CN106756898A - The preparation method of antibacterial hydrophobic ZnO nanorod - Google Patents
The preparation method of antibacterial hydrophobic ZnO nanorod Download PDFInfo
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Abstract
A kind of preparation method of antibacterial hydrophobic ZnO nanorod, comprises the following steps：Step one, titanium sheet mechanical polishing treatment, successively polishes titanium sheet, smooth to surface, polishing titanium sheet is sequentially placed into acetone, absolute ethyl alcohol and deionized water and is respectively cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, standby；Step 2, prepares ZnO Seed Layers, and the polishing titanium sheet that step one is obtained plates one layer of uniform ZnO Seed Layer as substrate；Step 3, prepare ZnO nanorod, the substrate for scribbling ZnO Seed Layers that step 2 is obtained is inverted and is suspended in the aqueous solution of zinc nitrate hexahydrate and hexamethylenetetramine, carry out natural cooling after hydro-thermal reaction, ZnO nanorod is after being dried after being cleaned with deionized water after taking-up substrate.Its advantage is：With preferable antibacterial effect, produced without high-temperature heating, also without pernicious gas, it is economic and environment-friendly；Wide spectrum, efficient and persistent antibiotic property, and with certain biocompatibility.
Description
Technical field
The present invention relates to titanium-based technical field of biological materials, specifically a kind of system of antibacterial hydrophobic ZnO nanorod
Preparation Method.
Background technology
Titanium-based biomaterial possesses good biocompatibility, mechanical property and excellent corrosion resistance, and
It is widely used in orthopedic and dental implant material.However, the related infection of implant frequently occur in surgical procedure or
Post operation, causes implant operative failure, and this is mainly caused by sticking for bacterium with being formed for biomembrane.Once biomembrane is being planted
Enter body surface face to be formed, chronic infection can occur therewith, and traditional therapy based on antibiotic is typically no well
Effect, because bacterial antibiotic and chemical sterilants have certain drug resistance, this will eventually lead to the removal of implant.
Removing implant can increase hospital stays and the medical expense of patient, bring huge pain to patient in this process, very
The life security of patient can extremely be threatened.
Therefore, titanium-based biomaterial should be endowed from antibacterial functions, and lot of documents was also reported various to medical bio
Implantation material surface it is antibacterial modified.Process for modifying surface particularly coating technology can assign titanium implantses surface and be resisted with good
The coating of bacterium performance, such as antibiotic-loaded, the polymer coating of the antibacterial of bioactivity, inorganic fungicide doping coating,
The coating of anti-adhesive and the coating of organic bactericide load of non-antibiotic etc..Therefore, a kind of antibacterial, hydrophobic how is prepared
Nanometer rods are current problem demanding prompt solutions.
The content of the invention
The invention aims to solve above-mentioned technological deficiency, there is provided a kind of durable antibacterial effect, efficiently, wide spectrum
The preparation method of antibacterial hydrophobic ZnO nanorod, specifically includes following steps：
Step one, titanium sheet mechanical polishing treatment
Titanium sheet is polished successively with 240,600,1200 and 2400 mesh diamond dust on polishing machine, it is smooth to surface, will throw
Light titanium sheet is respectively cleaned by ultrasonic 15 minutes in being sequentially placed into acetone, absolute ethyl alcohol and deionized water, spontaneously dries at room temperature, standby；
Step 2, prepares ZnO Seed Layers
The polishing titanium sheet that step one is obtained as substrate, using sol-gel process or atomic layer deposition method or high vacuum
Magnetron sputtering method plates one layer of uniform ZnO Seed Layer；
Step 3, prepares ZnO nanorod
The substrate for scribbling ZnO Seed Layers that step 2 is obtained is inverted and is suspended in containing the water nitric acid of 0.015-0.025mol/L six
In zinc, the aqueous solution of 0.015-0.025mol/L hexamethylenetetramines, hydrothermal temperature is 70-90 DEG C, the hydro-thermal reaction time
It it is 3-6 hours, natural cooling after reaction is ZnO nanorod after being dried after being cleaned with deionized water after taking-up substrate.
Preferably, the concentration of zinc nitrate hexahydrate is for 0.025mol/L, the concentration of hexamethylenetetramine in step 3
0.025mol/L。
Sol-gel process described in step 2, concretely comprises the following steps：
1) ethanol solution of 0.35-0.85mol/L acetic acid dihydrates zinc and 0.35-0.85mol/L monoethanolamines is prepared, afterwards
Persistently stirring obtains water white transparency colloid for 2-4 hours and preserves 20-24 hours at room temperature, treats that colloidal sol is fully aged, that is, obtain
Precursor solution；
2) 20-30 μ L precursor solutions are coated to titanium sheet using rotary coating instrument, early stage 500-1000 turns to continue 10-15
Second, later stage 3000-5000 turns to continue 20-30 seconds, is dried up with nitrogen afterwards, and spin coating process is repeated 2 times；
3) titanium sheet that Seed Layer is coated with after is fired 40-60 minutes at 400-500 DEG C, is slowly dropped to room temperature.
