Method for forming a film, apparatus for forming a film, and method for manufacturing an article

Abstract

To provide a film formation method advantageous for both of defect suppression and throughput.SOLUTION: A film formation method comprises: an arrangement step of discretely arranging a plurality of droplets of a curable composition containing a polymerizable compound being a non-volatile component and a solvent being a volatile component on a substrate; an analysis step of analyzing an image obtained by imaging a process of formation of a continuous liquid film on the substrate by connecting each of the plurality of droplets with the adjacent droplets on the substrate after the arrangement step; and a formation step of forming a cured film by curing the liquid film. When the analysis result obtained in the analysis step satisfies a prescribed condition indicating that the formation state of the liquid film is sufficient, the step shifts to the formation step.SELECTED DRAWING: Figure 3

Description

Technical Field

[0001] The present invention relates to a film forming method, a film forming apparatus, and an article manufacturing method.

Background Art

[0002] As the demand for miniaturization of semiconductor devices progresses, in addition to conventional photolithography techniques, a microfabrication technique that forms a pattern of a composition on a substrate by molding and curing an uncured composition on the substrate with a mold has attracted attention. Such a technique is called an imprint technique and can form a fine pattern on the order of several nanometers on a substrate.

[0003] As one of the imprint techniques, for example, there is a photo-curing method. An imprint apparatus employing the photo-curing method forms a pattern on a substrate by molding a photo-curable composition supplied to a shot region on the substrate with a mold, irradiating light to cure the composition, and separating the mold from the cured composition.

[0004] Patent Document 1 discloses an imprint method using a composition containing a solvent and a polymerizable material. This imprint method includes a step of bonding the compositions supplied on the substrate to form a liquid film on the substrate surface, a step of evaporating the solvent from the composition, and a step of polymerizing the polymerizable material in the composition to form a cured film.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] In the method described in Patent Document 1, when moving to the step of volatilizing the solvent in a state where the formation of the liquid film is insufficient, an air gap remains between the compositions, and the formed on the substrate solidDefects occur in the body layer. To address this problem, one possible approach is to wait for a predetermined time sufficient for such an air-gap-free liquid film to form, and then proceed to a step where the solvent is evaporated. However, if the liquid film formation is completed within that time, waiting for a certain period of time will reduce throughput.

[0007] The present invention provides, for example, a film formation method that is advantageous in achieving both defect suppression and throughput. [Means for solving the problem]

[0008] According to one aspect of the present invention, the present invention comprises a placement step of discretely arranging a plurality of droplets of a curable composition containing a polymerizable compound, which is a non-volatile component, and a solvent, which is a volatile component, on a substrate, and an analysis step of analyzing images obtained by imaging the process after the placement step in which each of the plurality of droplets combines with adjacent droplets on the substrate to form a continuous liquid film on the substrate, A volatilization step is performed to enhance the solvent volatilization effect compared to the process in which the liquid film is formed, thereby volatilizing the solvent contained in the liquid film. The process includes a forming step of curing the liquid film to form a cured film, and when the analysis results obtained in the analysis step satisfy predetermined conditions indicating that the liquid film is sufficiently formed, The process then proceeds to the volatilization step, and thereafter, A film formation method is provided, characterized by proceeding to the aforementioned formation step. [Effects of the Invention]

[0009] According to the present invention, for example, it is possible to provide a film formation method that is advantageous in achieving both defect suppression and throughput. [Brief explanation of the drawing]

[0010] [Figure 1] A diagram showing the configuration of the film forming apparatus according to the first embodiment. [Figure 2] A flowchart of the film formation method according to the first embodiment. [Figure 3] A diagram illustrating the process of liquid film formation. [Figure 4] A diagram showing the composition arranged on a substrate. [Figure 5]A diagram showing an example of the signal intensity distribution in the liquid film formation process. [Figure 6] A diagram showing an example of the frequency analysis result of the signal intensity distribution. [Figure 7] A diagram showing the configuration of the liquid film formation part according to the third embodiment. [Figure 8] A flowchart of the film formation method according to the fourth embodiment. [Figure 9] A diagram showing a state where an unbonded part of the composition has occurred. [Figure 10] A diagram showing an example of the detected unbonded part. [Figure 11] A flowchart of the film formation method according to the eighth embodiment. [Figure 12] A diagram explaining the outline of the planarization process. [Figure 13] A diagram explaining the article manufacturing method.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. Note that the following embodiments do not limit the invention according to the claims. Although a plurality of features are described in the embodiments, not all of these plurality of features are essential for the invention, and the plurality of features may be arbitrarily combined. Further, in the accompanying drawings, the same or similar configurations are given the same reference numerals, and redundant explanations are omitted.

[0012] <First Embodiment> Hereinafter, the film forming apparatus in the embodiment will be described. The film forming apparatus is used for manufacturing devices such as semiconductor devices as articles, arranges an uncured composition on a substrate, forms the arranged composition with a mold, and forms a film of the composition on the substrate. In the present embodiment, the film forming apparatus may be a film forming apparatus that employs a photocuring method. Since the photocuring method is employed, the composition is a photocurable moldable material.

[0013] When considering equipment for mass production of semiconductor devices and the like, pattern transfer methods and apparatus that apply imprint lithography using photocuring are known. The photocuring imprint method is generally carried out as follows: First, a composition that hardens with ultraviolet light is supplied to the shot area on the wafer, which is the target of the imprint, using a supply mechanism (dispenser) such as an inkjet nozzle. Then, a mold on which the device pattern is drawn is brought into contact with the composition. Once the composition has sufficiently penetrated into the pattern of the mold, light (ultraviolet (UV)) is irradiated to harden the composition. After that, the mold is separated from the composition. This makes it possible to form a fine pattern with good line width variation on the wafer. Therefore, in one example, film formation apparatus 1 may be an imprint apparatus that transfers the pattern of the above-described mold to a composition on a substrate.

