US20230256465A1 - Scaling and coating of continuous multi-material stripes and patterns - Google Patents
Scaling and coating of continuous multi-material stripes and patterns Download PDFInfo
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- US20230256465A1 US20230256465A1 US18/305,258 US202318305258A US2023256465A1 US 20230256465 A1 US20230256465 A1 US 20230256465A1 US 202318305258 A US202318305258 A US 202318305258A US 2023256465 A1 US2023256465 A1 US 2023256465A1
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- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/0254—Coating heads with slot-shaped outlet
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C5/00—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work
- B05C5/02—Apparatus in which liquid or other fluent material is projected, poured or allowed to flow on to the surface of the work the liquid or other fluent material being discharged through an outlet orifice by pressure, e.g. from an outlet device in contact or almost in contact, with the work
- B05C5/027—Coating heads with several outlets, e.g. aligned transversally to the moving direction of a web to be coated
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- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
- B05C9/06—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying two different liquids or other fluent materials, or the same liquid or other fluent material twice, to the same side of the work
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
- B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
- B29C48/307—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets specially adapted for bringing together components, e.g. melts within the die
Definitions
- the various embodiments of this disclosure relate generally to coating thin films and, more particularly, to an apparatus and method for producing scaled and patterned thin films.
- Slot die coating is a method of creating thin films on a substrate from liquid materials.
- the essence of the process is a die consisting of two halves separated by a shim, with a pressurized reservoir, or chamber, machined into one of the halves containing fluid.
- the purpose of the shim is to create a gap between the two halves through which the fluid may flow.
- the purpose of the chamber is to uniformly distribute the fluid therein along the width of the gap.
- slot die designs are generally limited to lines or stripes that are the opening of the shim, thereby limiting the ability of the slot die to create other desired patterns.
- Patterned film deposition is a powerful manufacturing paradigm with applications spanning optoelectronics, sensors, computing, and wearable energy conversion.
- Liquid-phase film deposition techniques have long been recognized as suitable for rapid, continuous, low-waste processing near room temperature. Several of these techniques are adaptations of earlier graphical printing technologies, and thus the devices themselves are colloquially referred to as “printed.” This nomenclature also reflects the perception that liquid-phase coating and patterning methods are amenable to roll-to-roll (R2R) manufacturing with significant economies of scale.
- R2R roll-to-roll
- scalability challenges in manufacturing have persisted, despite considerable progress in the materials and structures available for printed devices.
- One contributing factor may be that patterned coating techniques in use today have remained fundamentally unchanged for decades. It follows that new processing methods may prove broadly valuable for the field of printed thin film devices, if they can be adapted to wide-area deposition.
- Some exemplary embodiments of this disclosure provide an apparatus and a system for scaling and patterning thin film materials. Other exemplary embodiments provide methods of producing scaled and patterned thin film materials.
- a hybrid scaling patterning system To realize a system capable of producing on-demand, patterned films of high uniformity, there is provided a hybrid scaling patterning system.
- This system allows for single-step deposition of multi-material patterned thin films, and thus, improved patterned thin film processing for technologies that require more elaborate or arbitrary film patterns.
- a method comprises co-laminar flowing of at least a first material and a second material within a slot die and depositing from a slot of the slot die a width-wise multi-material stripe pattern of the first and second materials, wherein the material of adjacent stripes of the width-wise multi-material stripe pattern differ across a width of the slot.
- the method can further comprise feeding the first material into the slot die via a set of first inlets, feeding the second material into the slot die via a set of second inlets, and forming a stripe-patterned co-laminar flow in an interaction channel of the slot die, wherein a continuous flow path exists between the first set of inlets and the interaction channel, and wherein a continuous flow path exists between the second set of inlets and the interaction channel.
- the method can further comprise controlling uniformity of the width-wise multi-material stripe pattern.
- the method can further comprise dimensionally scaling the width-wise multi-material stripe pattern.
- the width-wise multi-material stripe pattern can be deposited on a surface of a substrate.
- the substrate can be selected from the group consisting of paper, glass, thin plastic film, and thin metallic film.
- the first and second materials can flow through the slot die in a planar, continuous laminar flow.
- the first and second materials can flow through the slot die in a planar, continuous creeping flow.
- a method comprises feeding two or more fluid materials into a slot die via two or more sets of fluid inlets, each respective fluid material feeding into the slot die via a respective set of fluid inlets and depositing a width-wise multi-material stripe pattern of the two or more fluid materials, wherein adjacent stripes of the width-wise multi-material stripe pattern comprise different fluid materials.
- the method can further comprise controlling a width of at least a portion of the stripes in the width-wise multi-material stripe pattern.
- the method can further comprise dimensionally scaling at least a portion of the width-wise multi-material stripe pattern.
- the slot die can comprise a first plate, a second plate, and a shim separating the plates.
- the method can further comprise interacting the two or more fluid materials in an interaction channel of the slot die, wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel, wherein the two or more fluid materials flow through the slot die in a flow selected from the group consisting of a planar, continuous laminar flow and a planar, continuous creeping flow, and wherein the width-wise multi-material stripe pattern is deposited on a surface of a substrate.
- each respective set of the fluid inlets can be both positioned at a fluid inlet height position between a top and bottom of the slot die, the distance between the top and bottom of the slot die defining a height of the slot die and positioned at a fluid inlet width position between a first side and a second side of the slot die, the distance between the sides of the slot die defining a width of the slot die.
- each fluid inlet height position of a respective set of the fluid inlets can the same.
- each fluid inlet width position of a respective set of the fluid inlets can be different.
- each respective set of the fluid inlets can present a horizontal line of spaced-apart fluid inlets.
- each horizontal line of spaced-apart fluid inlets can be at a different fluid inlet height position one from another.
- a method comprises feeding two or more different fluid materials into a slot die via two or more sets of fluid inlets, each respective fluid material feeding into the slot die via a respective set of fluid inlets, interacting the two or more different fluid materials in an interaction channel of the slot die, wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel, depositing a width-wise multi-material stripe pattern of the two or more different fluid materials on a surface of a substrate, and at least one of controlling a width of at least a portion of the stripes in the width-wise multi-material stripe pattern, and/or dimensionally scaling at least a portion of the width-wise multi-material stripe pattern, wherein no adjacent stripes of the width-wise multi-material stripe pattern comprise the same fluid material.
- an apparatus for depositing the width-wise multi-material stripe pattern can comprise the slot die, a set of first inlets for the feeding of the first material into the slot die, a set of second inlets for the feeding of the second material into the slot die, and an interaction channel of the slot die for forming a stripe-patterned co-laminar flow of the first material and the second material.
- an apparatus for depositing the width-wise multi-material stripe pattern according to any of the exemplary methods can comprise the slot die and an interaction channel of the slot die for interacting the two or more fluid materials, wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel.
- the slot die can comprise a first plate, a second plate, and a shim separating the plates.
- the slot die can be a shimfree slot die.
- the interaction channel can define a volume extending in a flow direction from an upstream upper portion to a downstream lower portion.
- the volume of the interaction channel can have a converging cross-sectional area from the upstream upper portion to the downstream lower portion.
- an apparatus for patterning thin films comprises a slot die having a body comprising first and second plates, at least two fluid inlets, one fluid inlet for feeding a first material into the slot die and the other fluid inlet for feeding a second material into the slot die, and at least two channels formed inside of the slot die, one channel for receiving the first material, and the other channel for receiving the second material, each of the channels having a channel inlet end and a channel outlet end.
- the first and second materials can travel from the channel inlet ends of the channels to the channel outlet ends of the channels in a planar, continuous laminar flow.
- each of the channels can be converging channels.
- a total width of all the channel inlet ends of the converging channels can be greater than a total width of all the channel outlet ends of the converging channels.
- a width of the channel inlet end of each of the converging channels can be greater than a width of the channel outlet end of each of the converging channels.
- the apparatus can comprise eight inlets.
- the apparatus can comprise eight converging channels.
- the first and second materials can travel from the channel inlet ends of the channels to the channel outlet ends of the channels in a planar, continuous creeping flow.
- the apparatus can comprise a material selected from the group consisting of stainless steel, aluminum, nylon, polycarbonate and combinations thereof.
- the apparatus can be configured to generate a multi-material stripe pattern from interaction between the first and second materials within the die body.
- a method of preparing a multi-material, patterned thin film material comprises providing an apparatus having a slot die having a body comprising first and second plates; at least two inlets, one inlet for feeding a first material into the slot die and the other inlet for feeding a second material into the slot die; and at least two channels formed inside of the slot die, one channel for receiving the first material, and the other channel for receiving the second material, each of the channels having a channel inlet end and a channel outlet end, and feeding the first material into the slot die through the one inlet and feeding the second material into the slot die through the other inlet, wherein the first and second materials travel from the channel inlet ends of the channels to the channel outlet ends of the channels in a planar, continuous laminar flow.
- the slot die used in the method need not include a shim.
- each of the channels used in the method can be converging channels.
- a total width all of channel inlet ends of the converging channels can be greater than a total width of all of the channel outlet ends of the converging channels.
- a width of the channel inlet end of each of the converging channels can be greater than a width of the channel outlet end of each of the converging channels.
- the first and second materials can travel from the channel inlet ends of the channels to the channel outlet ends of the channels in a planar, continuous creeping flow
- the invention can further comprise depositing a fluid onto a substrate surface.
- the substrate can be selected from the group consisting of paper, glass, thin plastic film, and thin metallic film.
- a method of making patterned thin film materials includes designing a surface pattern, inputting parameters of the designed surface pattern into a computer, passing a substrate having a substrate surface under a hybrid patterning apparatus, and patterning the designed surface pattern onto the passing substrate surface using the hybrid patterning apparatus.
- an apparatus for patterning thin films comprises a slot die comprising a first plate, a second plate, and a shim separating the plates, at least two fluid inlets, a first fluid inlet positioned at a first fluid inlet height position between a top and bottom of the slot die, the distance between the top and bottom of the slot die defining a height of the slot die, positioned at a first fluid inlet width position between a first side and a second side of the slot die, the distance between the sides of the slot die defining a width of the slot die; and configured for feeding a first fluid material into the slot die and to the shim, and a second fluid inlet positioned at a second fluid inlet height position, positioned at a second fluid inlet width position different than the first fluid inlet width position, and configured for feeding a second fluid material into the slot die and to the shim, and at least three channels formed at least in part by the shim inside of the slot die, a first inlet channel fluidly communicative with
- the first, second, and third channels can be configured to enable fluidic communication through the slot die in a planar, continuous laminar flow.
