin film properties, so as to solve the above-mentioned problems.

[0038] (Methods to solve the problem)

[0039] The present invention is proposed to achieve the purpose of the present invention as described above, and discloses a substrate processing method, comprising: a pressurization step, raising the pressure in a chamber to a first pressure higher than normal pressure; a first decompression step, after the pressurization step, reducing the pressure in the chamber from the first pressure to a second pressure; and a second decompression step, after the first decompression step, reducing the pressure in the chamber from the second pressure to a third pressure lower than normal pressure.

[0040] The pressurizing step, the first depressurizing step, and the second depressurizing step may be repeatedly performed several times.

[0041] The pressurizing step may include: a pressure increasing step of increasing the pressure in the chamber to the first pressure; and a high pressure maintaining step of maintaining the pressure in the chamber at the first pressure for a predetermined time after the pressure increasing step.

[0042] The pressurization step is to increase the pressure in the chamber to the first pressure, thereby bonding the pressurized gas with impurities on the substrate to form by-products; the first decompression step is to reduce the pressure in the chamber from the first pressure to the second pressure, thereby moving the by-products to the surface of the substrate or outside the substrate; the second decompression step is to reduce the pressure in the chamber from the second pressure to the third pressure that is lower than normal pressure, thereby discharging the by-products existing in the internal space of the chamber to the outside of the chamber.

[0043] The second pressure may be normal pressure.

[0044] The method may further include a pressure maintaining step of maintaining the pressure in the chamber at the second pressure for a predetermined time after the first decompression step.

[0045] The method may further include a thin film forming step of forming a thin film on the substrate after the second decompression step.

[0046] The method may further include a thin film forming step of forming a thin film on the substrate. The thin film forming step may include: a first thin film forming step of forming a thin film on the substrate before the pressurizing step; and a second thin film forming step of further forming a thin film on the substrate after the second depressurizing step.

[0047] The first thin film forming step and the second thin film forming step may form thin films of the same type or different types.

[0048] A single-layer film is formed on the substrate through the first thin-film forming step and the second thin-film forming step; the first thin-film forming step forms a portion of the thickness of the single-layer film, and the second thin-film forming step can form a portion or all of the remaining thickness of the single-layer film.

[0049] A thin film forming step of forming a thin film on the substrate before the pressurizing step may be included.

[0050] The thin film forming step may form a thin film on the substrate in the chamber in which the pressurizing step, the first depressurizing step, and the second depressurizing step are performed.

[0051] The thin film forming step is to form a thin film on the substrate in another chamber by using the chamber and the transport chamber to perform the pressurization step, the first depressurization step, and the second depressurization step.

[0052] The thin film forming step may form the thin film on the substrate in a chamber of a substrate processing apparatus that is separate from the chamber of the substrate processing apparatus that performs the pressurizing step, the first depressurizing step, and the second depressurizing step.

[0053] The thin film may constitute at least a portion of a gate insulating film of a transistor.

[0054] The thin film may include at least one of a metal element, a Group 4 element, nitrogen, and oxygen.

[0055] The thin film contains a non-metallic element or a metallic element, and may be a film composed of a single element, a film composed of two or more elements, or a composite of films of different types.

[0056] The pressurizing step may utilize a gas containing one or more elements selected from hydrogen (H), oxygen (O), nitrogen (N), chlorine (Cl), and fluorine (F).

[0057] The chamber may be a single-wafer type for processing a single substrate at a time or a batch type for processing multiple substrates at a time.

[0058] (Effects of the Invention)

[0059] The substrate processing method of the present invention is to increase the pressure through an annealing process in a high-temperature gas environment after forming a thin film, and then rapidly reduce the pressure, thereby removing impurities in the film and improving film properties such as composition or particle size.

[0060] In addition, the substrate processing method of the present invention performs an independent voltage-variable annealing process after a thin film is formed on the substrate, and thus can be applied to a wide range of substrate processing methods.

[0061] In addition, the substrate processing method of the present invention can also perform uniform heat treatment in three-dimensional semiconductor products with a high aspect ratio due to high pressure and can uniformly exhaust impurities due to rapid decompression.

[0062] In addition, the substrate processing method of the present invention suppresses the surface solidification phenomenon caused by surface bonding, can maintain a continuous heat treatment effect, and promotes the movement of metal atoms, which can make the grain boundary (Grain Boundary) thinner or increase the grain size (Grain Size), thereby improving the properties of the metal film.

[0063] In addition, the substrate processing method of the present invention selects appropriate gas to pressurize the chamber to an appropriate environment before injecting raw material gas containing elements that form a thin film while the substrate is in the chamber, and then depressurizes the chamber again, thereby reducing defects on the surface of the substrate, which has the effect of improving the thin film properties.

[0064] In addition, the substrate processing method of the present invention injects raw material gas during the process of forming a thin film of a desired thickness on the substrate to form a thin film of at least a portion of the thickness, and then temporarily stops film formation. In this state, the chamber is pressurized using a suitable gas, and then the chamber is depressurized again to improve the properties of the thin film with a portion of the thickness, and the method is repeatedly performed, thereby having the effect of improving the properties of the thin film.

[0065] In particular, the substrate processing method of the present invention effectively removes impurities present in the substrate, and thus has the advantage of improving the properties of the thin film at a relatively low temperature and low energy compared to conventional high temperature or high energy heat treatment processes. BRIEF DESCRIPTION OF THE DRAWINGS

[0066] Figure 1This is a graph schematically showing problems in conventional substrate processing.

[0067] Figure 2 It is a graph schematically showing the effect of the substrate treatment of the present invention.

[0068] Figures 3 to 5 It is a schematic diagram for explaining the substrate processing method of the present invention.

[0069] Figure 6 This is a diagram showing problems in conventional substrate processing.

