US20210292903A1

Movatterモバイル変換

Info

Publication number: US20210292903A1
Application number: US17/340,575
Authority: US
Inventors: Sang In LEE
Original assignee: Nova Engineering Films Inc
Current assignee: Nova Engineering Films Inc
Priority date: 2018-09-05
Filing date: 2021-06-07
Publication date: 2021-09-23
Also published as: US20200071830A1; US11072858B2

Abstract

An injecting assembly includes a nozzle that is formed with a mixture channel, a mixture opening communicating with the mixture channel, a shaper channel, and a shaper opening communicating with the shaper channel. A mixture of a precursor and a supercritical fluid (SCF) passes through the mixture channel. Waves of the mixture are periodically injected toward a surface of a substrate at the mixture opening. A stream of a shaping fluid flows through the shaper channel and is injected toward the substrate at the shaper opening. The stream of the shaping fluid confines the waves of the mixture. Molecules of the precursor penetrate into the substrate by impact of the wave fronts reaching the surface of the substrate. The molecules of the precursor can react with molecules of a material of the substrate to improve surface properties of the substrate.

Description

CROSS-REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No. 16/559,139, filed on Sep. 3, 2019, which claims the benefit of U.S. Provisional Patent Application No. 62/727,417, filed on Sep. 5, 2018 and U.S. Provisional Patent Application No. 62/756,548, filed on Nov. 6, 2018, which are incorporated by reference herein in their entirety.

BACKGROUNDField of the Disclosure

The present disclosure generally relates to surface treatment, and specifically to a method of improving surface properties of substrate by pulsing a mixture of a precursor and supercritical carrier fluid toward the substrate.

Description of the Related Arts

Infiltration/impregnation is used to improve surface properties of porous materials. In vapor phase infiltration/impregnation (VPI) processes, vapor phase precursors can diffuse into substrates and subsequently reacted with materials of the substrates to transform into solid states. For example, VPI processes can be used to form hybrid organic-inorganic materials from diffusion of metalorganic precursors into organic polymers. Infiltration/impregnation usually includes a hold step, during which adsorbed molecules of a precursor can diffuse into a porous material to improve properties of the porous material. However, with conventional injecting techniques, the hold step is time consuming and has low productivity. For example, molecules of the precursor can be drifted and scattered while traveling to the surface of the porous material and therefore a limited number of molecules of the precursor arrive at the surface and diffuse into the porous material. Also, the molecules that arrive at the surface may not have sufficient energy to penetrate into the porous material with the desired depth. Consequently, there are insufficient molecules of the precursor that can diffuse into the porous material for improving properties of the porous material.

SUMMARY

Embodiments relate to a method of improving surface properties of a substrate with pulses of a mixture of a precursor and a supercritical fluid (SCF). Waves of the mixture are periodically injected toward the substrate. The substrate is placed at atmosphere pressure that is lower than the critical pressure of the SCF. As the mixture propagates toward the substrate, the SCF converts to a gas phase and expands, causing a high velocity of the waves towards the substrate. The high velocity of the waves can reduce or eliminate drifting and scattering of the precursor and can also drive molecules of the precursor to penetrate into the substrate. The penetration length/depth is larger than the diffusion length/depth in a conventional infiltration process. The substrate can include an inorganic solid, organic solid, composite material, polymer, or viscous liquid. The penetration is also enhanced by impact of the wave fronts reaching the substrate. The molecules of the precursor that penetrate into the substrate can react with molecules of a material at the surface to improve properties of the surface.

In some embodiments, an injecting assembly of a surface treatment apparatus injects the waves of the mixture toward the substrate. The injecting assembly includes a nozzle formed with a mixture channel and a mixture opening. The mixture passes through a mixture channel to reach the mixture opening. The mixture opening periodically injects the waves toward the substrate. Shapes of the waves can be controlled by an angle of the mixture opening.

In some embodiments, the injecting assembly can also inject a shaping fluid toward the substrate to confine and/or shape the waves of the mixture. The shaper opening surrounds the mixture opening and communicates with the shaper channel. The shaping fluid passes through the shaper channel to reach the shaper opening. The shaper opening injects a stream of the shaping fluid toward the substrate. The shaping fluid can be the SCF in the mixture.

In some embodiments, in addition to the injecting assembly, the surface treatment apparatus may include an actuating assembly that drives the substrate to move relative to the injecting assembly. The actuating assembly includes a plurality of rollers and a motor that drives the rollers to rotate. The rollers are arranged on a top side and bottom side of the substrate. Rotation of the rollers moves the substrate in relative to the injecting assembly. The substrate moves during injecting of the waves so that different portions of the surface of the substrate can be treated.

In some embodiments, the surface treatment apparatus can also include a plasma generator that generates plasma radicals. The substrate is exposed to the plasma radicals. The plasma radicals can react with the molecules of the precursor that penetrate into the substrate to transform the molecules of the precursor into a solid state.

BRIEF DESCRIPTION OF THE DRAWINGS

The teachings of the embodiments can be readily understood by considering the following detailed description in conjunction with the accompanying drawings.

FIG. 1 is a schematic view of an injecting assembly, in accordance with an embodiment.

FIG. 2A illustrates periodic ballistic injection by a nozzle toward a substrate, in accordance with an embodiment.

FIG. 2B shows an example duty cycle of the periodic ballistic injection, in accordance with an embodiment.

FIG. 3 illustrates penetration of a precursor molecule into a substrate, in accordance with an embodiment.

FIGS. 4A through 4C illustrate a circular nozzle, in accordance with an embodiment.