- the first, second, and third channels can be configured to enable fluidic communication through the slot die in a planar, continuous flow.
- the slot die can comprise a material selected from the group consisting of stainless steel, aluminum, nylon, polycarbonate and combinations thereof.
- narrowing of the third channel width along a primary axis of flow can cause interaction between the first fluid material and the second fluid material that is not disruptive to pattern formation.
- the slot die can have a width defined from a first side of the slot die to a second side of the slot die, a thickness defined from a front face of the slot die to a rear face of the slot die, and a height defined from a top of the slot die to a bottom of the slot die.
- the first fluid inlet can be a first fluid material inlet.
- the second fluid inlet can be a second fluid material inlet.
- the fluid multi-material outlet can be configured to deposit a fluid multi-material onto a substrate.
- the third interaction channel can define a volume extending in a flow direction from an upstream upper portion to a downstream lower portion.
- the volume of the third interaction channel can have a converging cross-sectional area from the upstream upper portion to the downstream lower portion.
- the first inlet, the second inlet and third interaction channel can form a channel system configured to provide fluidic communication between the first fluid material inlet and the third interaction channel, the second fluid material inlet and the third interaction channel, and the third interaction channel and the fluid multi-material outlet.
- the first material inlet can be located on one of the front and rear faces of the slot die.
- the second material inlet can be located on one of the front and rear faces of the slot die.
- the third interaction channel can define a volume extending in a flow direction from an upstream upper portion to a downstream lower portion, the upstream upper portion located along the height of the slot die below both the first and second material inlets, and the downstream lower portion located along the height of the slot die above the fluid multi-material outlet.
- the volume of the third interaction channel can converge in cross-sectional area from the upstream upper portion to the downstream lower portion.
- the channel system can be configured to provide the fluidic communication in a planar, continuous laminar flow.
- the channel system can be configured to provide the fluidic communication in a planar, continuous creeping flow.
- the channel system can further comprise one or more additional interaction channels.
- each of the additional interaction channels can be communicative at an upstream end to the first and second fluid material inlets, and at a downstream end to the fluid multi-material outlet.
- an apparatus for patterning thin films comprises a slot die comprising a first plate, a second plate, and a shim separating the plates, a first set of fluid inlets for feeding a first fluid material into the slot die, a second set of fluid inlets for feeding a second fluid material into the slot die at the same time as the feeding of the first fluid material, a first set of inlet channels defined at least in part by the shim laterally spaced apart along a width of the slot die and configured to receive the first fluid material, each of the inlet channels of the first set of inlet channels having a channel inlet coincident with a respective fluid inlet of the first set of fluid inlets in the slot die, a second set of inlet channels defined at least in part by the shim laterally spaced apart along the width of the slot die and configured to receive the second fluid material, each of the inlet channels of the second set of inlet channels having a channel inlet coincident with a respective fluid inlet of the second set of fluid inlets in the
- the slot die can be configured to generate a scaled multi-material stripe pattern from interaction between the first and second fluid materials within the third interaction channel.
- the first set of fluid inlets can lie in a row at a first height of the slot die across the width of the slot die.
- the second set of fluid inlets can lie in a row at a second height of the slot die across the width of the slot die.
- the first height can be different than the second height, such that the length of each of the inlet channels of the first set is different than the length of each of the inlet channels of the second set.
- a method of thin film material deposition on a substrate comprises feeding a first fluid material into a slot die via a first fluid inlet, feeding a second fluid material into the slot die via a second fluid inlet, forming a fluid multi-material by interacting the first fluid material and the second fluid material in an interaction channel within the slot die, the interaction channel in fluidic communication with the first and second fluid inlets, and depositing the fluid multi-material onto the substrate via an outlet of the slot die in fluidic communication with the interaction channel, wherein the first and second materials flow through the slot die in a planar, continuous laminar flow.
- the interaction channel can define a volume extending in a flow direction from an upstream upper portion to a downstream lower portion.
- the volume of the interaction channel can have a converging cross-sectional area from the upstream upper portion to the downstream lower portion.
- the substrate can be selected from the group consisting of paper, glass, thin plastic film, and thin metallic film.
- a patterning system comprises a disclosed apparatus, a first fluid material, and a second fluid material different than the first fluid material, wherein the first fluid material is introduced into the slot die via the first fluid material inlet, wherein the second fluid material is introduced into the slot die via the second fluid material inlet, wherein the first and second fluid materials interact within the third interaction channel to form a fluid multi-material, and wherein the fluid multi-material exits the slot die via the fluid multi-material outlet.
- FIG. 1 illustrates a hybrid patterning apparatus in accordance with an exemplary embodiment of the disclosure.
- FIGS. 2 A- 2 B illustrate components of a hybrid patterning apparatus, in accordance with an exemplary embodiment of this disclosure.
- FIGS. 3 A- 3 B illustrate the internal cavity geometry of a hybrid patterning apparatus, without internal scaling of the pattern, and corresponding deposition of a heterogeneous film pattern comprising multi-material stripes of two distinct materials in an alternating sequence.
- FIGS. 4 A- 4 B illustrate the internal cavity geometry of a hybrid patterning apparatus with internal scaling of the pattern, in accordance with an exemplary embodiment of this disclosure.
- FIGS. 5 A- 5 B illustrate test results related to single material deposition in narrow stripes, in accordance with an exemplary embodiment of this disclosure.
- FIGS. 6 A- 6 B illustrate results from a start and stop mechanism of the hybrid apparatus, in accordance with an exemplary embodiment of this disclosure.
- FIGS. 7 A- 7 B illustrate test results related to multi-material deposition, in accordance with an exemplary embodiment of this disclosure.
- FIGS. 8 A- 8 B illustrate a simultaneous deposition of PDMS and PVA during flow start-up and after contact between two fluid regions.
- FIGS. 9 A- 9 B illustrate multi-material stripe film structures constructed from various multi-material configurations and the static force balance for interacting stripes, in accordance with an exemplary embodiment of the disclosure.
- FIG. 10 illustrates a pattern with converging internal geometry in accordance with an exemplary embodiment of the disclosure.
- FIG. 11 illustrates a pattern with converging, multi-material stripes of two materials in alternating sequence in accordance with an exemplary embodiment of the disclosure.
- Ranges may be expressed herein as from “about” or “approximately” or “substantially” one particular value and/or to “about” or “approximately” or “substantially” another particular value. When such a range is expressed, other exemplary embodiments include from the one particular value and/or to the other particular value.
- substantially free of something can include both being “at least substantially free” of something, or “at least substantially pure”, and being “completely free” of something, or “completely pure”.
- the various exemplary embodiments of this disclosure relate to a system and apparatus for the patterning of thin films.
- the methods of manufacturing patterned thin films using the hybrid system are also described herein.
- a coating tool 100 e.g. slot die, hybrid patterning apparatus
- a heterogeneous liquid film 101 comprising two or more liquid materials in a horizontally-patterned configuration
- an array of two or more fluid inlets 102 e.g., a flow of ink or other coating fluid 103 into the hybrid coating apparatus, and a region of outflow of ink or other coating fluid 104 out of hybrid coating apparatus 100 and onto a substrate to form a liquid film.
- hybrid patterning apparatus can further include substrate 106 , ink or coating fluid 107 outflow from hybrid patterning apparatus 100 , liquid bridge 108 between coating tool outlet region and deposited liquid film, and a die plate 109 of the hybrid patterning apparatus 100 .
- one or more liquid bridges form between the coating tool outlet and the substrate.
- the transfer of fluid through each liquid bridge forms a patterned liquid film on the substrate surface.
- the volumetric flow rate Q, substrate velocity V relative to the coating tool, and the coating gap H between tool outlet and substrate are input parameters that can be varied during operation.
- FIGS. 2 A- 2 B shows slot die components in certain exemplary embodiments of the disclosure.
- the hybrid slot coating tool can include a slot die that includes a die body having two halves, or first and second plates, 201 a , 201 b , separated by one or more shims 202 with cutout(s) forming a slot-shaped cavity 202 positioned between first and second plates 201 a , 201 b for containing fluid to be deposited. It further includes an array of inlets 203 for delivering coating fluid to discrete regions of the internal geometry, an external manifold or distribution chamber 204 for coating fluid delivered to inlet array 203 .
- FIG. 1 shows slot die components in certain exemplary embodiments of the disclosure.
- the hybrid slot coating tool can include a slot die that includes a die body having two halves, or first and second plates, 201 a , 201 b , separated by one or more shims 202 with cutout(s) forming a slot-shaped cavity 202 positioned between
- FIG. 2 B shows an alternate view of this exemplary embodiment of the hybrid patterning apparatus, with first and second plates, 205 a , 205 b , separated by one or more shims 206 with cutout(s) forming an internal slot-shaped cavity, internal distribution chambers, channels or cavities with inlet ends 207 integrated into one or more of the plates, 205 a , 205 b .
- the internal distribution chambers, channels or cavities are converging.
- the purpose of shim(s) 206 is to create a slot gap between first and second plates 205 a , 205 b through which the fluid may flow.
- slot gap can lead from cavity to an opening or a series of channel outlet ends.
- cutouts in the shims define the geometry of the slot, and the shims can be interchanged to implement different flow behaviors and patterning strategies.
- At least two fluid inlets can be used to feed fluid to the slot.
- multiple separate fluid inlets can be used (e.g., 3 inlets, 4 inlets, 5 inlets, 6 inlets, 7 inlets, 8 inlets, 9 inlets, 11 inlets, 13 inlets, 15 inlets, 17 inlets, 20 inlets).
- the shim configuration can be used for simultaneous deposition of two or more coating materials as alternating stripes.
- a heterogeneous multi-material stripe pattern is produced when two fluids are fed into alternating inlets (for example, corresponding both to alternating height positions of two rows of inlets, and alternating width positions of each inlet of the two rows of inlets, alternating laterally along a width of the slot die) of the hybrid slot coating tool. While slot coating has previously been adapted for deposition of narrow stripes of a single material, depositing two or more coating fluids simultaneously into a single-layer pattern is at least one novelty to this disclosure.
