System including heating means and actinic radiation source and method of using the same

Abstract

To provide a planarized layer that has no height difference or small height difference between both ends of a surface.SOLUTION: A system may include: heating means for heating a photocurable composition on a substrate; an actinic radiation source configured to emit actinic radiation at a wavelength less than 700 nm; and a controller configured to determine a targeted temperature to be produced by first heating means to achieve a photo-curing temperature of the photocurable composition when the photocurable composition is exposed by the actinic radiation source, wherein the photo-curing temperature is higher than an ambient temperature. A method may include: supplying the photocurable composition onto a substrate; photo-curing a layer of the photocurable composition at a photo-curing temperature higher than an ambient temperature to form a cured layer; and baking the cured layer to form a baked layer. The system and method can allow a thickness change of layer to be 0% or closer to 0%.SELECTED DRAWING: Figure 3

Description

[Technical field]

[0001] The present disclosure relates to a system including a heating means and a source of actinic radiation, and a method of using the system. [Background technology]

[0002] Inkjet adaptive planarization (IAP) is used in microelectronic manufacturing. As the dimensions of microelectronic components continue to shrink, processes involving IAP become more challenging. The IAP process may include providing a photocurable composition onto a substrate and placing the substrate in contact with the photocurable composition. The IAP process may further include photocuring a layer of the photocurable composition by exposing the photocurable composition to actinic radiation to form a cured layer. The photocuring is performed at room temperature, e.g., 20°C. The cured layer is then baked to form a baked layer. The thickness of the baked layer is less than the thickness of the photocurable composition. The thickness variation reduces the planarization performance of the baked layer formed by the IAP process described above. Summary of the Invention [Problem to be solved by the invention]

[0003] The surface of the resulting fired layer may have a non-uniform topography, with localized areas of low elevation and localized areas of high elevation. A planarized layer that does not have any elevation difference across such a surface, or at least has a small elevation difference, is desired. [Means for solving the problem]

[0004] In an embodiment, the system includes a first heating means for heating the photocurable composition on the substrate; an actinic radiation source configured to emit actinic radiation at a wavelength less than 700 nm; and a controller configured to determine a target temperature produced by the first heating means to achieve a photocure temperature of the photocurable composition when the photocurable composition is exposed to the actinic radiation source, where the photocure temperature is greater than ambient temperature.

[0005] In an embodiment, the system comprises a machine, and the first heating means and the source of actinic radiation are in the same station within the machine.

[0006] In another embodiment, the system further includes a first substrate chuck configured to hold the substrate when the photocurable composition is at the photocuring temperature and exposed to actinic radiation.

[0007] In certain embodiments, the system further includes a second substrate chuck configured to hold the substrate when the photocurable composition is exposed to the first heating means; and a substrate transfer tool configured to transfer the substrate with the photocurable composition between the first substrate chuck and the second substrate chuck.

[0008] In yet another embodiment, the system further includes a delivery head configured to deliver the photocurable composition onto the substrate.

[0009] In still yet another embodiment, the system further includes a station configured to place a top material in contact with the photocurable composition overlying the substrate.

[0010] In a further embodiment, the system further comprises a second heating means configured to heat a cured layer corresponding to the photocurable composition to form a baked layer, the second heating means being configured to heat the substrate and the cured layer to a bake temperature higher than the photocuring temperature.

[0011] In another embodiment, the system further includes a temperature sensor configured to generate a first signal corresponding to a temperature of the photocurable composition, and the controller is further configured to receive the first signal and transmit a second signal to activate the actinic radiation source when the temperature is within ±5°C of the photocuring temperature.

[0012] In another aspect, a method includes providing a photocurable composition on a substrate, the photocurable composition comprising a multifunctional monomer; photocuring the photocurable composition while the photocurable composition is at a photocure temperature greater than ambient temperature, forming a cured layer on the substrate; and baking the cured layer to form a baked layer, the baking being performed at a bake temperature greater than the photocure temperature.

[0013] In an embodiment, the light cure temperature is greater than 25°C.

[0014] In a particular embodiment, the firing temperature is up to 500°C.

[0015] In another embodiment, the photocurable composition is at the photocuring temperature while it is in contact with the substrate and upper.

[0016] In yet another embodiment, the cured thickness is the thickness of the cured layer of the photocurable composition before baking, the baked thickness is the thickness of the baked layer, and the thickness change is

[0017] ((T2-T1) / T1) x 100%

[0018] (Wherein, T1 is the cured thickness,

[0019] T2 is the fired thickness,

[0020] The thickness change is within the range of -2.0% to 2.0%.

[0021] In further embodiments, the multifunctional monomer comprises a difunctional monomer, a trifunctional monomer, or a tetrafunctional monomer.

[0022] In another embodiment, the multifunctional monomer comprises two or more vinyl groups.

[0023] In certain embodiments, the multifunctional monomer comprises at least one aromatic ring structure.

[0024] In yet another embodiment, the multifunctional monomer comprises an acrylate group.

[0025] In yet another embodiment, the photocurable composition has a multifunctional monomer content of at least 90% by weight of the photocurable composition.

[0026] In a further embodiment, the method further includes receiving a bake temperature at which the cured layer is to be baked; and determining a photocuring temperature based on the bake temperature.

[0027] In a further aspect, the system includes a light curing station configured to form a cured layer on the substrate at a light curing temperature, the light curing temperature being greater than ambient temperature; a bake station configured to bake the cured layer at a bake temperature to form a baked layer; and a controller configured to determine the light curing temperature based at least in part on the bake temperature.

[0028] In an embodiment, the photocuring station includes a heating means configured to heat the photocurable composition on the substrate to a temperature that is at or closer to the photocuring temperature than ambient temperature; and an actinic radiation source configured to emit radiation at wavelengths less than 700 nm.

[0029] In another embodiment, the system further includes a robotic arm configured to move the substrate having the cured layer from the light curing station to the bake station.

[0030] Embodiments are illustrated by way of example and not limitation in the accompanying figures. [Brief description of the drawings]

[0031] [Figure 1] 1 is a diagrammatic representation of a cross-sectional view of a substrate, a layer of photocurable composition, and a portion of an upper prior to photocuring the photocurable composition. [Diagram 2] 2 is a diagrammatic representation of a cross-sectional view of the substrate and layers of FIG. 1 after photocuring and baking. [Diagram 3] FIG. 1 is a schematic diagram of a machine that can be used to form layers from photocurable compositions. [Figure 4] FIG. 2 is a schematic diagram of another machine that can be used to form layers from photocurable compositions. [Diagram 5] FIG. 1 is a schematic diagram of a system, including a machine, that can be used to form layers from a photocurable composition. [Figure 6] FIG. 2 is a process flow diagram for forming a layer from a photocurable composition. [Figure 7] 1 illustrates a cross-sectional view of a portion of a substrate chuck and a substrate during dispensing of a droplet of a photocurable composition onto the substrate. [Figure 8] 8 is a diagram illustrating a cross-sectional view of the substrate chuck and substrate of FIG. 7 as the upper material and the substrate-droplet combination are moved closer to each other. [Figure 9] 9 is a diagrammatic illustration of a cross-sectional view of the substrate chuck, substrate and upper material of FIG. 8 during the formation of a layer of photocurable composition. [Figure 10] 10 is a diagrammatic representation of a cross-sectional view of the substrate chuck, substrate, upper material, and photocurable composition layers of FIG. 9 during a pre-exposure heating operation. [Figure 11] 11 is a diagrammatic illustration of a cross-sectional view of the substrate chuck, substrate, upper material, and layer of photocurable composition of FIG. 10 during photocuring of the layer of photocurable composition to form a hardened layer. [Figure 12] 12 illustrates a cross-sectional view of the substrate chuck, substrate, upper material, and hardened layer of FIG. 11 after removing the upper material and firing the hardened layer to form a fired layer. [Figure 13] 1 is a graph illustrating the thickness change caused by a photocure operation as a function of photocure temperature for substrate features of different sizes. [Figure 14] 1 is a graph showing the thickness change caused by the baking operation as a function of photocuring temperature for different baking temperatures. [Figure 15] 1 is a graph illustrating the thickness change caused by a baking operation as a function of photocuring temperature for different photocurable compositions. [Figure 16]1 is a graph showing the thickness change caused by the bake operation as a function of actinic radiation dose for different photocuring temperatures. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0032] Those skilled in the art will appreciate that elements in the figures are illustrated for simplicity and clarity and have not necessarily been drawn to scale. For example, the dimensions of some of the elements in the figures may be exaggerated relative to other elements to help improve understanding of embodiments of the present invention.

[0033] The following description, in conjunction with the drawings, is provided to aid in understanding the teachings disclosed herein. The following discussion focuses on specific embodiments of the teachings. This focus is provided to aid in describing the teachings and should not be construed as a limitation on the scope or applicability of the teachings.

[0034] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention belongs. Materials, methods and examples are for illustrative purposes only and are not intended to be limiting. Unless described herein, many details regarding the operation of specific materials and processes are conventional and can be found in textbooks and other sources in the art.

[0035] Before describing the details of the systems and methods that can be used to achieve the benefits described herein, reference is made to Figures 1 and 2, which describe thickness variations due to processing and planarization performance and illustrate how the shape of a layer of photocurable composition can change during processing. Specific thicknesses and depths are provided to illustrate specific examples, but not to limit the scope of the invention, which is defined in the appended claims.

[0036] 1 includes a cross-sectional view of a substrate 10, a layer 20 of photocurable composition prior to photocuring (hereafter the "pre-cured layer"), and a portion of an upper material 30 having a flat bottom surface. Substrate 10 includes features 12 and grooves 14 between features 12. Dimension 16 corresponds to the depth of grooves 14, which for this particular example is 200 nm.