FIGS. 5A and 5B illustrate a linear nozzle, in accordance with an embodiment.

FIG. 6 illustrates two area nozzles, in accordance with an embodiment.

FIG. 7 illustrates a mixing system for mixing fluids and controlling flow of fluids into a nozzle, in accordance with an embodiment.

FIG. 8 is a schematic cross-sectional view of a surface treatment apparatus including an actuating assembly, in accordance with an embodiment.

FIG. 9 is a schematic cross-sectional view and a top view of a surface treatment apparatus including a plasma generator, in accordance with an embodiment.

FIG. 10 is a schematic cross-sectional view of a surface treatment apparatus including an exhausting assembly, in accordance with an embodiment.

FIG. 11 is a schematic cross-sectional view of a surface treatment apparatus including two injecting assemblies, in accordance with an embodiment.

FIG. 12 is a flow chart illustrating a process for improving surface properties of a substrate, in accordance with an embodiment.

The figures depict various embodiments for purposes of illustration only.

DETAILED DESCRIPTION

In the following description of embodiments, numerous specific details are set forth in order to provide more thorough understanding. However, note that the embodiments may be practiced without one or more of these specific details. In other instances, well-known features have not been described in detail to avoid unnecessarily complicating the description.

Embodiments are described herein with reference to the figures where like reference numbers indicate identical or functionally similar elements. Also in the figures, the left most digits of each reference number correspond to the figure in which the reference number is first used.

Embodiments relate to treating a surface of a substrate by periodically injecting waves of a mixture including a precursor and a supercritical fluid (SCF) towards the substrate. The surface of the substrate is treated through penetration of molecules of the precursor into the substrate by impact of the wave fronts reaching the surface of the substrate. A stream of a shaping fluid may also be injected toward the substrate to confine the waves of the mixture. The substrate may be exposed to plasma radicals to react with the molecules of the precursor that penetrate into the substrate, thereby transform into a solid state.

FIG. 1 is a schematic view of an injectingassembly100, in accordance with an embodiment. The injectingassembly100 periodically injects a precursor mixed with a SCF toward asubstrate110 to improve surface properties of thesubstrate110. The injectingassembly100 may include, among other components, amixing system120, anozzle130, a sprayingchamber180, and a casing190.

Themixing system120 mixes the precursor with the SCF. Themixing system120 includes aprecursor container140, aprecursor pump150, aprecursor vessel160, aSCF container145, aSCF pump155, aSCF vessel165, a mixingchamber170, and a plurality ofvalves180.

The precursor container140 stores a precursor. The precursor can be a gas, liquid, or nano-sized solid. In some embodiments, the precursor has a boiling point higher than the temperature of the substrate or the temperature at which the injecting is performed. The precursor may exist as gas, liquid, or solid at atmospheric pressure. The precursor may include organic compounds, metalorganic compounds, or inorganic compounds. The precursor can be a Si-containing precursor, Aluminum-containing metal-organic precursor, Gallium-containing metal-organic precursor, transition metal-containing metal-organic precursor, noble metal-containing metal-organic precursor, and so on. Example materials of the precursor include: Trimethylaluminum, DMAON (C₁₁H₂₆AlON: Al(CH₃)₂NC(CH₃)₃CH₂C(CH₃)₂OCH₃,