[0070] Figures 7 to 9 It is a schematic diagram for illustrating a substrate processing method according to another embodiment of the present invention.

[0071] Fig.10 It is a graph for illustrating the voltage transformation step of the present invention.

[0072] Fig.11 FIG. 1 is a schematic diagram schematically showing a substrate processing apparatus for processing a substrate according to the present invention.

[0073] (Explanation of Reference Numerals)

[0074] 11: Loosely bonded impurities 12: Strongly bonded impurities

[0075] 13: Unbound impurities 20: Titanium (Ti)

[0076] 21: Nitrogen (N) 100: Substrate

[0077] 200: Oxide film 300: Gate electrode

[0078] 500: substrate processing device DETAILED DESCRIPTION

[0079] Hereinafter, the substrate processing method of the present invention will be described below with reference to the accompanying drawings.

[0080] The terms used in this specification and claims shall not be limited and interpreted according to the conventional or dictionary meanings, but shall be interpreted according to the meanings and concepts of the technical items consistent with the present invention.

[0081] The embodiments described in this specification and the structures shown in the drawings are preferred embodiments of the present invention, and do not represent all technical concepts of the present invention. Therefore, from the perspective of the present application, various equivalents and modifications that can be replaced are possible.

[0082] In the specification of the present invention, thin films formed on a semiconductor substrate may have different material types and shapes, respectively, and therefore it should be understood that a suffix called "layer" may also be added.

[0083] This is a characteristic of semiconductor technology, which is due to the use of masking and etching, diffusion, deposition, ion implantation, sputtering and other techniques of photolithography technology to manufacture semiconductor substrates of various types and shapes.

[0084] For example, this is because the thin film itself can be buried or stacked, and a structure can be manufactured with other materials buried or stacked on the substrate surface and the thin film.

[0085] Therefore, for example, "oxide film" and "oxide layer", "metal film" and "metal layer", "semiconductor" and "silicon", etc. or similar expressions are interpreted equally to each other within an appropriate range according to the technical idea of ​​the present invention, and sometimes can also be interpreted as variations.

[0086] In the specification of the present invention, the terms "chamber", "reactor", "reaction chamber", "furnace", etc. are not intended to limit specific forms or structures, but should only mean devices that perform known integrated circuit processes such as semiconductor wafer film formation and etching in a sealed space, or similar devices, and these terms may be used interchangeably depending on the circumstances.

[0087] In addition, the present invention aims to improve various surface defects occurring during the processing of semiconductor substrates, so "surface" does not only mean the surface of the semiconductor substrate, but may be the surface (surface) or interface (boundary) of a thin film formed on the semiconductor substrate depending on the circumstances.

[0088] In addition, according to the technical concept of the present invention, "surface" does not only mean the "interface" observed optically, but can also mean a predetermined depth to a thin film or semiconductor substrate. This is due to the surface treatment characteristics of the present invention, and therefore should be taken for granted throughout the entire specification of the present invention.

[0089] The substrate processing method of the present invention includes: a pressurization step of increasing the pressure in the chamber to a first pressure higher than normal pressure; a first decompression step of reducing the pressure in the chamber from the first pressure to a second pressure after the pressurization step; and a second decompression step of reducing the pressure in the chamber from the second pressure to a third pressure lower than normal pressure after the first decompression step.

[0090] In addition, the substrate processing method of the present invention may further include a pressure maintaining step of maintaining the pressure in the chamber at a second pressure for a predetermined time after the first decompression step.

[0091] In addition, the substrate processing method of the present invention may include a thin film forming step of forming a thin film before or after performing the pressurization step, the first decompression step and the second decompression step. The thin film forming step at this time will be described as various embodiments below.

[0092] The substrate processing method of the present invention is defined as a pressure changing step including a pressure increasing step, a first pressure reducing step and a second pressure reducing step.

[0093] like Figures 3 to 5 and Figures 7 to 9 As shown, the pressure changing step is a step of increasing the pressure in the chamber to a first pressure higher than normal pressure and then decreasing the pressure from the first pressure to a pressure lower than normal pressure, and can be performed by various methods.

[0094] For example, the pressure changing step is to adjust the supply of the pressurized gas to increase or decrease the pressure in the chamber, thereby controlling the pressure in the chamber. As another example, the exhaust in the chamber is adjusted to control the pressure in the chamber.

[0095] At this time, of course, the supply and exhaust volumes of the pressurized gas in the chamber may also be adjusted together to control the pressure in the chamber.

[0096] The pressure changing step can repeatedly perform the following process several times: the pressure in the chamber is changed to a first pressure higher than normal pressure, that is, the pressure in the chamber is increased to a first pressure higher than normal pressure, and then changed from the first pressure to a pressure lower than normal pressure, that is, decreased from the first pressure to a pressure lower than normal pressure.

[0097] In more detail, the pressure changing step increases the pressure in the chamber to a first pressure higher than normal pressure, then decreases it to a second pressure lower than the first pressure, and then may immediately decrease it to a third pressure lower than the second pressure and normal pressure.

[0098] In this case, various pressure ranges can be applied to the first pressure, the second pressure, and the third pressure.

[0099] As an example, the first pressure may have a value in the range of 1 atmosphere (760 Torr) to 10 atmospheres.

[0100] In addition, the second pressure may be normal pressure, that is, 1 atmosphere (760 Torr), and the third pressure may have a value within a range of 0.01 Torr to 1 atmosphere (760 Torr).

[0101] In another aspect, the pressure changing step may be performed in a chamber heated at a temperature in a range of 400 degrees Celsius to 800 degrees Celsius.

[0102] That is, the pressure changing step not only increases and decreases the pressure in the chamber, but also simultaneously heats the chamber to a temperature in the range of 400 degrees Celsius to 800 degrees Celsius to perform the pressure change, thereby actively removing impurities.

