CN107815668A - Rotary atomic layer deposition reactor for batch modification of hollow fiber membrane - Google Patents
Rotary atomic layer deposition reactor for batch modification of hollow fiber membrane Download PDFInfo
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- CN107815668A CN107815668A CN201711265063.XA CN201711265063A CN107815668A CN 107815668 A CN107815668 A CN 107815668A CN 201711265063 A CN201711265063 A CN 201711265063A CN 107815668 A CN107815668 A CN 107815668A
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- cavity
- fibre membrane
- hollow
- ald
- rotation
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- 239000012528 membrane Substances 0.000 title claims abstract description 55
- 238000000231 atomic layer deposition Methods 0.000 title abstract description 9
- 238000012986 modification Methods 0.000 title abstract description 4
- 230000004048 modification Effects 0.000 title abstract description 4
- 239000012510 hollow fiber Substances 0.000 title abstract 5
- 230000008021 deposition Effects 0.000 claims abstract description 22
- 238000007789 sealing Methods 0.000 claims abstract description 13
- 239000000376 reactant Substances 0.000 claims abstract description 10
- 230000003993 interaction Effects 0.000 claims abstract description 4
- 239000000835 fiber Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000010926 purge Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 7
- 230000033228 biological regulation Effects 0.000 claims description 6
- 239000012159 carrier gas Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 206010037544 Purging Diseases 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229920001973 fluoroelastomer Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 23
- 238000002474 experimental method Methods 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 239000002657 fibrous material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 235000012489 doughnuts Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- 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]
- C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
-
- 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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
-
- 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
- C23C16/458—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 supporting substrates in the reaction chamber
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- External Artificial Organs (AREA)
Abstract
The invention relates to a rotary atomic layer deposition device for batch modification of a hollow fiber membrane, which is used for realizing rotation and uniform deposition of the hollow fiber membrane in a cavity. The rotary reactor comprises a cavity and an upper cover, the top of the cavity and the upper cover are sealed through a sealing ring, and the whole device can reach the vacuum degree required by an experiment. The motor with the magnet is fixed on the cover of the cavity, and the magnet in the cavity rotates along with the rotation of the motor by utilizing the interaction force of the magnet. Thereby driving the porous rotary disc to rotate. The hollow fiber membrane is fixed on the porous rotary disc. The rotating speed of the motor is adjusted to drive the hollow fiber membrane to rotate, so that reactants pulsed into the cavity are uniformly diffused in the cavity and uniformly deposited on the surface of the membrane. The device accelerates the diffusion of reactants by rotating the sample, so that the whole cavity is uniformly filled with the reactants, thereby realizing the purpose of depositing modified fiber materials on a large scale, and having the advantages of high efficiency, high yield and the like.
Description
Technical field
Patent of the present invention is related to ald reactor, there is provided a kind of evenly controllable batch is modified doughnut
The rotary ald reactor on surface.
Background technology
Polyalcohol stephanoporate separation material plays an important role in fields such as water process, water-oil separating, particulate matter filterings.Phase
Compared with Flat Membrane, hollow-fibre membrane has many advantages, such as effective filter table area of unit volume is larger, component manufacture letter
It is single, it is not necessary to feed and permeate sept and pretreatment and safeguard simpler etc..Therefore, hollow-fibre membrane is at chemical wastewater
There is potential application in reason, blood oxygenation, the biomedical material of haemodialysis and food-processing industry.It is expected in order to reach
Target by physics or chemical method to the performance on polymeric film material surface, it is necessary to carry out hydrophilic modification.But polymer
Traditional method of material surface modifying, such as chemical modification, filling-modified, blending and modifying or wait and need to use substantial amounts of chemistry
Reagent, modifying process is cumbersome, and modified porous material performance boost space is smaller, modified incomplete, can not realize to aperture
Precision control.Importantly, the generation of a large amount of organic wastewaters substantially increases the difficulty and economy of subsequent processes
Cost.
Ald（Atomic layer deposition, ALD）It is a kind of advanced ultrathin membrane deposition technique, by
Have in its course of reaction from restricted, therefore obtained sedimentary has good conformality, and Subnano-class can be realized
Thickness control.Uniformly conformally deposit, therefore be increasingly becoming because it can be realized in the 3 D pore canal of complexity at a lower temperature
The important means that polyalcohol stephanoporate separation material is modified.