- the array of inlets 102 , 203 , 401 can include a first set of fluid inlets that lie in a row at a first height of the slot die across the width of the slot die, and a second set of fluid inlets that lie in a row at a second height of the slot die across the width of the slot die, wherein the first height is different than the second height, such that the length of each of the inlet channels of the first set is different than the length of each of the inlet channels of the second set.
- FIG. 3 A shows a shim material with cutout or cavity in a die plate forming an internal slot cavity. It further illustrates a region of cavity 301 corresponding to flow through each of fluid inlets 203 , or from each of fluid outlets 207 . Separation between different coating fluid species throughout the internal cavity is shown at 302 . In some exemplary embodiments, the separation between the different coating fluid species is a physical separation. Separate outlet regions 303 correspond to separate flow streams within the coating apparatus. As shown in FIG. 3 B , in some exemplary embodiments, hybrid patterning apparatus 304 can be assembled using the internal geometry shown in FIG. 3 A . FIG. 3 B further illustrates inflow of first coating fluid species 305 , inflow of a second coating fluid species 306 , and outflow of a heterogenous film comprising stripe-shaped regions of composition alternating between the first and second fluid species 307 .
- the slot die body can be made of any machinable material typically used in making slot die. These include but are not limited to stainless steel, aluminum, titanium, nylon, polycarbonate and combinations thereof.
- the material used to make slot die body generally is a function of the fluid that will be deposited. There should be compatibility between the slot die and the fluid with respect to chemical, electrical, mechanical, and physical properties.
- a pattern-scaling mechanism can cause interaction between different coating fluids without a shim, which is not disruptive to the pattern formation.
- a shim material with cutout or cavity in die block forms an internal slot cavity.
- Cavity region 400 corresponds to flow through each of inlets 401 , or from each of outlets 407 .
- Region 402 corresponds to maximum width W 1 of channels where multiple coating fluid species interact. In some exemplary embodiments, the species interact physically.
- Region 403 corresponds to width W 2 of channels and is connected to outlet region of the hybrid patterning apparatus. In some exemplary embodiments, W 2 ⁇ W 1 .
- Region 404 corresponds to varying width channels connecting cavity regions 402 and 403 .
- hybrid patterning apparatus 405 can be assembled using the internal geometry shown in FIG. 4 A .
- FIG. 4 B further illustrates inflow of first coating fluid species 406 , inflow of a second coating fluid species 407 , and outflow of a scaled heterogenous multi-material stripe-patterned film 408 .
- the internal tool geometry is considerably reduced. Rather, a multi-material stripe phase field is established by the array of inlet channels opening into a single-wide slot, without a physical barrier separating the fluids in the channels.
- Narrowing of the channel width along the primary axis of flow produces a proportional narrowing of each phase region, a useful phenomenon that single-phase slot extrusion cannot exploit. This represents an improvement over previous tool designs, where the minimum achievable center-to-center distance of the narrow stripe pattern is essentially attributable to the precision of tool fabrication and assembly.
- the present invention can comprise an apparatus for patterning thin films including the slot die, at least two fluid inlets 406 , 407 , a first fluid inlet configured for feeding a first fluid material into the slot die and a second fluid inlet configured for feeding a second fluid material into the slot die, and at least three channels formed inside of the slot die, a first inlet channel configured to receive the first fluid material, a second inlet channel configured to receive the second fluid material, and a third interaction channel 402 , 404 , wherein each of the first and second inlet channels have a channel inlet coincident with the respective first and second fluid inlets 406 , 407 in the slot die, wherein the third interaction channel 402 , 404 is communicative at an upstream end to the first and second inlet channels and configured to receive a flow of the first fluid material and the second fluid material, and at a downstream end to a fluid multi-material outlet 403 in the slot die through which
- the apparatus for patterning thin films can comprise the slot die, a first set of fluid inlets for feeding the first fluid material into the slot die, a second set of fluid inlets for feeding the second fluid material into the slot die, a first set of inlet channels laterally spaced apart and configured to receive the first fluid material, each of the inlet channels of the first set of inlet channels having a channel inlet coincident with a respective fluid inlet of the first set of fluid inlets in the slot die, a second set of inlet channels laterally spaced apart and configured to receive the second fluid material, each of the inlet channels of the second set of inlet channels having a channel inlet coincident with a respective fluid inlet of the second set of fluid inlets in the slot die, and a third interaction channel communicative connected at an upstream end to the first and second sets of inlet channels, and at a downstream end to the fluid multi-material outlet in the slot die through which a pattern of alternating first fluid material and second fluid material can flow, wherein the first set of inlet
- the feature size capability of the hybrid slot coating can be tied to the minimum stripe width that can be deposited through an isolated liquid bridge.
- FIG. 5 A illustrates the coating tool configuration used to produce this pattern feature under steady flow conditions.
- the fractional deviation in stripe width from tool inlet spacing, expressed as w* ⁇ (w - w 0 )/w 0 is plotted in FIG. 5 B against the dimensionless quantity Q* ⁇ Q/(VGw 0 ), which represents fluid volume per unit width of substrate.
- Correlations between w* and Q*, and between H and Q* comprise a two-parameter process input domain for controlling stripe geometry. Variations across the different coating fluids in FIG.
- aqueous polyvinyl alcohol (PVA) is more viscous than the other fluids by an order of magnitude, and both surface tension and contact angle of a surfactant-doped 1.3% aqueous dispersion of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) is significantly lower than that of aqueous PVA.
- PVA polyvinyl alcohol
- the coating tool 100 can include mechanisms to start and stop the scaling and patterning process.
- FIG. 6 A shows a configuration of the hybrid slot coating tool used to produce a segmented narrow stripe of 15% aqueous PVA on flexible PET substrate. The break in the stripe is produced by periodic flow cutoff and startup through a single inlet.
- FIG. 6 B shows a comparison of actuation performance for various control schemes, measured as the length of the tapering at the leading and trailing edges of each stripe segment. The sum of l START and l STOP can be considered a lower limit on the minimum feature size along the x-axis.
- FIG. 6 B compares the severity of this measurement for the various flow actuation schemes.
- the substrate can be moved at any suitable velocity to enable coating of the substrate.
- a velocity of 25-100 feet per second is particularly preferred.
- Any suitable film forming polymer can be used in the coating dispersion used in the process of this invention.
- Typical film forming polymers include, for example, but are not limited to, polycarbonates, polyesters, polyamides, polyurethanes, polystyrenes, polyarylethers, polyarylsulfones, polybutadienes, polysulfones, polyethersulfones, polyethylenes, polypropylenes, polyimides, polymethylpentenes, polyphenylene sulfides, polyvinyl butyral, polyvinyl acetate, polysiloxanes, polyacrylates, polyvinyl acetals, polyamides, polyimides, amino resins, phenylene oxide resins, terephthalic acid resins, epoxy resins, phenolic resins, polystyrene and acrylonitrile copolymers, polyvinylchloride, vinylchloride and vinyl acetate copolymers, acrylate copo
- the coating dispersion used in the process can include, but are not limited to, polyvinyl alcohol (PVA), Mowiol® 4-88, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), Clevios PH1000, doped with 1% Triton X-100 surfactant and 6% ethylene glycol, polydimethylsiloxane (PDMS), Dow Corning 200® fluid, glycerol, and used in 95% concentration, and vacuum pump oil (VPO).
- PVA polyvinyl alcohol
- Mowiol® 4-88 poly(3,4-ethylenedioxythiophene):polystyrene sulfonate
- Clevios PH1000 doped with 1% Triton X-100 surfactant and 6% ethylene glycol, polydimethylsiloxane (PDMS), Dow Corning 200® fluid, glycerol, and used in 9
- Solid phase materials can also be included.
- Polyethylene terephthalate film (PET), ES301400, can be used as a flexible substrate for deposition of patterned films.
- PET shim stock can also be used to define the internal geometry of the hybrid slot coater, whose die block material is polymethyl methacrylate (PMMA), optically clear cast acrylic.
- PMMA polymethyl methacrylate
- This disclosure also includes a method of preparing a patterned thin film material.
- a desired surface pattern is first designed.
- the parameters of the designed surface pattern are input into a computer.
- a substrate having a substrate surface is passed under a hybrid patterning apparatus, and the designed surface pattern is patterned onto the passing substrate surface using the hybrid patterning apparatus.
- Substrates and fluids suitable for use in this disclosure can be any material one of ordinary skill would use in a thin film apparatus.
- Suitable substrates for use in accordance with this disclosure include, but are not limited to, paper, glass, thin plastic film, and thin metallic film. Plastic film is the preferred substrate.
- Suitable substrates can be flexible, rigid, uncoated, precoated, as desired.
- the substrates can comprise a single layer or be made up of multiple layers.
- Suitable fluids that may be deposited in the patterning of the substrate include, but are not limited to, dispersions and organic and inorganic polymer solutions.
- simultaneous coating of two or more miscible liquids can consolidate the processing of multi-material stripe patterns into a single step.
- Deposition of each liquid species separately, in rows of narrow non-overlapping stripes is the more conventional approach. Both strategies are compared with 10% aqueous PVA solutions coated on flexible PET substrate.
- FIG. 7 A shows a process response of stripe width for narrow stripes of 10% aqueous PVA using the conventional approach, and for FIG. 7 B alternating stripes of PVA and un-doped 1.3% aqueous PEDOT:PSS using the hybrid patterning apparatus.
- the volumetric flowrate, Q is specified as the average value per stripe.
- the single-phase approach shown in FIG. 7 A requires multiple coating beads in the deposition region, each corresponding to an individual stripe.
- FIGS. 8 A- 8 B illustrates the behavior of two immiscible liquids, PDMS and 24% aqueous PVA, processed simultaneously using the multi-material stripe patterning approach.
- concentration of aqueous PVA has been selected to match the kinematic viscosity of 1000 cSt of the PDMS solution.
- the developing flow sequence begins in FIG. 8 A with fully-developed deposition flow of PVA, followed by flow startup of PDMS. PDMS accumulates within localized coating beads until interaction between the two liquid phases occurs, resulting in unsteady deposition flow characterized by enhanced spreading of both liquids along the width of the coating tool as shown in FIG. 8 B .
- ⁇ A and ⁇ B are the surface tensions of the two liquids
- ⁇ AB denotes the interfacial tension between liquid phases
- their contact angles are given by ⁇ A and ⁇ B .