[0103] In addition, the pressure changing step takes the process of increasing the pressure in the chamber to a first pressure and then decreasing it to a third pressure lower than normal pressure as a unit cycle, and this unit cycle can be repeated N times.

[0104] That is, the pressurizing step, the first depressurizing step, and the second depressurizing step may be repeatedly performed several times.

[0105] By repeatedly performing this process, impurities or defects existing in the first thin film layer can be processed with a higher degree of completion before forming the substrate surface or the second thin film layer.

[0106] In addition, the pressure changing step may further include a pressure maintaining step of maintaining the pressure in the chamber at the second pressure for a predetermined time after the first decompression step.

[0107] The pressurization step is a step of increasing the pressure in the chamber so that the pressure in the chamber is a first pressure higher than normal pressure, more preferably a pressure in the range of 1 atmosphere to 10 atmospheres, and can be performed by various methods.

[0108] In particular, the pressurizing step increases the pressure in the chamber to a first pressure, thereby causing the pressurized gas to react with impurities on the substrate to form byproducts.

[0109] The pressurizing step can increase the pressure in the chamber to a first pressure higher than normal pressure by controlling at least one of a supply amount and an exhaust amount of the pressurized gas.

[0110] Accordingly, the pressurizing step allows the pressurized gas to penetrate not only the surface of the substrate or film but also deep into the interior, and the pressurized gas that penetrates into the surface and interior of the substrate or film reacts with impurities present in the substrate or film to form by-products.

[0111] At this time, the pressurized gas may also be any type of gas previously disclosed, and as an example may include one or more elements such as hydrogen (H), oxygen (O), nitrogen (N), chlorine (Cl), fluorine (F), etc.

[0112] More specifically, if the impurity on the substrate or the film surface is chlorine (Cl), it is advantageous to use hydrogen (H 2 ) gas as the pressurizing gas because it is reduced to hydrogen chloride (HCl) in the pressurizing step.

[0113] As an example, a pressurizing step using hydrogen gas as the pressurizing gas will be described below.

[0114] The hydrogen gas injected into the chamber due to the pressurization not only increases the density of hydrogen molecules, but also makes the activity of the hydrogen molecule gas in the chamber faster.

[0115] In particular, hydrogen is the lightest element, so it can diffuse evenly in a tortuous structure on the surface of a substrate or a film, and is therefore more likely to react with impurities on the sidewalls or bottom of a trench with a high aspect ratio, thereby facilitating the formation of by-products.

[0116] Specifically, if the chamber is pressurized using hydrogen (H2), then depending on the applied conditions, hydrogen, as a relatively light atom, can penetrate to a certain depth from the surface of the silicon lattice structure, i.e., the interior of the substrate or film, in addition to the surface of the silicon atoms (i.e., the surface of the substrate or film).

[0117] On the other hand, chlorine (Cl) as an impurity is in a weakly bonded state with silicon atoms, so if hydrogen atoms penetrate into the surface and the inside of the substrate or the thin film, they can cause a reduction reaction with chlorine (Cl).

[0118] Thus, the pressurization step can promote the reaction of chlorine (Cl) and hydrogen (H) as trace impurities remaining on the substrate or the film, thereby eventually forming hydrogen chloride (HCl) as a by-product.

[0119] As another example, in the case of a TiN thin film, if a portion of the thin film is formed, the raw material gas may be exhausted to stop the film formation, and in this state, H 2 gas may be injected into the chamber to increase the pressure of the chamber.

[0120] During the pressurization period, not only the density of hydrogen molecules in the chamber is increased, but also the activity of hydrogen molecule gas in the chamber is made faster.

[0121] Therefore, the reaction between the hydrogen molecules and the relatively weakly bonded residual chlorine (Cl) element or the relatively strongly bonded chlorine (Cl) element is further activated, and is reduced to hydrogen chloride (HCl) gas which is useful for exhaust.

[0122] On the other hand, the above-mentioned embodiment is only an example for explaining the execution process of the pressurization step, and is not limited to this gas. As long as it is a gas that can form a by-product through a reaction, any gas can be applied.

[0123] That is, the conditions or number of times of the pressure changing step, the temperature range, the type of gas element injected, etc. may depend on the type or thickness of the thin film to be formed, the type of process, etc.

[0124] The pressurizing step may include: a pressure increasing step of increasing the pressure in the chamber to a first pressure; and a high pressure maintaining step of maintaining the pressure in the chamber at the first pressure for a predetermined time after the pressure increasing step.

[0125] The pressure increasing step is a step of increasing the pressure in the chamber to a first pressure, and can increase the pressure in the chamber from normal pressure to a first pressure higher than the normal pressure set in advance.

[0126] On the other hand, as another example, in the case of repeatedly performing the entire cycle of the pressure changing step, the pressure increasing step is performed after completing the second pressure reducing step described later, and the pressure in the chamber can be increased from a low pressure lower than normal pressure to a first pressure higher than the normal pressure set in advance.

[0127] The high-pressure maintaining step, which is a step of maintaining the pressure in the chamber at the first pressure for a predetermined time after the pressure increasing step, may be performed by various methods.

[0128] The high-pressure maintaining step is a step of maintaining the pressure in a state where the pressure in the chamber is increased to a first pressure higher than normal pressure by the pressure increasing step, and the pressure can be maintained by controlling at least one of the supply amount and exhaust amount of the pressurized gas.

[0129] In this case, the high pressure maintaining step maintains the pressure in the chamber at the high pressure first pressure for a predetermined time period after the pressure increasing step, thereby allowing the pressurized gas to approach the surface of the substrate or the film and penetrate into the inside and remain active.

[0130] That is, the high-pressure maintaining step supplies a sufficient amount of pressurized gas into the chamber, fully enhancing the thermal vibration of silicon crystal atoms, and maintaining an environment in which impurities located on the substrate or film react with the pressurized gas.