[0014] In EUV photolithography processes, the depth of focus (DOF) of the projected image of fine circuit patterns has been becoming increasingly shallower recently due to the increase in numerical aperture (NA). In recent examples, the allowable DOF for an EUV lithography system with NA=0.33 is said to be 300-110 nm (depending on the illumination mode). The allowable DOF for an EUV lithography system with NA=0.55 is said to be 160-40 nm (depending on the illumination mode). However, it has been found that it is difficult to obtain sufficient surface planarization performance to fall within such allowable ranges using conventional spin coater methods for applying SOC films. In particular, with spin coating, a uniform film thickness layer is created on the wafer by the viscosity of the SOC coating agent dropped onto the wafer and the centrifugal force due to the spin. Therefore, if there are areas with long-period changes in the wiring density of the underlying pattern of the process wafer that are 5 μm or more, the boundaries of the changes in wiring density will be raised and appear on the surface of the SOC film.

[0015] Therefore, in recent years, a planarization method applying the above-described imprint technology has been studied. In this method, a super straight, which is a member without a pattern formed thereon, is pressed against a liquid composition supplied onto a wafer. When the spread of the composition has reached everywhere, UV exposure is performed to cure the composition, and then the super straight is separated. The term "imprint" is often used in the concept of transferring by pressing a pattern drawn on a mold, but in the planarization process, no pattern is drawn on the super straight.

[0016] Referring to FIG. 12, an outline of the planarization process using the imprint technology by the photocuring method will be described. In the planarization process using the imprint technology by the photocuring method, the substrate (wafer) can be planarized through the supply process of FIG. 12(a), the contact process of FIG. 12(b), the curing process of FIG. 12(c), and the mold separation process of FIG. 12(d). In FIG. 12, a circuit pattern has already been formed on the surface of the substrate W chucked by the substrate chuck C, and for example, unevenness due to a pattern of about 80 to 100 nm may exist. The requirement for planarization in this embodiment is to planarize the surface unevenness due to this pattern.

[0017] In the supply process shown in Figure 12(a), composition ML as a planarizing material is supplied from dispenser DP to the surface of substrate W, which is chucked by substrate chuck C. Dispenser DP is positioned on a bridge (not shown) suspended on a base plate that also serves as a guide in the Z direction for the substrate stage holding the substrate chuck C. Composition ML is supplied to the entire surface of the substrate by scanning substrate 2, which is chucked by substrate chuck C, once or multiple times under dispenser DP. Dispenser DP may be a jetting module that supplies composition ML in droplet form. Dispenser DP can supply composition ML with a distribution in the amount supplied, depending on the arrangement of uneven patterns formed on the surface of substrate W. Specifically, composition ML can be supplied such that the droplet density is high in areas with a high ratio of recesses in the pattern on the substrate surface, and low in areas with a low ratio. Therefore, when supplying composition ML by dispenser DP, substrate alignment measurement may be performed to align the position of the pattern pre-formed on substrate 2 with the density pattern of the composition ML to be supplied.

[0018] In the contact process shown in Figure 12(b), a superstraight SS (also called a "planar template"), which is a component with an outer diameter equal to or greater than that of the substrate W and has a flat surface without a pattern formed on it, comes into contact with the composition ML, and the superstraight SS is pressed against the entire surface of the substrate W. As a result, the composition ML spreads in layers (hereinafter referred to as "filling" or "spreading").

[0019] In the curing process shown in Figure 12(c), while the Super Straight SS is in contact with the composition ML on the substrate W, ultraviolet light from the light source IL is irradiated over the entire surface of the substrate W (either as repeated partial exposures). This causes the layered composition ML to harden.

[0020] In the demolding step shown in Figure 12(d), the Super Straight SS is separated from the cured composition ML on the substrate W. In this way, the surface irregularities of the substrate W caused by the pattern are flattened. Note that the purpose here is not to correct the flatness of low spatial frequency components such as the distortion of the overall substrate profile relative to the absolute plane. Such components are compensated for by the focus tracking control of the exposure apparatus in the subsequent pattern formation step.

[0021] Thus, the planarization process using imprint technology is a technique that achieves nano-order planarization by supplying a composition according to the step height of the substrate, contacting the supplied composition with a flat, thin material called a superstraight, and curing the composition. However, the use of a superstraight is not essential in the planarization process. If a solvent is added to the composition, planarization may be achieved without using a superstraight. Therefore, there may also be a type of planarization process in which the composition is allowed to spread naturally and planarize without contacting it with a superstraight, and then the composition is cured.

[0022] Therefore, in one example, the film formation apparatus can be a planarization apparatus that utilizes imprint technology. In the following explanation, the film formation apparatus will be described as a planarization apparatus as a specific example.

[0023] Figure 1 is a schematic diagram showing the configuration of the film forming apparatus 1 according to this embodiment. In the attached drawing, the Z axis is taken in the vertical direction, and the X and Y axes are taken in a plane perpendicular to the Z axis and are perpendicular to each other. In the following, the directions parallel to the X, Y, and Z axes will be referred to as the X direction, Y direction, and Z direction, respectively.

[0024] In Figure 1, the film forming apparatus 1 may comprise a composition placement unit 2, a liquid film forming unit 3, a composition curing unit 4, and a control unit 5. The substrate 6 is transported to the composition placement unit 2, the liquid film forming unit 3, and the composition curing unit 4, respectively, by a transport device (not shown). The composition placement unit 2, the liquid film forming unit 3, and the composition curing unit 4 may each be housed in separate chambers, or they may be housed in a single chamber.

[0025] The composition placement unit 2 includes a substrate stage 7 that holds and moves the substrate 6 (wafer), and a placement unit 8 (dispenser) that places the composition on the substrate 6 in droplet form. The placement unit 8 can place the composition 9, which includes a solvent and a polymerizable material, on the substrate 6 while moving in the XY direction. Alternatively, the substrate stage 7 may move the substrate 6 in the XY direction while the placement unit 8 places the composition 9 on the substrate 6. This places the composition 9 on the substrate 6.

[0026] The composition is a curable composition that hardens when curing energy is applied. The curing energy can be electromagnetic waves, heat, etc. Electromagnetic waves may be, for example, light selected from a wavelength range of 10 nm to 1 mm, such as infrared rays, visible light, ultraviolet rays, etc. The curable composition may harden by irradiation with light or by heating. Of these, the photocurable composition that hardens by irradiation with light contains at least a polymerizable compound and a photopolymerization initiator, and may further contain a non-polymerizable compound or solvent as needed. The non-polymerizable compound is at least one selected from the group consisting of sensitizers, hydrogen donors, internal release agents, surfactants, antioxidants, polymer components, etc. The viscosity of the curable composition (viscosity at 25°C) may be, for example, 1 mPa·s to 100 mPa·s. Substrate materials may include, for example, glass, ceramics, metals, semiconductors, resins, etc. If necessary, a component made of a material other than the substrate may be provided on the surface of the substrate. The substrates are, for example, silicon wafers, compound semiconductor wafers, and quartz glass.