- the force balance can be expressed as:
- equations (1)-(3) predict the formation of the shallow sloped cross section illustrated in FIG. 9 D .
- the contact angles predicted for the liquid-liquid-gas contact line correspond to preferential wetting of the lower-surface tension liquid along the surface of the higher surface tension liquid.
- equilibrium contact angles at the solid surface arise from movement of the unpinned liquid-liquid-solid contact line.
- the shim configuration illustrated in FIG. 10 generates an internal flow field for multi-material stripe patterns at high resolution.
- the converging section of the slot acts as a mechanism for scaling of the entire pattern, reducing the average width of stripes from an initial value, w ⁇ 1 ⁇ W 1 /N to a smaller value near the outlet region.
- w ⁇ 2 ⁇ W 2 /N is the total number of stripes
- W 1 is the overall slot width upstream from the converging section
- W 2 is the slot width near the outlet.
- the angle ⁇ is relevant to design of the channel length L required for a given inlet configuration and desired pattern, although both the inlet configuration and L are kept fixed in this study for purposes of comparison.
- FIG. 11 shows internal flow through a converging slot of alternating stripes of 10% PVA.
- Optical images of internal flow are organized in FIG. 11 for various permutations of W 1 /W 2 and ⁇ .
- the channel depth equal to the slot gap G, is kept fixed at 76 ⁇ m.
- Volumetric flowrate per stripe is 140 ⁇ L is in the top row of FIG. 11 , and 40 ⁇ L is in the bottom row of FIG. 11 .
- values as low as 5 ⁇ L/s produce the same results without any resolvable variation.
Abstract
A hybrid scaling and patterning apparatus for producing thin films with multi-material, customized patterns is disclosed. The apparatus includes a slot die body integrated with multiple inlets and corresponding converging channels passing materials through the die body in a planar, continuous laminar flow. The hybrid scaling and patterning apparatus may be used in a method of preparing multi-material, patterned thin film materials.
Description
- This application is a divisional of U.S Application No. 16/767,676 filed 28 May 2020, which is a National Stage Entry of International Application No. PCT/US 18/63688 filed 3 Dec. 2018, which claims the benefit of U.S Provisional Pat. Application No 62/593,323 filed 1 Dec. 2017, the entire contents and substance of which each are hereby incorporated by reference as if fully set forth below.
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- The various embodiments of this disclosure relate generally to coating thin films and, more particularly, to an apparatus and method for producing scaled and patterned thin films.
- There are many processes for creating thin films, and these methods were developed to meet the manufacturing needs of specific technologies. For example, existing solution coating technologies such as slot die, curtain, and knife coating are able to manufacture thin films. These techniques were designed for creating high quality films in continuous single sheets. These techniques, however, have a limited ability to create patterns.
- Slot die coating is a method of creating thin films on a substrate from liquid materials. The essence of the process is a die consisting of two halves separated by a shim, with a pressurized reservoir, or chamber, machined into one of the halves containing fluid. The purpose of the shim is to create a gap between the two halves through which the fluid may flow. The purpose of the chamber is to uniformly distribute the fluid therein along the width of the gap. As a result, slot die designs are generally limited to lines or stripes that are the opening of the shim, thereby limiting the ability of the slot die to create other desired patterns.
- Patterned film deposition is a powerful manufacturing paradigm with applications spanning optoelectronics, sensors, computing, and wearable energy conversion. Liquid-phase film deposition techniques have long been recognized as suitable for rapid, continuous, low-waste processing near room temperature. Several of these techniques are adaptations of earlier graphical printing technologies, and thus the devices themselves are colloquially referred to as “printed.” This nomenclature also reflects the perception that liquid-phase coating and patterning methods are amenable to roll-to-roll (R2R) manufacturing with significant economies of scale. However, scalability challenges in manufacturing have persisted, despite considerable progress in the materials and structures available for printed devices. One contributing factor may be that patterned coating techniques in use today have remained fundamentally unchanged for decades. It follows that new processing methods may prove broadly valuable for the field of printed thin film devices, if they can be adapted to wide-area deposition.
- Wetting and microfluidic phenomena are integral to the operation of various coating techniques. Spin coating involves centrifugal force-assisted spreading of liquid on a rotating substrate. Blade and slot coating utilize viscous shear and surface tension to distribute coating liquid in a thin film. Spray coating achieves film uniformity by the transfer of coating fluid as evenly-dispersed droplets. While the patterning capabilities of these particular methods are limited, they can be combined with subtractive techniques such as laser ablation and localized dissolution to define a desired pattern. Alternatively, a physical mask can be used, as is common with screen printing and photolithography. Finally, a more recent approach has been the modification of wetting behavior by localized plasma or chemical pre-treatment of the substrate.
- The most direct and consolidated approach to pattern printing, however, is mask-less selective deposition. Inkjet, flexographic, and gravure printing all embody this approach, and have been used in recent years to fabricate a diverse range of patterned thin film devices. However, these methods are generally more suited to low-viscosity coating liquids, which considerably limits their applicability and versatility. Furthermore, the tooling requirements for gravure and flexographic transfer are both significant and pattern-specific. And for inkjet printing, droplet impact spreading is counter-productive to pattern quality, while nozzle clogging is a practical problem that further constrains processing and material formulation. The sum of these observations is that no single deposition method today encapsulates all the advantages desirable for low-cost manufacturing at large scale.
- Replicating the advantages of traditional slot coating in a similar, pattern-capable process is an appealing prospect.
- Some exemplary embodiments of this disclosure provide an apparatus and a system for scaling and patterning thin film materials. Other exemplary embodiments provide methods of producing scaled and patterned thin film materials.
- To realize a system capable of producing on-demand, patterned films of high uniformity, there is provided a hybrid scaling patterning system. This system allows for single-step deposition of multi-material patterned thin films, and thus, improved patterned thin film processing for technologies that require more elaborate or arbitrary film patterns.
- According to some exemplary embodiments, a method comprises co-laminar flowing of at least a first material and a second material within a slot die and depositing from a slot of the slot die a width-wise multi-material stripe pattern of the first and second materials, wherein the material of adjacent stripes of the width-wise multi-material stripe pattern differ across a width of the slot.
- In any of exemplary embodiments of the present invention, the method can further comprise feeding the first material into the slot die via a set of first inlets, feeding the second material into the slot die via a set of second inlets, and forming a stripe-patterned co-laminar flow in an interaction channel of the slot die, wherein a continuous flow path exists between the first set of inlets and the interaction channel, and wherein a continuous flow path exists between the second set of inlets and the interaction channel.
- In any of exemplary embodiments of the present invention, the method can further comprise controlling uniformity of the width-wise multi-material stripe pattern.
- In any of exemplary embodiments of the present invention, the method can further comprise dimensionally scaling the width-wise multi-material stripe pattern.
- In any of exemplary embodiments of the present invention, the width-wise multi-material stripe pattern can be deposited on a surface of a substrate.
- In any of exemplary embodiments of the present invention, the substrate can be selected from the group consisting of paper, glass, thin plastic film, and thin metallic film.
- In any of exemplary embodiments of the present invention, the first and second materials can flow through the slot die in a planar, continuous laminar flow.
- In any of exemplary embodiments of the present invention, the first and second materials can flow through the slot die in a planar, continuous creeping flow.
- In another exemplary embodiment, a method comprises feeding two or more fluid materials into a slot die via two or more sets of fluid inlets, each respective fluid material feeding into the slot die via a respective set of fluid inlets and depositing a width-wise multi-material stripe pattern of the two or more fluid materials, wherein adjacent stripes of the width-wise multi-material stripe pattern comprise different fluid materials.
- In any of exemplary embodiments of the present invention, the method can further comprise controlling a width of at least a portion of the stripes in the width-wise multi-material stripe pattern.
- In any of exemplary embodiments of the present invention, the method can further comprise dimensionally scaling at least a portion of the width-wise multi-material stripe pattern.
- In any of exemplary embodiments of the present invention, the slot die can comprise a first plate, a second plate, and a shim separating the plates.
- In any of exemplary embodiments of the present invention, the method can further comprise interacting the two or more fluid materials in an interaction channel of the slot die, wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel, wherein the two or more fluid materials flow through the slot die in a flow selected from the group consisting of a planar, continuous laminar flow and a planar, continuous creeping flow, and wherein the width-wise multi-material stripe pattern is deposited on a surface of a substrate.
- In any of exemplary embodiments of the present invention, each respective set of the fluid inlets can be both positioned at a fluid inlet height position between a top and bottom of the slot die, the distance between the top and bottom of the slot die defining a height of the slot die and positioned at a fluid inlet width position between a first side and a second side of the slot die, the distance between the sides of the slot die defining a width of the slot die.
- In any of exemplary embodiments of the present invention, each fluid inlet height position of a respective set of the fluid inlets can the same.
- In any of exemplary embodiments of the present invention, each fluid inlet width position of a respective set of the fluid inlets can be different.
- In any of exemplary embodiments of the present invention, each respective set of the fluid inlets can present a horizontal line of spaced-apart fluid inlets.
- In any of exemplary embodiments of the present invention, each horizontal line of spaced-apart fluid inlets can be at a different fluid inlet height position one from another.
- In another exemplary embodiment, a method comprises feeding two or more different fluid materials into a slot die via two or more sets of fluid inlets, each respective fluid material feeding into the slot die via a respective set of fluid inlets, interacting the two or more different fluid materials in an interaction channel of the slot die, wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel, depositing a width-wise multi-material stripe pattern of the two or more different fluid materials on a surface of a substrate, and at least one of controlling a width of at least a portion of the stripes in the width-wise multi-material stripe pattern, and/or dimensionally scaling at least a portion of the width-wise multi-material stripe pattern, wherein no adjacent stripes of the width-wise multi-material stripe pattern comprise the same fluid material.
- In another exemplary embodiment, an apparatus for depositing the width-wise multi-material stripe pattern according to any of the exemplary methods can comprise the slot die, a set of first inlets for the feeding of the first material into the slot die, a set of second inlets for the feeding of the second material into the slot die, and an interaction channel of the slot die for forming a stripe-patterned co-laminar flow of the first material and the second material.
- In another exemplary embodiment, an apparatus for depositing the width-wise multi-material stripe pattern according to any of the exemplary methods can comprise the slot die and an interaction channel of the slot die for interacting the two or more fluid materials, wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel.