[0131] Accordingly, the high pressure maintaining step can maintain the environment in the chamber so that the pressurized gas can react with the impurities to fully form by-products.

[0132] The first depressurizing step, which is a step of reducing the pressure in the chamber from the first pressure to the second pressure after the pressurizing step, may be performed by various methods.

[0133] In particular, the first decompression step, in which the pressure in the chamber is reduced from the first pressure to the second pressure to move the byproducts to the surface of the substrate or outside the substrate, can be performed by various methods.

[0134] On the other hand, in this case, of course, the by-products may also move to the surface of the film or to the outside of the film.

[0135] The first decompression step can reduce the pressure in the chamber from the first pressure to the second pressure by controlling at least one of a supply amount of the injected pressurized gas and an exhaust amount in the chamber.

[0136] As the pressure in the chamber drops rapidly, byproducts formed by the pressurization step may be directed toward the surface of the substrate or outside the substrate.

[0137] More specifically, the first decompression step may cause out-gassing as follows: by-products formed by the pressurization step and located inside the substrate or film move toward the surface of the substrate or film, while by-products located on the surface of the substrate or film may be discharged to the outside of the substrate or film.

[0138] On the other hand, the first decompression step can reduce the pressure in the chamber from the first pressure to a pre-set pressure, and the second pressure serving as the pre-set pressure at this time can be normal pressure, that is, atmospheric pressure.

[0139] More specifically, the case where the pressurized gas is hydrogen gas and the impurity is chlorine (Cl) is described as follows.

[0140] As an example, the first depressurizing step may move hydrogen chloride (HCl) as a by-product formed in the pressurizing step toward the surface of the substrate or the film and the outside of the substrate or the film through the first depressurizing step.

[0141] The pressure maintaining step, which is a step of maintaining the pressure in the chamber at the second pressure for a predetermined time after the first depressurizing step, may be performed by various methods.

[0142] For example, the pressure maintaining step may maintain the pressure in the chamber at the second pressure for a predetermined time in a state where the pressure in the chamber is reduced from the first pressure to the second pressure by the first decompression step.

[0143] At this time, the pressure maintaining step may maintain the pressure in the chamber at normal pressure or a second pressure higher than normal pressure for a predetermined time period.

[0144] The second decompression step is a step of reducing the pressure in the chamber from the second pressure to a third pressure lower than normal pressure after the first decompression step to discharge the byproducts existing in the internal space of the chamber to the outside of the chamber, and can be performed by various methods.

[0145] The second decompression step may be a step of discharging by-products to the outside of the chamber to ultimately remove impurities present on the substrate.

[0146] The second decompression step evacuates the space inside the chamber, thereby reducing the pressure inside the chamber from the second pressure to a third pressure lower than normal pressure, more preferably 0.01 Torr to 1 atmosphere (760 Torr). By reducing the pressure inside the chamber in this way, the by-products present in the chamber can be discharged to the outside of the chamber.

[0147] That is, the second decompression step evacuates the internal space so that the byproducts moved to the surface of the substrate or the film or to the outside of the substrate or the film in the first decompression step can be discharged to the outside of the chamber.

[0148] Next, an experiment for confirming the effectiveness of the voltage transformation step of the present invention will be described below.

[0149] For example, when a tungsten (W) thin film is formed by a deposition method, it is confirmed that the resistivity of the thin film is improved by about several tens of percent by repeating a partial film formation-voltage transformation process, and the withstand voltage characteristics of the thin film are improved.

[0150] In addition, when using B2H6 or SiH4 seeding and then WF2 to deposit a tungsten film, partial film formation-voltage transformation treatment is repeated, which improves the film resistivity by about tens of percentages and confirms that the film's withstand voltage characteristics are improved.

[0151] The degree of this improvement may vary depending on conditions such as temperature, degree of pressure change, application of change cycles, etc.

[0152] On the other hand, the experimental results described above are meaningful because leading-edge semiconductor products contain billions of components, so even a 1% to 2% or less improvement in characteristics can have a significant impact on productivity.

[0153] In particular, impurities in an anionic state such as Cl (chlorine) residues have an adverse effect on the threshold voltage of the transistor, which manifests itself in its impact on the operating speed and reliability, and therefore must be removed as much as possible. The effectiveness of the present invention is fully confirmed by the experimental results described above.

[0154] In addition, The TiN film with a thickness of 2000 mm was processed on a semiconductor substrate at a temperature of 430°C, and the properties of the film were tested and evaluated. The reduction rate of Cl residue in the entire film reached tens of percent, especially in the surface of the film. The resistivity of the film was also improved by about tens of percent.

[0155] The above-mentioned substrate processing method of the present invention can be performed after the film of the required thickness is completely formed, but it is also effective to perform it after a part of the film is formed within the thickness of the entire film.

[0156] This is especially true when the desired final thickness of the film is greater.

[0157] Figure 2 The effect of the substrate processing method of the present invention is idealized and shown to illustrate the impurity removal effect when the film forming process is performed four times and the voltage change step of the present invention is inserted in three cycles between each film forming process.

[0158] In addition, in another thin film experiment for confirming the effectiveness of the present invention, When a TiN film with a thickness of 1000 mm / s is subjected to the voltage transformation step of the present invention repeatedly at 400° C. to 700° C., it can be confirmed that the sheet resistance of the film is improved by several percentages to tens of percentages.

[0159] In addition, in other experiments for confirming the effectiveness of the present invention, for example, in the case of a tungsten (W) thin film or a composite thin film composed of tungsten (W) and TiN, it was confirmed that the resistivity of the thin film was significantly improved.

[0160] In addition, the voltage transformation step of the present invention not only has the effect brought about by removing impurities as described above, but also can obtain various additional effects.

