CN110760819A - Method for rapidly modifying atomic layer deposition film by using ozone - Google Patents
Method for rapidly modifying atomic layer deposition film by using ozone Download PDFInfo
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- CN110760819A CN110760819A CN201910982293.0A CN201910982293A CN110760819A CN 110760819 A CN110760819 A CN 110760819A CN 201910982293 A CN201910982293 A CN 201910982293A CN 110760819 A CN110760819 A CN 110760819A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
Abstract
The invention relates to a method for quickly realizing atomic layer deposition film modification by utilizing ozone, which is a method for quickly realizing the atomic layer deposition modification on the surface of an inert film by utilizing the ozone as an oxygen source precursor to react with a metal source precursor. The metal source precursor adsorbed on the surface of the film is decomposed by high-activity ozone, methyl or ethyl groups in the metal source precursor are converted into hydroxyl groups, active sites on the surface of the film are rapidly increased, and the technical problem of nucleation growth under the surface layer in the inert film modification process is solved. And then, utilizing the deionized water oxygen source precursor and the metal source precursor to realize the surface modification of the activated film. After the atomic layer deposition activation, the modified substance grows uniformly on the surface of the film, the speed is improved by more than 4.6 times, the mechanical strength is improved by about 10%, the hydrophilicity is improved by more than 50%, and the permeability is improved by more than 36%. The anti-pollution performance is enhanced, and the anti-static adsorption pollution performance to protein or polysaccharide pollutants is improved by more than 30%.
Description
Technical Field
The invention belongs to the field of water treatment for film modification and film pollution control, and relates to a method for quickly realizing atomic layer deposition modification on the surface of an inert film by using ozone as an oxygen source precursor and reacting with a metal source precursor.
Background
The membrane method water treatment technology has the advantages of small occupied area, stable water treatment effect and the like, is a leading technology for realizing high-efficiency water treatment, but the rapid development of the membrane technology is limited by the problem of membrane pollution. The membrane modification technology is an effective method for fundamentally delaying membrane pollution by changing the property of a membrane material to inhibit the adsorption of pollutants.
Compared with the traditional membrane modification methods such as immersion precipitation, surface coating, blending modification and the like, the Atomic Layer Deposition (ALD) technology has the advantages of three-dimensional shape retention and controllable process, can accurately control the thickness of a deposition layer on a nanometer scale, and is a novel membrane modification technology developed in recent years. At present, the membrane used in membrane water treatment technology is a polymer organic membrane. These organic membranes are generally relatively inert in nature, so that the ALD membrane modification process is manifested as significant subsurface nucleation growth, resulting in an increase in membrane hydrophilicity often accompanied by a decrease in membrane flux, which limits the rapid development of ALD technology in the field of membrane modification to some extent.
To address the above issues, studies have reported that a uniform, conformal deposition of the modifying species can be achieved by nitric acid or plasma pretreatment prior to modification of the ALD film. Chen et Al activated by treating PP film surface with nitric acid, Al2O3And TiO2The metal oxide is deposited on the surface of the activated PP film more uniformly, and the permeability of the modified film is improved by 38% (J.Mem.Sci.,2015,487, 109-116). Xu et al use air plasma to activate PTFE film surface to realize TiO2The pure water flux of the modified film was increased to 1.5 times (j.mem. sci.,2013,443, 62-68). However, the functionalization process of the membrane surface is complex and is difficult to realize wide application. In addition, membrane materials are susceptible to damage through high energy irradiation or harsh chemical reactions, which potentially adversely affects the mechanical strength of the membrane.
Disclosure of Invention
The invention provides a method for quickly realizing atomic layer deposition film modification by using ozone, which is a method for quickly realizing the atomic layer deposition modification on the surface of an inert film by using ozone as an oxygen source precursor to react with a metal source precursor. The invention aims to decompose a metal source precursor adsorbed on the surface of a film through high-activity ozone, convert methyl or ethyl and other groups in the precursor into hydroxyl, quickly increase the active sites on the surface of the film, and solve the technical problem of nucleation and growth under the surface layer in the inert film modification process. The modification mode is that ozone is used as an oxygen source precursor, and the ozone and the metal source precursor rapidly generate chemical adsorption reaction on the surface of the film, and active sites on the surface of the film are increased through pre-deposition. And then, utilizing the deionized water oxygen source precursor and the metal source precursor to realize the surface modification of the activated film. The rapid and uniform film forming is achieved, and the mechanical strength, permeability and pollution resistance of the activated film are improved.