- In any of exemplary embodiments of the present invention the slot die can comprise a first plate, a second plate, and a shim separating the plates.
- In any of exemplary embodiments of the present invention, the slot die can be a shimfree slot die.
- In any of exemplary embodiments of the present invention, the interaction channel can define a volume extending in a flow direction from an upstream upper portion to a downstream lower portion.
- In any of exemplary embodiments of the present invention, the volume of the interaction channel can have a converging cross-sectional area from the upstream upper portion to the downstream lower portion.
- According to some exemplary embodiments of this disclosure, an apparatus for patterning thin films comprises a slot die having a body comprising first and second plates, at least two fluid inlets, one fluid inlet for feeding a first material into the slot die and the other fluid inlet for feeding a second material into the slot die, and at least two channels formed inside of the slot die, one channel for receiving the first material, and the other channel for receiving the second material, each of the channels having a channel inlet end and a channel outlet end.
- In any of exemplary embodiments of the present invention, the first and second materials can travel from the channel inlet ends of the channels to the channel outlet ends of the channels in a planar, continuous laminar flow.
- In any of exemplary embodiments of the present invention, each of the channels can be converging channels.
- In any of exemplary embodiments of the present invention, a total width of all the channel inlet ends of the converging channels can be greater than a total width of all the channel outlet ends of the converging channels.
- In any of exemplary embodiments of the present invention, a width of the channel inlet end of each of the converging channels can be greater than a width of the channel outlet end of each of the converging channels.
- In any of exemplary embodiments of the present invention, the apparatus can comprise eight inlets.
- In any of exemplary embodiments of the present invention, the apparatus can comprise eight converging channels.
- In any of exemplary embodiments of the present invention, the first and second materials can travel from the channel inlet ends of the channels to the channel outlet ends of the channels in a planar, continuous creeping flow.
- In any of exemplary embodiments of the present invention, the apparatus can comprise a material selected from the group consisting of stainless steel, aluminum, nylon, polycarbonate and combinations thereof.
- In any of exemplary embodiments of the present invention, the apparatus can be configured to generate a multi-material stripe pattern from interaction between the first and second materials within the die body.
- According to some exemplary embodiments, a method of preparing a multi-material, patterned thin film material, comprises providing an apparatus having a slot die having a body comprising first and second plates; at least two inlets, one inlet for feeding a first material into the slot die and the other inlet for feeding a second material into the slot die; and at least two channels formed inside of the slot die, one channel for receiving the first material, and the other channel for receiving the second material, each of the channels having a channel inlet end and a channel outlet end, and feeding the first material into the slot die through the one inlet and feeding the second material into the slot die through the other inlet, wherein the first and second materials travel from the channel inlet ends of the channels to the channel outlet ends of the channels in a planar, continuous laminar flow.
- In any of exemplary embodiments of the present invention, the slot die used in the method need not include a shim.
- In any of exemplary embodiments of the present invention, each of the channels used in the method can be converging channels.
- In any of exemplary embodiments of the present invention, a total width all of channel inlet ends of the converging channels can be greater than a total width of all of the channel outlet ends of the converging channels.
- In any of exemplary embodiments of the present invention, a width of the channel inlet end of each of the converging channels can be greater than a width of the channel outlet end of each of the converging channels.
- In any of exemplary embodiments of the present invention, there can be eight inlets.
- In any of exemplary embodiments of the present invention, there can be eight converging channels.
- In any of exemplary embodiments of the present invention, the first and second materials can travel from the channel inlet ends of the channels to the channel outlet ends of the channels in a planar, continuous creeping flow
- In any of exemplary embodiments of the present invention, the invention can further comprise depositing a fluid onto a substrate surface.
- In any of exemplary embodiments of the present invention, the substrate can be selected from the group consisting of paper, glass, thin plastic film, and thin metallic film.
- According to other exemplary embodiments of this disclosure, a method of making patterned thin film materials includes designing a surface pattern, inputting parameters of the designed surface pattern into a computer, passing a substrate having a substrate surface under a hybrid patterning apparatus, and patterning the designed surface pattern onto the passing substrate surface using the hybrid patterning apparatus.
- In another exemplary embodiment, an apparatus for patterning thin films comprises a slot die comprising a first plate, a second plate, and a shim separating the plates, at least two fluid inlets, a first fluid inlet positioned at a first fluid inlet height position between a top and bottom of the slot die, the distance between the top and bottom of the slot die defining a height of the slot die, positioned at a first fluid inlet width position between a first side and a second side of the slot die, the distance between the sides of the slot die defining a width of the slot die; and configured for feeding a first fluid material into the slot die and to the shim, and a second fluid inlet positioned at a second fluid inlet height position, positioned at a second fluid inlet width position different than the first fluid inlet width position, and configured for feeding a second fluid material into the slot die and to the shim, and at least three channels formed at least in part by the shim inside of the slot die, a first inlet channel fluidly communicative with the first fluid inlet and configured to receive the first fluid material, a second inlet channel fluidly communicative with the second fluid inlet and configured to receive the second fluid material, and a third interaction channel fluidly communicative with the first and second inlet channels, wherein each of the first and second inlet channels have a channel inlet coincident with the respective first and second fluid inlets in the slot die, wherein the third interaction channel is communicative at an upstream end to the first and second inlet channels and configured to receive a flow of the first fluid material and the second fluid material, and at a downstream end to a fluid multi-material outlet in the slot die through which a pattern of the first fluid material and the second fluid material can flow, wherein the third interaction channel defines a volume extending in a flow direction from the upstream end to the downstream end and configured such that the third interaction channel is free of a physical barrier separating the flow of the first fluid material and the second fluid material, wherein the volume of the third interaction channel has a converging cross-sectional area from a width of the upstream end to a width of the downstream end, which is smaller than the width of the upstream end, wherein the apparatus is configured to receive a flow of the first fluid material simultaneous to a flow of the second fluid material and deposit a width-wise multi-material stripe pattern of the first fluid material and the second fluid material on a surface of a substrate.
- In any of exemplary embodiments of the present invention, the first, second, and third channels can be configured to enable fluidic communication through the slot die in a planar, continuous laminar flow.
- In any of exemplary embodiments of the present invention, the first, second, and third channels can be configured to enable fluidic communication through the slot die in a planar, continuous flow.
- In any of exemplary embodiments of the present invention, the slot die can comprise a material selected from the group consisting of stainless steel, aluminum, nylon, polycarbonate and combinations thereof.
- In any of exemplary embodiments of the present invention, narrowing of the third channel width along a primary axis of flow can cause interaction between the first fluid material and the second fluid material that is not disruptive to pattern formation.
- In any of exemplary embodiments of the present invention, the slot die can have a width defined from a first side of the slot die to a second side of the slot die, a thickness defined from a front face of the slot die to a rear face of the slot die, and a height defined from a top of the slot die to a bottom of the slot die.
- In any of exemplary embodiments of the present invention, the first fluid inlet can be a first fluid material inlet. The second fluid inlet can be a second fluid material inlet. The fluid multi-material outlet can be configured to deposit a fluid multi-material onto a substrate.
- In any of exemplary embodiments of the present invention, the third interaction channel can define a volume extending in a flow direction from an upstream upper portion to a downstream lower portion.
- In any of exemplary embodiments of the present invention, the volume of the third interaction channel can have a converging cross-sectional area from the upstream upper portion to the downstream lower portion.
- In any of exemplary embodiments of the present invention, the first inlet, the second inlet and third interaction channel can form a channel system configured to provide fluidic communication between the first fluid material inlet and the third interaction channel, the second fluid material inlet and the third interaction channel, and the third interaction channel and the fluid multi-material outlet.
- In any of exemplary embodiments of the present invention, the first material inlet can be located on one of the front and rear faces of the slot die. The second material inlet can be located on one of the front and rear faces of the slot die.
- In any of exemplary embodiments of the present invention, the third interaction channel can define a volume extending in a flow direction from an upstream upper portion to a downstream lower portion, the upstream upper portion located along the height of the slot die below both the first and second material inlets, and the downstream lower portion located along the height of the slot die above the fluid multi-material outlet.
- In any of exemplary embodiments of the present invention, the volume of the third interaction channel can converge in cross-sectional area from the upstream upper portion to the downstream lower portion.
- In any of exemplary embodiments of the present invention, the channel system can be configured to provide the fluidic communication in a planar, continuous laminar flow.
- In any of exemplary embodiments of the present invention, the channel system can be configured to provide the fluidic communication in a planar, continuous creeping flow.
- In any of exemplary embodiments of the present invention, the channel system can further comprise one or more additional interaction channels.
- In any of exemplary embodiments of the present invention, at least a portion of each of the additional interaction channels can be communicative at an upstream end to the first and second fluid material inlets, and at a downstream end to the fluid multi-material outlet.
- In another exemplary embodiment, an apparatus for patterning thin films comprises a slot die comprising a first plate, a second plate, and a shim separating the plates, a first set of fluid inlets for feeding a first fluid material into the slot die, a second set of fluid inlets for feeding a second fluid material into the slot die at the same time as the feeding of the first fluid material, a first set of inlet channels defined at least in part by the shim laterally spaced apart along a width of the slot die and configured to receive the first fluid material, each of the inlet channels of the first set of inlet channels having a channel inlet coincident with a respective fluid inlet of the first set of fluid inlets in the slot die, a second set of inlet channels defined at least in part by the shim laterally spaced apart along the width of the slot die and configured to receive the second fluid material, each of the inlet channels of the second set of inlet channels having a channel inlet coincident with a respective fluid inlet of the second set of fluid inlets in the slot die, and a third interaction channel defined at least in part by the shim communicative at an upstream end to the first and second sets of inlet channels, and at a downstream end to a fluid multi-material outlet in the slot die through which a multi-material stripe pattern of alternating first fluid material and second fluid material can flow, wherein the first set of inlet channels and the second set of inlet channels are arranged in an alternating order, such that an inlet channel of the first set of inlet channels is followed by an inlet channel of the second set of inlet channels as viewed laterally across the width of the slot die, wherein the third interaction channel is configured to receive at the upstream end alternating, simultaneous flows of the first fluid material and the second fluid material from the alternating layout of inlet channels, wherein the third interaction channel defines a volume extending in a flow direction from the upstream end to the downstream end and is further configured such that the third interaction channel is free of a physical barrier separating the flows of the first fluid material and the second fluid material, and wherein the volume of the third interaction channel has a converging cross-sectional area from a width of the upstream end to a width of the downstream end, which is smaller than the width of the upstream end.