[0161] For example, the pressure in the chamber is increased to a first pressure higher than normal pressure, thereby increasing the thermal vibration of silicon crystal atoms. Impurities weakly bonded to silicon surface atoms are removed through the increased thermal vibration, and recrystallization or migration of the substrate surface is promoted, thereby obtaining an annealing effect.

[0162] This recrystallization further strengthens the molecular bonding between the elements that make up the film, and even if impurities remain, they can prevent them from reacting with the substrate surface again and sticking together.

[0163] In addition, it can be flexibly utilized to planarize the surface of a bare substrate and remove some particles and dangling bonds of silicon.

[0164] On the other hand, the substrate processing method of the present invention may perform a voltage changing step before forming a thin film in the thin film forming step, during forming a thin film, or after forming the thin film.

[0165] Hereinafter, various embodiments are described with reference to the accompanying drawings, and the voltage transformation step is the same as described above, and thus the description of the voltage transformation step is omitted.

[0166] As a first embodiment of the substrate processing method of the present invention, a thin film forming step of forming a thin film on the substrate after the voltage changing step may be further included.

[0167] To help understand the substrate processing method of the first embodiment, refer to Figure 6 The following is an example of a method for forming a gate electrode of a BCAT (Buried Channel Array Transistor).

[0168] In order to manufacture the gate electrode 300 by the BCAT technique, the semiconductor substrate 100 , for example, a substrate made of silicon crystal, is etched to form a groove, and then the oxide film 200 - the gate electrode 300 layers are sequentially formed.

[0169] The gate electrode 300 is generally formed by a deposition method. In the case where TiN (titanium nitride) is used as the electrode material, a method is mainly used in which TiCl4 and N2 or NH3 raw material gases are injected into a reaction chamber where a substrate is placed to cause a deposition reaction at a high temperature.

[0170] This is N2 or NH3 gas nitriding Ti under the high temperature environment inside the chamber, and the Ti element and N element bond to form a TiN film on the substrate. After the reaction, the remaining gas is reduced to H2 or HCl for recovery.

[0171] At this time, for the discharge of the recovered gas, when the pressure of the chamber is higher than the normal pressure, the exhaust valve connected to the chamber can be opened to discharge the recovered gas naturally, or the exhaust pump can be used to discharge the recovered gas forcibly.

[0172] As described above, in the case where the gate electrode 300 is formed using the TiCl 4 gas, a trace amount of chlorine (Cl) that has not been discharged after the reduction reaction may permeate the oxide film and remain.

[0173] Furthermore, it also remains near the very thin silicon interface and can become impurities ( Figure 6 of the expansion).

[0174] In addition, in order to improve not only these impurities but also the defects on the substrate surface which exist before the formation of the TiN film or are regenerated during the formation process, the researchers of the present invention have proposed different new methods.

[0175] That is, the substrate is pre-processed in various ways and annealed before forming a desired kind of thin film.

[0176] A so-called pretreatment method by voltage change has been developed, which is as follows: a bare substrate is treated with ozone (O 3 ) and hydrogen fluoride (HF) and the like for surface oxidation and treatment, or before or after such treatment, or even without such treatment, the chamber is pressurized to a suitable gas environment and then depressurized again.

[0177] This method can effectively remove impurities or defects caused by other reasons in the silicon interface lattice.

[0178] For this purpose, the thin film forming step as a step of forming a thin film on the substrate after the voltage changing step may be performed by various methods.

[0179] The thin film forming step can form a thin film on the substrate or a previously formed thin film after repeatedly performing the voltage changing step, and can form the thin film in a state where impurities are sufficiently removed after completing the surface treatment of the substrate or the thin film, thereby enhancing its effect.

[0180] On the other hand, the thin film forming step and the pressure changing step can be performed in-situ.

[0181] That is, the thin film forming step may be performed successively to forming a thin film on the substrate in the chamber in which the pressure changing step is performed.

[0182] As another example, a substrate transfer step may be further included, wherein after the pressure changing step, the substrate is transferred to another chamber through a transport chamber connected to the chamber performing the pressure changing step.

[0183] In this case, the thin film forming step may form a thin film on the substrate in a state where the substrate is transferred to another chamber by a transfer chamber connected to the chamber performing the pressure changing step in the substrate transferring step.

[0184] That is, a thin film can be formed by transferring the substrate from the chamber performing the pressure changing step to another chamber in the same substrate processing apparatus through the transfer chamber in a vacuum state without being exposed to the atmospheric pressure alone in the state of performing the pressure changing step.

[0185] On the other hand, as another example, a substrate transporting step of transporting a substrate from the substrate processing apparatus that performs the voltage changing step to a chamber of another substrate processing apparatus after the voltage changing step may be included.

[0186] In this case, the thin film forming step may form the thin film on the substrate transported to a chamber of another substrate processing apparatus.

[0187] That is, the thin film forming step may be performed as an ex-situ method, and the substrate may be transported from the substrate processing apparatus that performs the pressure changing step to another chamber of the substrate processing apparatus, and then a thin film may be formed on the substrate.

[0188] On the other hand, as a second embodiment of the substrate processing method of the present invention, it may include: a first thin film forming step of forming a thin film on the substrate before the voltage changing step; and a second thin film forming step of forming a thin film on the substrate after the voltage changing step.

[0189] In order to help understand the substrate processing method of the second embodiment, a method of processing a semiconductor substrate after a TiN (titanium nitride) thin film is formed is exemplified.

[0190] In order to form a TiN thin film on a semiconductor substrate by a deposition method, TiCl 4 , N 2 or NH 3 raw material gas is generally injected into a reaction chamber where the semiconductor substrate is placed, and then reacted at a high temperature.