Trisilylamine, PDMS (Polydimethylsiloxane), Silane coupling agents, Tetradimethylaminotitanium, Tetradimethylaminozirconium, Tetradimethylaminosilicon, silver sulfate, diol, thiol, amino, thio, and acids in carboxyl groups.
Theprecursor pump150 pumps the precursor into theprecursor vessel160. In some embodiments, the precursor is pressurized to a pressure higher than a pressure in theprecursor container140 to convert the precursor from a gas phase or liquid phase in theprecursor container140 to a pressurized liquid phase in theprecursor vessel160. In some embodiment, the precursor stays as a gas phase in theprecursor vessel160.
TheSCF container145 stores a gas that can form a SCF at certain ranges of temperature and pressure above a critical point. The critical point of a SCF corresponds to a critical temperature and a critical pressure of the SCF, below which the SCF forms a gas phase. The SCF has no liquid/gas phase boundary and does not exhibit surface tension at a temperature and pressure above its critical point. The SCF dissolves the precursor and is used as a carrier fluid for carrying the precursor to thesubstrate220. The SCF experiences an instantaneous volume expansion as it forms the gas phase. The instantaneous volume expansion can increase momentum and kinetic energy of the precursor and drive molecules of the precursor to penetrate into thesubstrate110.
Various materials can be used as the SCF. One example material is carbon dioxide (CO₂). Its critical pressure is 73.8 bar, and its critical temperature is 31.1° C. Therefore, the SCF forms a gas phase as it enters into an ambient environment at atmospheric pressure and ambient temperature from a pressurized environment. Also, CO₂is relatively inexpensive, nonflammable, and chemically inert. It will not be involved in the reaction between molecules of the precursor and molecules of a material at the surface of the substrate. In some embodiments, the SCF or its gas phase is conserved during the injecting process so that the use of CO₂also does not create a problem with respect to the greenhouse effect. The SCF can also be other materials that are in liquid or gas phase in ambient condition, such as Methane, Ethane, Propane, Ethylene, Propylene, Methanol, Ethanol, Acetone, etc.
TheSCF pump155 pumps the gas and pressurize the gas to a pressure above the critical pressure of the SCF to form the SCF. The SCF flows into theSCF vessel165, where the pressure is maintained.
The SCF and the precursor both flow into the mixingchamber170 and are mixed to form the mixture. The mixingchamber170 is at a pressure above the critical pressure of the SCF to maintain the SCF in the mixture. In some embodiments, the pressure of the mixture is above 10 bar. The mixture can be either in a liquid phase or a gas phase.
The casing190 encloses thesubstrate110, at least a portion of thenozzle130, and the sprayingchamber180. The casing190 provides a controlled environment (such as temperature, residual moisture level, gas, particulates, etc) at atmospheric pressure. It is advantageous that the injection is conducted at atmospheric pressure. First, a vacuum pump is not required. Second, the injectingassembly100 can be more compact and less expensive. In some embodiments, the chamber is filled with a medium, such as Nitrogen.
Thenozzle130 injects a fluid (either gas or liquid) or spray a liquid toward thesubstrate110. Thenozzle130 injects the mixture into the sprayingchamber180 toward thesubstrate110. As the mixture is released into the chamber that is at atmospheric pressure, the pressure of the mixture drops to a pressure below the critical pressure of the SCF, causing an instantaneous expansion of the SCF. The instantaneous expansion of the SCF drives the precursor to move at a high velocity toward thesubstrate110. In some embodiments, the precursor flows toward thesubstrate110 at a velocity of at least 100 several hundred meters per second. With the high velocity, the precursor gains high kinetic energy, which can drive molecules of the precursor to penetrate into thesubstrate110. In contrast to conventional infiltration/impregnation processes which are governed by the diffusion of the molecules of the precursor at the surface of the substrate, ballistic injection causes more molecules to enter into the substrate to a larger depth, so called enhanced diffusion by shock waves. The high velocity also saves time of the precursor reaching thesubstrate110. In some embodiment, the precursor may arrive at the surface of thesubstrate110 within no more than 5 milliseconds. Such injection of the pressured mixture is referred as “ballistic injection” due to the explosive volume expansion (or depressurizing phenomena such as detonation) of the SCF. Compared with conventional injection technologies, the ballistic injection is more efficient for surface treatment due to higher kinetic energy.
In some embodiments, thenozzle130 periodically injects the pressured mixture as pulses into thechamber140. The periodical injection of the pressurized mixture generates pulsating waves that propagate through the medium. Such injection of the pressured mixture is referred as “periodic ballistic injection.” The wave-fronts form shock waves at the surface of thesubstrate110. The shock waves can further enhance penetration of the molecules of the precursor into thesubstrate110. Compared with continuous injection, periodic injection of the mixture modulates the density and the pressure of the medium, creates ballistic waves of the precursor. Also, the propagations of the ballistic waves and the wave fronts generate stronger impact on thesubstrate110. With the periodic ballistic injection, hold steps are not necessary or can be minimized for the penetration. More details regarding periodic ballistic injection and penetration of the molecules of the precursor are described below in conjunction withFIGS. 2A, 2B, and 3.
FIG. 2A illustrates periodic ballistic injection by thenozzle130 toward asubstrate220, in accordance with an embodiment. An embodiment of the nozzle210 is thenozzle130 inFIG. 1. InFIG. 2A, the nozzle210 injects twowaves230 and235 toward thesubstrate220, as an example. Awave front225 of thewave230 reaches a surface of thesubstrate220. Molecules of the precursor at thewave front225 move ballistically with high kinetic energy and impinge against the surface. By impact of thewave front225, a shock wave has created at the surface of the substrate. Theshock wave260 is at a center of the surface. Theshock waves250 and270 are at edges of the surface. As thewave front225 reaches the center of the surface, theshock wave260 is formed at the center of the substrate. Further moving of thewave front225 generatesshock waves250 and270 at the edge of the substrate when (the edges of) the wave front meets the edges of the substrate. The high kinetic energy of the precursor and the shock waves over the surface of the substrate drive the molecules at thewave front225 to penetrate into thesubstrate220, resulting in a larger propagation/penetration depth than the diffusion in conventional impregnation/infiltration methods.
