WO2018092067A1 - Appareil de revêtement en couche mince et procédés de formation d'un revêtement en couche mince - Google Patents

Appareil de revêtement en couche mince et procédés de formation d'un revêtement en couche mince Download PDF

Info

Publication number
WO2018092067A1
WO2018092067A1 PCT/IB2017/057182 IB2017057182W WO2018092067A1 WO 2018092067 A1 WO2018092067 A1 WO 2018092067A1 IB 2017057182 W IB2017057182 W IB 2017057182W WO 2018092067 A1 WO2018092067 A1 WO 2018092067A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
solution
gas
spin
thin film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2017/057182
Other languages
English (en)
Inventor
Maged Abdelmonem ABDELSAMIE
Aram AMASSIAN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
King Abdullah University of Science and Technology KAUST
Original Assignee
King Abdullah University of Science and Technology KAUST
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by King Abdullah University of Science and Technology KAUST filed Critical King Abdullah University of Science and Technology KAUST
Publication of WO2018092067A1 publication Critical patent/WO2018092067A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
    • B05D3/0406—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being air
    • B05D3/042—Directing or stopping the fluid to be coated with air
    • 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
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B11/00—Machines or apparatus for drying solid materials or objects with movement which is non-progressive
    • F26B11/18—Machines or apparatus for drying solid materials or objects with movement which is non-progressive on or in moving dishes, trays, pans, or other mainly-open receptacles
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00—Arrangements for supplying or controlling air or other gases for drying solid materials or objects
    • F26B21/50—Ducting arrangements from the source of air or other gases to the materials or objects being dried
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B3/00—Drying solid materials or objects by processes involving the application of heat
    • F26B3/02—Drying solid materials or objects by processes involving the application of heat by convection, i.e. heat being conveyed from a heat source to the materials or objects to be dried by a gas or vapour, e.g. air
    • F26B3/04—Drying solid materials or objects by processes involving the application of heat by convection, i.e. heat being conveyed from a heat source to the materials or objects to be dried by a gas or vapour, e.g. air the gas or vapour circulating over or surrounding the materials or objects to be dried
    • 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
    • B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
    • B05D1/005—Spin coating
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0402—Apparatus for fluid treatment
    • H10P72/0406—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like
    • H10P72/0408—Apparatus for fluid treatment for cleaning followed by drying, rinsing, stripping, blasting or the like for drying
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0448—Apparatus for applying a liquid, a resin, an ink or the like