[0191] That is, in N 2 or NH 3 Ti is nitrided in the ambient environment, and the Ti element is a bonding N element, forming a TiN film on the semiconductor substrate.

[0192] The residual gas after the reaction is reduced to H2 or HCl for recovery.

[0193] At this time, for the discharge of the recovered gas, when the pressure of the chamber is higher than the normal pressure, the exhaust valve connected to the chamber can be opened to discharge the recovered gas naturally, or the recovered gas can be discharged by force using an exhaust pump.

[0194] Ideally, all Ti elements constituting the film should be bonded to N elements without residue, but even with this reduction reaction, a portion of Cl (chlorine) elements still remain weakly or strongly bonded to Ti elements, or exist alone in the TiN film, causing defects in the TiN film.

[0195] In addition, as described above, in order to improve the film defects caused by the above-mentioned various reasons, the researchers of the present invention have proposed a new method.

[0196] That is, the following method is proposed: in the process of forming a desired type of thin film, the film formation process is divided into multiple steps, and between these steps, the substrate is processed by performing intermediate processing by using a method of increasing the gas pressure in the chamber using appropriate elements while stopping the film formation and then reducing the pressure again.

[0197] To this end, the first thin film forming step is a step of forming a thin film on the substrate before performing the voltage changing step, and any thin film forming method disclosed in the past can also be used.

[0198] The second thin film forming step, which is a step of additionally forming a thin film on the substrate after the voltage changing step, can be performed by various methods.

[0199] At this time, the second thin film forming step can form the same kind of thin film as the thin film formed by the first thin film forming step. More specifically, for forming a single thin film of the same kind, a part of the thin film is formed by the first thin film forming step, and then the remaining thin film can be formed by the second thin film forming step.

[0200] Furthermore, the second thin film forming step may also form a portion of the remaining thickness of the same kind of thin film.

[0201] On the other hand, as another example, the second thin film forming step may form a thin film of a different kind from that formed in the first thin film forming step.

[0202] For example, in the formation When the film thickness is 100mm, the film is formed in four times, and each time the film is formed Furthermore, the pressure changing step proposed by the present invention can be performed between separate film forming processes.

[0203] The second thin film forming step can form a thin film on the thin film previously formed by repeatedly performing the first thin film forming step after the voltage changing step, and the thin film is formed in a state where the surface treatment of the thin film is completed and impurities are sufficiently removed, thereby enhancing its effect.

[0204] On the other hand, at least one of the first thin film forming step and the second thin film forming step may be performed in-situ with the voltage changing step.

[0205] That is, at least one of the first thin film forming step and the second thin film forming step may form a thin film on the substrate in the chamber where the pressure changing step is performed.

[0206] As another example, at least one of the first thin film forming step and the second thin film forming step may form a thin film on the substrate in another chamber via a transport chamber connected to the chamber performing the pressure changing step.

[0207] In this case, at least one of the first thin film forming step and the second thin film forming step can form a thin film on the substrate in a state of being transported to another chamber via a transfer chamber connected to the chamber performing the pressure changing step.

[0208] That is, a thin film can be formed in a vacuum state without being separately exposed to atmospheric pressure in relation to the pressure changing step by being transported from a chamber in which the pressure changing step is performed or to be performed to another chamber in the same substrate processing apparatus through a transport chamber.

[0209] In addition, as another example, at least one of the first thin film forming step and the second thin film forming step may form a thin film on the substrate in a chamber of another substrate processing apparatus separate from the substrate processing apparatus performing the voltage changing step.

[0210] In this case, at least one of the first thin film forming step and the second thin film forming step may form a thin film on a substrate transported to a chamber of another substrate processing apparatus.

[0211] That is, at least one of the first thin film forming step and the second thin film forming step can be carried out as an ex-situ method, and the substrate can be transferred from the substrate processing apparatus that performs the voltage change step to another substrate processing apparatus in an inner chamber to form a thin film on the substrate.

[0212] On the other hand, as a third embodiment of the substrate processing method of the present invention, a thin film forming step may be further included, wherein the thin film forming step forms a thin film on the substrate before the voltage changing step.

[0213] In order to help understand the substrate processing method of the third embodiment, a method of processing a semiconductor substrate after a TiN (titanium nitride) thin film is formed is exemplified.

[0214] In order to form a TiN thin film on a semiconductor substrate by a deposition method, TiCl4, N2 or NH 3 The raw material gas is injected into a reaction chamber where a semiconductor substrate is placed, and then reacts at a high temperature.

[0215] That is, Ti is nitrided in an N2 or NH3 environment, and the Ti element is bonded to the N element to form a TiN thin film on the semiconductor substrate.

[0216] The residual gas after the reaction is reduced to H2 or HCl for recovery.

[0217] At this time, for the discharge of the recovered gas, when the pressure of the chamber is higher than the normal pressure, the exhaust valve connected to the chamber can be opened to discharge the recovered gas naturally, or the recovered gas can be discharged by force using an exhaust pump.

[0218] Ideally, all Ti elements constituting the film should be bonded to N elements without residue, but even with this reduction reaction, a portion of Cl (chlorine) elements still remain weakly or strongly bonded to Ti elements, or exist alone in the TiN film, causing defects in the TiN film.

[0219] As described above, in order to improve the film defects caused by the above-mentioned various reasons, the researchers of the present invention proposed a new method.

[0220] That is, the method is as follows: once a desired type of thin film is formed, the gas in the chamber is exhausted, and after appropriate exhaust or before exhaust, such as Figure 1 The substrate processing is shown to be performed by selecting and using a suitable gas to increase the gas pressure in the chamber and then reducing the pressure again as a subsequent process in a so-called pressure change step.

[0221] Therefore, the thin film forming step can be a step of forming a thin film on the substrate before performing the above-mentioned voltage changing step, and any thin film forming method disclosed in the past can also be used.