In some embodiments, the molecules of the precursor propagate/penetrate into thesubstrate220 up to a depth of 10 nm. The depth of the propagation/penetration can be controlled by changing pulsing frequency, duty cycle, injection time, other parameters of the periodic ballistic injection, or some combination thereof. Also, the pulsing frequency and/or duty cycle can be controlled to reduce or eliminate drifting and scattering of the mixture while it propagates through the medium in the chamber.
FIG. 2B shows an example duty cycle of the periodic ballistic injection, in accordance with an embodiment. The nozzle210 injects the mixture during theON times283 and287 and does not inject the mixture during theOFF times285 and289. In the embodiment ofFIG. 2B, the duration of theON times283 and287 equals the duration of theOFF times285 and289, so that the duty cycle is 50%. In other embodiments, the duty cycle can be less than 50% (i.e., the ON times are shorter than the OFF times) or higher than 50% (i.e., the ON times are longer than the OFF times).
The pulsing frequency of the periodic ballistic injection can vary. In some embodiments, the pulsing frequency is in a range from a few Hz to hundreds Hz.
FIG. 3 illustrates penetration of aprecursor molecule310 into asubstrate320, in accordance with an embodiment. Theprecursor molecule310 is at awave front330. It reaches asurface325 of thesubstrate320 at a high velocity. Also, impact of thewave front330 at thesurface325 may generate shock waves as a result of energetic ballistic molecular bombardments and results in shock wave propagation335. The velocity and shock wave propagation drive theprecursor molecule310 to penetrate into thesubstrate320. The penetration is faster and deeper, compared with conventional infiltration/impregnation methods. A distance that theprecursor molecule310 travels within thesubstrate320 is a propagation/penetration depth350 of theprecursor molecule310. In one embodiment, the propagation/penetration depth350 is at least 10 nm.
Theprecursor molecule310 reacts with one or more molecules of a material of thesubstrate320 to form anew molecule340 beneath thesurface325. Thesurface325 can be a viscous liquid surface. Thesubstrate320 can include inorganic solids, organic solids, composite materials, polymers, viscous liquids, starches, living organ tissues, cartilages, proteins, structurally loosen networks (such as reticular fibers, starches, bio-degradable plastics, etc), or some combination thereof. In some embodiments, thesubstrate320 is flexible and porous. Examples of thesubstrate320 include a polymer with porosity for liquid electrolyte applications (e.g. a separator in lithium ion battery), synthetic polymers with ionic properties without porosity for non-gas permeable applications (e.g. a proton conductor for proton exchange membrane (PEM) fuel cells), catalytic polymers with or without porosity (e.g. desalination membrane), etc.
The reaction may include an oxide formation (e.g., formation of Al₂O₃, SiO₂, TiO₂, ZrO₂, WO₃, or HfO₂), or nitride formation (e.g, formation of SiN, AlN, or BN), carbide formation, other types of chemical reaction, or some combination thereof. The reaction may include cross linking of theprecursor molecule310 with one or more molecules of the material of thesubstrate320, such as molecules of a loosen structure of a viscous material.
The reaction improves properties of thesurface325, including physical properties, electrical properties, mechanical properties, chemical properties, or some combination thereof. Improved properties of thesurface325 can include higher working temperature, larger strength, improved wettability with gel/liquid electrolyte at thinner Li-ion battery separator, better resistance against bio-rejection of organ tissues, against better wettability with ocean water, better resistance against scratch or wear, higher hardness, or higher conversion efficiency in fuel cells through increased cationic conductivity, and so on.
FIGS. 4A through 4C illustrate acircular nozzle400, in accordance with an embodiment.FIG. 4A is a schematic perspective view of thenozzle400, in accordance with an embodiment.FIG. 4B is a schematic cross-sectional view of thenozzle400, in accordance with an embodiment.FIG. 4C is a schematic top view of thenozzle400, in accordance with an embodiment. Thenozzle400 periodically injects waves of a mixture of a precursor and a supercritical fluid for treating a surface of a substrate and also injects a shaping fluid to confine the waves. The waves of the mixture and the shaping fluid flow along the Y direction. Thenozzle400 has a circular cross section, as shown inFIG. 4C. In the embodiment ofFIGS. 4A through C, thenozzle400 includes apressure controller410, aflow controller430, astream controller440, amixture inlet450, and ashaper inlet460. Thenozzle400 can an embodiment of thenozzle130 inFIG. 1 or the nozzle210 inFIG. 2A.
Thepressure controller410 controls pressure of the mixture. Thepressure controller410 includes a body formed with amixture chamber415 and ashaper chamber419. Themixture chamber415 receives the mixture from themixture inlet450. Themixture chamber415 has a volume that is determined based on a desired pressure of the mixture. In some embodiments, the mixture from themixture inlet450 is pressurized and has an initial pressure P_s. Themixture chamber415 has a smaller cross-sectional area in the X direction than themixture inlet450 in the X direction, as illustrated inFIG. 4B, so that themixture chamber415 can decrease the pressure of the mixture. In some embodiments, the body of thepressure controller410 is not formed with themixture chamber415 so that the mixture flows from themixture inlet450 directly into themixture channel433 without change in pressure.
Theshaper chamber419 receives the shaping fluid from theshaper inlet460. Theshaper chamber419 has a volume that is determined based on a desired pressure of the shaping fluid. In some embodiments, theshaper chamber419 changes the pressure of the shaping fluid to a pressure P₁. The volume of theshaper chamber419 is larger than the volume of themixture chamber415 so that P₁is lower than P₀. P₁can be in a range from 30 bar to 100 bar. The shaping fluid can be a SCF or a gas. In some embodiments, the shaping fluid is the same material as the SCF in the mixture. In embodiments where the shaping fluid is a SCF, P₁is higher than the critical pressure of the SCF.
Theflow controller430 controls flow of the mixture and flow of the shaping fluid within thenozzle400 and from thenozzle400. Theflow controller430 includes anorifice plate420 and a body formed with amixture channel433, amixture opening435, ashaper channel437, and ashaper opening439.