Definitions

  • Organic solar cells including small molecule photovoltaics and bulk heteroj unction solar cells utilize thin-film active layers with an electron donor and acceptor blend.
  • bulk heteroj unction solar cells may include a blend of donor and acceptor materials that are casted and then allowed to phase separate and self- assemble into an interpenetrating network between two electrodes.
  • scalable processing techniques generally suffice with respect to forming thin-film active layers on par with laboratory-based processing techniques (such as spin coating) for solar cell applications, the success of those techniques is generally limited to polymer-based solar cells.
  • those techniques suffer from various shortcomings, particularly with respect to scalability, among other things.
  • spin coating is a conventional laboratory-based technique with losses of greater than 95% of material during coating. Further, spin coating is not compatible with continuous manufacturing processes (e.g., roll-to-roll manufacturing). In addition, drying profiles cause non-uniformity on large area substrates.
  • conventional scalable manufacturing techniques e.g., blade coating, wire-bar coating, slot die coating, etc.
  • conventional techniques fail to provide adequate control over the microstructure and morphology of the thin-film active layers necessary for solar cell applications.
  • conventional techniques cannot provide rapid solvent evaporation at low temperatures, leading to pinholes, cracks, and other defects, as well as over- crystallization and non-uniform distribution.
  • embodiments of the present disclosure describe a thin-film coating apparatus and methods of thin-film coating.
  • embodiments of the present disclosure describe an apparatus for thin film coating comprising a mount configured to secure a substrate, a coating device proximate to the mount and configured to deposit a solution on the substrate, and a dryer component fluidly coupled to the mount and configured to spin a gas proximate to deposited solution to dry the deposited solution and form a thin film coating.
  • Embodiments of the present disclosure also describe an apparatus for thin film coating comprising a coating device configured to deposit a solution on a substrate; and a dryer component configured to spin gas proximate to the deposited solution to dry the deposited solution and form a thin film coating.
  • Embodiments of the present disclosure further describe a method of forming a thin-film coating comprising depositing a solution on a substrate and spinning a gas proximate to the deposited solution to dry the deposited solution and form a thin film coating.
  • FIG. 1 is a schematic diagram of a thin-film coating apparatus, according to one or more embodiments of the present disclosure.
  • FIG. 2 is a flowchart of a method of forming a thin-film coating, according to one or more embodiments of the present disclosure.
  • FIGS. 3a-3c are microscopy images including a polarized optical microscopy (POM) image of p-DTS(FBTTh 2 )2:PC7iBM films coated by wire-bar coating from CB with 21% w/w (DIO/solutes) (3a); a POM image of a region near an edge of the film in (a) showing coffee -ring effect (3b); and a transmission electron microscopy (TEM) image of p- DTS(FBTTh 2 ) 2 :PC7iBM films coated from CB with 21% w/w (DIO/solutes) (3c), according to one or more embodiments of the present disclosure.
  • POM polarized optical microscopy
  • TEM transmission electron microscopy
  • FIG. 4a is a 2D GIWAXS image of p-DTS(FBTTh 2 ) 2 :PC7iBM wire-bar coated film at room temperature, according to one or more embodiments of the present disclosure.
  • FIG. 4b is a graphical view of line cuts of integrated scattering intensity versus q (nm _1 ) of wire-bar coated samples processed with identical DIO content (21% 2/2 DIO/solutes) at room temperature (black) and at 45 °C (red), with a spin-coated reference sample (blue) (inset highlights scattering from p-DTS(FBTTh2)2 alkyl-stacking peak (001)), according to one or more embodiments of the present disclosure.
  • FIG. 4c is a 2D GIWAXS color plot showing a logarithmic plot of integrated scattering intensity as a function of time (s) measured in situ during wire-bar coating of p- DTS(FBTTh 2 )2:PC 7 iBM from CB with 21% w/w (DIO/solutes) at room temperature, according to one or more embodiments of the present disclosure.
  • FIG. 4d is a graphical view of an integrated scattering intensity of solvent scattering (black) and p-DTS(FBTTh2)2 alkyl-staking scattering (Xooi) (red) calculated from in situ GIWAXS in (c) (thickness of films was 120 +/- 10 nm), according to one or more embodiments of the present disclosure.