[0037] The top surface of pre-cured layer 20 of photocurable composition is flat because the photocurable composition is fluid and contacts the flat bottom surface of upper material 30. Dimension 22 corresponds to the thickness of pre-cured layer 20 between feature 12 and the bottom surface of upper material 30. In this particular example, dimension 22 is 40 nm. Dimension 24 corresponds to the thickness of pre-cured layer 20 between the bottom of groove 14 and the bottom surface of upper material 30. Dimension 24 is the sum of dimension 16 (depth of groove 14) and dimension 22 (thickness of pre-cured layer above feature 12). Dimension 24 can be determined using Equation 1 below:

[0038] D 24 =D 16 +D 22 (Equation 1)

[0039] During the ceremony,

[0040] D 24 is of dimension 24,

[0041] D 16 is of dimension 16,

[0042] D 22 is dimension 22.

[0043] If we use the previously described depth for dimension 16 and the previously described thickness for dimension 22,

[0044] D 24 = 200nm + 40nm = 240nm.

[0045] When the pre-cured layer 20 is photocured, the monomers in the photocurable composition polymerize to form a cured layer. During polymerization, covalent bonds are formed between the monomers in the photocurable composition, drawing the atoms closer together and causing the photocurable composition to shrink. After photocuring, the cured layer is baked to form the baked layer 40 in FIG. 2. Additional crosslinks occur during baking, further shrinking the polymerized material. In addition, some polymer rearrangement and relaxation may occur during baking. At high temperatures, reactions such as oxidation, decomposition, degradation of the material, or a combination of these may also occur.

[0046] Polymerization and any of the reactions previously described may contribute to thermal shrinkage. FIG. 2 includes substrate 10 and fired layer 40 after removal of upper material 30. In a particular example, fired layer 40 has shrunk 5% compared to pre-cured layer 20 (-5% thickness change). Dimension 42 corresponds to the thickness of fired layer 40 above feature 12, and dimension 44 corresponds to the thickness of fired layer 40 in and above groove 14. Because of the -5% thickness change, dimension 42 is 95% of dimension 22, and dimension 44 is 95% of dimension 24. Thus, dimension 42 is 38 nm and dimension 44 is 228 nm.

[0047] While the top surface of the pre-cured layer was at the same elevation, fired layer 40 has a top surface where different regions are at different elevations. Dimension 48 corresponds to the elevation difference along the top surface of fired layer 40 between (1) the portion of fired layer 40 that overlies feature 12 of substrate 10 and (2) the portion of fired layer 40 above groove 14. Dimension 48 can be determined using Equation 2 below.

[0048] D 48 =D 42 -(D 44 -D 16 ) (Equation 2)

[0049] During the ceremony,

[0050] D 48 is of dimension 48,

[0051] D 42 is of dimension 42,

[0052] D 44 has size 44.

[0053] When using these dimension values,

[0054] D 48 =38nm-(228nm-200nm)=10nm.

[0055] By reducing the thickness change due to photocuring and baking, dimension 48 can be reduced, which can aid in planarization performance: if the thickness change is -1%, dimension 48 can be reduced to 1.6 nm, and if the thickness change is 0%, dimension 48 can be 0 nm.

[0056] As described herein, the amount of thickness variation can be reduced by photocuring the photocurable composition at a temperature higher than ambient temperature. Ambient temperature is the temperature of the room in the machine where the photocuring station is located. For example, ambient temperature can be in the range of 20°C to 25°C. Photocuring at a photocuring temperature can help reduce thickness variation associated with photocuring, and baking can produce a fired layer having a top surface with less height difference along the top surface compared to a different fired layer made from the same photocurable composition where the pre-cured layer is photocured at ambient temperature and subsequently baked. The reduced amount of thickness variation results in better planarization performance.

[0057] In this specification, the thickness change may be between any two of: (1) a pre-cured layer of a photocurable composition, (2) a cured layer corresponding to the pre-cured layer, or (3) a baked layer corresponding to the pre-cured layer. Unless expressly stated to the contrary, thickness changes are expressed as a percentage.

[0058] The thickness change is given by Equation 3 below:

[0059] ((T2-T1) / T1)×100% (Equation 3)

[0060] (In the formula,

[0061] T1 is the thickness of the layer at a relatively early point in the process;

[0062] T2 is the thickness of the layer at a relatively late point in the process).

[0063] For example, T1 can be the thickness of the pre-cured layer and T2 can be the thickness of the cured layer or the thickness of the fired layer. Alternatively, T1 can be the thickness of the cured layer and T2 can be the thickness of the fired layer. Negative values ​​correspond to shrinkage and positive values ​​correspond to expansion. Thickness change is described in terms of how far the thickness change is from 0%. Thus, while literally -4.0% is less than -1.0%, a thickness change of -4.0% can be reduced to -1.0%.

[0064] The thickness measurements to determine thickness variations should be at substantially the same locations and surface features, e.g., over protrusions, in recesses, in scribe lanes between dies, etc. The thickness measurements should be in an area of ​​the substrate surrounded by an exclusion zone extending from the outer edge toward the center of the substrate for a distance in the range of 1 mm to 9 mm, e.g., 3 mm. The thickness measurements can be made using an atomic force microscope (AFM); an interferometer; an ellipsometer; a profilometer; or any suitable instrument for measuring the thickness of a layer or the surface profile of a layer. As an alternative to thickness measurements, the relative height difference at two locations may be measured, which may provide a representation of the planarization of the planarized layer. In an embodiment, a contour map may be created from the top surface of the layer to illustrate the elevation changes along such a surface.

[0065] The thickness change may be a single thickness change, or an average of multiple thickness changes between pairs of thickness measurements, or an average from a contour map corresponding to the top surface of the uncured, cured, or fired layer.

[0066] The system can be configured to perform dispensing, pre-exposure heating, photocuring and baking operations for the photocurable composition. The operations previously listed for the system may be performed in a single machine, such as machine 300 in FIG. 3 or machine 400 in FIG. 4, or may be distributed between two or more machines, such as machines 501 and 503 in FIG. 5. The system is highly suitable for IAP processes. The system can also be used to form patterned layers from photocurable compositions.

[0067] After reading this specification, a person skilled in the art will be able to determine the number of machines and corresponding operations when designing a system. In the description below, the system of Figure 3 will be described before describing the systems of Figures 4 and 5.

[0068] FIG. 3 includes a schematic diagram of a top view of a system in the form of a machine 300 that can be used to form overlying layers on a substrate from a photocurable composition.

[0069] The machine 300 includes a substrate transfer tool 310, a substrate pod 321, a feed station 323, a pre-exposure heating and light curing station 326, a post-exposure bake station 329, a controller 350, and a memory 352. The feed station 323 can include a substrate chuck 333, and the post-exposure bake station 329 can include a substrate chuck 339 and a feed head 346. The substrate chuck 333 can be coupled to a stage (not shown) such that the substrate chuck 333 can move between stations 323 and 326. The pre-exposure heating and light curing station 326 can be configured to perform a pre-exposure heating operation and a light curing operation. As described below with respect to FIG. 4, the pre-exposure heating operation can be performed at one station and the light curing operation can be performed at a different station.

[0070] Many of the previously mentioned components are described below with respect to the functions that each performs. Further details regarding the operation of the components, and in particular stations 323, 326 and 329, are described in more detail later in this specification with respect to the manner in which machine 300 is used.

[0071] The substrate transfer tool 310 can be configured to transfer one or more substrates to or from any of the substrate pods 321, the supply station 323, the pre-exposure heating and light curing station 326, and the post-exposure baking station 329. The substrate transfer tool 310 can be or include one or more parts of an equipment front-end module (EFEM). The parts of the EFEM can include one or more of each of the following: a robot arm, a robot hand adapted to hold a wafer, a sensor, a motor for moving the robot arm, another motor for moving the robot arm, etc. The robot arm can be configured to move the substrate with the hardened layer between stations, for example, from the pre-exposure heating and light curing station 326 to the post-exposure baking station 329. In an embodiment, a particular substrate and top material may have a similar shape and size.

[0072] Substrate pod 321 can hold multiple substrates. The substrates can be removed from substrate pod 321, processed in a station of machine 300, such as stations 323, 326, 329, or a combination thereof, and returned to substrate pod 321 once processing within machine 300 has been partially or completely completed.

[0073] The feed station 323 can be configured to receive a substrate and dispense the photocurable composition onto the substrate. When the substrate is on the substrate chuck 333, a feed head 346 can be used to dispense the photocurable composition onto the substrate. The feed head 346 can include one or more nozzles that dispense the photocurable composition. The dotted lines in the feed head 346 are used to indicate that the photocurable composition is dispensed along the bottom side of the feed head 346. The feed head 346 can be configured to be stationary or moving as it dispenses the photocurable composition. Further details regarding the photocurable composition and methods of dispensing and processing the photocurable composition are provided later in this specification. A stage coupled to the substrate chuck 333 can transport the substrate and the photocurable composition overlying the substrate from the feed station 323 to the pre-exposure heating and photocuring station 326.

[0074] The pre-exposure heating and light curing station 326 can be configured to perform two operations. The pre-exposure heating and light curing station 326 can be configured to heat the photocurable composition prior to exposure to actinic radiation. The pre-exposure heating and light curing station 326 can be configured to light cure the photocurable composition by exposing the photocurable composition to actinic radiation. In another embodiment, the operations performed by the pre-exposure heating and light curing station 326 can be separated into two different stations. FIG. 4 includes a system having a machine 400. The pre-exposure heating and light curing station 326 is replaced by a pre-exposure heating station 425 and a light curing station 427.

[0075] Heating means associated with the pre-exposure heating and light curing station 326 illustrated in FIG. 3 may be actuated to heat the photocurable composition. Further details regarding the heating means for the pre-exposure heating and light curing station 326 are provided later in this specification. It may be difficult to obtain a temperature measurement of the photocurable composition directly. Thus, the temperature of the photocurable composition may correspond to different temperatures within the pre-exposure heating and light curing station 326. The temperature of the photocurable composition, whether in the form of droplets or a subsequently formed pre-cured layer, may be correlated to the temperature of the substrate chuck 333, the substrate overlying the substrate chuck 333, or a top material, if present, in contact with the photocurable composition. The temperature of the photocurable composition may be determined using the temperature of the substrate chuck 333, the substrate overlying the substrate chuck 333, or a top material, if present. Because direct temperature measurement of the photocurable composition may be impractical, a user of the system may use the temperature of the substrate chuck 333, the substrate, or a top material, if present, to control operation.