[0027] In this embodiment, composition 9 is a curable composition that hardens when irradiated with light of a specific wavelength. The curable composition contains at least a polymerizable compound, which is a non-volatile component, and a solvent, which is a volatile component. The solvent is a solvent in which the polymerizable compound dissolves. Examples of such solvents include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, and nitrogen-containing solvents. In this specification, a cured film means a film obtained by polymerizing and curing composition 9 on a substrate.

[0028] The liquid film forming unit 3 includes a substrate stage 10 that holds and moves the substrate 6, a gas supply port 12 that supplies gas to the space above the substrate 6 within the liquid film forming unit 3, and a gas outlet 13 that discharges gas from within the liquid film forming unit 3. Furthermore, the liquid film forming unit 3 includes a gas control unit 14 that controls the gas supply port 12 and the gas outlet 13. In the liquid film forming unit 3, an opening 11 is formed at the top of the substrate stage 10. Above the opening 11, a light source unit 15 for illuminating the substrate 6, an imaging unit 16 for observing the state of the liquid film on the substrate 6, and an optical system 17 are arranged. The optical system 17 irradiates the substrate 6 placed on the substrate stage 10 with light from the light source unit 15 and guides the reflected light from the substrate 6 to the imaging unit 16. For example, an LED or a VCSEL (Vertical Cavity Emitting Laser) may be used for the light source unit 15, but other light source devices may also be used. The imaging unit 16 may use, for example, a CCD camera or a CMOS camera, but other imaging devices may also be used. Light emitted from the light source unit 15 is directed towards the aperture 11 via the optical system 17. The light emitted from the light source unit 15 is of a wavelength that does not harden the composition 9, and the lower part of the aperture 11 is sealed with a cover glass 18 that transmits this light. In the liquid film forming unit 3, the imaging unit 16 observes the liquid film formation state of the composition 9 on the substrate 6.

[0029] The composition curing unit 4 includes a substrate stage 19 that holds and moves the substrate 6, a mold 21 (super straight, planarization plate) that is brought into contact with the liquid film 20 on the substrate 6, a mold holding unit 22 that holds the mold 21, and an irradiation unit 23 that irradiates light to cure the composition 9. The irradiation unit 23 may include a light source. The light source may consist of lamps such as mercury lamps, but is not limited to a specific light source as long as it is a light source that transmits light through the mold 21 and emits light of a wavelength that cures the composition 9. The mold 21 is made of a material that transmits light irradiated from the irradiation unit 23. The mold holding unit 22 holds the mold 21 by adsorption. By irradiating light from the irradiation unit 23 with the mold 21 (flat surface of the mold 21) in contact with the liquid film 20 on the substrate 6, the liquid film 20 on the substrate 6 can be cured to form a cured film (planarization film).

[0030] The control unit 5 can control the entire film forming apparatus 1. Specifically, the control unit 5 controls the transport device (not shown), the placement unit 8, the light source 15, the imaging unit 16, the gas control unit 14, the mold holding unit 22, the irradiation unit 23, and the substrate stages 7, 10, and 19. The control unit 5 can also function as a processing unit for analyzing images obtained by imaging. The control unit 5 may be composed of a general-purpose or dedicated computer with a program installed, or a combination of all or part of these.

[0031] Each of the board stages 7, 10, and 19 is equipped with a chuck (vacuum chuck or electrostatic chuck) not shown, which can be used to secure the board 6.

[0032] The film formation method using the film formation apparatus 1 will be explained with reference to the flowchart in Figure 2. Step S101 is a placement step in which the composition 9 is placed on the substrate 6. The substrate 6, which has been transported to the composition placement section 2 by the transport device, is placed on the substrate stage 7 and fixed by a chuck. The control unit 5 controls the placement section 8 to discretely place the composition 9 on the substrate 6. The substrate 6 on which the composition 9 has been placed is transported out of the composition placement section 2 by the transport device.

[0033] Step S102 is a step in which a liquid film is formed on the substrate. Step S102 is also an analysis step in which images obtained by the imaging unit 16 are captured of the process in which a continuous liquid film is formed on the substrate 6 by the merging of multiple droplets of composition 9 with adjacent droplets on the substrate 6, and the images are analyzed. The substrate 6 on which the composition 9 is placed is transported to the liquid film forming unit 3 by a transport device, placed on the substrate stage 10, and fixed by a chuck. Multiple droplets of composition 9, which are discretely placed on the substrate 6 by the placement unit 8, begin to spread on the surface of the substrate 6 immediately after being placed on the substrate. Figure 3 is a diagram showing the spread of multiple droplets of composition 9 on the surface of the substrate 6. Initially, multiple droplets of composition 9, which are discretely placed, begin to spread on the substrate 6. As the spread of multiple droplets of composition 9 progresses, adjacent droplets merge with each other, and finally, the spaces between the composition 24 (between droplets) are filled, and a liquid film 20 is formed. By filling the gaps between the compositions 24 before the process of forming the cured film, which will be explained later, the occurrence of defects on the cured film can be suppressed.

[0034] On the other hand, since the solvent contained in composition 9 begins to volatilize immediately after composition 9 is placed on the substrate 6, the viscosity of composition 9 increases over time, and the rate at which it spreads on the substrate 6 slows down. For this reason, a process to suppress the volatilization of the solvent may be added in the liquid film formation step S102. In one example, after the placement step, the control unit 5 controls the gas control unit 14 to supply solvent vapor from the gas supply port 12 to the space above the substrate 6 so as to suppress the volatilization of the solvent contained in composition 9 (liquid film 20) (first supply step). This makes it possible to suppress the rate of solvent volatilization.

[0035] Furthermore, in step S102, the formation state of the liquid film by composition 9 is observed using the imaging unit 16. The control unit 5 performs image analysis on the image data obtained by the imaging unit 16. Then, in S103, the control unit 5 determines whether the liquid film 20 has been formed by determining whether the results of the image analysis satisfy predetermined conditions (hereinafter referred to as "formation conditions") that indicate that the liquid film has been sufficiently formed.