  • FIG. 4e is a 2D GIWAXS color plot showing a logarithmic plot of integrated scattering intensity as a function of time (s) measured in situ during wire-bar coating of p- DTS(FBTTh2) 2 :PC 7 iBM from CB with 21% w/w (DIO/solutes) at 45°C, according to one or more embodiments of the present disclosure.
  • FIG. 4f is a graphical view of an integrated scattering intensity of solvent scattering (black) and p-DTS(FBTTh2)2 alkyl-staking scattering (Xooi) (red) calculated from in situ GIWAXS in (e) (thickness of films was 120 +/- 10 nm), according to one or more embodiments of the present disclosure.
  • FIG. 5a is a 2D GIWAXS image of p-DTS(FBTTh 2 )2:PC 7 iBM film wire-bar coated from pure CB at room temperature, according to one or more embodiments of the present disclosure.
  • FIG. 5b is a 2D GIWAXS color plot showing a logarithmic plot of integrated scattering intensity as a function of time(s) measured in situ during wire-bar coating of p- DTS(FBTTh2)2:PC7iBM from pure CB at room temperature, according to one or more embodiments of the present disclosure.
  • FIGS. 6a-6d are schematic diagrams of stages of a spin-coating processing including deposition (6a), spin-up (6b), spin-off (6c), and evaporation (6d), according to one or more embodiments of the present disclosure.
  • FIGS. 8a-8c are 2D GIWAXS images of p-DTS(FBTTh 2 ) 2 :PC7iBM films coated by spin coating (8a) and modified wire-bar coating (8b), with a graphical view of line cuts of integrated scattering intensity versus q (nm _1 ) of p-DTS(FBTTh2)2:PC7iBM samples coated by modified wire -bar coating (black curve) and spin coated (red curve) (8c), according to one or more embodiments of the present disclosure. Both samples were processed with identical DIO content; 21% w/w (DIO/solutes).
  • FIG. 9 is a current density-voltage (J-V) curve of solar cell devices fabricated from p-DTS(FBTTh2)2:PC7iBM blends coated by spin coating with total solute concentration 35 mg/mL (black) and new wire-bar coating at different concentrations, including 35 mg/mL (red), 25 mg/mL (blue), 17 mg/mL (pink),and 12.5 mg/mL (green), according to one or more embodiments of the present disclosure. All sample were coated in air from CB with 21% w/w (DIO/solutes). Notably, fabricated solar cell devices in glove-box by spin coating observed higher performance (PCE > 7%).
  • Embodiments of the present disclosure describe a thin-film coating apparatus and methods of forming thin-film coatings.
  • the thin-film coating apparatus and methods can achieve unprecedented control over the kinetics of drying and uniformity of drying, without substrate rotation.
  • the thin-film coating apparatus and methods overcome the challenges of over-crystallization and non-uniform drying to produce high quality, uniform thin films suitable for small molecule solar cells (e.g., organic solar cells), among other applications. It can accelerate drying to achieve rapid solvent evaporation at low temperatures sufficient to prevent significant crystallization and/or over-crystallization in a solvent- saturated environment and/or prevent increased diffusion favoring crystallization.
  • the thin-film apparatus and methods achieve these and other advantages by spinning a gas proximate to coating material, as opposed to spinning the coating material, to dry it. In the absence of substrate rotation, the invention avoids the loss of significant amounts of coating material as waste during the coating process. Furthermore, the thin-film apparatus is production compatible and suitable for scalable manufacturing as it is capable of high throughput and high-speed thin-film coating. In this way, the invention of the present disclosure minimizes defects and improves thin film quality, operational efficiency, and scalability over convention methods and devices to produce uniform and/or substantially uniform thin film coatings.
  • depositing refers to etching, doping, epitaxy, thermal oxidation, sputtering, casting, depositing, spin-coating, evaporating, applying, treating, and any other technique and/or method known in the art.
  • spinning refers to rotating, circulating, agitating, flowing, and streaming.
  • FIG. 1 is a schematic diagram of a thin-film coating apparatus, according to one or more embodiments of the present disclosure.
  • the thin-film coating apparatus may include a mount 101 configured to secure a substrate 102.
  • a coating device 103 e.g., a wire-bar coater is shown