[0222] The thin film forming step is followed by repeated voltage changing steps to complete the surface treatment of the substrate or the thin film, thereby fully removing impurities and enhancing the effect thereof, thereby improving the properties of the thin film.

[0223] On the other hand, the thin film forming step and the pressure changing step can be performed in-situ.

[0224] That is, the thin film forming step may form a thin film on the substrate in the same chamber as the chamber in which the voltage changing step is performed, and the voltage changing step may be performed successively.

[0225] As another example, the method may further include a substrate conveying step of conveying the substrate to another chamber that performs the pressure changing step through a transport chamber connected to the chamber that performs the thin film forming step after the thin film forming step.

[0226] In this case, the thin film forming step can be performed by transporting the film through a transfer chamber connected to a chamber performing the pressure changing step to a chamber performing the pressure changing step after the thin film is formed.

[0227] That is, the substrate does not need to be exposed to the atmospheric pressure alone in the state of performing the thin film forming step, but can be transported to another chamber in the same substrate processing apparatus where the pressure changing step is to be performed through the transport chamber in a vacuum state.

[0228] On the other hand, as another example, a substrate transporting step of transporting a substrate from another substrate processing apparatus performing the thin film forming step to a chamber of a substrate processing apparatus performing the voltage changing step after the thin film forming step may be further included.

[0229] In this case, the thin film forming step may form the thin film on the substrate in a chamber of another substrate processing apparatus separate from the substrate processing apparatus performing the voltage changing step.

[0230] That is, the thin film forming step is performed as an ex-situ method, and the substrate is transferred from a substrate processing apparatus for performing the thin film forming step to a chamber in another substrate processing apparatus, and the pressure changing step can be performed in the film.

[0231] On the other hand, the film of the present invention contains non-metallic elements or metallic elements, and is a film composed of a single element, a film composed of two or more elements, or a film composite of different types of films, etc., and can also be applied to any type of film previously disclosed.

[0232] More specifically, the thin film may have various structures such as a metallic oxide film, a metal nitride, a metal oxynitride, silicon oxide, silicon nitride, silicon oxynitride, a metal film, a single-layer film, a composite film, a double-layer film, and the like.

[0233] In addition, the thin film may constitute at least a part of a gate insulating film of a transistor.

[0234] In addition, the thin film may include at least one of a metal element, a Group 4 element, nitrogen, and oxygen.

[0235] Furthermore, the thin film may include at least one of titanium (Ti), tungsten (W), tantalum (Ta), and molybdenum (Mo).

[0236] For a substrate processing apparatus for executing the substrate processing method as described above, please refer to the attached Fig.11 The details are described below.

[0237] like Fig.11 As shown, a substrate processing device 500 for executing the substrate processing method of the present invention may include: a chamber 510; a gas supply tool 520 for supplying pressurized gas into the chamber 510; an exhaust tool 530 for exhausting or pumping gas in the chamber 510; and a controller 540 for controlling the gas supply tool 520 and the exhaust tool 530 to adjust the pressure in the chamber 510.

[0238] The chamber 510 may be a single-wafer device that processes a single substrate each time. The substrate processing device 500 may include at least one chamber and a transport module, a load lock chamber, and may be applicable to various embodiments such as a serial method and a cluster method.

[0239] In addition, the chamber 510 may be a batch type chamber for processing a plurality of substrates at a time, which means that the substrate processing apparatus includes at least one batch type vertical chamber, and may include a transport module and a loading port.

[0240] The gas supply tool 520 is connected to the chamber 510 through a supply line 524 to supply pressurized gas into the chamber 510 , and may have various structures.

[0241] For example, the gas supply tool 520 may include: a storage device 521 for storing required pressurized gas; a booster pump 522 for supplying the pressurized gas stored in the storage device 521 to the chamber 510 ; and a gas supply regulating valve 523 .

[0242] The exhaust tool 530 is connected to the chamber 510 through an exhaust line 534 to exhaust or pump gas from the chamber 510 , and may have various structures.

[0243] For example, the exhaust tool 530 may include: an exhaust pump 532 for exhausting the chamber 510 ; and an exhaust regulating valve 533 for regulating the exhaust volume in the chamber 510 .

[0244] The controller 540 can control the air supply pump 522 or the air supply regulating valve 523 to adjust the air extraction related items when supplying the pressurized gas and whether the valve is opened or closed, the degree of opening and closing, and the opening and closing time.

[0245] In addition, the controller 540 controls the exhaust pump 532 or the exhaust regulating valve 533 to adjust the exhaust-related items and whether the valve is opened or closed, the degree of opening and closing, and the opening and closing time during exhaust.

[0246] Sometimes, in order to utilize the natural exhaust method, the exhaust pump 532 or the exhaust regulating valve 533 may not be manually adjusted during exhaust, and the exhaust pump may not be required.

[0247] In addition, the controller 540 may include pre-set values ​​or pre-set programs for the air supply tool 520 and the air exhaust tool 530 .

[0248] For example, the operating time of various pumps, whether various valves are switched on or off, the switching time, the switching degree, etc. can be stored in numerical form, and a binary program can be stored, so that appropriate control can be performed based on these numerical values.

[0249] The above-mentioned substrate processing method of the present invention also has the following effects.

[0250] Among the various advantages of the present invention, the use of hydrogen, the lightest element, in a voltage-switching manner is particularly advantageous for the manufacture of semiconductor devices with three-dimensional structures.

[0251] Light hydrogen molecules can easily penetrate the interior of trenches with large aspect ratios, and the process of increasing or decreasing pressure applies the same pressure regardless of the depth or height of the structure of the element formed on the semiconductor substrate, which is particularly beneficial for the manufacture of semiconductor elements with three-dimensional structures.