[0036] Referring to Figures 4 and 5, examples of image analysis in S102 and determination processing in S103 will be explained. Figure 4 shows an example of compositions 9 discretely arranged on a substrate 6, and Figure 5 shows the signal intensity distributions 26, 27, and 28 of the image data at the positions of the straight line 25 in Figure 4. The image data obtained by the imaging unit 16 may include signal intensity distributions due to the characteristics of the substrate 6, light source unit 15, optical system 17, and imaging unit 16. Therefore, the signal intensity distributions 26, 27, and 28 are obtained by subtracting the signal intensity distribution of the substrate 6 before the arrangement of the compositions 9, which has been acquired in advance. The measurement of the signal intensity distribution before the arrangement of the compositions 9 may be performed on the same substrate 6, or on a different substrate that has undergone similar processing.

[0037] At the placement position 29 of composition 9, the illuminance decreases because some of the light emitted from the light source 15 is absorbed by composition 9, and the illuminance decreases even further on the side surface of composition 9 because the amount of light reflected toward the imaging unit 16 is small. As composition 9 spreads on the substrate 6, the exposed surface of the substrate 6 between the discretely placed composition 9 becomes narrower, and the signal intensity distribution 26 changes as shown in signal intensity distribution 27. Furthermore, when a liquid film 20 is formed by composition 9, the exposed portion of the substrate 6 surface disappears, the illuminance of the areas where composition 9 is not placed decreases, and the signal intensity distribution 27 changes as shown in signal intensity distribution 28. The control unit 5 can determine that a liquid film 20 has been formed at the position of the straight line 25 when the signal intensity 31 within the liquid film formation region 30 of the signal intensity distribution 28 falls below a predetermined threshold. In one example, the "formation condition" described above can be that the signal intensity 31 obtained from the image data obtained by the imaging unit 16 falls below a predetermined threshold within all liquid film formation regions 30 on the substrate 6. If the analysis results satisfy the formation conditions, that is, if the signal intensity 31 falls below a predetermined threshold in all liquid film formation regions 30 on the substrate 6, the control unit 5 determines that a liquid film 20 has been formed on the substrate 6, and the process proceeds to step S104. Examples of actions to be taken when the analysis results do not satisfy the formation conditions will be described in the fourth embodiment and subsequent embodiments.

[0038] Step S104 is a volatilization step in which the solvent contained in the liquid film 20 is volatilized by enhancing the volatilization effect of the solvent compared to the process in S102 in which composition 9 (liquid film 20) is formed. This volatilization step may also be understood as a waiting step in which the system waits for a predetermined time to allow the solvent contained in the liquid film 20 to volatilize. However, during the waiting period, environmental adjustments are made to enhance the volatilization effect of the solvent compared to the process in S102 in which composition 9 (liquid film 20) is formed. In one example, the control unit 5 stops the supply of solvent vapor from the gas supply port 12, which was performed as the first supply step, before the start of the volatilization step. That is, it stops the treatment to suppress the volatilization of the solvent contained in the liquid film 20. As a result, in the volatilization step of S104, the volatilization effect of the solvent contained in the liquid film 20 is enhanced compared to the process in which the liquid film 20 is formed. During the volatilization process, the control unit 5 may control the gas control unit 14 to supply clean dry air (CDA) from the gas supply port 12 to the space above the substrate in order to further enhance the volatilization effect of the solvent (second supply process). At this time, the gas inside the liquid film forming section 3 may also be exhausted from the exhaust port 13. Alternatively, the inside of the liquid film forming section 3 may be depressurized and baked. After that, the substrate 6 is transported out of the liquid film forming section 3 by a transport device. Note that the gas supplied to the space above the substrate is not limited to CDA. For example, a gas selected from CDA, oxygen, nitrogen, helium, etc. may be supplied. The supply of these gases promotes the filling of the composition into the unbonded areas.

[0039] Step S105 is a forming step in which the liquid film 20 formed on the substrate 6 is cured to form a cured film. The substrate 6, on which the liquid film 20 has been formed in the liquid film forming section 3, is transported to the composition curing section 4 by a transport device, placed on the substrate stage 19, and fixed by a chuck. The control unit 5 drives at least one of the mold holding section 22 and the substrate stage 19 to bring the liquid film 20 on the substrate 6 into contact with the mold 21 (or its flat surface). With the liquid film 20 and the mold 21 in contact, the control unit 5 irradiates light with the irradiation section 23 to cure the composition 9. This forms a cured film on the substrate 6. solid A layer is formed. A hardened film ( solidAfter the body layer is formed, the control unit 5 separates the cured film from the mold 21 by driving at least one of the mold holding unit 22 and the substrate stage 19. If the composition curing unit 4 is of a type that performs planarization without using the mold 21, the control unit 5 waits for the composition 9 to spread naturally and become planar, and then the control unit 5 cures the composition 9 by irradiating it with light using the irradiation unit 23.

[0040] As described above, in the film forming apparatus 1 of this embodiment, the imaging unit 16 detects the liquid film formation state on the substrate 6 during the liquid film formation process, and the apparatus moves to the volatilization process at an appropriate timing according to the detected liquid film formation state. According to this embodiment, since the apparatus can move to the volatilization process at the timing when the formation of the liquid film is confirmed, it is advantageous in terms of throughput compared to the conventional example in which the apparatus waits for a predetermined time regardless of the liquid film formation state before moving to the volatilization process. Note that the volatilization of the solvent contained in the composition 9 begins immediately after the composition 9 is placed on the substrate 6. If it is known that the volatilization will be completed within the period of process S102, it is not necessary to include a volatilization process as S104. In that case, the apparatus may move to the formation process instead of the waiting process in response to the image analysis result indicating that the formation conditions are met. According to the above embodiment, a film forming method is provided that is advantageous in achieving both defect suppression and throughput.

[0041] <Second Embodiment> In the second embodiment, in S102, the control unit 5 performs frequency analysis on the image data obtained by the imaging unit 16, and in S103, it determines that a liquid film 20 has been formed when the periodic component in which the composition 9 is placed falls below a predetermined threshold.