- In any of exemplary embodiments of the present invention, the slot die can be configured to generate a scaled multi-material stripe pattern from interaction between the first and second fluid materials within the third interaction channel.
- In any of exemplary embodiments of the present invention, the first set of fluid inlets can lie in a row at a first height of the slot die across the width of the slot die.
- In any of exemplary embodiments of the present invention, the second set of fluid inlets can lie in a row at a second height of the slot die across the width of the slot die.
- In any of exemplary embodiments of the present invention, the first height can be different than the second height, such that the length of each of the inlet channels of the first set is different than the length of each of the inlet channels of the second set.
- In another exemplary embodiment, a method of thin film material deposition on a substrate comprises feeding a first fluid material into a slot die via a first fluid inlet, feeding a second fluid material into the slot die via a second fluid inlet, forming a fluid multi-material by interacting the first fluid material and the second fluid material in an interaction channel within the slot die, the interaction channel in fluidic communication with the first and second fluid inlets, and depositing the fluid multi-material onto the substrate via an outlet of the slot die in fluidic communication with the interaction channel, wherein the first and second materials flow through the slot die in a planar, continuous laminar flow.
- In any of exemplary embodiments of the present invention, the interaction channel can define a volume extending in a flow direction from an upstream upper portion to a downstream lower portion.
- In any of exemplary embodiments of the present invention, the volume of the interaction channel can have a converging cross-sectional area from the upstream upper portion to the downstream lower portion.
- In any of exemplary embodiments of the present invention, the substrate can be selected from the group consisting of paper, glass, thin plastic film, and thin metallic film.
- In another exemplary embodiment, a patterning system comprises a disclosed apparatus, a first fluid material, and a second fluid material different than the first fluid material, wherein the first fluid material is introduced into the slot die via the first fluid material inlet, wherein the second fluid material is introduced into the slot die via the second fluid material inlet, wherein the first and second fluid materials interact within the third interaction channel to form a fluid multi-material, and wherein the fluid multi-material exits the slot die via the fluid multi-material outlet.
- Other aspects and features of exemplary embodiments of this disclosure will become apparent to those of ordinary skill in the art, upon reviewing the following description of specific, exemplary embodiments of this disclosure in concert with the various figures. While features of this disclosure may be discussed relative to certain exemplary embodiments and figures, all exemplary embodiments of this disclosure can include one or more of the features discussed in this application. While one or more exemplary embodiments may be discussed as having certain advantageous features, one or more of such features may also be used with the other various exemplary embodiments discussed in this application. In similar fashion, while exemplary embodiments may be discussed below as system or method exemplary embodiments, it is to be understood that such exemplary embodiments can be implemented in various devices, systems, and methods. As such, discussion of one feature with one exemplary embodiment does not limit other exemplary embodiments from possessing and including that same feature.
- The accompanying Figures, which are incorporated in and constitute a part of this specification, illustrate several aspects described below.
-
FIG. 1 illustrates a hybrid patterning apparatus in accordance with an exemplary embodiment of the disclosure. -
FIGS. 2A-2B illustrate components of a hybrid patterning apparatus, in accordance with an exemplary embodiment of this disclosure. -
FIGS. 3A-3B illustrate the internal cavity geometry of a hybrid patterning apparatus, without internal scaling of the pattern, and corresponding deposition of a heterogeneous film pattern comprising multi-material stripes of two distinct materials in an alternating sequence. -
FIGS. 4A-4B illustrate the internal cavity geometry of a hybrid patterning apparatus with internal scaling of the pattern, in accordance with an exemplary embodiment of this disclosure. -
FIGS. 5A-5B illustrate test results related to single material deposition in narrow stripes, in accordance with an exemplary embodiment of this disclosure. -
FIGS. 6A-6B illustrate results from a start and stop mechanism of the hybrid apparatus, in accordance with an exemplary embodiment of this disclosure. -
FIGS. 7A-7B illustrate test results related to multi-material deposition, in accordance with an exemplary embodiment of this disclosure. -
FIGS. 8A-8B illustrate a simultaneous deposition of PDMS and PVA during flow start-up and after contact between two fluid regions. -
FIGS. 9A-9B illustrate multi-material stripe film structures constructed from various multi-material configurations and the static force balance for interacting stripes, in accordance with an exemplary embodiment of the disclosure. -
FIG. 10 illustrates a pattern with converging internal geometry in accordance with an exemplary embodiment of the disclosure. -
FIG. 11 illustrates a pattern with converging, multi-material stripes of two materials in alternating sequence in accordance with an exemplary embodiment of the disclosure. - To facilitate an understanding of the principles and features of the various exemplary embodiments of the invention, various illustrative exemplary embodiments are explained below. Although exemplary embodiments of the invention are explained in detail, it is to be understood that other exemplary embodiments are contemplated. Accordingly, it is not intended that the invention is limited in its scope to the details of construction and arrangement of components set forth in the following description or illustrated in the drawings. The invention is capable of other exemplary embodiments and of being practiced or carried out in various ways. Also, in describing the exemplary embodiments, specific terminology will be resorted to for the sake of clarity.
- It must also be noted that, as used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural references unless the context clearly dictates otherwise. For example, reference to a component is intended also to include composition of a plurality of components. References to a composition containing “a” constituent is intended to include other constituents in addition to the one named.
- Also, in describing the exemplary embodiments, terminology will be resorted to for the sake of clarity. It is intended that each term contemplates its broadest meaning as understood by those skilled in the art and includes all technical equivalents which operate in a similar manner to accomplish a similar purpose.
- Ranges may be expressed herein as from “about” or “approximately” or “substantially” one particular value and/or to “about” or “approximately” or “substantially” another particular value. When such a range is expressed, other exemplary embodiments include from the one particular value and/or to the other particular value.
- Similarly, as used herein, “substantially free” of something, or “substantially pure”, and like characterizations, can include both being “at least substantially free” of something, or “at least substantially pure”, and being “completely free” of something, or “completely pure”.
- By “comprising” or “containing” or “including” is meant that at least the named compound, element, particle, or method step is present in the composition or article or method, but does not exclude the presence of other compounds, materials, particles, method steps, even if the other such compounds, material, particles, method steps have the same function as what is named.
- It is also to be understood that the mention of one or more method steps does not preclude the presence of additional method steps or intervening method steps between those steps expressly identified. Similarly, it is also to be understood that the mention of one or more components in a composition does not preclude the presence of additional components than those expressly identified.
- The materials described as making up the various elements of the invention are intended to be illustrative and not restrictive. Many suitable materials that would perform the same or a similar function as the materials described herein are intended to be embraced within the scope of the invention. Such other materials not described herein can include, but are not limited to, for example, materials that are developed after the time of the development of the invention.
- The various exemplary embodiments of this disclosure relate to a system and apparatus for the patterning of thin films. The methods of manufacturing patterned thin films using the hybrid system are also described herein.
- Referring now to
FIG. 1 , there is shown a coating tool 100 (e.g. slot die, hybrid patterning apparatus), aheterogeneous liquid film 101 comprising two or more liquid materials in a horizontally-patterned configuration, an array of two or morefluid inlets 102, a flow of ink orother coating fluid 103 into the hybrid coating apparatus, and a region of outflow of ink orother coating fluid 104 out ofhybrid coating apparatus 100 and onto a substrate to form a liquid film. As shown incross-section view 105, hybrid patterning apparatus can further includesubstrate 106, ink orcoating fluid 107 outflow fromhybrid patterning apparatus 100,liquid bridge 108 between coating tool outlet region and deposited liquid film, and adie plate 109 of thehybrid patterning apparatus 100. - During operation, one or more liquid bridges form between the coating tool outlet and the substrate. The transfer of fluid through each liquid bridge, in turn, forms a patterned liquid film on the substrate surface. The volumetric flow rate Q, substrate velocity V relative to the coating tool, and the coating gap H between tool outlet and substrate are input parameters that can be varied during operation.
-
FIGS. 2A-2B shows slot die components in certain exemplary embodiments of the disclosure. As shown inFIG. 2A , the hybrid slot coating tool can include a slot die that includes a die body having two halves, or first and second plates, 201 a, 201 b, separated by one ormore shims 202 with cutout(s) forming a slot-shapedcavity 202 positioned between first andsecond plates inlets 203 for delivering coating fluid to discrete regions of the internal geometry, an external manifold ordistribution chamber 204 for coating fluid delivered toinlet array 203.FIG. 2B shows an alternate view of this exemplary embodiment of the hybrid patterning apparatus, with first and second plates, 205 a, 205 b, separated by one ormore shims 206 with cutout(s) forming an internal slot-shaped cavity, internal distribution chambers, channels or cavities with inlet ends 207 integrated into one or more of the plates, 205 a, 205 b. In some exemplary embodiments, the internal distribution chambers, channels or cavities are converging. The purpose of shim(s) 206 is to create a slot gap between first andsecond plates - As shown in
FIGS. 3A-3B , the shim configuration can be used for simultaneous deposition of two or more coating materials as alternating stripes. As illustrated, a heterogeneous multi-material stripe pattern is produced when two fluids are fed into alternating inlets (for example, corresponding both to alternating height positions of two rows of inlets, and alternating width positions of each inlet of the two rows of inlets, alternating laterally along a width of the slot die) of the hybrid slot coating tool. While slot coating has previously been adapted for deposition of narrow stripes of a single material, depositing two or more coating fluids simultaneously into a single-layer pattern is at least one novelty to this disclosure. - As shown in each of
FIGS. 1-5A and 6A , the array ofinlets -
FIG. 3A shows a shim material with cutout or cavity in a die plate forming an internal slot cavity. It further illustrates a region ofcavity 301 corresponding to flow through each offluid inlets 203, or from each offluid outlets 207. Separation between different coating fluid species throughout the internal cavity is shown at 302. In some exemplary embodiments, the separation between the different coating fluid species is a physical separation.Separate outlet regions 303 correspond to separate flow streams within the coating apparatus. As shown inFIG. 3B , in some exemplary embodiments,hybrid patterning apparatus 304 can be assembled using the internal geometry shown inFIG. 3A .FIG. 3B further illustrates inflow of firstcoating fluid species 305, inflow of a secondcoating fluid species 306, and outflow of a heterogenous film comprising stripe-shaped regions of composition alternating between the first and secondfluid species 307. - The slot die body can be made of any machinable material typically used in making slot die. These include but are not limited to stainless steel, aluminum, titanium, nylon, polycarbonate and combinations thereof. The material used to make slot die body generally is a function of the fluid that will be deposited. There should be compatibility between the slot die and the fluid with respect to chemical, electrical, mechanical, and physical properties.