[0076] When the temperature of the substrate chuck 333, substrate or upper material is at the target temperature or within a tolerance of such temperature, the heating means can be deactivated or placed in a holding state to keep the substrate chuck 333 or substrate at the target photocuring temperature or within a tolerance of such temperature. Such a temperature tolerance can be the target temperature ±5° C., 2° C., 1° C. or 0.5° C. When photocuring a photocurable composition, the target temperature can be the same as or different from the desired photocuring temperature. The target temperature can be determined after the desired photocuring temperature is known. Further details regarding the target temperature are described in the method of using the machine 300.

[0077] A pre-exposure heating and light curing station 326 can be used to form a cured layer from the photocurable composition overlying the substrate. If the overlying material is not already in contact with the photocurable composition, the overlying material can be placed in contact with the droplets of the photocurable composition to cause the droplets of the photocurable composition to coalesce and form a pre-cured layer of the photocurable composition. If the pre-cured layer is at a light curing temperature, the pre-cured layer of the photocurable composition can be photocured by exposing the pre-cured layer to actinic radiation. The actinic radiation causes polymerization of the polymerizable material in the photocurable composition. The cured layer refers to the layer of polymerized photocurable composition after the pre-cured layer of the photocurable composition has been photocured using actinic radiation and before the layer of polymerized photocurable composition is further processed during a post-exposure bake operation. Once the photocuring operation is complete, the overlying material can be removed. The substrate transport tool 310 can transport the substrate and the cured layer from the pre-exposure heating and light curing station 326 to the post-exposure bake station 329.

[0078] The post-exposure bake station 329 can further polymerize or crosslink the photocurable composition in the cured layer, cause different reactions of components in the photocurable composition, drive off volatile components in the photocurable composition, etc. The post-exposure bake station 329 can have any of the designs described for the pre-exposure heating and light curing station 326, including the heating means. The heating means for the post-exposure bake station 329 can be the same as or different from the heating means for the pre-exposure heating and light curing station 326. In an embodiment, the post-exposure bake station 329 can include heating means configured to operate at a higher temperature compared to the pre-exposure heating and light curing station 326. The temperature used for the post-exposure bake can be at least 150° C. The maximum processing temperature associated with the post-exposure bake station 329 can be as high as 500° C. Sufficient heat shielding can be used to help ensure that heat from the post-exposure bake station 329 does not adversely affect the operation of other parts of the machine 300.

[0079] Each of the substrate chucks 333 and 339 may be a vacuum chuck, a pin-type chuck, a groove-type chuck, an electrostatic chuck, an electromagnetic chuck, etc. The substrate chucks 333 and 339 may be of the same type, such as a vacuum chuck, or may be of different types. For example, one of the substrate chucks may be a vacuum chuck and the other of the substrate chucks may be an electrostatic chuck or an electromagnetic chuck. Each of the substrate chucks 333 and 339 may or may not have a heating element, a cooling element, or both, that can be used to heat or cool the substrate and layer, and, if present, an overlying material on the substrate.

[0080] A stage may be coupled to one or more of the substrate chucks and may be used to move the substrate chucks within the machine 300. Different stages may be coupled to different substrate chucks, or a combination of such substrate chucks may be coupled to the same stage. A stage may also allow for the use of fewer substrate chucks. The substrate chuck may be coupled to a stage that can be moved between at least two of the different stations. Thus, each station need not have its own dedicated substrate chuck. In a non-limiting example, the substrate may be loaded onto a substrate chuck 333 coupled to a stage disposed in a feed station 323, and after dispensing the photocurable composition, the stage may move the substrate chuck 333, substrate and photocurable composition to the pre-exposure heating and photocuring station 326. After the operations at the pre-exposure heating and photocuring station 326 are completed and the substrate and cured layer are removed, the stage may move the substrate chuck 333 back to the feed station 323 to receive another subsequent substrate. In an alternative embodiment, described below with respect to FIG. 4, each station may have its own substrate chuck.

[0081] Controller 350 can control machine 300 in Figure 3, machine 400 in Figure 4, or machine 501 in Figure 5. The description of controller 350 below focuses on machine 300 in Figure 3. The description of controller 350 also applies to machine 400 in Figure 4 and machine 501 in Figure 5, except where specific details of machines 400 and 501 are described.

[0082] The controller 350 may be in communication with any of the components of the machine 300 previously described, and potentially other components within or outside the machine 300. The controller 350 may operate using a computer readable program, optionally stored in the memory 352. The controller 350 may include a processor (e.g., a central processing unit of a microprocessor or microcontroller), a field programmable gate array (FPGA), an application specific integrated circuit (ASIC), or the like. The controller 350 may be within the machine 300. In another embodiment of the system (not shown), the controller 350 may be at least a part of a computer external to the machine 300, such computer being bidirectionally coupled to the machine 300. The memory 352 may include a non-transitory computer readable medium that includes instructions for performing actions related to or during a transport operation. Memory 352 may further include data tables that controller 350 may access to assist in determining operational parameters, such as local areal density of applied photocurable composition, target temperature, photocure temperature, dose of actinic radiation, post-exposure bake temperature, or another parameter used in the methods described below. Like controller 350, memory 352 may be part of the system and may be within machine 300 or external to machine 300. In alternative embodiments, any component may include a local controller that provides some of the functionality otherwise provided by controller 350.

[0083] The operations previously described performed by any particular station may be moved to another station or combined with another station. For example, dispensing, pre-heating, and light curing may occur in the same station, pre-heating and light curing may occur in the same station, etc. In another configuration, operations performed by one station may occur in separate stations. Figure 4 includes a schematic diagram of a top view of another system in the form of a machine 400 that can be used to form a fired layer on a substrate. Machine 400 is the same as machine 300, except as described below.

[0084] Pre-exposure heating and light curing station 326 in Figure 3 is replaced in Figure 4 by pre-exposure heating station 425 and light curing station 427. The design for each of stations 425 and 427 may be more easily optimized compared to pre-exposure heating and light curing station 326, which performs both pre-exposure heating and light curing operations. Separate stations 425 and 427 may add cost to machine 400 compared to machine 300 due to more parts, and the footprint of machine 400 may be larger than the footprint of machine 300.

[0085] The delivery head 346 in FIG. 3 is replaced by a delivery module 440 in FIG. 4. The delivery module 440 is configured to deliver the photocurable composition onto the substrate when the substrate is at the delivery station 423. The delivery station 423 provides the functionality previously described for the delivery station 323. The delivery module 440 may be a gantry-based system that includes an end 442 coupled to a rail (not shown) and allows the delivery module 440 to move in a direction corresponding to up and down in FIG. 4. The delivery module 440 includes a bridge 444 coupled to the end 442 and allows it to pass over the substrate chuck 433. The delivery head 446 is coupled to the bridge 444 and is configured to move along the bridge 444 between the left-hand side and the right-hand side in FIG. 4. The delivery head 446 may include one or more nozzles that deliver the photocurable composition. The dotted lines in the delivery head 446 are used to indicate that the photocurable composition is delivered along the bottom side of the delivery head 446. The dispensing module 440 is configured to dispense the photocurable composition at different areal densities, as described below for the dispensing head 346 .

[0086] Substrate chucks 433, 435 and 437 have any of the configurations previously described for substrate chucks 333 and 339. In FIG. 4, each station has a dedicated substrate chuck. Any one of substrate chucks 433, 435 and 437 may be coupled to a stage that can facilitate substrate chuck movement. Substrate chuck 433 may be moved to facilitate during application of the photocurable composition. In comparison to substrate chuck 433, substrate chucks 435 and 437 may not need to move and need not be coupled to a stage. In another embodiment, any one or more of the substrate chucks in FIG. 4 can be replaced with a substrate chuck similar to substrate chuck 333 coupled to a stage that allows movement between any two or more of stations 423, 425 and 427 illustrated in FIG. 4.

[0087] Controller 350 is in communication with stations 423, 425 and 427 in FIG. 4 and their components, and facilitates the dispensing, pre-exposure heating and light curing operations previously described with respect to FIG.

[0088] All of the stations in machine 300 or machine 400 may not be in a single machine. Any one or more of stations 323, 326, 329, 423, 425, and 427 may be located in different machines. As a non-limiting example, the temperature at which post-exposure bake station 329 operates may be too high for one or more other stations of the machine. During photocuring in station 326 in FIG. 3 or station 427 in FIG. 4, post-exposure bake station 329 may interfere with proper temperature control of the pre-cured layer of photocurable composition.

[0089] 5 includes a system 500 including machines 501 and 503. Machine 501 is the same as machine 300 in FIG. 3, except that post-exposure bake station 329 and substrate chuck 339 have been moved to machine 503. Machine 503 may further include substrate transfer tool 510, substrate pod 521, controller 550, and memory 552. Substrate transfer tool 510 provides the same functionality as described for substrate transfer tool 310, and substrate pod 521 provides the same functionality as described for substrate pod 321.

[0090] Controller 550 and memory 552 can be used to provide functionality supporting substrate transport tool 510, substrate pod 521, post-exposure bake station 329, and substrate chuck 339. Controller 550 can have any of the configurations and components described for controller 350, and memory 552 can have any of the configurations and components described for memory 352.

[0091] Controllers 350 and 550 can be in communication with one another. For example, one or both of controllers 350 and 550 can be used to verify that a particular lot of substrates with hardened layers in substrate pod 521 have completed processing in machine 501 before firing the substrates and hardened layers in post-exposure bake station 329 in machine 503. In another embodiment, machines 501 and 503 can share a common controller, a common memory, or both a common controller and a common memory, rather than having separate controllers or separate memories in machines 501 and 503.