Preferably, step 1) in acetic acid dihydrate zinc concentration be 0.75mol/L, monoethanolamine concentration be 0.75mol/L；
Step 2) in spin coating parameters be that 1000 turns of early stage continues 15s, 5000 turns of later stage continues 30s；
Step 3) in fire parameter be 500 DEG C at 60 minutes.
For atomic layer deposition method, specific method is：
1) burnett's solution as presoma is prepared as zinc source and oxygen source using diethyl zinc (DEZ) and water, then to base
Bottom is deposited, and is 80-100 DEG C specially in depositing temperature, and deposition pressure is 20-40Pa, and deposition flow is the condition of 10-20
Under, using water flowing pulse 0.1s, High Purity Nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen clean 20s as one circulate into
Row deposition (H2O/N2/DEZ/N2=0.1:20:0.1:20s), cycle-index is 200-300, and ZnO Seed Layers are obtained in substrate.
Preferably, step 1) in reactive deposition temperature be 100 DEG C, deposition pressure be 40Pa, deposition flow be 20, reaction follow
Ring number of times is 300.
For high vacuum magnetron sputtering method, specific method is：
1) rf magnetron sputtering is utilized, first allows pressure to drop to 6.0 × 10-4Below Pa, then leads to high-purity argon as work gas
Body is 2.0-3.0Pa to pressure, and sputter temperature is 15-25 DEG C, and sputtering power is 100-120W, sputtering time 80-120 seconds.
Preferably, step 1) in sputter temperature be 25 DEG C, sputtering power be 120W, sputtering time 120s；Six water of step 3
Nitric acid zinc concentration is 0.025mol/L, the concentration of hexamethylenetetramine is 0.025mol/L.
The preparation method of antibacterial hydrophobic ZnO nanorod, its advantage is：
(1) uniformly plated in substrate using sol-gel process, atomic layer deposition method, three kinds of methods of high vacuum magnetron sputtering
ZnO Seed Layers, while the thickness of ZnO Seed Layers can be controlled by regulating and controlling relevant parameter, with preferable antibacterial effect, without height
Temperature heating, also without pernicious gas produce, it is economic and environment-friendly；
(2) organic antibacterial agents such as antibiotic are compared to, ZnO nano-rod array has wide spectrum, efficient and persistent antibacterial
Property, and with certain biocompatibility, meanwhile, hydrophobic surface has antiscale and pollution-proof performance, may be used to prepare titanium-based gold
Category biomedical implant material and Medical instruments Appliances, prevent from being implanted into fouling and the bacterial biof iotalm shape of stand tube material surface
Into；
(3) preparation method is simple and easy to apply, is produced without toxic and harmful, economic and environment-friendly, and table is prepared using the technology of the present invention
Face has three kinds of preparation methods of the ZnO nano-rod array of excellent antibacterial, and enforcement difficulty is small, and equipment investment is few, consumes resource
It is few；
Brief description of the drawings
Fig. 1 is the antibacterial OD column comparison diagrams of ZnO Seed Layers and nanometer rods to staphylococcus aureus.
Wherein, ALD：Ald；sol：Collosol and gel；spu：High vacuum magnetron sputtering；ZnOs：Zinc oxide seed
Layer；ZnO：Nanometic zinc oxide rod array；
Fig. 2 is the SEM figures after titanium sheet mechanical polishing treatment in embodiment 1.
The ZnO Seed Layers SEM figures that Fig. 3 is obtained for sol-gel process in embodiment 1.
The ZnO Seed Layers SEM figures that Fig. 4 is obtained for atomic layer deposition method in embodiment 2.
The ZnO Seed Layers SEM figures that Fig. 5 is obtained for high vacuum magnetron sputtering in embodiment 3.
Fig. 6 is the SEM figures of hydro-thermal after sol-gel process in embodiment 1.
Fig. 7 is the SEM figures of hydro-thermal after atomic layer deposition method in embodiment 2.
Fig. 8 is the SEM figures of hydro-thermal after high vacuum magnetron sputtering in embodiment 3.
Fig. 9 is the contact angle figure of polishing titanium sheet in embodiment 1.