Compared with traditional membrane surface modification method, the hydrophobic membrane surface of hydrophilic modifying is hydrophilic through ald oxide
Modified, its uniformity and good shape retention, hydrophily substantially increase, anti-protein contamination ability enhancing；By changing deposition time
Number, its permeance property and rejection can adjust step by step, therefore before there is the application of business by ALD technique modified hollow fibre membrane
Scape.
However, the ald reactor used at present is largely fixed cavity, deposition chambers are smaller, and substrate is in chamber
Static condition is in vivo, easily occurs dead angle during deposition reaction, reactant diffusion is uneven, causes film surface to deposit
It is uneven；And sample capacity is less, production efficiency is relatively low, limits use range and yield.Therefore urgently exploitation is a kind of new
Reaction cavity to solve the problem that ALD is not suitable for high-volume and deposits the fiber-like material of modified high filtration area.
The content of the invention
Patent of the present invention provides one kind suitable for the modified doughnut of high-volume deposition to solve above-mentioned technical problem
The ald rotatable reactor of film, uniform film surface hydrophilic modification can be efficiently carried out, realize carrying for separating property
Rise.
To achieve the above object, the present invention program is as follows：
A kind of rotation ald reactor modified towards hollow-fibre membrane batch, including cavity and upper lid, the top of cavity
Portion and upper lid are tightly connected by sealing ring, and cavity bottom is provided with air inlet pipe and escape pipe；Motor with magnet is fixed on
The top of lid, motor drive magnet rotors by rotating shaft；There is same magnet in cavity, under the interaction force of magnet,
Magnet in cavity rotates with the rotation of motor；Support is fixed on cavity wall, and magnet is fixed on support by rotating shaft
On；Turn the tip of the axis connection porous wheel, hollow-fibre membrane is suspended on porous wheel.
Wherein, the arrangement of porous wheel mesopore is arranged for concentric circles, and hollow-fibre membrane is suspended on porous turn by raw material band
On disk.The sealing ring is fluororubber O-type sealing ring.Support is screwed on cavity wall, facilitates sample to be put into and take
Go out.
Carried out the invention also discloses a kind of rotation ald reactor modified towards hollow-fibre membrane batch former
The technique of sublayer deposition reaction, atomic layer deposition step are as follows：
Step 1: cavity（1）Heating is heated to ald reaction temperature, opens motor（6）, adjust rotating speed；
Step 2: using high pure nitrogen as carrier gas, presoma titanium tetrachloride is passed through into air inlet pipe（10）Pulse enters cavity（1）And stop
Stay a period of time；Precursor gas is in hollow-fibre membrane（9）Stirring under be dispersed in cavity（1）It is interior, and with it is hollow
Tunica fibrosa（9）Fully contact, monolayer Chemisorption occurs on film surface, then pass to nitrogen 200s purging excess
Reactant and accessory substance, from escape pipe（11）Discharge system；
Step 3: then continuing to using high pure nitrogen as carrier gas, presoma oxygen source H is passed through2O, by H2O passes through air inlet pipe（10）Pulse
Into cavity（1）And stay for some time；Precursor gas is in hollow-fibre membrane（9）Stirring under be dispersed in cavity
（1）It is interior, and and hollow-fibre membrane（9）Fully contact, monolayer chemical reaction occurs with the titanium tetrachloride of film adsorption, so
Nitrogen 200s purgings excessive reactant and accessory substance are passed through afterwards, from escape pipe（11）Discharge system；Step 2 and step 3 are complete
The ald reaction of Cheng Houwei one cycles；
Step 4: after the ald for repeating 50-200 circulation reacts, lid is removed（5）, and support（8）And cavity
（1）The screw of connection, then hollow-fibre membrane will be hung（9）Porous wheel（2）Take out.