[0092] Attention is now directed to a method of forming a baked layer on a substrate using machine 300. FIG. 6 includes a process flow diagram of the method described with respect to FIGS. 3 and 7-12. A specific process flow is described below with the diagram, but this diagram is directed to an IAP process. Many different process flows can be used and still achieve the benefits of using the concepts described herein. For example, the process may be used for imprint lithography, where the patterned resist layer is a photocurable composition made using a patterned top material. As used hereafter, the unpatterned top material is referred to as the blank and the patterned top material is referred to as the template. Other variations from the process flow are described later in this specification. After describing the method for machine 300, it is described how the processing may change when using other alternatives, such as machine 400 in FIG. 4 or system 500 in FIG. 5. Substrate chuck 333 in FIGS. 7-9, 11, 12 may include heating means, temperature sensors, or both, as illustrated, for example, in FIG. 10. To simplify understanding of the operations taking place in conjunction with FIGS. 7-9, 11 and 12, the heating means and temperature sensor within substrate chuck 333 in FIG. 10 are not shown in FIGS.

[0093] 3, the method may include transferring a substrate from a substrate pod 321 to a supply station 323. The controller 350 or a local controller may transmit a signal for the substrate transfer tool 310 to remove the substrate from the substrate pod 321 and move the substrate to the supply station 323. The substrate transfer tool 310 may place the substrate on a substrate chuck 333 in the supply station 323.

[0094] The method may include providing a photocurable composition on a substrate in block 222 of FIG. 6. The photocurable composition may include a polymerizable material and a photoinitiator. The photocurable composition may or may not include a solvent. In further embodiments, the photocurable composition may contain other additives. Non-limiting examples of other additives may be surfactants, dispersants, stabilizers, inhibitors, dyes, or combinations thereof.

[0095] The polymerizable material may include a single monomeric compound or a mixture of monomeric compounds. In an embodiment, the polymerizable material may include a multifunctional monomer. The multifunctional monomer in the photocurable composition may comprise a majority of the photocurable composition on a weight percent basis. In an embodiment, the content of the multifunctional monomer in the photocurable composition may be at least 60% by weight based on the total weight of the photocurable composition, or at least 70% by weight based on the total weight of the photocurable composition, or at least 80% by weight, or at least 90% by weight, or at least 92% by weight, or at least 95% by weight. In another embodiment, the content of the multifunctional monomer may be up to 99.5% by weight based on the total weight of the photocurable composition, for example up to 99% by weight, or up to 98% by weight, or up to 97% by weight, or up to 95% by weight, or up to 93% by weight, or up to 90% by weight based on the total weight of the photocurable composition. Furthermore, the content of the polyfunctional monomer may be within a range that includes any of the minimum and maximum values ​​described above, for example, within a range of 60% by weight to 99.5% by weight, 70% by weight to 99% by weight, 80% by weight to 98% by weight, or 90% by weight to 97% by weight, based on the total weight of the photocurable composition.

[0096] In an embodiment, the multifunctional monomer may be a difunctional monomer, a trifunctional monomer, or a tetrafunctional monomer. The functional group may be a vinyl group, an acrylate group, an acrylamide group, a methacrylate group, a maleimide group, an epoxy group, a lactone group, an acetal group, a cyclic ether group, a lactam group, a hydroxyl group, a carboxyl group, a sulfide group, or an amine group, among others. The multifunctional monomer compound may include the same type of functional group (e.g., all functional groups in the multifunctional monomer compound are vinyl groups) or may include different types of functional groups. In an embodiment, the multifunctional monomer may include a multifunctional acrylate monomer, a multifunctional vinyl monomer, or a combination thereof.

[0097] In certain embodiments, the multifunctional monomer may include at least two acrylate groups, or at least three or at least four acrylate groups. As used herein, the term acrylate monomer refers to a substituted or unsubstituted acrylate monomer. Non-limiting examples of substituted acrylate monomers can be C1-C8 alkyl acrylates, such as methacrylate or ethyl acrylate.

[0098] In other embodiments, the multifunctional monomer may contain at least two, or at least three, or at least four vinyl groups.

[0099] In an embodiment, the multifunctional monomer may include both acrylate and vinyl groups. In another embodiment, the multifunctional monomer may further include one or more aromatic ring structures.

[0100] Another multifunctional monomer may contain two or more vinyl groups and at least one aromatic ring structure, such as one or more benzene rings. In embodiments, the multifunctional monomer may include a vinylbenzene or divinylbenzene compound. In certain embodiments, the multifunctional monomer may be a biphenyl or diphenylmethane compound containing two, three, or four vinyl groups.

[0101] Table 1 below contains a list of exemplary multifunctional monomer compounds that can be used as the polymerizable material in the photocurable composition. The list is intended to be illustrative, not comprehensive, and is not intended to limit the polymerizable material compounds that can be used.

[0102] [Table 1-1] [Table 1-2]

[0103] The photoinitiator may include a single photoinitiator compound or a mixture of photoinitiator compounds. In the same or another embodiment, the photoinitiator compound may be an oxime ester compound. The oxime ester compound has the structure of formula (1):

[0104] [ka]

[0105] [In the formula,

[0106] R1 is an aromatic or heterocyclic ring system;

[0107] R2 is H or C1-C8 alkyl;

[0108] R3 is H or C1-C8 alkyl. may have the following structure:

[0109] In certain embodiments, the photoinitiator of the photocurable composition may further comprise a photoinitiator compound that is not an oxime ester compound.

[0110] Table 2 below contains a list of exemplary photoinitiator compounds that can be used in the photocurable compositions. The list is intended to be illustrative, not comprehensive, and is not intended to limit the photoinitiator compounds that can be used.

[0111] [Table 2]

[0112] Irgacure compounds are available from BASF SE, Ludwigshafen am Rhein, Germany. Omnirad is available from IGM Group, Waalwijk, The Netherlands.

[0113] The amount of photoinitiator in the photocurable composition may be at least 1.0% by weight based on the total weight of the photocurable composition, at least 1.5% by weight, at least 2.0% by weight, at least 2.5% by weight, at least 3.0% by weight, at least 3.5% by weight, or at least 4.0% by weight based on the total weight of the photocurable composition. In another embodiment, the amount of photoinitiator in the photocurable composition may be up to 10.0% by weight based on the total weight of the photocurable composition, up to 8.0% by weight, up to 7.0% by weight, up to 6.0% by weight, up to 5.0% by weight, or up to 4.0% by weight based on the total weight of the photocurable composition. The amount of photoinitiator in the photocurable composition may be any value between any of the minimum and maximum numbers stated above, for example, within the range of 1.0% to 10.0% by weight, 1.5% to 8.0% by weight, or 2.0% to 7.0% by weight based on the total weight of the photocurable composition.

[0114] In an embodiment, the photocurable composition may be essentially solvent-free. As used herein, unless otherwise indicated, the term solvent refers to a compound that can dissolve or disperse a polymerizable material, but does not itself polymerize during photocuring of the photocurable composition. The term "essentially solvent-free" herein means that the amount of solvent is up to 5% by weight, based on the total weight of the photocurable composition. In certain embodiments, the amount of solvent can be up to 3% by weight, up to 2% by weight, up to 1% by weight, based on the total weight of the photocurable composition, or the photocurable composition may be solvent-free except for unavoidable impurities.

[0115] In another embodiment, the photocurable composition may include a solvent in an amount greater than 5 wt %, based on the total weight of the photocurable composition. In certain embodiments, the amount of solvent may be at least 10 wt %, based on the total weight of the photocurable composition, or at least 15 wt %, at least 20 wt %, or at least 25 wt %, based on the total weight of the photocurable composition. In another embodiment, the amount of solvent may be up to 40 wt %, up to 30 wt %, up to 20 wt %, or up to 10 wt %, based on the total weight of the photocurable composition. In certain embodiments, the amount of solvent in the photocurable composition may be between any of the minimum and maximum numbers stated above, for example, within the range of 5 wt % to 40 wt %, 10 wt % to 30 wt %, or 15 wt % to 20 wt %, based on the total weight of the photocurable composition.

[0116] The surfactant may comprise a single surfactant compound or a mixture of surfactants. The surfactant compound may be a fluorine-containing compound, and in embodiments, the surfactant may be a fluoroorganic compound. Table 3 below includes a list of exemplary surfactant compounds that may be used in the photocurable composition. The list is intended to be illustrative, not comprehensive, and is not intended to limit the surfactant compounds that may be used.

[0117] [Table 3]

[0118] Capstone™ FS-3100 is available from The Chemours Company of Wilmington, DE, USA.

[0119] The surfactant may be up to 5.0 wt.%, based on the total weight of the photocurable composition. In certain embodiments, the amount of surfactant may be up to 3.0 wt.%, up to 2.0 wt.%, or up to 0.9 wt.%, based on the total weight of the photocurable composition.

[0120] Returning to the methods of Figures 3 and 7, as illustrated in Figure 7, dispensing head 346 dispenses droplets 322 of photocurable composition onto the exposed surface of substrate 302. During the dispensing operation, substrate chuck 333 can be coupled to a stage configured to move substrate chuck 333 (as illustrated by the arrow adjacent substrate 302 in Figure 7). In another embodiment, dispensing head 346 moves and substrate chuck 333 remains stationary. Thus, substrate 302 can move and dispensing head 346 can remain stationary or move as well.

[0121] The substrate 302 can have an exposed surface with protuberances at a relatively high elevation compared to adjacent depressions. In FIG. 7, the exposed surface of the substrate 302 has protrusions 3022 and depressions 3024. The substrate 302 has localized regions with protrusions 3022 at a relatively high areal density compared to the depressions 3024, and other localized regions with depressions 3024 at a relatively high areal density compared to the protrusions 3022. Where the protrusions 3022 occupy a relatively large proportion of the localized region, the photocurable composition is dispensed at a low areal density, and where the depressions 3024 occupy a relatively large proportion of the different localized region, the photocurable composition is dispensed at a high areal density. In reality, the exposed surface of the substrate 302 is significantly more complex than depicted in FIG. 7 and is not limited to only two elevations. The exposed surface of the substrate 302 in FIG. 7 is simplified to aid in understanding the concepts described herein.