[0252] Another advantage of the present invention is that the type of gas used for pressurization can be selected according to the state of the contaminants in the membrane.

[0253] For example, not only hydrogen but also other elements such as oxygen can be used.

[0254] Depending on the types of impurities known, any element that undergoes a reduction reaction with the impurities and helps remove the impurities can be applied to the voltage-variable annealing of the present invention.

[0255] Another of the various advantages of the present invention is that it allows for a more vertical entry and exit of pressurized gas for use in a pressure swing process.

[0256] This advantage is very important. Usually, during the pretreatment process, the pretreatment gas tends to flow horizontally, and the pretreatment effect tends to be gradually transferred from the film surface to the inside of the film, so the pretreatment effect of the deep bottom surface and the shallow bottom surface of the groove with a large aspect ratio may be different.

[0257] However, the present invention has the following advantages: due to the effect of voltage variation, the annealing effect in the vertical direction of the film becomes uniform, and the annealing quality of the deep bottom surface of the groove is also more uniform, thereby minimizing the dispersion of the annealing quality of the entire film.

[0258] Another advantage of the present invention is that it further activates the thermal vibration of the thin film elements, promotes the recrystallization of the thin film elements, and preferably changes the grain size of the crystal in the process, thereby improving electrical and physical properties such as leakage current and resistivity.

[0259] The above is only a partial description of the preferred embodiments that can be implemented by the present invention. Therefore, it is well known that the scope of the present invention cannot be limited to the above embodiments, and the technical ideas of the present invention described above and its fundamental technical ideas should all be included in the scope of the present invention.

Claims

1. A substrate processing method, characterized in that: include: a pressurizing step of increasing the pressure in the chamber to a first pressure higher than normal pressure; a first depressurizing step, after the pressurizing step, reducing the pressure in the chamber from the first pressure to a second pressure; The second decompression step is performed after the first decompression step, to reduce the pressure in the chamber from the second pressure to a third pressure lower than normal pressure.

2. The substrate processing method according to claim 1, characterized in that: The pressurizing step, the first depressurizing step, and the second depressurizing step are repeatedly performed several times.

3. The substrate processing method according to claim 1, characterized in that: The pressurization step comprises: a pressure increasing step of increasing the pressure in the chamber to the first pressure; A high-pressure maintaining step is performed after the pressure increasing step, maintaining the pressure in the chamber at the first pressure for a predetermined time.

4. The substrate processing method according to claim 1, characterized in that: The pressurization step is: increasing the pressure in the chamber to the first pressure, thereby bonding the pressurized gas with impurities on the substrate to form byproducts; The first decompression step is: reducing the pressure in the chamber from the first pressure to the second pressure, thereby moving the byproducts toward the surface of the substrate or outside the substrate; The second decompression step is: The pressure in the chamber is reduced from the second pressure to the third pressure which is lower than normal pressure, and the byproducts existing in the internal space of the chamber are discharged to the outside of the chamber.

5. The substrate processing method according to claim 1, characterized in that: The second pressure is normal pressure.

6. The substrate processing method according to claim 1, characterized in that: Also includes: A pressure maintaining step of maintaining the pressure in the chamber at the second pressure for a predetermined time after the first depressurizing step.

7. The substrate processing method according to claim 1, characterized in that: Also includes: The thin film forming step is to form a thin film on the substrate after the second decompression step.

8. The substrate processing method according to claim 1, characterized in that: Also includes: A thin film forming step of forming a thin film on a substrate; The thin film forming step includes: a first thin film forming step of forming a thin film on the substrate before the pressurizing step; The second thin film forming step is to further form a thin film on the substrate after the second decompression step.

9. The substrate processing method according to claim 8, characterized in that: The first thin film forming step and the second thin film forming step form thin films of the same type or different types.

10. The substrate processing method according to claim 8, characterized in that: forming a single-layer film on the substrate through the first thin film forming step and the second thin film forming step; The first thin film forming step is to form a portion of the thickness of the single layer film, The second thin film forming step is to form a part or all of the remaining thickness of the single layer film.

11. The substrate processing method according to claim 1, characterized in that: include: The thin film forming step is to form a thin film on the substrate before the pressurizing step.

12. The substrate processing method according to any one of claims 8 to 11, characterized in that: The thin film forming step is: A thin film is formed on the substrate in the chamber in which the pressurizing step, the first depressurizing step, and the second depressurizing step are performed.

13. The substrate processing method according to any one of claims 8 to 11, characterized in that: The thin film forming step is: A thin film is formed on the substrate in another chamber by the chamber and the transport chamber performing the pressurizing step, the first depressurizing step, and the second depressurizing step.

14. The substrate processing method according to any one of claims 8 to 11, characterized in that: The thin film forming step is: A thin film is formed on the substrate in a chamber of a substrate processing apparatus that is separate from the chamber of the substrate processing apparatus that performs the pressurizing step, the first depressurizing step, and the second depressurizing step.

15. The substrate processing method according to any one of claims 8 to 11, characterized in that: The thin film constitutes at least a part of a gate insulating film of a transistor.

16. The substrate processing method according to any one of claims 8 to 11, characterized in that: The thin film includes at least one of a metal element, a Group 4 element, nitrogen, and oxygen.

17. The substrate processing method according to any one of claims 8 to 11, characterized in that: The thin film contains a non-metallic element or a metallic element, and is a film composed of a single element, a film composed of two or more elements, or a composite of films of different types.

18. The substrate processing method according to any one of claims 1 to 11, characterized in that: The pressurization step is: Utilizes a gas containing one or more elements of hydrogen, oxygen, nitrogen, chlorine, and fluorine.

19. The substrate processing method according to any one of claims 1 to 11, characterized in that: The chamber is, Single-wafer method that processes a single substrate each time or batch method that processes multiple substrates simultaneously each time.

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