  • a dryer component 105 may be fluidly coupled to the mount and configured to spin a gas proximate to the deposited solution to dry the deposited solution and form a thin film coating.
  • the apparatus shown in FIG. 1 includes a mount 101 combined with a temperature controller 106, the mount 101 and temperature controller 106 are each independently optional.
  • the apparatus for thin film coating comprises a coating device 103 configured to deposit a solution 104 on a substrate 102 and a dryer component 105 configured to spin gas proximate to the deposited solution to dry the deposited solution and form a thin film coating.
  • the mount 101 may be utilized to secure the substrate 102. As shown in FIG. 1, the mount 101 may secure the substrate 102 by supporting only a single surface of the substrate (e.g., the bottom surface) without any lateral or horizontal support. In other embodiments (not shown), the mount 101 may secure the substrate 102 by constraining the substrate 102 and/or preventing the substrate 102 from moving in any lateral direction (e.g., pressure is applied to at least two opposing side surfaces of the substrate to constrain the substrate from moving in a lateral direction). These examples shall not be limiting as the mount may utilize any method and/or apparatus known in the art capable of securing a substrate. As described above, a mount is optional.
  • the coating device 103 may include any coating device suitable to deposit the solution on the substrate.
  • the coating device may be proximate to and/or include the mount.
  • the coating device includes scalable and/or high speed coating devices.
  • the coating device may include, but is not limited to, one or more of a bar-coater, slot-die-coater, blade-coater, knife-coater, roll-coater, wire-bar coater, dip-coater, and spray-coater.
  • the coating devices 103 may be low-speed coating devices, high-speed coating devices, or combinations thereof.
  • the coating speed of a low-speed coating device ranges from about 5 mm/s to about 10 mm/s; and the coating speed of a high-speed coating device is about 100 mm/s and/or greater than about 100 mm/s.
  • the coating speed of the coating device 103 may range from about 5 mm/s to about 100 mm/s. In many embodiments, the coating speed of the coating device is about 100 mm/s or is greater than about 100 mm/s. In other embodiments, the coating speed of the coating device is less than 100 mm/s. For example, the coating speed of the coating device may range from about 5 mm/s to about 10 mm/s. These ranges shall not be limiting as any other range is possible depending on the coating device used.
  • the solution to be deposited may include any solution known in the art.
  • the solution to be deposited is a small molecule material.
  • the small molecule material may be any material suitable for organic photovoltaic applications, including, but not limited to solar cells.
  • the small molecule material may include, for example, small molecule OPV formulations.
  • the small molecule material includes p- DTS(FBTTh2):PC7iBM and one or more of a bulk solvent and an additive solvent.
  • the bulk solvent may include chlorobenzene (CB).
  • the additive solvent may include 1,8-diiodooctane (DIO). In many embodiments, concentration of the additive solvent is about 21% w/w (DIO/solutes).
  • the small molecule material may be characterized as a material other than a polymer or polymer-based material.
  • the solution (e.g., small molecule material) may be deposited as a layer.
  • a thickness of the deposited solution may range from about 50 to about 300 nm.
  • the thickness may range from about 100 nm to about 120 nm or about 100 nm to about 105 nm.
  • the thickness of the solution is at least about 50 nm, at least about 100 nm, at least about 150 nm, at least about 200 nm, at least about 250 nm, or at least about 300 nm.
  • the dryer component 105 may include any component suitable for providing the uniformity, morphology, and microstructure necessary for high performance solar cells (e.g., solar cells fabricated from p-DTS(FBTTh2)2:PC7iBM blends).
  • the dryer component 105 may be fluidly coupled to the optional mount, if present, and/or configured to spin a gas proximate to (e.g., above) the layer of deposited solution to dry the deposited solution and form the thin film coating.
  • the dryer component may form a vortex of gas proximate to and/or above the deposited solution in a scalable process that emulates the drying kinetics of spin coating.