[0122] To achieve an appropriate local areal density of the photocurable composition along the exposed surface of the substrate 302, the controller 350 or local controller can transmit signals to move the delivery head 346, a stage coupled to the substrate chuck 333 (if the substrate chuck 333 is coupled to a stage), or both, in the desired direction at the desired speed, such that the delivery head 346 delivers droplets 322 of the photocurable composition at the desired speed.

[0123] 3, 7 and 8, a stage coupled to the substrate chuck 333 can transport the substrate 302 and the droplets of photocurable composition 322 from the supply station 323 to the pre-exposure heating and light curing station 326. The controller 350 or a local controller can transmit signals to cause the stage to move the substrate chuck 333, the substrate 302 and the droplets of photocurable composition 322 from the supply station 323 to the pre-exposure heating and light curing station 326.

[0124] The process further includes contacting the photocurable composition with an upper material at block 224 of FIG. 6. The upper material 422 can be used to assist in forming a cured layer from the droplets 322 of the photocurable composition. In an embodiment, the upper material 422 can be a blank with a flat bottom surface facing the substrate 302 and the droplets 322. Each of the machines 300, 400 and 501 can include an upper material handler that can be used to move and position the upper material 422. In the same or a different embodiment, the upper material 422 can be held by a flattening head in the pre-exposure heating and light curing station 326.

[0125] The overlying material 422 has a transmittance of at least 70%, at least 80%, at least 85%, or at least 90% for the actinic radiation used to photocure the photocurable composition. The overlying material 422 may include a glass-based material, silicon, an organic polymer, a siloxane polymer, a fluorocarbon polymer, sapphire, spinel, another similar material, or any combination thereof. The glass-based material may include soda-lime glass, borosilicate glass, alkali-barium silicate glass, aluminosilicate glass, quartz, fused silica, and the like. In an embodiment, the actinic radiation may be ultraviolet light, and a glass-based material may be used for the overlying material 422. The overlying material 422 may have a thickness in the range of 30 microns to 2000 microns. The contact surface of the overlying material 422 may have a surface area that is at least 90% of the area of ​​the substrate 302, and may have a surface area the same or greater than that of the substrate 302.

[0126] The contact surface of the upper material 422 has a two-dimensional shape including a circle, an oval, a rectangle (including a square), a hexagon, etc. In the embodiment illustrated in Figure 8, the contact surface does not have any depressions or protrusions and can be referred to as a blank. In an alternative embodiment, the upper material has depressions and protrusions that are then transferred to the photocurable composition.

[0127] 3, 8 and 9, the controller 350 or local controller can transmit a signal to bring the upper material 422 and the droplets 322 closer together and into contact. The upper material 422 can be moved, the substrate chuck 333 can be moved, or both the upper material 422 and the substrate chuck 333 can be moved. As the upper material 422 is in contact with the droplets 322 of the photocurable composition, the droplets 322 can coalesce to form a pre-cured layer 502 of the photocurable composition. A top surface 512 of the pre-cured layer 502 meets the contact surface of the bottom of the upper material 422.

[0128] The process further includes heating the pre-cured layer of the photocurable composition in block 226 of FIG. 6. Block 226 may occur when the photocurable composition is between the substrate 302 and the upper material 422 and / or may begin before or during block 224. During the photocuring or subsequent baking operation, the pre-cured layer 502, or the cured layer formed from the pre-cured layer 502, may have a thickness change after photocuring, after the subsequent baking operation, or both. If the pre-cured layer 502 is exposed to actinic radiation, the target temperature for the pre-exposure heating may depend on the desired photocuring temperature. The desired photocuring temperature may depend on the thickness change between the pre-cured layer 502 and the corresponding baked layer after photocuring and baking, or the thickness change between the cured layer and the corresponding baked layer.

[0129] High photocuring temperatures may allow for 0% or near 0% thickness change between the pre-cured layer 502 and the corresponding baked layer, or between the cured layer and the corresponding baked layer. The desired photocuring temperature may depend on the materials in the photocurable composition. Of the materials in the photocurable composition, the polymerizable material has the greatest effect on the temperature selected. The photoinitiator, which may include a single photoinitiator compound or a mixture of photoinitiator compounds, may have a smaller effect on the temperature selected. Other materials in the photocurable composition may have no effect or no significant effect on the temperature selected for pre-exposure heating.

[0130] Empirical data can be generated to determine the desired photocuring temperature. After photocuring and baking, the thickness of the baked layer can be thicker, thinner, or approximately the same as the thickness of the pre-cured layer 502 or the cured layer. A graph can be generated from the empirical data to determine thickness variation. Important variables for the graph can include (1) the particular photocurable composition, (2) post-exposure bake temperature, (3) photocuring temperature, and (4) dose of actinic radiation during photocuring. Data for thickness variation and the four variables can be stored in a table in memory 352. For each line in the graph, three of the four variables can be held constant and the last of the three or four variables is varied to determine the effect on thickness variation. For example, for a particular photocurable composition, the bake temperature and dose are held constant and the photocuring temperature is varied. Further details regarding the empirical data can be found later in the Examples section of this specification.

[0131] The thickness variation between the pre-cured layer 502 and the corresponding baked layer may be within a tolerance range of a target thickness variation. The target thickness variation may be 0%, and the tolerance range may be within a range of values ​​that provide good planarization performance. The tolerance range may be ±2.0% (-2.0% to 2.0%), ±1.0%-1.0% to 1.0%, or ±0.5%-0.5% to 0.5%. For example, a product specification may have a thickness variation of 0%±1.0%, and thus the thickness variation may be within the range of -1.0% to 1.0%. For a particular combination of a particular photocurable composition and a particular bake temperature, a thickness variation of 0% may not be achievable. For example, such a combination may only achieve a thickness variation of -1% at best. A desired photocuring temperature may be selected that corresponds to a thickness variation of -1% or thereabouts.

[0132] The empirical data can be stored in a table in memory 352 or in a database external to machine 300. Controller 350 can receive information regarding the photocurable composition, dose of actinic radiation, bake temperature, or combinations thereof, used to form the baked layer and determine the desired photocuring temperature to be used.

[0133] After the desired light curing temperature is determined, the controller 350 or the local controller can determine a target temperature during pre-exposure heating. The target temperature may be the same as or different from the desired light curing temperature. For example, the substrate 302, pre-cured layer 502, and top material 422 may or may not be cooled between pre-exposure heating and light curing of the pre-cured layer 502. Pre-exposure heating and light curing of the pre-cured layer may occur at the pre-exposure heating and light curing station 326, and the target temperature and the desired light curing temperature may be the same. Briefly referring to FIG. 4, the pre-cured layer 502 may be cooled as the substrate 302, pre-cured layer 502, and top material 422 move from the pre-exposure heating station 425 to the light curing station 427. The target temperature may be higher than the desired light curing temperature because the pre-cured layer 502 is cooled to the desired light curing temperature once in the light curing station 427. After reading this specification, one of ordinary skill in the art will be able to determine the target temperatures for a particular equipment setting and potential temperature change between pre-exposure heating and photo-curing of the pre-cured layer 502 .

[0134] The heating means is used to heat the substrate 302, the pre-curing layer 502, and the upper material 422 to a target temperature. With reference to FIG. 10, the heating means may include a resistive heating element 622 in the substrate chuck 333, or a radiant heating element 624 disposed on the substrate chuck 333. The radiant heating element 624 may include a heat lamp, an infrared lamp, or the like. Although not shown, the heating means may include an electromagnet to assist heating using electromagnetic induction, a microwave generator to generate microwaves, a pump to assist flow of a heated fluid through channels in the substrate chuck 333, or a fan to assist convection with passing a heated gas over the substrate 302, the pre-curing layer 502, and the upper material 422. The heating means may include only one type of heating means (e.g., a resistive heating element, an electromagnet for electromagnetic induction heating, a radiative heating element, a microwave generator, a pump for flowing a heated fluid within the substrate chuck 333, or a fan to assist convection heating) or may include a combination of different types of heating means (a combination of any two or more of the foregoing).

[0135] The heating means provides heat so that the substrate 302, pre-cured layer 502 and top material 422 reach a target temperature that is higher than the ambient temperature. The room in which the machine 300 is located may have an ambient temperature of 20° C. In such a room, the temperature of the pre-cured layer 502 may be increased by heating to cause the pre-cured layer 502 to be at least 21° C. when exposed to actinic radiation. The room may reach an ambient temperature of 24° C. during operation of the machine 300 and the temperature of the pre-cured layer 502 may be increased by heating to cause the pre-cured layer 502 to be at least 25° C. when exposed to actinic radiation. Depending on the ambient temperature, the target temperature may be at least 21° C., at least 25° C., at least 30° C., at least 35° C., or at least 40° C.

[0136] If the photocurable composition in the pre-cured layer 502 is exposed to a high enough temperature, the photocurable composition may substantially polymerize without being exposed to actinic radiation. Thus, the target temperature should not be so high that the photocurable composition substantially polymerizes during the pre-exposure heat. In an embodiment, the target temperature may be up to 150° C. In this case, at 150° C., an insubstantial amount of polymerization may occur. In another embodiment, the target temperature of the pre-exposure heat may be up to 100° C., up to 80° C., or up to 70° C. The target temperature of the pre-exposure heat may be any value between any of the minimum and maximum numbers stated above, for example, within the range of 21° C. to 150° C., 25° C. to 100° C., 30° C. to 80° C., or 35° C. to 70° C.