Theorifice plate420 changes sizes of an opening of themixture chamber415 that communicates with themixture channel433 and/or an opening of theshaper chamber419 that communicates with theshaper channel437. Theorifice plate420 can be used to reduce the pressure of the mixture and/or shaping fluid, restricting flow of the mixture and/or shaping fluid, measuring flow rate of the mixture and/or shaping fluid, etc.
Themixture channel433 passes the mixture from themixture chamber415 to themixture opening435. The cross-section of themixture channel433 in the X direction is smaller than the cross-section of themixture chamber415 in the X direction, as indicated inFIG. 4B. In some embodiments, a width of themixture channel433 in the X direction is in a range from 0.005 inch to 0.05 inch.
Themixture opening435 injects pulses of the mixture toward the substrate. The mixingopening435 is at a tip of thenozzle400. The mixture opening has an angle θ, as shown inFIG. 4B. Shapes of the waves can be changed by changing the angle θ. For instance, the waves are narrower if the angle θ is changed to be smaller.
Theshaper channel437 passes the shaping fluid from theshaper chamber419 to theshaper opening439. Theshaper channel437 has a smaller cross-sectional area in the X direction than theshaper chamber419, as indicated inFIG. 4B. In some embodiments, a width of theshaper channel437 in the X direction a range from 0.005 inch to 0.05 inch. Theshaper opening250 injects a stream of the shaping fluid toward the substrate. Theshaper opening439 surrounds themixture opening435 so that the stream of the shaping fluid can confine the waves of the mixture injected by themixture opening435. In the embodiment ofFIGS. 4A through 4C, theshaper opening439 is ring shaped, and themixture opening435 is a circular hole. In other embodiments, theshaping opening439 and/or themixture opening435 can have other shapes.
As the waves of the mixture are confined by the stream of the shaping fluid, expansion of the waves can be reduced or even avoided. Therefore, decrease in the pressure and velocity of the mixture can be reduced or avoided. Also, uniform injection of the precursor in the X-Z plane can be achieved. The stream of the shaping fluid can also shape the waves or function as a lens to disperse, collimate, or focus the waves. A physical component may be added to thenozzle400 to further confine the waves.
Thestream controller440 controls flow rate and shape of both the waves of the mixture and the shaping fluid stream. Thestream controller440 is arranged on top of themixture opening435 andshaper opening439 along the Y direction. Thestream controller440 includes acap fitting443, ashim plate445, and ataper447. Thecap fitting443 is arranged on the body of theflow controller430 in the vicinity of themixture opening435 andshaper opening439 along the flow direction of the mixture and shaping fluid. Theshim plate445 can be used to change a protrusion height D shown inFIG. 4B. D represents a distance from the bottom of the cap fitting443 to a bottom of the body of theflow controller430 along the X direction. As D is adjusted, the flow rate and shape of the waves of the mixture are changed. The shim plate can also be used to change the width of theshaper channel437 in the X direction. As the width of theshaper channel437 is adjusted, the flow rate of the shaping fluid stream can be changed.
Thetaper447 is formed on the body of theflow controller430 and is located at a side of theshaper opening439. Thetaper447 has an angle α and a height d, as shown inFIG. 4B. The flow rate and shape of the shaping fluid stream can be adjusted by changing either the angle α or height d. As the angle α is changed to be smaller or the height d is changed to be smaller, the shaping fluid stream is narrower.
FIGS. 5A and 5B illustrate alinear nozzle500, in accordance with an embodiment.FIG. 5A is a perspective view of thelinear nozzle500, in accordance with an embodiment. Thelinear nozzle500 periodically injects waves of a mixture of a precursor and a supercritical fluid for improving surface properties of a substrate. Thelinear nozzle500 also injects a shaping fluid to confine the waves. Thelinear nozzle500 has a rectangular cross section. In the embodiment ofFIGS. 5A and 5B, thelinear nozzle500 includes a pressure controller510, one ormore flow controllers530, one ormore stream controllers540, amixture inlet550, and ashaper inlet560. In other embodiments, thelinear nozzle500 can include other components or less components. Thelinear nozzle500 can an embodiment of thenozzle130 inFIG. 1 or the nozzle210 inFIG. 2A.
FIG. 5B illustratesvarious configures501,502,503,504, and505 of thelinear nozzle500, in accordance with an embodiment. Theconfiguration501 includes a plurality of circular nozzles that are arranged along a straight line. Each circular nozzle includes aflow controller531 and astream controller541. An embodiment of theflow controller531 is theflow controller430 inFIG. 4. An embodiment of thestream controller541 is thestream controller440 inFIG. 4.
Theconfiguration502 includes a plurality offlow controllers532 and acommon stream controller542. Theflow controllers532 are arranged along a straight line. An embodiment of theflow controller532 is theflow controller430 inFIG. 4. Thestream controller542 controls flow rate and shape of a shaping fluid stream and waves of the mixture injected by thelinear nozzle500.
Theconfiguration503 includes a flow controller and astream controller543. The formed with ashaper opening563 and a plurality ofmixture openings573 arranged along a straight line. Themixture openings573 communicate with a common mixture channel (not shown inFIG. 5B), but is associated with aseparate taper583. An embodiment of thetaper583 is thetaper447 inFIGS. 4A-C. Theshaper opening563 surrounds themixture openings573 to inject a stream of shaping fluid to confine waves injected by themixture openings573.
Theconfiguration504 includes a flow controller and astream controller544. The flow controller is formed with ashaper opening564 and a plurality ofmixture openings574 arranged along a straight line. Themixture openings574 communicates with a common mixture channel (not shown inFIG. 5B) and are associated with a common taper584. Theshaper opening564 surrounds themixture openings574 to inject a stream of shaping fluid to confine waves injected by themixture openings574.
Theconfiguration505 includes a flow controller and astream controller545. The formed with ashaper opening565 and amixture opening575. Themixture opening575 has a shape of a rectangular and is associated with ataper585. Theshaper opening565 surrounds themixture opening575 to inject a stream of shaping fluid to confine waves injected by themixture openings575.
FIG. 6 illustrates twoarea nozzles600 and650, in accordance with an embodiment. Thearea nozzle600 includes a plurality offlow controllers610 and acommon stream controller620. Eachflow controller610 can periodically inject waves of a mixture of a precursor and a SCF and can also inject a stream of shaping fluid to confine the waves. An embodiment of aflow controller610 is theflow controller430 inFIG. 4B. Theflow controllers610 are arranged into a two-dimensional array. Thestream controller620 controls the stream of the shaping fluid injected by eachflow controller610.