  • the dryer component may be configured to dry the deposited solution at a substantially uniform rate without substrate rotation to achieve effective and efficient usage of the deposited solution (e.g., without significant losses of solution and/or deposited solution), while aiding in film uniformity.
  • the dryer component may further accelerate the drying and/or evaporation rates of the solvent from the deposited solution at low enough temperatures (e.g., room temperature) sufficient to prevent significant crystallization and/or overcrystallization.
  • the dryer component may also provide a substantially uniform rate of drying/evaporation to prevent the formation of concentration gradients in the deposited material, as well as the formation of defects, such as pinholes, cracks, coffee-ring effect, etc.
  • the dryer component may include a supply conduit for supplying a gas or a vacuum (e.g., to spin gas proximate to the deposited solution and/or to dry the deposited solution and/or layer of deposited solution), a rotating head fluidly coupled to the supply conduit, and a motor component coupled to the rotating head and configured to rotate the rotating head.
  • the dryer component may be adjusted to modify an air-substrate distance (e.g., to facilitate drying, uniformity of drying, etc.).
  • the gas is supplied through the supply conduit and spun via the rotating head as it exits an outlet of the rotating head.
  • a vacuum is applied through the supply conduit and rotating head to spin gas proximate to the deposited solution.
  • the spinning gas may create a vortex of gas.
  • the motor component permits adjustment of the spinning rate (e.g., an adjustable rate) in revolutions per minute, for example.
  • the outlet of the rotating head may include a slit.
  • the gas may include air and/or any inert gas, such as nitrogen, including mixtures thereof. In some embodiments, the inert gas may include nitrogen.
  • the thin-film apparatus is used at temperatures sufficient (e.g., sufficiently low temperatures) to prevent significant crystallization while drying.
  • a suitable temperature includes, but is not limited to, about room temperature.
  • the temperature controller 106 is optional and not required.
  • the thin-film apparatus may include a temperature controller.
  • the temperature controller may be utilized to accelerate the drying kinetics of the coating material (e.g., drying rate and/or evaporation rate of the deposited solution) by raising the coating temperature to between about 25 °C to about 90°C.
  • the temperature controller to accelerate drying must be carefully controlled because it may result in over-crystallization and non-uniform drying. Drying the deposited solution at an elevated temperature may increase diffusion of molecules and result in over-crystallization of the thin film coating. In addition, non-uniform drying may form a solute concentration gradient and lead to the formation of a coffee -ring effect, pinholes and/or cracks in areas with relatively low solute concentration. In addition, the dryer component outperforms use of a temperature controller with respect to accelerated and substantially uniform drying. Consequently, a temperature controller is optional and generally not required.
  • the thin-film coating apparatus may reproducibly provide high quality, uniform thin films suitable for, for example, bulk heterojunction coatings for organic photovoltaics applications (e.g., small molecule solar cells).
  • the thin-film coating apparatus minimizes the amount of coating material lost or consumed during coating by eliminating substrate rotation.
  • the coating material loss may be less than about 95%.
  • the coating material loss may be less than about 20%, less than about 15%, less than about 10%, less than about 5%, or less than about 1% (with a lower boundary including no coating material loss).
  • Coating material consumption for thin-films may be about 25 times less than conventional apparatuses and techniques for coating speeds on the order of several meters per minute.
  • the thin-film coating apparatus may be compatible with roll-to-roll manufacturing and may be used for high-speed coating in scalable manufacturing.
  • FIG. 2 is a flowchart of a method of forming a thin-film coating, according to an embodiment of the present disclosure. Any of the embodiments previously discussed may be utilized in connection with this embodiment.
  • the method may comprise depositing 201 a solution on a substrate and spinning 202 a gas proximate to the deposited solution to dry the deposited solution and form a thin film coating.