[0137] During pre-exposure heating, the controller 350 or local controller can receive temperature data from the temperature sensors 632 or 634 and transmit signals to cause the heating means, such as resistive heating elements 622 or radiative heating elements 624, to heat the substrate 302, pre-cured layer 502 and top material 422 to a target temperature.

[0138] The method may include photocuring the photocurable composition to form a cured layer in block 228 of FIG. 6. Referring to FIG. 3, for a particular photocurable composition, memory 352 may include information regarding a target wavelength or target range of wavelengths for actinic radiation, a target dose or target range of doses to use for the photocurable composition, or other data related to photocuring of the photocurable composition. Using such information, controller 350 or local controller can determine parameters for exposing the photocurable composition to actinic radiation. Controller 350 can access empirical data, as previously described, that can provide the desired photocuring temperature for a particular photocurable composition, the bake temperature used during a post-exposure bake, the dose of actinic radiation used to photocure the pre-cured layer 502, or a combination thereof. The temperature at the time of photocuring is referred to herein as the actual photocuring temperature. The actual photocuring temperature may be at or near the desired photocuring temperature. The actual photocuring temperature may be any of the target temperatures and tolerance ranges previously described.

[0139] 3, 10 and 11, the controller 350 and local controller can receive a signal from the temperature sensor or a derivative of such a signal and determine whether the temperature is at the desired photo-curing temperature or within a tolerance range thereof (e.g., ±5° C., ±2° C., ±1° C. or ±0.5° C.). If the temperature is at the desired photo-curing temperature or within a tolerance range thereof, the controller 350 or local controller can transmit a signal to activate the actinic radiation source 732, as illustrated in FIG.

[0140] Actinic radiation is emitted from an actinic radiation source 732. At least 70% of the actinic radiation that reaches the top material 422 is transmitted through the top material 422. The actinic radiation transmitted through the top material 422 activates photoinitiators in the photocurable composition in the pre-cured layer 502 to assist in the polymerization of the polymerizable material in the photocurable composition. The actinic radiation can have a wavelength of at least 10 nm and less than 700 nm. The actinic radiation can be ultraviolet radiation having a wavelength in the range of 10 nm to 400 nm, more particularly in the range of 100 nm to 360 nm. A supplier of the photocurable composition may provide a target wavelength or a target range of wavelengths to use to photocure the photocurable composition.

[0141] The energy from exposure to actinic radiation forms a cured layer 702 (FIG. 11) from the pre-cured layer 502 (FIG. 10). The cured layer 702 has an upper surface 712. The energy substantially polymerizes the polymerizable material to form a polymeric material. The polymeric material may be a single polymeric compound or may be a copolymer. Although substantially polymerized by exposure to actinic radiation, the polymerizable material in the pre-cured layer 502 may not fully polymerize. Further polymerization may occur during a post-exposure bake of the cured layer 702. A supplier of the photocurable composition may provide a target dose or a target range of doses to use for the photocurable composition. Alternatively, one of skill in the art may generate empirical data to determine a dose or range of doses that may be used for a particular photocurable composition.

[0142] The method may further include removing the upper material 422 from the curable layer 702. The photocurable composition may include an internal release agent that remains in the curable layer 702 after polymerization. The internal release agent can help reduce the chance of damaging the curable layer 702 or removing some or all of the curable layer 702 when removing the upper material 422.

[0143] The method may include baking the cured layer to form a baked layer, at block 229 of FIG. 6. During the baking operation, material in the cured layer 702 may be further polymerized, crosslinked, or both. When forming the baked layer 802 in FIG. 12, the baking operation may also serve to remove relatively volatile components, if present, from the cured layer 702. The baked layer 802 has an upper surface 812. The baking operation may or may not result in an additional thickness change between the cured layer 702 and the baked layer 802.

[0144] 3, 11 and 12, the controller 350 or the local controller can transmit a signal for the substrate transfer tool 310 to remove the substrate 302 and the cured layer 702 from the pre-exposure heating and light curing station 326 and move the substrate 302 and the cured layer 702 to the post-exposure bake station 329. The substrate transfer tool 310 can place the substrate 302 on a substrate chuck 339 in the post-exposure bake station 329.

[0145] A heating means in the post-exposure bake station 329 is used to heat the cured layer 702 (FIG. 11) to form the baked layer 802 (FIG. 12). Any of the heating means previously described for the pre-exposure heating operation can be used for the bake operation. The heating means provides heat at a temperature higher than that used for the pre-exposure heating operation. The bake temperature can be at least 100° C. higher than the photocuring temperature. The bake temperature can be at least 100° C., at least 150° C., or at least 200° C. The bake temperature should not be so high that significant decomposition or another deleterious effect on the baked layer 802 occurs. The bake temperature can be up to 500° C., up to 450° C., or up to 400° C. The bake temperature can be any value between any of the minimum and maximum numbers stated above, for example, within the range of 100° C. to 500° C., 150° C. to 450° C., or 200° C. to 400° C. In certain embodiments, the firing temperature may be in the range of 350°C to 400°C.

[0146] The soak time is the time that the substrate 302 and overlying polymer layer are at the bake temperature. The soak time should be sufficient to achieve the necessary or desired amount of further polymerization, or to reduce the amount of volatile components in the polymer layer to a desired amount, or both. The soak time may be at least 0.25 minutes, at least 1 minute, or at least 3 minutes. After a sufficiently long time, further exposure to the bake temperature may not sufficiently improve the polymer layer (e.g., a sufficient amount of polymerization has occurred and the amount of volatile components remaining is sufficiently low to not cause problems during subsequent processing, etc.) or may begin to have deleterious effects, such as, for example, roughening of the top surface 812 of the baked layer 802 or possible delamination of the baked layer 802 from the substrate 302. The soak time may be up to 60 minutes, up to 30 minutes, or up to 15 minutes. The soaking time may be any value between the minimum and maximum numbers stated above, for example, within the range of 0.25 minutes to 60 minutes, 1 minute to 30 minutes, or 3 minutes to 15 minutes.

[0147] The firing operation can be performed using a gas. The gas may include materials that are relatively inert to the cured layer 702 and the fired layer 802. The materials can include N2, CO2, noble gases (Ar, He, etc.), or mixtures thereof. The gas may be free of oxidizing materials, such as O2, O3, N2O, etc., or may include 10 mol% or less, or 0.5 mol% or less of oxidizing materials.

[0148] As shown, the post-exposure bake station 329 is configured to process a single substrate at a time. In another embodiment, the post-exposure bake station 329 can be configured to process multiple substrates during the same bake operation. The post-exposure bake station 329 can include a cassette or other suitable substrate container, or can accept a cassette or other suitable substrate container capable of holding multiple substrates. The post-exposure bake station 329 can be within the machine 300 or can be external to the machine 300.

[0149] 3, the controller 350 or local controller can transmit a signal for the post-exposure bake station 329 to flow an inert gas into the post-exposure bake station 329 and for the heating means to maintain the substrate 302 and the hardened layer 702 at a desired temperature for a soaking time. After the soaking time, the controller 350 or local controller can transmit a signal for the substrate transfer tool 310 to remove the substrate 302 and the baked layer 802 from the post-exposure bake station 329. The substrate 302 and the baked layer 802 can be moved by the substrate transfer tool 310 to a cold plate to reduce the temperature of the substrate 302 and the baked layer 802 before transferring the substrate 302 and the baked layer 802 back to the substrate pod 321. After the cool down is complete, the controller 350 or local controller can transmit a signal for the substrate 302 and the baked layer 802 to be moved to the substrate pod 321.

[0150] This method is primarily described with respect to machine 300 in Figure 3. The method for machine 400 in Figure 4 and system 500 including machines 501 and 503 in Figure 5 may be substantially the same, except as described below.

[0151] 5, the post-exposure bake can occur in a machine 503 that is separate from the machine 501 that performs the feeding, pre-exposure heating and light curing. A human, robot, tram, etc. can also transport a substrate pod having a substrate and a cured layer from machine 501 to machine 503, and the cured layer can be baked to form a baked layer.

[0152] In the machine 400 in FIG. 4, the key operations in the method are performed by dedicated stations. Pre-exposure heating is performed in the pre-exposure heating station 425 and photo-curing is performed in the photo-curing station 427, as compared to the pre-exposure heating and photo-curing station 326, which performs both pre-exposure heating and photo-curing. Each of the stations 425 and 427 can be optimized for its respective operation, but processing can be more complicated. When the substrate with the pre-cured layer of heated photo-curable composition is transported from the pre-exposure heating station 425 to the photo-curing station 427, some cooling of the heated pre-cured layer can occur before photo-curing is performed. The target temperature during pre-exposure heating can be higher than the desired photo-curing temperature to compensate for the cooling during transport between stations 425 and 427. As a non-limiting example, the desired photo-curing temperature can be 60° C. The target temperature can be 63° C. to allow for a temperature drop of 3° C. between the end of the pre-exposure heating and the photo-curing of the heated pre-cured layer. Process control can also be more difficult.

[0153] Machine 400 has a gantry-based feeding module 440. A gantry-based design may be useful if the machine has multiple feeding stations that share feeding module 440. As another alternative, feeding module 440 may be redesigned to fit within feeding station 423. As another alternative, feeding station 323 in FIG. 3 may replace feeding station 423 and feeding module 440 in FIG. 4.

[0154] Machine 400 can also have a stationary substrate chuck, which can simplify the design of machine 400 since no stages are required. Machine 300 (FIG. 3) and machine 501 (FIG. 5) may be modified so that each station has a stationary substrate chuck.

[0155] However, when using stationary substrate chucks, the substrate transfer tool 310 may transfer the substrate, pre-cured layer, and top material between different substrate chucks, causing the top material to shift in position relative to the substrate during transfer. When using stationary substrate chucks, the substrate transfer tool 310 may be used to slow down transfer operations between stations to reduce the possibility of shifting the top material relative to the substrate. In another embodiment, any two or more of the substrate chucks 433, 435, and 437 in FIG. 4 may be replaced by the substrate chuck 333 in FIG. 3 coupled to a stage, and the substrate chuck 333 may be moved rather than moving the substrate between the substrate chucks 433, 435, and 437 in FIG. 4.