Wherein：
The presoma pulse enters cavity（1）Burst length be 0.1-0.5s, the residence time is 50-100s.Suspension
Hollow-fibre membrane（9）The quantity of film wire be 500-1000 roots, modified external surface area is 1-2m2.Motor（6）Rotational speed regulation model
Enclose for 10-60r/min.Carry out the cavity of ald reaction（1）Temperature is 80-150 DEG C.
Hollow-fibre membrane is fixed on rotating disk by present invention design, by regulation motor rotating speed, is driven sample film rotation, is made
Pulse is entered the reactant of cavity and uniformly spread in cavity, in film surface uniform deposition.Production capacity can be by increasing cavity
Size and increase.Can be by adjusting rotary rpm, to adapt to different sedimentary conditions.
Beneficial effect：
1. by expanding reaction cavity, the filling area of film is improved, adds the useful load of hollow-fibre membrane, improves yield and effect
Rate；
2. deposition reaction uses the principle of magnetic force induction, by rotary sample, realize that reactant uniformly spreads, make it on film surface
Uniform adsorption, avoid due to adsorbing the problem of uneven when substrate is stood, so as to ensure the uniformity of deposition.
3. rotation avoids increasing unnecessary stirring system in cavity using the principle of magnetic force induction.Realize batch production,
Improve production efficiency.
Brief description of the drawings
Fig. 1 is the front view of present device.1：Cavity, 2：Porous wheel, 3：Magnet, 4：Sealing ring, 5：Upper lid, 6：Electricity
Machine, 7：Rotating shaft, 8：Support, 9：Hollow-fibre membrane, 10：Air inlet pipe, 11：Escape pipe.
Fig. 2 is the left view of present device.
Fig. 3 is the top view of present device.
Fig. 4 is the porous wheel schematic diagram of present device.
Fig. 5 is to be schemed in embodiment 1 by rotating the SEM of ald reactor batch modified hollow fibre membrane, and a figures are
Former film；B-d figures are respectively deposition 50 times, 100 times, 200 times.
Fig. 6 is the depositing Ti O on silicon chip that deposition reaction difference number obtains in embodiment 12Deposit thickness figure, deposition
Reaction times are respectively 50 times, 100 times, 150 times, 200 times.
Embodiment
The present invention will be further explained in conjunction with the embodiments.The following example is merely to illustrate the present invention, but and does not have to
To limit the practical range of the present invention.
A kind of rotation ald reactor modified towards hollow-fibre membrane batch, including cavity（1）With upper lid
（5）, cavity（1）Top and upper lid（5）Pass through sealing ring（4）It is tightly connected, cavity（1）Bottom is provided with air inlet pipe（10）With go out
Tracheae（11）；With magnet（3）Motor（6）It is fixed on Shang Gai（5）Top, motor（6）Pass through rotating shaft（7）Band moving magnet
（3）Rotate；In cavity（1）Inside there is same magnet（3）, under the interaction force of magnet, cavity（1）Interior magnet（3）With
Motor（6）Rotation and rotate；Support（8）It is fixed on cavity（1）In side wall, magnet（3）Pass through rotating shaft（7）It is fixed on support
（8）On；Rotating shaft（7）End connection porous wheel（2）, hollow-fibre membrane（9）It is suspended on porous wheel（2）On.Porous wheel
（2）The arrangement of mesopore is arranged for concentric circles, hollow-fibre membrane（9）Porous wheel is suspended on by raw material band（2）On.Sealing ring
（4）For fluororubber O-type sealing ring.Support（8）It is screwed in cavity（1）In side wall.
First by porous wheel（2）And magnet（3）Pass through rotating shaft（7）It is fixed on support（8）On, by hollow-fibre membrane（9）
It is suspended on porous wheel（2）On.Again with screw by support（8）It is fixed on cavity（1）It is interior, sealing ring（4）It is placed at the top of cavity, will
Equipped with motor（6）Upper lid（5）It is placed on cavity（1）On, to reach the effect of sealing.Open motor（6）Make magnet（3）Rotate,
Drive and magnet（3）Connected porous wheel（2）Rotation, hollow-fibre membrane（9）Start to rotate, vacuumized after adjusting rotating speed
And sedimentation experiment.