Thearea nozzle650 includes a flow controller and a stream controller660. The flow controller is formed with ashaper opening670 and a plurality ofmixture openings680. Eachmixture opening680 can periodically injects waves of a mixture of a precursor and a SCF. Themixture openings680 are arranged into a two-dimensional array. Themixture openings574 communicates with a common mixture channel (not shown inFIG. 6) and are associated with acommon taper680. Theshaper opening670 surrounds themixture openings680 to inject a stream of a shaping fluid to confine waves injected by themixture openings670.
FIG. 7 illustrates amixing system700 for mixing fluids and controlling flow of fluids into a nozzle, in accordance with an embodiment. Themixing system700 includes aSCF container710, afirst pressure pump720, aSCF vessel730, aprecursor container740, a mixingchamber750, a second pressure pump760, amixture vessel770, and a plurality ofvalves780. Themixing system700 is an embodiment of themixing system120 described in conjunction withFIG. 1.
In some embodiments, theSCF container710 stores a gas (such as carbon dioxide gas) that can convert to a SCF at a temperature and pressure above a critical temperature and critical pressure. The precursor is in a gas phases in theprecursor container740. For instance, the precursor can be a non-resolving precursor vaporized from either a liquid phase or a solid phase. The valves780-V₁,780-V₅,780-V₆,780-V₈,780-V₉,780-V₁₀, and780-V₁₁are open to mix the gas precursor and the gas in the mixingchamber750. The valves780-V₁₂and780-V₁₃are open to allow the mixture (i.e., the mixed gas) to flow into the second pressure pump760. The second pressure pump760 pumps the mixture into themixture vessel770 to produce a pressurized mixture. The pressurized mixture can be a mixture of the precursor and the SCF. The valves780-V₁₄and780-V₁₈are open to allow the pressurized mixture to themixture inlet790 to be injected by the nozzle.
In some embodiments, the precursor is in a gas phases in theprecursor container740. The valves780-V₆,780-V₈,780-V₉,780-V₁₀, and780-V₁₁are open to fill the gas precursor without the SCF in the mixingchamber750. The valves780-V₁₂and780-V₁₃are open to allow the precursor to flow into the pressure pump760. The pressure pump760 pumps the precursor into thevessel770 to produce a pressurized precursor, i.e. the SCF of the precursor. The pressurized precursor can be used itself as a source of the SCF. The valves780-V₁₄and780-V₁₈are open to allow the pressurized precursor to themixture inlet790 to be injected by the nozzle.
In some embodiments, the gas precursor is mixed with the SCF in the mixingchamber750. The valve780-V₀can be open to allow the gas in theSCF container710 to flow into thefirst pressure pump720. Thefirst pressure pump720 pumps the gas into theSCF vessel730 to increase the pressure of the gas and convert the gas into the SCF. The valves780-V₂and780-V₅are open so that the SCF flows from theSCF vessel730 to the mixingchamber750. The mixture of the precursor and SCF can be pressurized by the second pressure pump760.
The valves780-V₁₇and780-V₁₉can be used to make alternating pulses of the mixture and the SCF. For instance, SCF can be injected by opening the valves780-V₁₇and780-V₁₉and closing the valve780-V₁₈.
In some embodiments, the precursor is in a liquid phase. The valves780-V₀,780-V₂,780-V₅,780-V₆,780-V₈,780-V₉,780-V₁₀, and780-V₁₁are open to mix the liquid precursor with the SCF at the mixingchamber750. The mixture (i.e., the mixed liquid) flows into the mixture inlet when the780-Valves780-V₁₂,780-V₁₆and780-V₁₉are open. The valve780-V₁₃can be open while780-V₁₆and780-V₁₉are closed to allow the mixture to flow into the second pressure pump760 to be further pressurized.
In some embodiments, the SCF can be injected by the nozzle as a shaping fluid to confine the waves of the injected mixture. The valves780-V₂,780-V₃, and780-V₄are open to allow the SCF to flow into theshaper inlet795 of the nozzle for injecting a stream of the SCF.
In some embodiments, the gas in theSCF container710 can be used to flush the nozzle after injection of the mixture. The valves780-V₁,780-V₃,780-V₁₇and780-V₁₉are open after the injection to allow the gas to flow into themixture inlet790.
FIG. 8 is a schematic cross-sectional view of asurface treatment apparatus800 including an actuating assembly, in accordance with an embodiment. Thesurface treatment apparatus800 is configured to improve surface properties of asubstrate820. In addition to the actuating assembly, thesurface treatment apparatus800 also includes an injectingassembly810.
The injectingassembly810 periodically injects a mixture of a precursor and a SCF toward thesubstrate820. The injectingassembly810 includes a plurality ofnozzles830, achamber870, and acasing840. Thenozzles830 inject the mixture toward thesubstrate820. Thenozzles830 are enclosed in thecasing840. Thecasing840 provides a controlled environment at atmosphere pressure. The injectingassembly810 is also formed with an exhaust850 that allows remaining mixture to exit thechamber870. An embodiment of the injectingassembly830 is the injectingassembly100 inFIG. 1.
The actuating assembly drives the substrate to move relative to the injectingassembly810. The actuating assembly includes a plurality ofrollers860 arranged on opposite sides of thesubstrate820 and a motor (not shown inFIG. 8) that drives therollers860 to rotate. The rotation of the driving rollers moves the substrate in a direction indicated by the arrows inFIG. 8. In some other embodiments, the actuating assembly drives the injectingassembly810 to move relative to thesubstrate820 or drives both the injectingassembly810 and thesubstrate820 to move relative to each other.
In some embodiments, the substrate moves at a speed in a range from 1 centimeter per minute to 1,000 centimeters per minute. The moving speed of the substrate can be determined based on a material of the substrate, pulsing frequency of the mixture, a desired penetration depth, etc.
FIG. 9 is a schematiccross-sectional view905 and atop view907 of asurface treatment apparatus900 including aplasma generator920, in accordance with an embodiment. Thesurface treatment apparatus900 is configured to improve surface properties of asubstrate930. In addition to theplasma generator920, thesurface treatment apparatus900 also includes an injectingassembly910.
The injectingassembly910 periodically injects a mixture of a precursor and a SCF toward thesubstrate930. The injectingassembly910 includes a plurality ofnozzles940 and the exhausts (side-exhausts here) volatile by-products, SCF, excess precursor mixture and plasma gas, or some combination thereof through the exhaust. An embodiment of the injectingassembly910 is the injectingassembly100 inFIG. 1.