[0156] For any one or more of the systems illustrated in Figures 3-5, further processing options are available. In Figure 10, the substrate 302, pre-cured layer 502, and top material 422 are heated together during pre-exposure heating. The substrate 302, the photocurable composition (as droplets 322), or the top material 422 may be heated separately as part of the pre-exposure heating operation. The substrate 302 may be heated before or during application of the droplets 322 of the photocurable composition, the photocurable composition may be heated before application of the droplets 322 on the substrate 302, or the top material 422 may be heated before contacting the droplets 322 of the photocurable composition. Separate heating may complicate the pre-exposure heating operation. For example, the substrate 302, with or without the droplets 322, and the top material 422 may be heated separately before the top material 422 contacts the droplets 322. The temperatures of the substrate 302 and the top material 422 may be different, even when the temperatures are intended to be the same. One or both of the substrate 302, with or without the droplets 322, and the top material 422 can be heated to a target temperature above the desired photocuring temperature. After the pre-cured layer 502 is formed by contact with the top material 422, the combination of the substrate 302, pre-cured layer 502, and top material 422 can be cooled to a temperature at or near the desired photocuring temperature, at which point the pre-cured layer 502 is to be photocured.

[0157] When the substrate 302 and droplet 322 are in the feed station 323, the pre-exposure heating and light curing station 326 (FIGS. 3 and 5), or the pre-exposure heating station 425, or the light curing station 427 (FIG. 4), the upper material 422 can be placed in contact with the droplet 322. The upper material 422 can have a similar size and shape as the substrate 302. The substrate transfer tool 310 can be used to place the upper material 422 in contact with the droplet 322.

[0158] After reading this specification, one of ordinary skill in the art will understand that many system configurations and processing options are available without departing from the concepts described herein, and one of ordinary skill in the art will be able to determine the particular system configuration and the particular method to use to meet the needs or requirements for a particular application.

[0159] The process described above can be used to form a planarization layer or a patterned resist layer from the photocurable composition. The process described above can be incorporated as part of a manufacturing method to make an article. The article can be an electric circuit element, an optical element, a microelectromechanical system (MEMS), a recording element, a sensor, a mold, an integrated circuit, etc. The integrated circuit can be a solid-state memory (e.g., dynamic random access memory (DRAM), static random access memory (SRAM), flash memory and magnetoresistive memory (MRAM)), a microprocessor, a microcontroller, a graphics processing unit, a digital signal processor, a field programmable gate array (FPGA) or a semiconductor element, a power transistor, a charge-coupled device (CCD), an image sensor, etc.

[0160] The method may further include an etching process to transfer an image to the substrate, corresponding to the pattern in either or both of the fired layer or the patterned layer underlying the fired layer. The substrate may further be subjected to other processes for device (article) manufacture, including, for example, curing, oxidation, layering, deposition, doping, planarization, lithography, etching, removal of formative material, dicing, bonding and packaging, etc. The substrate may be processed to produce a number of articles (devices), for example, the substrate may be a semiconductor wafer.

[0161] Working Example The examples described below are provided to demonstrate that the thickness change of the layer formed from the photocurable composition can be affected by the temperature of the photocurable composition during photocuring.The examples are intended to aid in the understanding of the concepts described herein, and are not intended to limit the scope of the present invention, as defined in the appended claims.In the examples, the values ​​for thickness change are rounded to the nearest tenth of a percent.

[0162] Table 4 below includes the photocurable compositions A, B, C and D used in the examples. The values ​​in the table are the parts by weight for each of the components in the photocurable compositions.

[0163] [Table 4]

[0164] 1. Thickness changes caused by light curing are not affected by the contours of features within the substrate

[0165] Example 1 demonstrates that thickness change caused by photocuring is not significantly affected by different line / space dimensions. For all samples in Example 1, photocurable composition D was deposited on a substrate. For some of the substrates, photocurable composition D was patterned using a template with an area having a pattern of 200 nm lines and 200 nm spaces and another area having a pattern of 2 μm lines and 2 μm spaces. The etch depth of the template (50 nm) in these two areas was measured, so the initial height of the features made from photocurable composition D before photocuring is known. For all samples in Example 1, photocurable composition D was applied at 15 J / cm during photocuring. 2 The layers were exposed to actinic radiation at a dose of 100 μm / cm. Data was collected for photocuring temperatures ranging from 22° C. to 70° C. The thickness change was determined by Equation 3 above, where T1 is the etch depth of the template and T2 is the corresponding thickness of the cured layer. FIG. 13 contains data for different patterns and compares the thickness change. The Y-axis is the thickness change between the cured layer (after exposure to actinic radiation and before post-exposure bake) and the originally patterned layer of photocurable composition.

[0166] For a line corresponding to a pattern having 200 nm lines and 200 nm spaces ("center 200 nm"), the thickness change for the layer is approximately -0.1% when the temperature of the photocurable composition during exposure is in the range of 22° C. to 40° C. Increasing the temperature of the photocurable composition D during photocuring from 40° C. to 70° C. increases the thickness change for the layer from -0.1% to -0.6%.

[0167] For lines corresponding to a pattern having 2 μm lines and 2 μm spaces ("2 μm in the middle"), the thickness change for the layer is approximately -0.1% when the temperature of the photocurable composition during exposure is in the range of 22° C. to 30° C. Increasing the temperature of the photocurable composition D during photocuring from 30° C. to 70° C. increases the thickness change for the layer from -0.1% to -0.8%.

[0168] Figure 13 shows the same overall trend for both patterns. For the same photocuring temperature, the thickness change was not significantly affected by the different patterns used to form the lines and spaces from the photocurable composition. Thus, the thickness change, when expressed as a percentage, is not significantly dependent on the geometry of the underlying substrate.

[0169] 2. Thickness change caused by baking after exposure

[0170] Example 2 demonstrates the thickness change between the cured layer and the corresponding baked layer, and therefore, this thickness change corresponds to the bake operation and not the photocuring operation. The thickness change is determined by Equation 3 above, where T1 is the thickness of the cured layer and T2 is the thickness of the corresponding baked layer. For all samples in Example 2, the photocurable composition D was applied at 15 J / cm during photocuring. 2 The substrates were exposed to actinic radiation at a dose of 100 nm. Data was collected for light cure temperatures ranging from 22°C to 70°C. One subset of data was generated at a bake temperature of 350°C and a 2 minute soak time, and another subset of data was generated at a bake temperature of 400°C and a 2 minute soak time. Baking was performed in a N2 ambient. For each substrate, the thicknesses of the cured and fired layers were measured at an array of positions across the substrate.

[0171] FIG. 14 contains data comparing different bake temperatures. The data for both bake temperatures shows a linear increase in thickness change as the light cure temperature increases from 22° C. to 50° C. For the 350° C. bake, the thickness change at a light cure temperature of 22° C. is −0.7% and at a light cure temperature of 50° C. is 0.9%. For the 400° C. bake, the thickness change at a light cure temperature of 22° C. is −1.4% and at a light cure temperature of 50° C. is 1.1%. For both bake temperatures, the thickness change is substantially constant at approximately 1.0% for light cure temperatures in the range of 50° C. to 70° C. For the 350° C. bake, the thickness change at a light cure temperature of approximately 33° C. is approximately 0.0%. For the 400° C. bake, the thickness change at a light cure temperature of approximately 38° C. is approximately 0.0%.

[0172] The Y-axis in Figure 14 has a range of 3.0% (-1.5% to 1.5%), which is approximately 3.3 times larger than the range of the Y-axis in Figure 13, which has a range of 0.9% (99.1% to 100.0%). Thus, for photocurable composition D, the thickness change that occurs during baking is significantly larger than the thickness change that occurs during photocuring.

[0173] 3. Thickness variation between the cured layer and the corresponding baked layer for different photocurable compositions

[0174] Example 3 demonstrates the thickness change between the cured layer and the corresponding baked layer for photocurable compositions A, B, C and D. The thickness change is determined by Equation 3 above, where T1 is the layer thickness of the cured layer and T2 is the thickness of the corresponding baked layer.

[0175] The photocurable composition A was applied onto the substrate and flattened using a flat blank top material. The photocurable composition A was applied at 1.2 J / cm 2 Photocurable composition A was photocured to form a cured layer by exposing it to actinic radiation at a dose of 20 J / cm. Photocurable composition B was dispensed onto a substrate and flattened using a flat blank. Photocurable composition B was applied at a dose of 20 J / cm. 2 Photocurable Composition B was photocured to form a cured layer by exposing it to actinic radiation at a dose of 5 J / cm. Photocurable Composition C was dispensed onto a substrate and leveled using a flat blank. Photocurable Composition C was applied at 5 J / cm. 2 Photocurable Composition C was photocured to form a cured layer by exposing it to actinic radiation at a dose of 15 J / cm. Photocurable Composition D was dispensed onto a substrate and flattened using a flat blank. Photocurable Composition D was applied at a dose of 15 J / cm. 2 Photocurable Composition D was photocured by exposing it to actinic radiation at a dose of 1000 nm to form a cured layer. After photocuring, the substrate and cured layer were baked at a temperature of 350° C. in a N2 environment for a soak time of 2 minutes to form a baked layer on the substrate. The thickness change measurements were based on the film thickness measured before and after baking.

[0176] Figure 15 includes a graph of thickness change as a function of photocuring temperature for four photocurable compositions. Each of the slopes of the lines includes a primary portion having a positive slope and a plateau portion where the thickness change is substantially constant (thickness change is less than or equal to 0.2% absolute) with further increases in photocuring temperature. The transition temperature is the photocuring temperature where the primary portion of the line and the plateau portion of the line merge. Thus, the transition temperature indicates the point where further increases in photocuring temperature do not significantly affect the thickness change.