- In some exemplary embodiments, as shown in
FIGS. 4A-4B , a pattern-scaling mechanism can cause interaction between different coating fluids without a shim, which is not disruptive to the pattern formation. InFIG. 4A , a shim material with cutout or cavity in die block forms an internal slot cavity.Cavity region 400 corresponds to flow through each ofinlets 401, or from each ofoutlets 407.Region 402 corresponds to maximum width W1 of channels where multiple coating fluid species interact. In some exemplary embodiments, the species interact physically.Region 403 corresponds to width W2 of channels and is connected to outlet region of the hybrid patterning apparatus. In some exemplary embodiments, W2 < W1. Region 404 corresponds to varying width channels connectingcavity regions FIG. 4B ,hybrid patterning apparatus 405 can be assembled using the internal geometry shown inFIG. 4A .FIG. 4B further illustrates inflow of firstcoating fluid species 406, inflow of a secondcoating fluid species 407, and outflow of a scaled heterogenous multi-material stripe-patternedfilm 408. Compared to the coating apparatus configuration ofFIG. 3 , the internal tool geometry is considerably reduced. Rather, a multi-material stripe phase field is established by the array of inlet channels opening into a single-wide slot, without a physical barrier separating the fluids in the channels. Narrowing of the channel width along the primary axis of flow produces a proportional narrowing of each phase region, a useful phenomenon that single-phase slot extrusion cannot exploit. This represents an improvement over previous tool designs, where the minimum achievable center-to-center distance of the narrow stripe pattern is essentially attributable to the precision of tool fabrication and assembly. - As shown in the figures, and specifically referring again to
FIGS. 4A-4B , the present invention can comprise an apparatus for patterning thin films including the slot die, at least two fluid inlets 406, 407, a first fluid inlet configured for feeding a first fluid material into the slot die and a second fluid inlet configured for feeding a second fluid material into the slot die, and at least three channels formed inside of the slot die, a first inlet channel configured to receive the first fluid material, a second inlet channel configured to receive the second fluid material, and a third interaction channel 402, 404, wherein each of the first and second inlet channels have a channel inlet coincident with the respective first and second fluid inlets 406, 407 in the slot die, wherein the third interaction channel 402, 404 is communicative at an upstream end to the first and second inlet channels and configured to receive a flow of the first fluid material and the second fluid material, and at a downstream end to a fluid multi-material outlet 403 in the slot die through which a pattern of the first fluid material and the second fluid material can flow, wherein the third interaction channel defines a volume extending in a flow direction from the upstream end to the downstream end and configured such that the third interaction channel is free of a physical barrier separating the flow of the first fluid material and the second fluid material, and wherein the volume of the third interaction channel has a converging cross-sectional area from a width of the upstream end to a width of the downstream end, which is smaller than the width of the upstream end. - In another exemplary embodiment, the apparatus for patterning thin films can comprise the slot die, a first set of fluid inlets for feeding the first fluid material into the slot die, a second set of fluid inlets for feeding the second fluid material into the slot die, a first set of inlet channels laterally spaced apart and configured to receive the first fluid material, each of the inlet channels of the first set of inlet channels having a channel inlet coincident with a respective fluid inlet of the first set of fluid inlets in the slot die, a second set of inlet channels laterally spaced apart and configured to receive the second fluid material, each of the inlet channels of the second set of inlet channels having a channel inlet coincident with a respective fluid inlet of the second set of fluid inlets in the slot die, and a third interaction channel communicative connected at an upstream end to the first and second sets of inlet channels, and at a downstream end to the fluid multi-material outlet in the slot die through which a pattern of alternating first fluid material and second fluid material can flow, wherein the first set of inlet channels and the second set of inlet channels are arranged in an alternating order, such that an inlet channel of the first set of inlet channels is followed by an inlet channel of the second set of inlet channels as viewed laterally across the slot die, wherein the third interaction channel is configured to receive at the upstream end alternating flows of the first fluid material and the second fluid material from the alternating layout of inlet channels, wherein the third interaction channel defines a volume extending in a flow direction from the upstream end to the downstream end and is further configured such that the third interaction channel is free of a physical barrier separating the flows of the first fluid material and the second fluid material, and wherein the volume of the third interaction channel has a converging cross-sectional area from a width of the upstream end to a width of the downstream end, which is smaller than the width of the upstream end.
- In some exemplary embodiments, the feature size capability of the hybrid slot coating can be tied to the minimum stripe width that can be deposited through an isolated liquid bridge.
FIG. 5A illustrates the coating tool configuration used to produce this pattern feature under steady flow conditions. The fractional deviation in stripe width from tool inlet spacing, expressed as w* ≡ (w - w0)/w0, is plotted inFIG. 5B against the dimensionless quantity Q* ≡ Q/(VGw0), which represents fluid volume per unit width of substrate. Correlations between w* and Q*, and between H and Q* comprise a two-parameter process input domain for controlling stripe geometry. Variations across the different coating fluids inFIG. 5B indicate the influence of both viscosity and wettability on the process control. For comparison, 20% aqueous polyvinyl alcohol (PVA) is more viscous than the other fluids by an order of magnitude, and both surface tension and contact angle of a surfactant-doped 1.3% aqueous dispersion of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) is significantly lower than that of aqueous PVA. - In some exemplary embodiments, the
coating tool 100 can include mechanisms to start and stop the scaling and patterning process.FIG. 6A shows a configuration of the hybrid slot coating tool used to produce a segmented narrow stripe of 15% aqueous PVA on flexible PET substrate. The break in the stripe is produced by periodic flow cutoff and startup through a single inlet.FIG. 6B shows a comparison of actuation performance for various control schemes, measured as the length of the tapering at the leading and trailing edges of each stripe segment. The sum of lSTART and lSTOP can be considered a lower limit on the minimum feature size along the x-axis.FIG. 6B compares the severity of this measurement for the various flow actuation schemes. - These relationships between coating bead behavior and feature size control can be understood in the context of a balance of viscous, interfacial, and inertial forces at the dynamic liquid bridge beneath the tool. Viscous shear appears to limit lateral spreading of the coating bead along the coating outlet. Surface tension at the liquid-gas interface limits spreading counter to interfacial forces associated with the solid-liquid interfaces. The balance between liquid-gas and solid-liquid interfacial force is also a function of the shape of the liquid bridge, which provides an intuitive explanation for the positive correlation between H and w*.
- The substrate can be moved at any suitable velocity to enable coating of the substrate. For example, according to exemplary embodiments of the present invention, a velocity of 25-100 feet per second is particularly preferred.
- Any suitable film forming polymer can be used in the coating dispersion used in the process of this invention. Typical film forming polymers include, for example, but are not limited to, polycarbonates, polyesters, polyamides, polyurethanes, polystyrenes, polyarylethers, polyarylsulfones, polybutadienes, polysulfones, polyethersulfones, polyethylenes, polypropylenes, polyimides, polymethylpentenes, polyphenylene sulfides, polyvinyl butyral, polyvinyl acetate, polysiloxanes, polyacrylates, polyvinyl acetals, polyamides, polyimides, amino resins, phenylene oxide resins, terephthalic acid resins, epoxy resins, phenolic resins, polystyrene and acrylonitrile copolymers, polyvinylchloride, vinylchloride and vinyl acetate copolymers, acrylate copolymers, alkyd resins, cellulosic film formers, poly(amideimide), styrene-butadiene copolymers, vinylidenechloride-vinylchloride copolymers, vinylacetate-vinylidenechloride copolymers, styrene-alkyd resins, polyvinylcarbazole, and the like.
- In some exemplary embodiments, the coating dispersion used in the process can include, but are not limited to, polyvinyl alcohol (PVA), Mowiol® 4-88, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), Clevios PH1000, doped with 1% Triton X-100 surfactant and 6% ethylene glycol, polydimethylsiloxane (PDMS),
Dow Corning 200® fluid, glycerol, and used in 95% concentration, and vacuum pump oil (VPO). In addition, slurries, polymers, and inks such as those used in the manufacture of solid-state batteries can be used in the process. Solid phase materials can also be included. Polyethylene terephthalate film (PET), ES301400, can be used as a flexible substrate for deposition of patterned films. PET shim stock can also be used to define the internal geometry of the hybrid slot coater, whose die block material is polymethyl methacrylate (PMMA), optically clear cast acrylic. - This disclosure also includes a method of preparing a patterned thin film material. According to the method, a desired surface pattern is first designed. The parameters of the designed surface pattern are input into a computer. A substrate having a substrate surface is passed under a hybrid patterning apparatus, and the designed surface pattern is patterned onto the passing substrate surface using the hybrid patterning apparatus.
- Substrates and fluids suitable for use in this disclosure can be any material one of ordinary skill would use in a thin film apparatus. Suitable substrates for use in accordance with this disclosure include, but are not limited to, paper, glass, thin plastic film, and thin metallic film. Plastic film is the preferred substrate. Suitable substrates can be flexible, rigid, uncoated, precoated, as desired. The substrates can comprise a single layer or be made up of multiple layers. Suitable fluids that may be deposited in the patterning of the substrate include, but are not limited to, dispersions and organic and inorganic polymer solutions.
- In accordance with this disclosure, a system has been designed and fabricated for the purpose of producing customized thin films. Initial studies have been performed to demonstrate such a system and to produce basic patterns as seen in various emergent technologies.
- In some exemplary embodiments, simultaneous coating of two or more miscible liquids can consolidate the processing of multi-material stripe patterns into a single step. Deposition of each liquid species separately, in rows of narrow non-overlapping stripes, is the more conventional approach. Both strategies are compared with 10% aqueous PVA solutions coated on flexible PET substrate.