Embodiment 1
By hollow-fibre membrane（9）It is suspended on porous wheel（2）On, put cavity into（1）Interior, film wire quantity is 500, modified appearance
Area is 1m2.Regulation motor rotating speed is 20r/min, and the temperature of cavity 1 is increased to 100 DEG C, and keeps 60min so that cavity（1）
Interior temperature and pressure keeps stable.Precursor A（Titanium tetrachloride）With oxygen source B（H2O）It is attached separately in presoma steel cylinder, normal
Temperature is lower to be preserved.Nitrogen flow rate is 30sccm, and two kinds of presomas carry out ald reaction respectively using high pure nitrogen as carrier gas.
Titanium tetrachloride is first passed through in hollow-fibre membrane（9）Surface carries out ald reaction, then is passed through oxygen source H2O is in hollow-fibre membrane
（9）Surface carries out ald reaction.In order to determine cavity（1）The deposition effect of diverse location, in cavity（1）It is upper, in,
The diverse location suspension silicon chip of bottom three also simultaneously carries out ald reaction simultaneously.
First by titanium tetrachloride from air inlet（10）Cavity is entered in pulse（1）, the presoma burst length is 0.25s, during stop
Between be arranged to 50s, precursor gas is in hollow-fibre membrane（9）Stirring under be dispersed in cavity（1）It is interior, and with it is hollow
Tunica fibrosa（9）Monolayer Chemisorption occurs for fully contact, film surface.After deposition reaction, excessive reactant and
Accessory substance purges via nitrogen, from escape pipe（11）Discharge system, nitrogen purge time are set to 200s.Then H is passed through again2O enters
The ald reaction of row similarity condition, H2O is from air inlet（10）Cavity is entered in pulse（1）, the presoma burst length is
0.25s, residence time are arranged to 50s, are then passed through nitrogen purging again, and purge time is set to 200s.Titanium tetrachloride and H2O distinguishes
Reacted after carrying out ald to complete the ald of one cycle.Repeat 50 times, 100 times, 150 times, 200 times
The ald reaction of circulation.After experiment terminates, lid is removed（5）, then remove support（8）And cavity（1）The spiral shell of connection
Silk, will be hung with hollow-fibre membrane（9）Porous wheel（2）Take out.
Fig. 5 is by rotating ald reactor batch modified hollow fibre membrane in the present embodiment（9）SEM figure,
As seen from the figure, with the increase of frequency of depositing, surface engenders some little particulates.Frequency of depositing continues to increase, film surface by
Gradually covered by nano particle, TiO2Successful deposition is in hollow-fibre membrane（9）Surface.And can be by controlling ald
Cycle-index, it can accurately regulate and control deposit thickness.
Fig. 6 is TiO after the reaction of different number of deposition in the present embodiment2In the deposit thickness of silicon chip surface.Calculating to deposit
TiO2Be about 1.5/cycle in the growth rate of silicon chip surface, in same deposition number, diverse location deposit thickness difference compared with
Small, in error range, deposition is more uniform.
Embodiment 2
Atomic layer deposition process is same as Example 1, and process conditions difference is：Hang hollow-fibre membrane（9）Film wire number
Measure as 800, modified external surface area is 1.5m2.Regulation motor rotating speed is 10r/min, cavity（1）Temperature is 150 DEG C.Presoma
Burst length is 0.5s, and the residence time is arranged to 80s.
Embodiment 3
Atomic layer deposition process and embodiment（1）Identical, process conditions difference is：Hang hollow-fibre membrane（9）Film wire
Quantity is 1000, and modified external surface area is 2m2.Regulation motor rotating speed is 60r/min, cavity（1）Temperature is 80 DEG C.Presoma
Burst length is 0.1s, and the residence time is arranged to 100s.
Claims (9)
1. a kind of rotation ald reactor modified towards hollow-fibre membrane batch, it is characterised in that including cavity（1）
With upper lid（5）, cavity（1）Top and upper lid（5）Pass through sealing ring（4）It is tightly connected, cavity（1）Bottom is provided with air inlet pipe
（10）And escape pipe（11）；With magnet（3）Motor（6）It is fixed on Shang Gai（5）Top, motor（6）Pass through rotating shaft（7）Band
Moving magnet（3）Rotate；In cavity（1）Inside there is same magnet（3）, under the interaction force of magnet, cavity（1）Interior magnet
（3）With motor（6）Rotation and rotate；Support（8）It is fixed on cavity（1）In side wall, magnet（3）Pass through rotating shaft（7）It is fixed
In support（8）On；Rotating shaft（7）End connection porous wheel（2）, hollow-fibre membrane（9）It is suspended on porous wheel（2）On.