[0042] Frequency analysis of the illuminance distribution at the positions of the lines 25 of the discretely arranged composition 9 on the substrate 6 yields the analysis result 32 shown in Figure 6. Figure 6 is a semi-logarithmic graph with frequency on the horizontal axis and illuminance on the vertical axis, where the frequency on the horizontal axis is displayed logarithmically. The analysis result 32 includes components of the discretely arranged composition 9 and components due to the characteristics of the substrate 6, light source unit 15, optical system 17, and imaging unit 16. The component of the discretely arranged composition 9 in the analysis result 32 is shown as curve 33. In this embodiment, frequency component 34 is the frequency component due to the arrangement of composition 9, and frequency component 35 is the harmonic component of the arrangement of composition 9. As time progresses and composition 9 spreads, the frequency component 34 of the arrangement of composition 9 in curve 32 becomes smaller, as shown in curve 36. The control unit 5 can determine that a liquid film 20 has been formed at the position of the line 25 when the illuminance 37 of the frequency component 34 in Figure 6 falls below a predetermined threshold. Therefore, in this embodiment, the "formation condition" can be defined as the illuminance 37 of the frequency component 34 obtained from the frequency analysis of the image data obtained by the imaging unit 16 falling below a predetermined threshold in all liquid film formation regions 30 on the substrate 6. In S103, if the analysis result satisfies the formation condition, that is, if the illuminance 37 of the frequency component 34 obtained from the frequency analysis of the image data falling below a threshold in all liquid film formation regions 30 on the substrate 6, the control unit 5 determines that the liquid film 20 has been formed.

[0043] <Third Embodiment> Next, a film-forming apparatus of the third embodiment will be described with reference to Figure 7. Figure 7 is a diagram showing the configuration of the liquid film-forming section in the film-forming apparatus according to the third embodiment. The composition placement section 2, the composition curing section 4, and other configurations are the same as in the first embodiment (Figure 1).

[0044] The liquid film forming unit 38 shown in Figure 7 includes an illumination unit 39 above the opening 11 that illuminates a portion of the substrate 6, and an imaging unit 40 that observes the liquid film state in the area of ​​the substrate 6 illuminated by the illumination unit 39. Furthermore, the liquid film forming unit 38 may include an optical system 41 that irradiates the light illuminated by the illumination unit 39 toward the substrate 6 and guides the reflected light from the substrate 6 (or the composition 9 on it) to the imaging unit 40. The liquid film forming unit 38 may also include a drive unit 42. The drive unit 42 mounts the illumination unit 39, the imaging unit 40, and the optical system 41, and drives along a direction parallel to the surface of the substrate 6. The drive unit 42 can drive the imaging unit 40 to a range where it can observe the entire area of ​​the substrate 6. In addition to the parts described in the first embodiment, the control unit 5 can control the driving of the drive unit 42.

[0045] Next, the film formation method in this embodiment will be described. All steps except for step S102 shown in Figure 2 are the same as in the first embodiment.

[0046] In step S102 of this embodiment, after the substrate 6 is loaded into the liquid film forming unit 38, the imaging unit 40 images the composition 9 in a region narrower than the substrate 6. This allows for observation of the liquid film formation state with higher resolution. Furthermore, the control unit 5 drives the drive unit 42 to scan the imaging unit 40 and the substrate 6 relatively, and observes with the imaging unit 40. The control unit 5 can also shorten the scanning drive time by driving the drive unit 42 to selectively observe regions on the substrate 6 where liquid film formation is slow.

[0047] The image data obtained in this manner can be used to determine the formation state of the liquid film 20 after being processed in the same manner as in the first embodiment.

[0048] <Fourth Embodiment> Due to the viscosity of composition 9, etc., the gaps between the composition 24 (Figure 3) may not be filled even after a certain amount of time has passed, and the liquid film 20 may not be formed properly. Figure 9 shows the state in which unbonded portions 32 of composition 9 have occurred. Therefore, in the fourth embodiment, a recovery process will be described for the case in S103 when a predetermined time has elapsed without the image analysis result satisfying the above-mentioned formation conditions.

[0049] Figure 8 shows a flowchart of the film formation method in this embodiment. This flowchart is a modification of the flowchart in Figure 2 described in the first embodiment, with steps S801 and S801 added to the flowchart in Figure 2.

[0050] In S103, if the image analysis results do not satisfy the formation conditions, that is, if the signal intensity 31 in any of the liquid film formation regions 30 on the substrate 6 does not fall below a predetermined threshold, it is determined that the liquid film 20 has not been sufficiently formed on the substrate 6, and the process moves to step S801. In S801, the control unit 5 determines whether a predetermined time has elapsed since the start of step S102. If the predetermined time has not yet elapsed, the process returns to S102 and the analysis process continues. On the other hand, if the predetermined time has elapsed, it is determined that the liquid film 20 will not be sufficiently formed (the unbonded areas will not disappear) even if the process waits any longer, and the process moves to S802.

[0051] Step S802 is a recovery step in which unbonded areas are detected in the formed film where adjacent droplets are not sufficiently bonded, and recovery processing is performed on the detected unbonded areas. In one example, in recovery step S802, the control unit 5 measures the position coordinates (X,Y) of the unbonded areas 32 of the composition 9 based on the image data obtained by the imaging unit 16. Figure 10 shows an example in which three unbonded areas, 32a, 32b, and 32c, are detected from the image data. The position coordinates of the unbonded areas 32a, 32b, and 32c on the substrate 6 are (X1,Y1), (X2,Y2), and (X3,Y3), respectively.

[0052] The control unit 5 controls the transport device to unload the substrate 6 from the liquid film forming unit 3 and load it into the composition placement unit 2. The substrate 6 is placed on the substrate stage 7 and secured by a chuck. The control unit 5 controls the placement unit 8 to place the composition 9 in each of the unbonded portions 32a, 32b, and 32c. For example, the placement unit 8 is sequentially moved to positions corresponding to (X1,Y1), (X2,Y2), and (X3,Y3) on the substrate 6, and the composition 9 is placed there. Alternatively, the substrate stage 7 holding the substrate 6 may be moved below the placement unit 8 to place the composition 9.

[0053] Furthermore, the control unit 5 may adjust the amount of composition 9 to be placed according to the size of each of the unbonded portions 32a, 32b, and 32c. The amount of composition 9 can be determined in advance according to the area of ​​each of the unbonded portions 32a, 32b, and 32c.