Theplasma generator920 generates plasma radicals from a plasma gas. Thesubstrate940 is exposed to the plasma radicals. The plasma radicals can react with molecules of the precursor that have penetrated into the substrate to transform the molecules into a solid phase. The plasma gas can be a mixture of NH₃, H₂, N₂O, O₂, H₂O, O₃, or other gas with Argon. In one example, theplasma generator920 generates N* radicals by using a mixture of NH₃, Ar, and N₂. Theplasma generator920 generates H* radicals by using a mixture of Ar and H₂.
Exhaust gas950 is discharged from thesurface treatment apparatus900. The exhaust gas950 includes volatile by-products, SCF, excess precursor mixture and plasma gas, or some combination thereof through the exhaust.
FIG. 10 is a schematic cross-sectional view of asurface treatment apparatus1000 including an exhausting assembly, in accordance with an embodiment. Thesurface treatment apparatus1000 is configured to improve surface properties of asubstrate1040. In addition to the exhausting assembly, thesurface treatment apparatus1000 also includes an injectingassembly1010.
The injectingassembly1010 periodically injects a mixture of a precursor and a SCF toward thesubstrate1040. The mixture flows toward thesubstrate1040 along a Y axis. The injectingassembly1010 includes a plurality of nozzles1020. An embodiment of the injectingassembly1010 is the injectingassembly100 inFIG. 1.
The exhausting assembly includes a plurality ofexhausts1030. Anexhaust1030 can be an opening (such as a slit) that is formed along the Y axis in a body of thesurface treatment apparatus1000. Theexhausts1030 discharge volatile by-products, SCF, excess precursor mixture and plasma gas, or some combination thereof from thesurface treatment apparatus1000. In embodiments where thesurface treatment apparatus1000 includes a plasma generator that generates plasma radicals from a plasma gas, the remaining plasma gas or plasma radicals can be discharged through the exhausting assembly.
FIG. 11 is a schematic cross-sectional view of asurface treatment apparatus1100 including twoinjecting assemblies1110 and1150, in accordance with an embodiment. Thesurface treatment apparatus1100 improves surface properties of asubstrate1130 by using two different precursors. The injectingassembly1110 injects amixture1120 of a first precursor and a first SCF toward thesubstrate1130. An embodiment of the injectingassembly1110 is the injectingassembly100 inFIG. 1. Molecules of the first precursor penetrate into thesubstrate1130. The injectingassembly1150 injects asecond mixture1140 including a second precursor that is different from the first precursor toward thesubstrate1130. In some embodiments. the second precursor is mixed with a SCF, such as the first SCF. Molecules of the second precursor can react with the molecules of the first precursor that ballistically penetrated into thesubstrate1130 to transform the molecules of the precursor into a solid phase by chemical reactions. In some embodiments, the molecules of the second precursor can ballistically penetrated into thesubstrate1130 which is covered by a viscous liquid-state surface right after the injection of the first precursor and can be changed into a different composition and/or different chemical structures.
Thesurface treatment apparatus1100 can be used to prepare an organic-inorganic hybrid thin film. Molecules of the second precursor reacts with the ballistically injected molecules for the inorganic layer formed on the substrate surface by the first metallic precursor compound to form an organic-inorganic hybrid thin film.
FIG. 12 is a flow chart illustrating a process1200 for improving surface properties of a substrate, in accordance with an embodiment. The process can be performed by an injecting assembly that includes thenozzle400 inFIGS. 4A-C. The process may include different or additional steps than those described in conjunction withFIG. 12 in some embodiments or perform steps in different orders than the order described in conjunction withFIG. 12.
The process1200 includes passing1210 a mixture of a precursor and a SCF through a mixture channel of an injecting assembly. The mixture is pressurized and has a pressure above a critical pressure of the SCF. The precursor can be a gas, liquid, or nano-sized solid. An example of the precursor is TMA. An example of the SCF is carbon dioxide.
The process1200 also includes periodically injecting waves of the mixture toward the substrate at a mixture opening of the injecting assembly that communicates with the mixture channel. In some embodiments, the injecting assembly is placed under atmosphere pressure. After the waves of the mixture is injected, the SCF in the mixture expands instantaneously due to drop in pressure, causing the precursor to move at a high velocity toward the substrate. The waves propagate toward the substrate with a velocity above 100 meters per second. In some embodiments, a stream of a shaping fluid is injected toward the substrate at a shaper opening surrounding the mixture opening to confine the waves of the mixture. The stream of the shaping fluid can also shape the waves of the mixture. The shaping fluid can be the same material as the SCF in the mixture.
The process1200 further includes treating the surface of the substrate through penetration of molecules of the precursor into the substrate by impact of the wave fronts reaching the surface of the substrate. The wave fronts form shock waves at the surface of the substrate. The shock waves enhance the penetration of the molecules of the precursor. The molecules of the precursor can penetrate into the substrate with a depth in a range from 0.1 nm to 10 nm. In some embodiments, the molecules of the precursor cross link with molecules of a material in the substrate to improve surface properties of the substrate.
In some embodiment, a reactant precursor is injected toward the substrate. Molecules of the reactant precursor react with the molecules of the precursor that penetrate into the substrate to transform the molecules of the precursor into a solid state. In some embodiments, the substrate is exposed to plasma radicals. The plasma radicals react with the molecules of the precursor that penetrate into the substrate to transform the molecules of the precursor into a solid state.
The language used in the specification has been principally selected for readability and instructional purposes, and it may not have been selected to delineate or circumscribe the inventive subject matter. It is therefore intended that the scope of the disclosure be limited not by this detailed description, but rather by any claims that issue on an application based hereon. Accordingly, the disclosure of the embodiments is intended to be illustrative, but not limiting, of the scope of the disclosure, which is set forth in the following claims.