2. a kind of rotation ald reactor modified towards hollow-fibre membrane batch as claimed in claim 1, it is special
Sign is, porous wheel（2）The arrangement of mesopore is arranged for concentric circles, hollow-fibre membrane（9）Porous turn is suspended on by raw material band
Disk（2）On, it is put into reaction cavity（1）In.
3. a kind of rotation ald reactor modified towards hollow-fibre membrane batch as claimed in claim 1, it is special
Sign is, the sealing ring（4）For fluororubber O-type sealing ring.
4. a kind of rotation ald reactor modified towards hollow-fibre membrane batch as claimed in claim 1, it is special
Sign is, support（8）It is screwed in cavity（1）In side wall.
A kind of 5. rotation ald reactor modified towards hollow-fibre membrane batch as described in claim 1-4 is any
The technique for carrying out ald reaction, it is characterised in that atomic deposition step is as follows：
Step 1: cavity（1）Heating is heated to ald reaction temperature, opens motor（6）, adjust rotating speed；
Step 2: using high pure nitrogen as carrier gas, presoma titanium tetrachloride is passed through into air inlet pipe（10）Pulse enters cavity（1）And stop
Stay a period of time；Precursor gas is in hollow-fibre membrane（9）Stirring under be dispersed in cavity（1）It is interior, and with it is hollow
Tunica fibrosa（9）Monolayer Chemisorption occurs for fully contact, film surface, then passes to the anti-of nitrogen 200s purging excess
Thing and accessory substance are answered, from escape pipe（11）Discharge system；
Step 3: then continue to be passed through presoma oxygen source H2O, using high pure nitrogen as carrier gas, by H2O passes through air inlet pipe（10）Pulse
Into cavity（1）And stay for some time；Monolayer chemical reaction occurs for film surface, and it is excessive to then pass to nitrogen 200s purgings
Reactant and accessory substance, from escape pipe（11）Discharge system；It is the atomic layer of a circulation after the completion of step 2 and step 3
Deposition reaction；
Step 4: after the ald for repeating 50-200 circulation reacts, lid is removed（5）, and support（8）And cavity
（1）The screw of connection, then hollow-fibre membrane will be hung（9）Porous wheel（2）Take out.
6. a kind of rotation ald reactor modified towards hollow-fibre membrane batch as claimed in claim 5 carries out former
The technique of sublayer deposition reaction, it is characterised in that the presoma pulse enters cavity（1）Burst length be 0.1-0.5s,
The residence time is 50-100s.
7. a kind of rotation ald reactor modified towards hollow-fibre membrane batch as claimed in claim 5 carries out former
The technique of sublayer deposition reaction, it is characterised in that suspension hollow-fibre membrane（9）The quantity of film wire be 500-1000 roots, it is modified
External surface area is 1-2m2。
8. a kind of rotation ald reactor modified towards hollow-fibre membrane batch as claimed in claim 5 is carried out
The technique of ald reaction, it is characterised in that motor（6）Rotational speed regulation scope be 10-60 r/min.
9. a kind of rotation ald reactor modified towards hollow-fibre membrane batch as described in claim 5 is any enters
The technique of row ald reaction, it is characterised in that carry out the cavity of ald reaction（1）Temperature is 80-150 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711265063.XA CN107815668B (en) | 2017-12-05 | 2017-12-05 | Rotary atomic layer deposition reactor for batch modification of hollow fiber membranes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711265063.XA CN107815668B (en) | 2017-12-05 | 2017-12-05 | Rotary atomic layer deposition reactor for batch modification of hollow fiber membranes |
Publications (2)
| Publication Number | Publication Date |
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| CN107815668A true CN107815668A (en) | 2018-03-20 |
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