  • a solution is deposited on a substrate.
  • Depositing may generally refer to placing, coating, transferring, adding, providing, dipping, rolling, casting, and any other device or process for bringing a solution into contact with a substrate.
  • the solution may be deposited as a layer and/or coating.
  • the solution may include any of the solutions described herein.
  • the deposited solution may be uniform, substantially uniform, and/or non- uniform. Depositing may occur at any of the speeds described herein and any of the temperatures described herein.
  • a bar-coater may be utilized to deposit the solution on the substrate.
  • any coating device may be utilized to deposit the solution.
  • the coating device may include one or more of casting, bar-coating, slot-die-coating, blade-coating, knife-coating, roll-coating, wire-bar coating, dip- coating, and spray-coating.
  • a spinning gas is provided proximate to and/or above the deposited solution to dry the deposited solution and form a thin film coating.
  • the spinning may occur at any of the temperatures described herein. In many embodiments, the spinning occurs at about room temperature.
  • spinning substantially uniformly dries the deposited solution.
  • the deposited solution may be uniformly dried or substantially uniformly dried to produce a uniform (e.g., substantially uniform) and/or defect- free (e.g., substantially defect-free) thin film coating.
  • a vacuum and/or gas stream may be supplied and/or applied through the dryer components described herein.
  • spinning may include supplying a gas stream proximate to the deposited substrate via a rotating head of the dryer component.
  • spinning may include applying a vacuum proximate to the deposited solution via a rotating head of the dryer component.
  • Spinning may form a vortex of gas. Drying of the wet solution is controlled by spinning the surrounding gas (e.g., as in the case of a vacuum), or supplying spinning gas (e.g., as in the case of a gas stream).
  • the control over the spinning gas may be achieved by adjusting the distance between the dryer and/or spinning gas and the substrate.
  • p-DTS(FBTTli2)2 Due to slow drying kinetics, p-DTS(FBTTli2)2 must have enough time for nucleation and growth to occur without going through the vitrified state. Moreover, the presence of solvent (CB) in the wet film provided the kinetics for p- DTS(FBTTh2)2 crystallization which also led also over-crystallization of p-DTS(FBTTh2)2 (Error! Reference source not found.b). In Error! Reference source not found.b, line cuts of integrated scattering intensity versus q (nm -1 ) of wire-bar coated samples versus spin-coated reference sample are shown. The crystalline correlation length (CCL) and the relative crystallinity for the samples were calculated (Table 1).
  • Wire-bar coated sample at RT exhibited a much higher CCL (about 22.4 nm) than the spin coated sample (CCL about 13.6 nm), indicating larger crystallites for RT wire-bar coated sample. Moreover, the relative crystallinity for RT wire-bar coated sample was more than three time higher than the spin coated samples. Over-crystallization of p-DTS(FBTTli2)2 occurred for spin coating samples when an excessive amount of the additive DIO was used. Over-crystallization of p- DTS(FBTTli2)2 occurs when p-DTS(FBTTh2)2 crystallization occurs in an environment saturated with the solvents (either the bulk solvent or the additive solvent).
  • Wire-bar coating at 45DC resulted in a slight reduction in CCL to about 19 nm and relative crystallinity to about 3.1, as compared to wire-bar coating at RT. However, these values still indicated greater crystallinity for wire-bar coating samples than spin coating samples.
  • the failure of wire-bar coating at 45 DC to hinder p-DTS(FBTTh2)2 over-crystallization was attributed to the increase in the diffusion of p-DTS(FBTTli2)2 molecules at elevated temperatures that was expected to favor the crystal growth - specifically if the growth occurred in an environment saturated with a plasticizer (ca. CB).
  • Table 1 Summary of the relative crystallinity and crystalline correlation length of p-DTS(FBTTh2)2 , calculated from the alkyl-stacking peak (001)
  • Wire-bar coating at 45 DC 3.1 +/- 0.2 0.33 19 [0052] The observed crystallization behavior was mediated by crystal growth in an environment saturated with CB. However, DIO was used in the conditions discussed above. Therefore, it was investigated whether the same behavior was observable in the absence of DIO. Indeed, similar behavior was observed for additive-free wire-bar coated sample (Error! Reference source not found.) confirming that this crystallization behavior was dominated by the presences of the CB during crystal growth.