Claims

What is claimed is:

1. An apparatus for treating a surface of a substrate, comprising an injecting assembly that comprises a nozzle formed with:

a mixture channel configured to pass a mixture of a precursor and a supercritical fluid;

a mixture opening communicating with the mixture channel, the mixture opening configured to periodically inject waves of the mixture toward the surface of the substrate;

a shaper channel configured to pass a shaping fluid; and

a shaper opening configured to inject a stream of the shaping fluid toward the substrate at a shaper opening of the injecting assembly surrounding the mixture opening to confine the waves and increase a pressure of the waves on the substrate.

2. The apparatus ofclaim 1, wherein the injecting assembly is placed under atmosphere pressure.

3. The apparatus ofclaim 1, wherein a pressure of the mixture in the mixture channel is higher than a pressure of the shaping fluid in the shaper channel.

4. The apparatus ofclaim 1, wherein the injecting assembly further comprises:

a shaper chamber connected to the shaper channel, the shaping fluid flowing from the shaper chamber to the shaper opening through the shaper channel, the shaper chamber having a cross-sectional area larger than a cross-sectional area of the shaper channel for decreasing a pressure of the flow of the shaping fluid.

5. The apparatus ofclaim 1, wherein the injecting assembly further comprises one or more additional nozzles, the one or more additional nozzles and the nozzle arranged along a straight line.

6. The apparatus ofclaim 1, wherein the injecting assembly further comprises a plurality of additional nozzles, the additional nozzles together with the nozzle arranged into a two-dimensional array.

7. The apparatus ofclaim 1, further comprising a stream controller that comprises a cap fitting attached on the injecting assembly for shaping the waves of the mixture, the stream controller arranged on top of the mixture opening along a flowing direction of the mixture.

8. The apparatus ofclaim 1, further comprising a plasma generator configured to generate plasma radicals, the plasma radicals reacting with molecules of the precursor that penetrate into the substrate to transform the molecules of the precursor into a solid state.

9. The apparatus ofclaim 1, wherein the nozzle is further formed with an opening that is configured to inject a reactant precursor toward the substrate, molecules of the reactant precursor reacting with molecules of the precursor that penetrate into the substrate to transform the molecules of the precursor into a solid state.

10. The apparatus ofclaim 1, wherein a material of the shaping fluid is the same as a material of the supercritical fluid.

11. An apparatus for treating a surface of a substrate, comprising:

an injecting assembly that comprises a nozzle formed with:

a mixture channel configured to pass a mixture of a precursor and a supercritical fluid, and

a mixture opening communicating with the mixture channel, the mixture opening configured to periodically inject waves of the mixture toward the surface of the substrate; and

a plasma generator configured to generate plasma radicals, the plasma radicals reacting with molecules of the precursor that penetrate into the substrate to transform the molecules of the precursor into a solid state.

12. The apparatus ofclaim 11, wherein the injecting assembly is placed under atmosphere pressure.

13. The apparatus ofclaim 11, wherein a pressure of the mixture in the mixture channel is higher than a pressure of the shaping fluid in the shaper channel.

14. The apparatus ofclaim 11, wherein the injecting assembly further comprises one or more additional nozzles, the one or more additional nozzles and the nozzle arranged along a straight line.

15. The apparatus ofclaim 11, wherein the nozzle is further formed with:

a shaper channel configured to pass a shaping fluid; and

16. The apparatus ofclaim 11, further comprising a stream controller that comprises a cap fitting attached on the injecting assembly for shaping the waves of the mixture, the stream controller arranged on top of the mixture opening along a flowing direction of the mixture.

17. An apparatus for treating a surface of a substrate, comprising an injecting assembly that comprises a nozzle formed with:

an opening configured to inject a reactant precursor toward the substrate, molecules of the reactant precursor reacting with molecules of the precursor that penetrate into the substrate to transform the molecules of the precursor into a solid state.

18. The apparatus ofclaim 17, wherein the injecting assembly is placed under atmosphere pressure.

19. The apparatus ofclaim 17, wherein a pressure of the mixture in the mixture channel is higher than a pressure of the shaping fluid in the shaper channel.

20. The apparatus ofclaim 17, wherein the nozzle is further formed with:

a shaper channel configured to pass a shaping fluid; and