[0054] Subsequently, the control unit 5 controls the transport device to remove the substrate 6 from the composition placement unit 2 and transfer it to the liquid film forming unit 3. The substrate 6 is placed on the substrate stage 10 and secured by a chuck. The composition 9, which has been placed on the unbonded portions 32a, 32b, and 32c by the placement unit 8, begins to spread across the surface of the substrate 6.

[0055] Through this recovery process, composition 9 spreads to the unbonded portions 32a, 32b, and 32c, and a liquid film 20 is formed. After the completion of this recovery process, the process moves to the volatilization step in S104.

[0056] <Fifth Embodiment> In the fourth embodiment, the substrate 6 is moved from the liquid film forming section 3 to the composition placement section 2, where the composition 9 is placed in each of the unbonded sections 32a, 32b, and 32c. In contrast, in the fifth embodiment, the recovery process is performed in the liquid film forming section 3 without moving the substrate 6 from the liquid film forming section 3 to the composition placement section 2. In this embodiment, the control unit 5 drives the substrate stage 10 so that the unbonded section 32a is placed at the gas supply port 12. Subsequently, the control unit 5 controls the gas control unit 14 to supply the solvent from the gas supply port 12. This is then performed sequentially and similarly for the unbonded sections 32b and 32c.

[0057] In this embodiment, CDA may be supplied to the unbonded portion instead of the solvent. The supplied gas is not limited to CDA; it may also be oxygen, nitrogen, helium, or other gases. The supply of these gases promotes the filling of the unbonded portion with the composition.

[0058] According to this embodiment, at least, it is not necessary to move the substrate 6 from the liquid film forming section 3 to the composition placement section 2, as in the fourth embodiment, which is advantageous in terms of throughput.

[0059] <Sixth Embodiment> In the fourth and fifth embodiments, the recovery process involved supplying a solvent or gas to the unbonded portion, but other recovery processes are also possible.

[0060] For example, another example of a recovery process could be applying vibration to the substrate stage 10 (i.e., the substrate 6). For instance, an effective frequency for spreading the composition 9 can be determined in advance, and the substrate stage 10 can be vibrated at that frequency. This vibration promotes the filling of unbonded areas with the composition.

[0061] <Seventh Embodiment> In the fourth embodiment (Figure 8), the recovery process is performed after the liquid film formation process S102, but the timing of the recovery process is not limited to this. The recovery process may be performed at any time before the start of the cured film formation process S105. For example, during the execution of the analysis process S102 (i.e., the liquid film formation process), the amount of change in droplet merging within a predetermined time may be detected, and based on this amount of change, the occurrence of unbonded areas may be predicted, and the recovery process may be performed according to this prediction. Alternatively, the recovery process may be performed after the execution of the volatilization process S104.

[0062] <Eighth Embodiment> In the fourth to seventh embodiments, a recovery process was described for the case where a predetermined time has elapsed in S103 without the image analysis results satisfying the predetermined formation conditions. In the eighth embodiment, a process of removing the substrate will be described as a measure taken when a predetermined time has elapsed in S103 without the image analysis results satisfying the predetermined formation conditions.

[0063] Figure 11 shows a flowchart of the film formation method in this embodiment. This flowchart is a modification of the flowchart in Figure 8 described in the fourth embodiment. However, it is assumed that the film formation apparatus 1 in this embodiment is of the type that uses a mold 21, that is, a type in which the composition 9 is cured while the liquid film 20 and the mold 21 are in contact.

[0064] In this embodiment, if it is determined in S801 that a predetermined time has elapsed since the start of process S102, it is determined that the liquid film 20 will not be sufficiently formed (unbonded areas will not disappear) even if the process is waited any longer, and the process moves to S104. In S104, a volatilization process is performed. After the completion of the volatilization process, the substrate 6 is transferred from the liquid film forming section 3 to the composition curing section 4 by a transport device.

[0065] The process moves to S901. In S901, it is determined whether there are any unconnected parts. Specifically, if the image analysis result in S103 is determined to satisfy the formation conditions, then there are no unconnected parts. On the other hand, if the image analysis result in S103 does not satisfy the formation conditions, and the process has moved to S901 via S801, then there are unconnected parts.

[0066] If there are no unbonded portions, the formation process of S105 is carried out. In this embodiment, the formation process of S105 may include a contact process S902, a curing process S903, and a separation process S904. In the contact process S902, the control unit 5 drives at least one of the mold holding unit 22 and the substrate stage 19 to bring the liquid film 20 on the substrate 6 into contact with the mold 21 (or its flat portion). In the curing process S903, with the liquid film 20 and the mold 21 in contact, the control unit 5 irradiates the liquid film 20 with light using the irradiation unit 23 to cure it. This forms a cured film on the substrate 6. solid A body layer is formed. In the separation step S904, the control unit 5 separates the cured film from the mold 21 by driving at least one of the mold holding unit 22 and the substrate stage 19. Then, in the unloading step S905, the control unit 5 controls the transport device to unload the substrate 6 from the composition curing unit 4.

[0067] If there are unbonded areas (YES in S901), the process proceeds to S906. In S906, similar to S903, the control unit 5 irradiates the liquid film 20 with light using the irradiation unit 23 to cure it. Then, in the unloading process S905, the control unit 5 controls the transport device to unload the substrate 6 from the composition curing unit 4. In this way, for substrates with unbonded areas, the liquid film 20 is cured without contact between the liquid film 20 and the mold 21, and then the substrate is unloaded from the machine. Since the liquid film 20 is cured before the substrate is unloaded, the substrate is not unloaded while the solvent is evaporating from the liquid film 20, thus ensuring safety.

[0068] The control unit 5 stores implementation information indicating that the contact process S902 has been performed on the substrate 6. This implementation information allows for the distinction between whether the contact process has been performed or not for each substrate. The implementation information can be transmitted online from the control unit 6 to a higher-level system.

[0069] In the above example, the presence or absence of unbonded portions is determined by processes S102, S103, and S801, but the timing of the unbonded portion determination process is not limited to these steps and can be performed at any time before the contact process S902 is completed. For example, a detection unit may be provided in the composition curing section 4, and the detection of unbonded portions may be performed in parallel with the contact process S902.