The specific modification steps are described as follows:
a method for rapidly realizing modification of an atomic layer deposition film by using ozone comprises the following steps:
1) placing an organic polymer filter membrane to be modified in an atomic layer deposition cavity, setting the temperature of the cavity to be 50-120 ℃, the pressure of the cavity to be 10-200Pa, the temperature of an oxygen source precursor to be 20-50 ℃, the temperature of a metal source precursor to be 30-120 ℃ and the temperature of a conveying pipeline to be 50-120 ℃;
2) the metal source precursor is pulsed to the reaction cavity, the pulse time and the waiting time are respectively set to be 20-60ms and 5-20s, after the metal source precursor is adsorbed on the surface of the film to be saturated, nitrogen or argon is introduced into the reaction cavity, and the unadsorbed metal source precursor is discharged out of the cavity; then, the ozone oxygen source precursor is pulsed to a deposition cavity, the pulse time and the waiting time are respectively set to be 5-20ms and 5-20s, after the ozone oxygen source precursor and the metal source precursor are fully reacted, nitrogen or argon is introduced into the reaction cavity, and the unreacted ozone oxygen source precursor and reaction byproducts are discharged out of the cavity through cleaning;
3) repeating the second step for 10-20 times to complete the activation of the surface of the film;
4) the metal source precursor is pulsed to the reaction cavity, the pulse time and the waiting time are respectively set to be 20-60ms and 5-20s, after the metal source precursor is adsorbed on the surface of the film to be saturated, nitrogen or argon is introduced into the reaction cavity, and the unadsorbed metal source precursor is discharged out of the cavity; then, pulse the precursor of the deionized water oxygen source to a deposition cavity, setting the pulse time and the waiting time to be 10-20ms and 5-20s respectively, introducing nitrogen or argon into the reaction cavity for 10-30s after the precursor of the deionized water oxygen source and the precursor of the metal source are fully reacted, and discharging the unreacted precursor of the deionized water oxygen source and reaction byproducts out of the cavity by cleaning;
5) and repeating the step four 50-200 times to complete the surface modification of the film.
And 2) pulsing the metal source precursor to the reaction cavity, wherein the pulse time and the waiting time are respectively set to be 20-60ms and 5-20 s.
And (3) in the step 2), the ozone oxygen source precursor is pulsed to the deposition cavity, and the pulse and the waiting time are respectively set to be 5-20ms and 5-20 s.
In the step 4), the metal source precursor is pulsed to the reaction cavity, and the pulse and the waiting time are respectively set to be 20-60ms and 5-20 s.
In the step 4), the deionized water oxygen source precursor is pulsed to the deposition cavity, and the pulse and the waiting time are respectively set to 10-20ms and 5-20 s.
The time for introducing nitrogen or argon into the reaction cavity is preferably 10-30 s.
The metal source precursor is preferably a zinc source, a titanium source or an aluminum source.
The organic polymer filtering membrane is preferably a polycarbonate filtering membrane, a polyvinylidene fluoride filtering membrane or a polypropylene membrane.
The invention has the advantages that: firstly, after the inert film surface atomic layer deposition activation is carried out by using ozone as an oxygen source, the modified substance grows uniformly on the film surface and the speed is improved by more than 4.6 times. Secondly, the mechanical strength of the activated film obtained by the method is slightly enhanced, and compared with that before activation, the mechanical strength is improved by about 10 percent. And thirdly, the hydrophilicity of the activated and modified membrane prepared by the method is improved by over 50 percent, and the permeability is improved by over 36 percent. Fourthly, the activated and modified membrane prepared by the method has stronger anti-pollution performance, and the anti-static adsorption pollution performance of the membrane on protein or polysaccharide pollutants is improved by more than 30 percent.
Drawings
FIG. 1 is an SEM picture of the surface of an activated and modified membrane of example 1;
FIG. 2 is the static water contact angle of the activated modified membrane of example 1;
FIG. 3 is the pure water flux of the activated modified membrane of example 1;
FIG. 4 shows the amount of bovine serum albumin adsorbed by the activated and modified membrane of example 1.