  • Deposition During this stage, solution is deposited onto static or rotating substrates from micro-syringes. Then, the substrate is accelerated to the desired speed while spreading of the solution occurs due to centrifugal force.
  • the second stage involves accelerating up the substrate to its final desired rotation speed and is characterized by aggressive fluid expulsion from the substrate due to rotation.
  • inertia of the fluid driven by the accelerating substrate results in twisting motion of the fluid and the formation of spiral vortices leading to significant ejection of the ink out of the substrate.
  • Evaporation The fourth stage starts when the centrifugal out flow stops and consequently no further loss of the ink occurs. During this stage, the thinning behavior is dominated by solvent evaporation only. The evaporation rate is mediated by the difference in partial pressure of the ink species (volatiles) between the free surface of the ink layer and the bulk gas surrounding the ink at the liquid/vapor interface.
  • the primary drawback of spin coating arises from the initial steps, namely spin- up and spin-off, which involve ejection of the ink.
  • the last step involves drying of the solution via an interaction of the ink with the surrounding environment (ca. air, dry N 2 ). Airflow dynamics at the liquid/air interface during the evaporation step play a decisive role on the film uniformity, one of the main benefits of spin coating.
  • the evaporation mechanism during this step can be summarized as follows. Thin layer of the surrounding gas is spun with the substrate whereas the surrounding gas far from the substrate is much less mobile. Consequently, a gradient of the air speed further from the rotating substrate emerges leading to gradient in the partial pressure of the surrounding gas. This gradient in the partial pressure drives the evaporation of the voiatiles,
  • An invention of the present disclosure includes a new apparatus designed with a drying mechanism that does not require substrate rotation.
  • the apparatus may mimic the fluid dynamics on top of the substrate but avoids rotating the substrate thereby providing the advantage of curbing ink-loss and aiding film uniformity.
  • the invention of the present disclosure may be composed of conventional wire- bar coating combined with an apparatus for film drying control, illustrated in Error! Reference source not found..
  • the uniform distribution of the ink that was achieved at the initial steps of spin coating was managed by the alternative scalable techniques, such as wire- bar in the present invention.
  • air was spun on the sample surface (adjustable air-substrate distance).
  • the air (or inert gas) on top of the sample was spun after wet film was cast. This was done via applying vacuum or supplying an inert gas through a rotating slit on top of the sample.
  • the ⁇ - ⁇ stacking scattering revealed preferred edge-on preferential texture for both samples.
  • the relative crystallinity and CCL were calculated for both conditions; the calculation was done for three measurements per each condition, and reported in Table 2.
  • the samples had an average thicknesses of about 100-120 nm and about 100-105 nm for modified wire-bar coating and spin coating, respectively.
  • Samples coated by both coating methods exhibited similar relative crystallinity and average crystal size (CCL about 13-14 nm) of p-DTS(FBTTh2)2 crystallites. These results demonstrated that the new apparatus was effective in overcoming p-DTS(FBTTh2)2 over-crystallization.
  • Table 2 Summary of the relative crystallinity and crystalline correlation length of p-DTS(FBTTh2)2, calculated from the alkyl-stacking ; peak (001)
  • the errors include standard deviation for three measurements.
  • the thickness of the active layer was systematically reduced by reducing the solute concentration.
  • FF and Jsc improved gradually leading to an increase in PCE.
  • the best performance of the modified wire-bar coated devices was attained at a total solute concentration of 12.5 mg/mL which resulted in a slightly thicker film (about 118 nm) than the spin coated samples (about 105 nm).
  • the new wire-bar coated devices had a slightly higher Jsc but lower FF, resulting in slight improvement in the overall device performance.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