[0070] <Embodiment of Article Manufacturing Method> Next, a method for manufacturing articles (semiconductor IC elements, liquid crystal display elements, color filters, MEMS, etc.) using the aforementioned planarization apparatus will be described. This manufacturing method includes the steps of planarizing a composition placed on a substrate (wafer, glass substrate, etc.) using the aforementioned film forming apparatus as the planarization apparatus, and curing the composition. This forms a planarized film on the substrate. Then, the substrate on which the planarized film has been formed is processed, such as forming a pattern using a lithography apparatus, and the processed substrate is processed in other well-known processing steps to manufacture an article. Other well-known processes include patterning exposure and associated pre-processing, etching, resist stripping, dicing, bonding, packaging, etc. According to this manufacturing method, articles of higher quality than conventional methods can be manufactured.

[0071] Furthermore, the aforementioned film formation apparatus can also be applied to the imprint apparatus. The pattern of the cured material formed using the imprint apparatus is used permanently on at least a part of various articles, or temporarily during the manufacturing of various articles. Articles include electrical circuit elements, optical elements, MEMS, recording elements, sensors, or molds. Examples of electrical circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, as well as semiconductor elements such as LSI, CCD, image sensors, and FPGAs. Examples of molds include molds for imprinting.

[0072] The pattern of the cured material is either used as is as a component of at least a part of the above-mentioned article, or temporarily used as a resist mask. After etching or ion implantation is performed during the substrate processing process, the resist mask is removed.

[0073] Next, a method for manufacturing articles using an imprint device will be described. In step SA shown in Figure 13, a substrate 1z, such as a silicon substrate, on which a workpiece 2z such as an insulator is formed on its surface is prepared, and then an imprint material 3z is applied to the surface of the workpiece 2z by an inkjet method or the like. Here, multiple droplet-shaped imprint material 3z are shown applied to the substrate.

[0074] In step SB of Figure 13, the mold 4z for imprinting is positioned opposite the imprint material 3z on the substrate, with the side where the uneven pattern is formed facing it. In step SC of Figure 13, the substrate 1z to which the imprint material 3z has been applied is brought into contact with the mold 4z, and pressure is applied. The imprint material 3z fills the gap between the mold 4z and the workpiece 2z. In this state, when light is irradiated through the mold 4z as curing energy, the imprint material 3z hardens.

[0075] In process SD shown in Figure 13, after the imprint material 3z is cured, the mold 4z and the substrate 1z are separated, forming a pattern of the cured imprint material 3z on the substrate 1z. In this cured pattern, the recesses of the mold correspond to the protrusions of the cured material, and the protrusions of the mold correspond to the recesses of the cured material. In other words, the uneven pattern of the mold 4z is transferred to the imprint material 3z.

[0076] In process SE in Figure 13, etching is performed using the cured material pattern as an etching-resistant mask. This removes the areas on the surface of the workpiece 2z where there is no cured material or only a thin layer remains, creating grooves 5z. In process SF in Figure 13, removing the cured material pattern yields an article with grooves 5z formed on the surface of the workpiece 2z. Although the cured material pattern was removed here, it may also be used without removal after processing, for example, as an interlayer insulating film included in semiconductor devices, i.e., as a component of the article.

[0077] The disclosures herein include at least the following film formation methods and article manufacturing methods. (Item 1) A placement step involves discretely arranging multiple droplets of a curable composition containing a polymerizable compound, which is a non-volatile component, and a solvent, which is a volatile component, on a substrate. After the arrangement step, an analysis step is performed to analyze images obtained by capturing the process in which a continuous liquid film is formed on the substrate by each of the plurality of liquid droplets combining with adjacent liquid droplets on the substrate, A forming step of curing the liquid film to form a cured film, It has, If the analysis results obtained in the above analysis step satisfy predetermined conditions indicating that the liquid film formation state is sufficient, the process proceeds to the formation step. A film formation method characterized by the following: (Item 2) The process further includes a volatilization step that enhances the solvent volatilization effect compared to the process in which the liquid film is formed, thereby volatilizing the solvent contained in the liquid film. If the analysis results obtained in the analysis step satisfy the predetermined conditions, the process proceeds to the volatilization step, and then to the formation step. The film formation method described in item 1, characterized by the features described herein. (Item 3) The process further includes a first supply step of supplying solvent vapor to the space above the substrate after the arrangement step, By stopping the supply of the steam before the volatilization process, the volatilization effect is enhanced. The film formation method according to item 2, characterized by the features described above. (Item 4) The film formation method according to item 3, further comprising a second supply step of supplying a gas selected from clean dry air, oxygen, nitrogen, and helium to the space above the substrate during the volatilization step. (Item 5) The film formation method according to any one of items 1 to 4, characterized in that the predetermined condition is that the signal intensity of the image is below a predetermined threshold in all liquid film formation regions on the substrate. (Item 6) The signal intensity of the above image is, The film formation method according to item 5, characterized in that the signal intensity is obtained by subtracting the signal intensity of the image obtained by imaging the substrate before the plurality of droplets were placed by the arrangement step from the signal intensity of the image obtained by imaging the substrate after the plurality of droplets were placed by the arrangement step. (Item 7) The analysis step includes performing frequency analysis on the image, The film formation method according to any one of items 1 to 4, characterized in that the predetermined condition is that the illuminance of the frequency components obtained from the frequency analysis results is below a predetermined threshold in all liquid film formation regions on the substrate. (Item 8) The film formation method according to any one of items 1 to 7, characterized in that the image is an image captured by the imaging unit while scanning the imaging unit and the substrate relative to each other. (Item 9) A film formation method according to any one of items 1 to 8, further comprising a recovery step of detecting unbonded areas in the formed film where adjacent droplets are not sufficiently bonded if the analysis results do not satisfy the predetermined conditions within a predetermined time after the arrangement step, and performing a recovery process on the detected unbonded areas. (Item 10) The film-forming method according to item 9, characterized in that the recovery process includes placing a curable composition in the unbonded portion. (Item 11) The film-forming method according to item 9, characterized in that the recovery process includes supplying a solvent to the unbonded portion. (Item 12) The film formation method according to item 9, characterized in that the recovery process includes supplying the unbonded portion with a gas selected from clean dry air, oxygen, nitrogen, and helium. (Item 13) The film forming method according to item 9, characterized in that the recovery process includes applying vibrations of a predetermined frequency to the substrate. (Item 14) A film formation method according to any one of items 9 to 13, characterized in that the process proceeds to the formation step after the recovery step. (Item 15) The forming step is, A contact step of bringing the liquid film into contact with the flat surface of the mold, After the contact step, a curing step is performed in which the liquid film is cured while in contact with the flat surface of the mold to form a cured film. After the curing step, a separation step is performed to separate the cured film and the mold. Includes, A film forming method according to any one of items 1 to 8, further comprising a removal step of curing the liquid film without performing the contact step if the analysis result does not satisfy the predetermined conditions within a predetermined time after the placement step, and then removing the substrate. (Item 16) A configuration section in which multiple droplets of a curable composition containing a polymerizable compound, which is a non-volatile component, and a solvent, which is a volatile component, are discretely arranged on a substrate, An imaging unit captures the process by which a continuous liquid film is formed on the substrate as each of the plurality of liquid droplets combines with adjacent liquid droplets on the substrate. A processing unit for analyzing the image obtained by the aforementioned imaging, A forming section that hardens the liquid film from which the solvent has evaporated to form a hardened film, When the results of the above analysis satisfy predetermined conditions indicating that the liquid film formation state is sufficient, the formation of a hardened film by the forming unit is performed. A film forming apparatus characterized by the following features. (Item 17) A step of forming a film of a curable composition on a substrate using a film formation method described in any one of items 1 to 15, A step of processing the substrate on which the film has been formed in the above step, A method for manufacturing articles, characterized by having a substrate and manufacturing an article from the processed substrate.