Detailed Description
Example 1: the method for quickly modifying the atomic layer deposition film by using ozone in the embodiment is carried out by the following steps:
1) placing the polycarbonate organic polymer filtering membrane in an atomic layer deposition cavity, setting the temperature of the cavity to be 50 ℃ and the pressure of the cavity to be 10-100 Pa; the temperature of an oxygen source precursor is set to be 20 ℃, the temperature of a titanium source precursor is set to be 120 ℃, and the temperature of a conveying pipeline is set to be 120 ℃;
2) and pulsing the titanium source precursor to the reaction cavity, wherein the pulse time and the waiting time are respectively set to be 60ms and 5s, after the adsorption of the titanium source precursor on the surface of the film is saturated, nitrogen is introduced into the reaction cavity for 10s, and the unadsorbed titanium source precursor is discharged out of the cavity. Then, the ozone oxygen source precursor is pulsed to a deposition cavity, the pulse time and the waiting time are respectively set to be 5ms and 5s, after the ozone oxygen source precursor and the titanium source precursor are fully reacted, nitrogen is introduced into the reaction cavity for 10s, and the unreacted ozone oxygen source precursor and reaction byproducts are discharged out of the cavity through cleaning;
3) repeating the step two for 10 times to complete the activation of the film surface;
4) and pulsing the titanium source precursor to the reaction cavity, wherein the pulse time and the waiting time are respectively set to be 60ms and 5s, after the adsorption of the titanium source precursor on the surface of the film is saturated, nitrogen is introduced into the reaction cavity for 10s, and the unadsorbed titanium source precursor is discharged out of the cavity. Then, pulse the precursor of the deionized water oxygen source to a deposition cavity, wherein the pulse time and the waiting time are respectively set to be 20ms and 5s, after the precursor of the deionized water oxygen source and the precursor of the titanium source are fully reacted, nitrogen is introduced into the reaction cavity for 10s, and unreacted precursor of the deionized water oxygen source and reaction byproducts are discharged out of the cavity through cleaning;
5) and repeating the step four 200 times to complete the surface modification of the membrane.
The embodiment has the following beneficial effects:
firstly, after the surface atomic layer deposition and activation of the inert film is carried out by using ozone as an oxygen source, TiO2The growth on the surface and in the pores of the film is more uniform and the growth rate is improved by 4.7 times. As shown in figure 1 (TiO)2Scanning electron microscope pictures of the activated modified polycarbonate film) show that no obvious particulate matter is formed on the surface of the polycarbonate film and in the film holes.
Second, TiO obtained in the present embodiment2The mechanical strength of the activated modified polycarbonate membrane is slightly enhanced, and is improved by 9.3 percent compared with the original polycarbonate membrane.
Third, TiO obtained in the present embodiment2The hydrophilicity of the activated modified polycarbonate membrane is improved by 59.8 percent. As shown in FIG. 2, via TiO2After activation modification, the static water contact angle of the surface of the polycarbonate film is reduced from 58.0 degrees to 23.3 degrees.
Fourthly, TiO obtained in the present embodiment2The permeability of the activated modified polycarbonate membrane is improved by 43.8 percent. The pure water flux of the membrane measured by a dead-end filtration device under a constant pressure of 0.01MPa is shown in FIG. 3 and measured by TiO2After the activation modification, the pure water flux of the polycarbonate membrane is increased from 0.0169cm/s to 0.0243 cm/s.