FIG. 7A shows a process response of stripe width for narrow stripes of 10% aqueous PVA using the conventional approach, and forFIG. 7B alternating stripes of PVA and un-doped 1.3% aqueous PEDOT:PSS using the hybrid patterning apparatus. The volumetric flowrate, Q, is specified as the average value per stripe. The single-phase approach shown inFIG. 7A requires multiple coating beads in the deposition region, each corresponding to an individual stripe. In the case with two miscible liquid phases illustrated inFIG. 7B , deposition flow behaves as a single coating bead with local variations in liquid phase. Consequentially, spreading effects at the coating bead edges are less significant, resulting in a more robust patterning capability. Whereas the widths of single-phase narrow stripes vary significantly across inputs, as shown inFIG. 7A the results for simultaneously-coated alternating stripes inFIG. 7B are largely independent of H and Q. -
FIGS. 8A-8B illustrates the behavior of two immiscible liquids, PDMS and 24% aqueous PVA, processed simultaneously using the multi-material stripe patterning approach. Here, the concentration of aqueous PVA has been selected to match the kinematic viscosity of 1000 cSt of the PDMS solution. The developing flow sequence begins inFIG. 8A with fully-developed deposition flow of PVA, followed by flow startup of PDMS. PDMS accumulates within localized coating beads until interaction between the two liquid phases occurs, resulting in unsteady deposition flow characterized by enhanced spreading of both liquids along the width of the coating tool as shown inFIG. 8B . While complete description of liquid bridge dynamics observed above is beyond the scope of this investigation, the enhanced spreading aspect follows intuitively from the wetting transition illustrated below. Spreading of the lower-surface tension liquid over the surface of the higher-surface tension liquid is evident for three representative cases inFIG. 9A . Here, the surface tension of 24% aqueous PVA, PDMS, 95% glycerol, and VPO are 42 mN/m, 20 mN/m, 63 mN/m, and 31 mN/m, respectively. The interfacial tensions are 5.2 mN/m for aqueous PVA and PDMS, 8.2 mN/m for PVA and VPO, and 9.1 mN/m for glycerol and VPO. Given these interfacial properties, Young’s equation for wetting predicts the observed spreading behavior due to formation of the liquid-liquid interface. At the liquid-liquid-gas contact line inFIG. 9B , Young’s equation can be applied as follows: -
-
- Here, σA and σB are the surface tensions of the two liquids, σAB denotes the interfacial tension between liquid phases, and their contact angles are given by φA and φB. Similarly, at the liquid-liquid-solid contact line, the force balance can be expressed as:
-
- Thus, where the interfacial tension σAB is small compared to forces at the other interfaces, equations (1)-(3) predict the formation of the shallow sloped cross section illustrated in
FIG. 9D . In essence, the contact angles predicted for the liquid-liquid-gas contact line correspond to preferential wetting of the lower-surface tension liquid along the surface of the higher surface tension liquid. Similarly, equilibrium contact angles at the solid surface arise from movement of the unpinned liquid-liquid-solid contact line. - The shim configuration illustrated in
FIG. 10 generates an internal flow field for multi-material stripe patterns at high resolution. The converging section of the slot acts as a mechanism for scaling of the entire pattern, reducing the average width of stripes from an initial value, w̅1 ≡ W1/N to a smaller value near the outlet region. Here, w̅2 ≡ W2/N is the total number of stripes, W1 is the overall slot width upstream from the converging section, and W2 is the slot width near the outlet. The angle ϕ is relevant to design of the channel length L required for a given inlet configuration and desired pattern, although both the inlet configuration and L are kept fixed in this study for purposes of comparison. -
FIG. 11 shows internal flow through a converging slot of alternating stripes of 10% PVA. Initial experiments with two 10% aqueous PVA solutions, one with less than 2% food dye added, and one dye-free, demonstrate viability for this patterning approach. Optical images of internal flow are organized inFIG. 11 for various permutations of W1/W2 and ϕ. The channel depth, equal to the slot gap G, is kept fixed at 76 µm. Volumetric flowrate per stripe is 140 µL is in the top row ofFIG. 11 , and 40 µL is in the bottom row ofFIG. 11 . In addition to these flowrates, values as low as 5 µL/s produce the same results without any resolvable variation. Uniformity of stripe width is apparent in most cases, although some variation across the width of the slot is observed for ϕ = 60°, 75°, with narrower stripes located at the channel periphery. This implies reduced flowrate near the outer edge of the slot compared with the center, due to flow in the outer region experiencing the same pressure drop over a longer distance. At 46 gm, the smallest feature size achieved, the aspect ratio of each individual stripe is approximately unity (w1/G ≈ 1). - Numerous characteristics and advantages have been set forth in the foregoing description, together with details of structure and function. While the invention has been disclosed in several forms, it will be apparent to those skilled in the art that many modifications, additions, and deletions, especially in matters of shape, size, and arrangement of parts, can be made therein without departing from the spirit and scope of the invention and its equivalents as set forth in the following claims. Therefore, other modifications or exemplary embodiments as may be suggested by the teachings herein are particularly reserved as they fall within the breadth and scope of the claims here appended.
Claims (22)
1. A method comprising:
co-laminar flowing of at least a first material and a second material within a slot die; and
depositing from a slot of the slot die a width-wise multi-material stripe pattern of the first and second materials;
wherein the material of adjacent stripes of the width-wise multi-material stripe pattern differ across a width of the slot.
2. The method of claim 1 further comprising:
feeding the first material into the slot die via a set of first inlets;
feeding the second material into the slot die via a set of second inlets; and
forming a stripe-patterned co-laminar flow in an interaction channel of the slot die;
wherein a continuous flow path exists between the first set of inlets and the interaction channel; and
wherein a continuous flow path exists between the second set of inlets and the interaction channel.
3. The method of claim 1 further comprising controlling uniformity of the width-wise multi-material stripe pattern.
4. The method of claim 1 further comprising dimensionally scaling the width-wise multi-material stripe pattern.
5. The method of claim 1 , wherein the width-wise multi-material stripe pattern is deposited on a surface of a substrate; and
wherein the substrate is selected from the group consisting of paper, glass, thin plastic film, and thin metallic film.
6. The method of claim 2 , wherein the first and second materials flow through the slot die in a planar, continuous laminar flow.
7. The method of claim 2 , wherein the first and second materials flow through the slot die in a planar, continuous creeping flow.
8. A method comprising:
feeding two or more fluid materials into a slot die via two or more sets of fluid inlets, each respective fluid material feeding into the slot die via a respective set of fluid inlets; and
depositing a width-wise multi-material stripe pattern of the two or more fluid materials;
wherein adjacent stripes of the width-wise multi-material stripe pattern comprise different fluid materials.
9. The method of claim 8 further comprising controlling a width of at least a portion of the stripes in the width-wise multi-material stripe pattern.
10. The method of claim 8 further comprising dimensionally scaling at least a portion of the width-wise multi-material stripe pattern.
11. The method of claim 8 , wherein the slot die comprises a first plate, a second plate, and a shim separating the plates.
12. The method of claim 8 further comprising:
interacting the two or more fluid materials in an interaction channel of the slot die, wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel;
wherein the two or more fluid materials flow through the slot die in a flow selected from the group consisting of a planar, continuous laminar flow and a planar, continuous creeping flow; and
wherein the width-wise multi-material stripe pattern is deposited on a surface of a substrate.
13. The method of claim 12 , wherein each respective set of the fluid inlets are:
positioned at a fluid inlet height position between a top and bottom of the slot die, the distance between the top and bottom of the slot die defining a height of the slot die; and
positioned at a fluid inlet width position between a first side and a second side of the slot die, the distance between the sides of the slot die defining a width of the slot die.
14. The method of claim 13 , wherein each fluid inlet height position of a respective set of the fluid inlets is the same; and
wherein each fluid inlet width position of a respective set of the fluid inlets is different;
such that each respective set of the fluid inlets present a horizontal line of spaced-apart fluid inlets.
15. The method of claim 14 , wherein each horizontal line of spaced-apart fluid inlets is at a different fluid inlet height position one from another.
16. A method comprising:
feeding two or more different fluid materials into a slot die via two or more sets of fluid inlets, each respective fluid material feeding into the slot die via a respective set of fluid inlets;
interacting the two or more different fluid materials in an interaction channel of the slot die, wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel;
depositing a width-wise multi-material stripe pattern of the two or more different fluid materials on a surface of a substrate; and
at least one of:
controlling a width of at least a portion of the stripes in the width-wise multi-material stripe pattern; and/or
dimensionally scaling at least a portion of the width-wise multi-material stripe pattern;
wherein no adjacent stripes of the width-wise multi-material stripe pattern comprise the same fluid material.
17. An apparatus for depositing the width-wise multi-material stripe pattern according to the method of claim 1 comprising:
the slot die;
a set of first inlets for the feeding of the first material into the slot die;
a set of second inlets for the feeding of the second material into the slot die; and
an interaction channel of the slot die for forming a stripe-patterned co-laminar flow of the first material and the second material.
18. An apparatus for depositing the width-wise multi-material stripe pattern according to the method of claim 8 comprising:
the slot die; and
an interaction channel of the slot die for interacting the two or more fluid materials;
wherein a continuous fluidic path exists between each set of fluid inlets and the interaction channel.
19. The apparatus of claim 18 further comprising outlets;
wherein a continuous fluidic path exists between each outlet and the interaction channel; and
wherein the width-wise multi-material stripe pattern is deposited through at least a portion of the outlets.
20. The apparatus of claim 18 , wherein the slot die comprises a first plate, a second plate, and a shim separating the plates.
21. The apparatus of claim 18 , wherein the slot die is a shim-free slot die.
22. The apparatus of claim 18 , wherein the interaction channel defines a volume extending in a flow direction from an upstream upper portion to a downstream lower portion; and
wherein the volume of the interaction channel has a converging cross-sectional area from the upstream upper portion to the downstream lower portion.
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US18/305,258 US20230256465A1 (en) | 2017-12-01 | 2023-04-21 | Scaling and coating of continuous multi-material stripes and patterns |
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PCT/US2018/063688 WO2019109101A1 (en) | 2017-12-01 | 2018-12-03 | Device and method for scaling and coating of continuous multi-material stripes and patterns |
US202016767676A | 2020-05-28 | 2020-05-28 | |
US18/305,258 US20230256465A1 (en) | 2017-12-01 | 2023-04-21 | Scaling and coating of continuous multi-material stripes and patterns |
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US16/767,676 Division US11666936B2 (en) | 2017-12-01 | 2018-12-03 | Device and method for scaling and coating of continuous multi-material stripes and patterns |
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