[0078] The invention is not limited to the embodiments described above, and various modifications and variations are possible without departing from the spirit and scope of the invention. Accordingly, claims are attached to disclose the scope of the invention. [Explanation of symbols]

[0079] 1: Film forming apparatus, 2: Composition placement unit, 3: Liquid film forming unit, 4: Composition curing unit, 5: Control unit 5, 6: Substrate, 7, 10, 19: Substrate stage, 8: Supply unit, 9: Composition

Claims

1. A placement step involves discretely arranging multiple droplets of a curable composition containing a polymerizable compound, which is a non-volatile component, and a solvent, which is a volatile component, on a substrate. After the arrangement step, an analysis step is performed to analyze images obtained by capturing the process in which a continuous liquid film is formed on the substrate by each of the plurality of liquid droplets combining with adjacent liquid droplets on the substrate, A volatilization step is performed to enhance the solvent volatilization effect compared to the process in which the liquid film is formed, thereby volatilizing the solvent contained in the liquid film. A forming step of curing the liquid film to form a cured film, It has, If the analysis results obtained in the analysis step satisfy predetermined conditions indicating that the liquid film formation state is sufficient, the process proceeds to the volatilization step, and then to the formation step. A film formation method characterized by the following:

2. If the analysis results obtained in the analysis step do not satisfy the predetermined conditions, the process does not proceed to the volatilization step. The film formation method according to feature 1.

3. The process further includes a first supply step of supplying solvent vapor to the space above the substrate after the arrangement step, By stopping the supply of the steam before the volatilization process, the volatilization effect is enhanced. The film formation method according to feature 1.

4. The film forming method according to claim 3, further comprising a second supply step of supplying a gas selected from clean dry air, oxygen, nitrogen, and helium to the space above the substrate during the volatilization step.

5. The film formation method according to claim 1, characterized in that the predetermined condition is that the signal intensity of the image is below a predetermined threshold in all liquid film formation regions on the substrate.

6. The signal intensity of the above image is, The film forming method according to claim 5, characterized in that the signal intensity is obtained by subtracting the signal intensity of the image obtained by imaging the substrate before the plurality of droplets were placed in the arrangement step from the signal intensity of the image obtained by imaging the substrate after the plurality of droplets were placed in the arrangement step.

7. The analysis step includes performing frequency analysis on the image, The film formation method according to claim 1, characterized in that the predetermined condition is that the illuminance of the frequency components obtained from the frequency analysis results in all liquid film formation regions on the substrate falls below a predetermined threshold.

8. The film forming method according to claim 1, characterized in that the image is an image captured by the imaging unit while scanning the imaging unit and the substrate relative to each other.

9. The film formation method according to claim 1, further comprising a recovery step of detecting unbonded areas in the formed film where adjacent droplets are not sufficiently bonded if the analysis results do not satisfy the predetermined conditions within a predetermined time after the arrangement step, and performing a recovery process on the detected unbonded areas.

10. The film-forming method according to claim 9, characterized in that the recovery process includes placing a curable composition in the unbonded portion.

11. The film-forming method according to claim 9, characterized in that the recovery process includes supplying a solvent to the unbonded portion.

12. The film forming method according to claim 9, characterized in that the recovery process includes supplying a gas selected from clean dry air, oxygen, nitrogen, and helium to the unbonded portion.

13. The film forming method according to claim 9, characterized in that the recovery process includes applying vibrations of a predetermined frequency to the substrate.

14. The film forming method according to claim 9, characterized in that the process proceeds to the forming step after the recovery step.

15. The forming step is, A contact step of bringing the liquid film into contact with the flat surface of the mold, After the contact step, a curing step is performed in which the liquid film is cured while in contact with the flat surface of the mold to form a cured film. After the curing step, a separation step is performed to separate the cured film and the mold. Includes, The film forming method according to claim 1, further comprising a removal step of curing the liquid film without performing the contact step if the analysis results do not satisfy the predetermined conditions within a predetermined time after the placement step, and then removing the substrate.

16. A configuration section in which multiple droplets of a curable composition containing a polymerizable compound, which is a non-volatile component, and a solvent, which is a volatile component, are discretely arranged on a substrate, An imaging unit captures the process by which a continuous liquid film is formed on the substrate as each of the plurality of liquid droplets combines with adjacent liquid droplets on the substrate. A processing unit for analyzing the image obtained by the aforementioned imaging, It has a forming section which hardens the liquid film from which the solvent has evaporated to form a hardened film, If the results of the analysis satisfy predetermined conditions indicating that the liquid film formation state is sufficient, the solvent volatilization effect is increased compared to the liquid film formation process to volatilize the solvent contained in the liquid film, and then the hardened film is formed by the forming unit. A film forming apparatus characterized by the following features.

17. A step of forming a film of a curable composition on a substrate using the film forming method described in any one of claims 1 to 15, A step of processing the substrate on which the film has been formed in the above step, A method for manufacturing articles, characterized by having a substrate and manufacturing an article from the processed substrate.

Images