Fifthly, TiO obtained in the embodiment2The anti-pollution performance of the activated modified polycarbonate membrane to protein is improved by 36.3 percent. The adsorption amount of BSA on the membrane surface measured after adsorption for 12 hours to equilibrium after a membrane piece having a diameter of 5cm was placed in a BSA solution having a volume of 100mL and a concentration of 0.5g/L is shown in FIG. 4, and the adsorption amount of BSA on the original polycarbonate membrane was 76.3. mu.g/cm2，TiO2The adsorption capacity of the activated modified polycarbonate membrane to BSA is reduced to 48.6 mu g/cm2。
Example 2: the method for quickly modifying the atomic layer deposition film by using ozone in the embodiment is carried out by the following steps:
1) placing the polyvinylidene fluoride filter membrane in an atomic layer deposition cavity, setting the temperature of the cavity to be 120 ℃, setting the pressure of the cavity to be 50-200Pa, setting the temperature of an oxygen source precursor to be 50 ℃, setting the temperature of an aluminum source precursor to be 30 ℃, and setting the temperature of a conveying pipeline to be 50 ℃;
2) and pulsing an aluminum source precursor to the reaction cavity, wherein the pulse time and the waiting time are respectively set to be 20ms and 20s, after the aluminum source precursor is adsorbed on the surface of the film to be saturated, introducing argon gas into the reaction cavity for 30s, and discharging the unadsorbed aluminum source precursor out of the cavity. Then, the ozone oxygen source precursor is pulsed to a deposition cavity, the pulse time and the waiting time are respectively set to be 20ms and 20s, after the ozone oxygen source precursor and the aluminum source precursor are fully reacted, argon is introduced into the reaction cavity for 30s, and the unreacted ozone oxygen source precursor and reaction byproducts are discharged out of the cavity through cleaning;
3) repeating the step two for 20 times to complete the activation of the film surface;
4) and pulsing an aluminum source precursor to the reaction cavity, wherein the pulse time and the waiting time are respectively set to be 20ms and 20s, after the aluminum source precursor is adsorbed on the surface of the film to be saturated, introducing argon gas into the reaction cavity for 30s, and discharging the unadsorbed aluminum source precursor out of the cavity. Then, pulse the precursor of the deionized water oxygen source to a deposition cavity, wherein the pulse time and the waiting time are respectively set to 10ms and 20s, after the precursor of the deionized water oxygen source and the precursor of the aluminum source are fully reacted, argon is introduced into the reaction cavity for 30s, and unreacted precursor of the deionized water oxygen source and reaction byproducts are discharged out of the cavity through cleaning;
5) and repeating the step four 50 times to finish the surface modification of the membrane.
The embodiment has the following beneficial effects:
firstly, after the surface atomic layer deposition and activation of the inert film is carried out by using ozone as an oxygen source, Al2O3The growth on the surface and in the pores of the film is more uniform and the growth rate is improved by 4.6 times.
Second, Al obtained in the present embodiment2O3The mechanical strength of the activated modified polyvinylidene fluoride membrane is slightly enhanced, and is improved by 9.8 percent compared with that of a polyvinylidene fluoride raw membrane.
Third, Al obtained in the present embodiment2O3The hydrophilicity of the activated modified polyvinylidene fluoride membrane is improved by 56.2 percent.
Fourth, Al obtained in the present embodiment2O3The permeability of the activated modified polyvinylidene fluoride membrane is improved by 42.5 percent.
Fifth, Al obtained in the present embodiment2O3The anti-pollution performance of the activated modified polyvinylidene fluoride membrane to polysaccharide is improved by 42.8 percent.
Example 3: the method for quickly modifying the atomic layer deposition film by using ozone in the embodiment is carried out by the following steps:
1) placing the polypropylene filter membrane in an atomic layer deposition cavity, setting the temperature of the cavity to be 80 ℃, the pressure of the cavity to be 60-200Pa, the temperature of an oxygen source precursor to be 30 ℃, the temperature of a zinc source precursor to be 35 ℃ and the temperature of a conveying pipeline to be 60 ℃;
2) and pulsing the zinc source precursor to the reaction cavity, wherein the pulse time and the waiting time are respectively set to be 30ms and 10s, after the adsorption of the zinc source precursor on the surface of the film is saturated, introducing nitrogen into the reaction cavity for 20s, and discharging the unadsorbed zinc source precursor out of the cavity. Then, the ozone oxygen source precursor is pulsed to the deposition cavity, the pulse time and the waiting time are respectively set to 10ms and 10s, after the ozone oxygen source precursor and the zinc source precursor are fully reacted, nitrogen is introduced into the reaction cavity for 20s, and the unreacted ozone oxygen source precursor and reaction byproducts are discharged out of the cavity through cleaning;
3) repeating the second step for 15 times to complete the activation of the surface of the film;
4) and pulsing the zinc source precursor to the reaction cavity, wherein the pulse time and the waiting time are respectively set to be 30ms and 10s, after the adsorption of the zinc source precursor on the surface of the film is saturated, introducing nitrogen into the reaction cavity for 20s, and discharging the unadsorbed zinc source precursor out of the cavity. Then, pulse the precursor of the deionized water oxygen source to a deposition cavity, wherein the pulse time and the waiting time are respectively set to 10ms and 10s, after the precursor of the deionized water oxygen source and the precursor of the zinc source are fully reacted, nitrogen is introduced into the reaction cavity for 20s, and unreacted precursor of the deionized water oxygen source and reaction byproducts are discharged out of the cavity through cleaning;
5) and repeating the step four 100 times to finish the surface modification of the membrane.