Des modes de réalisation de la présente invention concernent un appareil de revêtement en couche mince comprenant un dispositif de revêtement conçu pour déposer une solution sur un substrat ; et un composant de séchage conçu pour faire tourner un gaz à proximité de la solution déposée afin de sécher la solution déposée et de former un revêtement en couche mince. Des modes de réalisation de la présente invention concernent en outre un procédé de formation d'un revêtement en couche mince comprenant le dépôt d'une solution sur un substrat et la rotation d'un gaz à proximité de la solution déposée pour sécher la solution déposée et former un revêtement en couche mince.
PCT/IB2017/057182 2016-11-16 2017-11-16 Appareil de revêtement en couche mince et procédés de formation d'un revêtement en couche mince Ceased WO2018092067A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662422831P 2016-11-16 2016-11-16
US62/422,831 2016-11-16

Publications (1)

Publication Number Publication Date
WO2018092067A1 true WO2018092067A1 (fr) 2018-05-24

Family

ID=60782274

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2017/057182 Ceased WO2018092067A1 (fr) 2016-11-16 2017-11-16 Appareil de revêtement en couche mince et procédés de formation d'un revêtement en couche mince

Country Status (1)

Country Link
WO (1) WO2018092067A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115463798A (zh) * 2022-09-22 2022-12-13 四川宇光光学玻璃有限公司 一种复合薄膜制备设备
CN117871576A (zh) * 2024-01-12 2024-04-12 浙江大学 一种检测快速反应产物演化的可视化方法及系统

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5234499A (en) * 1990-06-26 1993-08-10 Dainippon Screen Mgf. Co., Ltd. Spin coating apparatus
US6321463B1 (en) * 1999-05-25 2001-11-27 Ebara Corporation Substrate treating apparatus and method of operating the same
US20080190454A1 (en) * 2007-02-09 2008-08-14 Atsuro Eitoku Substrate treatment method and substrate treatment apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5234499A (en) * 1990-06-26 1993-08-10 Dainippon Screen Mgf. Co., Ltd. Spin coating apparatus
US6321463B1 (en) * 1999-05-25 2001-11-27 Ebara Corporation Substrate treating apparatus and method of operating the same
US20080190454A1 (en) * 2007-02-09 2008-08-14 Atsuro Eitoku Substrate treatment method and substrate treatment apparatus

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115463798A (zh) * 2022-09-22 2022-12-13 四川宇光光学玻璃有限公司 一种复合薄膜制备设备
CN117871576A (zh) * 2024-01-12 2024-04-12 浙江大学 一种检测快速反应产物演化的可视化方法及系统

Similar Documents

Publication Publication Date Title
Yuan et al. Volatile perovskite precursor ink enables window printing of phase‐pure FAPbI3 perovskite solar cells and modules in ambient atmosphere
Wang et al. A wenzel interfaces design for homogeneous solute distribution obtains efficient and stable perovskite solar cells
Singh et al. Understanding the formation of PEDOT: PSS films by ink-jet printing for organic solar cell applications
Remeika et al. Scalable solution coating of the absorber for perovskite solar cells
CN110854274B (zh) 一种钙钛矿薄膜的制备方法及其在太阳能电池中的应用
FR2949907A1 (fr) Procede de preparation d'un materiau composite pour electrode positive par extrusion en presence d'un solvant aqueux, electrode positive obtenue par le procede et applications
WO2018092067A1 (fr) Appareil de revêtement en couche mince et procédés de formation d'un revêtement en couche mince
KR102080748B1 (ko) 고품질 페로브스카이트 광 활성층 박막 제조 방법 및 이를 포함하는 페로브스카이트 태양전지
Ren et al. Inkjet printing technology for OPV applications
CN105190924B (zh) 有机半导体共混物
Yang et al. Toward all aerosol printing of high-efficiency organic solar cells using environmentally friendly solvents in ambient air
CN114318492A (zh) 一种钙钛矿单晶的制备方法以及光电器件
Liu et al. The influence mechanism of ink viscosity on ink transfer rates and film defects of the roll-to-roll printed organic photoactive layers
Gu et al. Mechanics manipulation in large-area organic solar modules achieving over 16.5% efficiency
ABDELSAMIE et al. A thin-film coating apparatus and methods of forming a thin-film coating
JP5686403B2 (ja) 有機半導体薄膜の製造方法
CN110624789A (zh) 一种倒置式粘涂法制备大面积薄膜的方法
Gao et al. P3HT stripe structure with oriented nanofibrils enabled by controlled inclining evaporation
Cardoso et al. Spin Coating: Process, Applications, Challenges, and Characterization Techniques
FR2941159A1 (fr) Procede de depot d'un materiau a la surface d'un objet.
US20090020221A1 (en) Method for Producing Self-Assembled Construction
CN109599490B (zh) 二元混合溶剂体系及其在制备钙钛矿材料中的用途
CN118555890A (zh) 一种基于两步顺序沉积技术的混合铅锡钙钛矿薄膜及其钙钛矿太阳能电池的制备方法
CN113241412A (zh) 一种有机光伏器件活性层的制备方法及其应用
CN116396637B (zh) 调节喷墨打印薄膜微观组分分布的方法、共混墨水及应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17818276

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17818276

Country of ref document: EP

Kind code of ref document: A1