[0177] For photocurable composition A, the primary portion extends from 22° C. with a thickness change of −4.8% to the transition temperature of 70° C. with a thickness change of −1.5%. The plateau portion of the line begins at the transition temperature of 70° C. The thickness change at a photocuring temperature of 80° C. is −1.6%.

[0178] For photocurable composition B, the primary portion extends from 22° C. with a thickness change of −3.9% to the transition temperature of 80° C. with a thickness change of −0.6%. The plateau portion of the line begins at the transition temperature of 80° C. The thickness change at a photocuring temperature of 90° C. is −0.8% and at a photocuring temperature of 100° C. is −0.6%.

[0179] For photocurable composition C, the primary portion spans from 22° C. with a thickness change of −0.4% to a transition temperature of 40° C. with a thickness change of 0.4%. The plateau portion of the line begins at a transition temperature of 40° C. At a photocuring temperature of 50° C. the thickness change is 0.4% and at a photocuring temperature of 60° C. the thickness change is 0.4%.

[0180] For photocurable composition D, the primary portion spans from 22° C. with a thickness change of −0.7% to the transition temperature of 50° C. with a thickness change of 0.9%. The plateau portion of the line begins at the transition temperature of 50° C. The thickness change at a photocuring temperature of 60° C. is 1.0% and the thickness change at a photocuring temperature of 70° C. is 0.9%.

[0181] Photocurable compositions C and D can be processed to produce 0% thickness variation between the baked and cured layer thicknesses. For photocurable composition C, 0% thickness variation can be achieved at a photocure temperature of 31° C., and for photocurable composition D, 0% thickness variation can be achieved at a photocure temperature of 35° C.

[0182] 4. Thickness change for different photocuring temperatures as a function of actinic radiation dose

[0183] Example 4 demonstrates the thickness change between the cured layer and the corresponding baked layer when the photocurable composition is photocured at different photocuring temperatures. The thickness change is determined by Equation 3 above, where T1 is the thickness of the cured layer and T2 is the thickness of the corresponding baked layer.

[0184] In Example 4, Photocurable Composition B was photocured at photocuring temperatures of 22° C., 60° C. and 80° C., and the corresponding cured layers were baked at 350° C. in a N2 environment for a soak time of 2 minutes.

[0185] Figure 16 contains data for the samples. For the same photocuring temperature, each of the lines shows an asymptotic increase in thickness change as a function of dose. At a dose of 1 J / cm 2 from 20 J / cm 2 As the dose is increased to 2.5 J / cm, the thickness change approaches 0% thickness change. A significantly lower dose can be used when photocuring at a relatively high temperature. 2 The thickness change at a dose of 20 J / cm and a photocuring temperature of 60°C is -3.8%. 2 The thickness change at a dose of 2.5 J / cm and a light curing temperature of 22°C is -3.9%. 2 The thickness change at a dose of 15 J / cm and a photocuring temperature of 80°C is -1.6%. 2 and a photocuring temperature of 60° C., the thickness change is −1.9%. Thus, a lower dose can be used at a higher photocuring temperature to achieve the same or better thickness change (close to 0%). The data in Example 4 suggests using a higher temperature so that a lower dose can be used.

[0186] Some photocurable compositions can use moderate photocuring temperatures (e.g., in the range of 30°C to 50°C) and achieve 0% thickness change. With reference to Example 3 and FIG. 15, photocurable compositions C and D can achieve 0% thickness change at photocuring temperatures of 31°C and 35°C, respectively. Thus, photocuring temperatures that are too high for photocurable compositions C or D may result in thickness changes far from 0% compared to the transition temperature.

[0187] Alternatively, the dose of actinic radiation may be reduced, which shifts the lines downward, including the lines for photocurable compositions C and D in FIG. 15. Empirical data can be generated to determine the dose that produces 0% thickness change when the photocuring temperature is at the transition temperature (the transition between the primary and plateau portions of the line), 40° C. for photocurable composition C, and 50° C. for photocurable composition D. For photocurable compositions C and D, further reduction in dose produces thickness change further away from 0%, so temperatures higher than the transition temperature do not significantly improve throughput. Thus, photocuring temperatures above 50° C. are a waste of energy and do not significantly improve the possibility of achieving 0% thickness change.

[0188] Using the embodiments described herein, the thickness change between baked and uncured layers or baked and cured layers of the photocurable composition can be kept closer to 0% when comparing photocuring temperatures higher than ambient temperature compared to photocuring at ambient temperature. At moderate photocuring temperatures, 0% thickness change can be achieved compared to photocuring temperatures that are too low or too high. Better dimensional stability helps make the process more robust and reproducible from substrate to substrate and production lot to production lot. The inventors have found that for each material, there is a photocuring thickness change that depends on the photocuring temperature and a baked thickness change that depends on the bake temperature. The inventors have found that choosing one of the photocuring thickness change and the baked thickness change to be positive and the other negative, gives an optimal thickness change as close to zero as possible.

[0189] It should be noted that not all of the acts described above are required in the overall description or examples, some of the particular acts may not be required, and one or more additional acts may be performed in addition to those described. Furthermore, the order in which the acts are listed is not necessarily the order in which they are performed.

[0190] Benefits, other advantages, and solutions to problems have been described above with respect to particular embodiments. However, the benefits, advantages, solutions to problems, and any features that may give rise to or make more pronounced any benefit, advantage, or solution should not be construed as essential, required, or essential features of any claim.

[0191] The specification and description of the embodiments described herein are intended to provide a general understanding of the structure of the various embodiments. The specification and description are not intended to serve as an exhaustive and comprehensive description of all of the elements and features of machines and systems using the structures or methods described herein. Separate embodiments may be provided in combination in a single embodiment, and conversely, various features described for brevity in the context of a single embodiment may be provided separately or in any subcombination. Furthermore, references to values ​​stated in ranges include every value within that range. Many other embodiments may become apparent to those skilled in the art only after reading this specification. Other embodiments may be used and derived from this disclosure, and structural substitutions, logical substitutions, or other changes may be made without departing from the scope of the disclosure. Thus, the disclosure should be considered illustrative and not restrictive.

Claims

1. a first heating means for heating the photocurable composition on the substrate; an actinic radiation source configured to emit actinic radiation at a wavelength less than 700 nm; and a controller configured to determine a target temperature to be generated by the first heating means to achieve a photocure temperature of the photocurable composition when the photocurable composition is exposed to a source of actinic radiation, the photocure temperature being greater than an ambient temperature; Including, the system.

2. 10. The system of claim 1, wherein the system includes a machine, and the first heating means and the source of actinic radiation are in the same station within the machine.

3. a first substrate chuck configured to hold the substrate while the photocurable composition is at a photocuring temperature and exposed to actinic radiation; The system of claim 1 further comprising:

4. a second substrate chuck configured to hold the substrate while the photocurable composition is exposed to the first heating means; and a substrate transfer tool configured to transfer a substrate having a photocurable composition between a first substrate chuck and a second substrate chuck; The system of claim 3 further comprising:

5. A delivery head configured to deliver a photocurable composition onto a substrate. The system of claim 1 further comprising:

6. a station configured to place a top material in contact with the photocurable composition overlying the substrate; The system of claim 1 further comprising:

7. A second heating means configured to heat the cured layer corresponding to the photocurable composition to form a baked layer, the second heating means being configured to heat the substrate and the cured layer to a bake temperature higher than the photocuring temperature. The system of claim 1 further comprising:

8. a temperature sensor configured to generate a first signal corresponding to a temperature of the photocurable composition; Further comprising: the controller is further configured to receive the first signal and transmit a second signal to activate the actinic radiation source when the temperature is within ±5° C. of the photocuring temperature. The system of claim 1 .

9. providing a photocurable composition onto a substrate, the photocurable composition comprising a multifunctional monomer; photocuring the photocurable composition while the photocurable composition is at a photocure temperature greater than ambient temperature, whereby a cured layer is formed on the substrate; and Firing the cured layer to form a baked layer, the baking being carried out at a baking temperature higher than the photo-curing temperature. The method includes:

10. The method of claim 9, wherein the light curing temperature is greater than 25°C.

11. 11. The method of claim 10, wherein the calcination temperature is up to 500°C.

12. The method of claim 9 , wherein the photocurable composition is at the photocuring temperature while in contact with the substrate and upper.

13. the cured thickness is the thickness of the cured layer of the photocurable composition before baking; The fired thickness is the thickness of the fired layer, The thickness change is ((T ２ -T １ ) / T １ )×100% (In the formula, T １ is the cured thickness, T ２ is the fired thickness, The thickness change is within the range of -2.0% to 2.0%.

10. The method of claim 9.

14. The method of claim 9 , wherein the multifunctional monomer comprises a difunctional monomer, a trifunctional monomer, or a tetrafunctional monomer.

15. The method of claim 9 , wherein the multifunctional monomer comprises two or more vinyl groups.

16. The method of claim 15 , wherein the multifunctional monomer comprises at least one aromatic ring structure.

17. The method of claim 9 , wherein the multifunctional monomer comprises an acrylate group.

18. The method of claim 9, wherein in the photocurable composition, the content of the multifunctional monomer is at least 90% by weight of the photocurable composition.

19. receiving a firing temperature at which the cured layer is to be fired; and Determining the light curing temperature based on the baking temperature The method of claim 9 further comprising:

20. a light curing station configured to form a cured layer on the substrate at a light curing temperature, the light curing temperature being greater than an ambient temperature; a bake station configured to bake the hardened layer at a bake temperature to form a baked layer; and a controller configured to determine a light curing temperature based at least in part on the bake temperature. Including, the system.

21. The light curing station a heating means configured to heat the photocurable composition on the substrate to a temperature that is at or is closer to the photocuring temperature than ambient temperature; and An actinic radiation source configured to emit radiation at wavelengths less than 700 nm The system of claim 20, comprising:

22. a robotic arm configured to move the substrate having the cured layer from the light curing station to a baking station; 21. The system of claim 20, further comprising:

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