The embodiment has the following beneficial effects:
firstly, after the ozone is used as an oxygen source to carry out atomic layer deposition and activation on the surface of the inert film, ZnO grows on the surface of the film and in film holes more uniformly, and the growth rate is improved by 5.3 times.
Secondly, the mechanical strength of the ZnO activated modified polypropylene film obtained by the embodiment is slightly enhanced, and is improved by 10.1% compared with that of a polyvinylidene fluoride original film.
And thirdly, the hydrophilicity of the ZnO activated modified polypropylene film obtained by the embodiment is improved by 60.3%.
And fourthly, the permeability of the ZnO activated and modified polypropylene film obtained by the embodiment is improved by 41.5 percent.
Fifthly, the anti-pollution performance of the ZnO activated modified polypropylene film obtained by the embodiment on protein is improved by 46.2%.
While the methods and techniques of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and/or modifications of the methods and techniques described herein may be made without departing from the spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (8)
1. A method for rapidly realizing modification of an atomic layer deposition film by using ozone is characterized by comprising the following steps:
1) placing an organic polymer filter membrane to be modified in an atomic layer deposition cavity, setting the temperature of the cavity to be 50-120 ℃, the pressure of the cavity to be 10-200Pa, the temperature of an oxygen source precursor to be 20-50 ℃, the temperature of a metal source precursor to be 30-120 ℃ and the temperature of a conveying pipeline to be 50-120 ℃;
2) the metal source precursor is pulsed to the reaction cavity, the pulse and the waiting time are set, after the metal source precursor is adsorbed on the surface of the film to be saturated, nitrogen or argon is introduced into the reaction cavity, and the unadsorbed metal source precursor is discharged out of the cavity; then, the ozone oxygen source precursor is pulsed to a deposition cavity, the pulse and the waiting time are respectively set, nitrogen or argon is introduced into the reaction cavity after the ozone oxygen source precursor and the metal source precursor are fully reacted, and the unreacted ozone oxygen source precursor and reaction byproducts are discharged out of the cavity through cleaning;
3) repeating the step 2) for 10-20 times to complete the activation of the surface of the film;
4) the metal source precursor is pulsed to the reaction cavity, the pulse and the waiting time are respectively set, after the metal source precursor is adsorbed on the surface of the film to reach saturation, nitrogen or argon is introduced into the reaction cavity, and the unadsorbed metal source precursor is discharged out of the cavity; then, pulse the precursor of the deionized water oxygen source to a deposition cavity, wherein the pulse time and the waiting time are respectively set, after the precursor of the deionized water oxygen source and the precursor of the metal source are fully reacted, nitrogen or argon is introduced into the reaction cavity, and the unreacted precursor of the deionized water oxygen source and reaction byproducts are discharged out of the cavity through cleaning;
5) and repeating the step 4) for 50-200 times to complete the surface modification of the film.
2. The method as set forth in claim 1, wherein the metal source precursor is pulsed into the reaction chamber in step 2), the pulse and the waiting time being set to 20-60ms and 5-20s, respectively.
3. The method of claim 1, wherein in step 2) the ozone oxygen source precursor is pulsed into the deposition chamber with pulse and wait times set to 5-20ms and 5-20s, respectively.
4. The method as set forth in claim 1, wherein the metal source precursor is pulsed into the reaction chamber in step 4), the pulse and the waiting time being set to 20-60ms and 5-20s, respectively.
5. The method of claim 1, wherein in step 4) the deionized water oxygen source precursor is pulsed into the deposition chamber with pulse and wait times set to 10-20ms and 5-20s, respectively.
6. The method of claim 1, wherein nitrogen or argon is introduced into the reaction chamber for 10 to 30 seconds.
7. The method of claim 1, wherein the metal source precursor is a zinc source, a titanium source, or an aluminum source.
8. The method according to claim 1, wherein the organic polymer filtration membrane is a polycarbonate membrane, a polyvinylidene fluoride membrane or a polypropylene membrane.
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