The contact angle figure of the ZnO Seed Layers that Figure 10 is obtained for sol-gel process in embodiment 1.
The contact angle figure of the ZnO Seed Layers that Figure 11 is obtained for atomic layer deposition method in embodiment 2.
The contact angle figure of the ZnO Seed Layers that Figure 12 is obtained for high vacuum magnetron sputtering in embodiment 3.
Figure 13 is the contact angle figure of hydro-thermal after sol-gel process in embodiment 1.
Figure 14 is the contact angle figure of hydro-thermal after atomic layer deposition method in embodiment 2.
Figure 15 is the contact angle figure of hydro-thermal after the high vacuum magnetron sputtering of embodiment 3.
The ZnO Seed Layers SEM figures that Figure 16 is obtained for sol-gel process in embodiment 7.
The ZnO Seed Layers SEM figures that Figure 17 is obtained for sol-gel process in embodiment 8.
Specific embodiment：
To be best understood from the present invention, the present invention is done further describe in detail with reference to the accompanying drawings and examples, but
The scope of protection of present invention is not limited to the scope that embodiment is represented.
Embodiment 1：
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing treatment：With 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively polishes titanium sheet, to surface it is smooth after, will polishing titanium sheet be sequentially placed into acetone, absolute ethyl alcohol and deionized water
It is each to be cleaned by ultrasonic 15 minutes, spontaneously dry at room temperature, it is standby；
(2) the polishing titanium sheet that will be obtained plates one layer of uniform ZnO Seed Layer as substrate using sol-gel process；Specifically
Method is to prepare the ethanol solution of 0.75mol/L acetic acid dihydrates zinc and 0.75mol/L monoethanolamines, and persistently stirring 4h is obtained afterwards
24h is preserved to water white transparency colloid and at room temperature, treat that colloidal sol is fully aged, that is, obtain precursor solution, use rotary coating
Instrument coats 30 μ L precursor solutions to titanium sheet, and its parameter continues 15 seconds for 1000 turns of early stage, and 5000 turns of later stage continues 30 seconds, it
Dried up with nitrogen afterwards, spin coating process is repeated 2 times, the titanium sheet that Seed Layer is coated with afterwards is fired 60 minutes at 500 DEG C, slow drop
To room temperature；
(3) 0.025mol/L zinc nitrate hexahydrates (Zn (NO are prepared first3)2)·6H2) and the methines four of 0.025mol/L six O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettles, scribble ZnO seeds by what step 2 was obtained
The substrate of layer is inverted and is suspended in the solution, and hydrothermal temperature is 90 DEG C, and the hydro-thermal reaction time is 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned with deionized water immediately.
Embodiment 2：
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing treatment：With 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, absolute ethyl alcohol and deionized water it is each
It is cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, it is standby；
(2) the polishing titanium sheet that will be obtained plates one layer of uniform ZnO Seed Layer, tool as substrate using atomic layer deposition method
Body is：Burnett's solution as presoma is prepared as zinc source and oxygen source using diethyl zinc (DEZ) and water, then substrate is carried out
Deposition, depositing temperature be 100 DEG C, deposition pressure is 40Pa, deposition flow be 20 under conditions of, with water flowing pulse 0.1s, height
Purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are deposited (H as a circulation2O/N2/DEZ/N2=
0.1:20:0.1:20s), cycle-index is 300, and ZnO Seed Layers are obtained in substrate.
(3) 0.025mol/L zinc nitrate hexahydrates (Zn (NO are prepared first3)2)·6H2) and the methines four of 0.025mol/L six O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettles, scribble ZnO seeds by what step 2 was obtained
The substrate of layer is inverted and is suspended in the solution, and hydrothermal temperature is 90 DEG C, and the hydro-thermal reaction time is 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned with deionized water immediately.
Embodiment 3：
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing treatment：With 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, absolute ethyl alcohol and deionized water it is each
It is cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, it is standby；
(2) the polishing titanium sheet that will be obtained plates one layer of uniform ZnO seed as substrate using high vacuum magnetron sputtering method
Layer；Specifically, using rf magnetron sputtering, first allowing pressure to drop to 6.0 × below 10-4Pa, it is working gas then to lead to high-purity argon
It is 3.0Pa to pressure, sputter temperature is 25 DEG C, and sputtering power is 120W, sputtering time 120s；
(3) 0.025mol/L zinc nitrate hexahydrates (Zn (NO are prepared first3)2)·6H2) and the methines four of 0.025mol/L six O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettles, scribble ZnO seeds by what step 2 was obtained
The substrate of layer is inverted and is suspended in the solution, and hydrothermal temperature is 90 DEG C, and the hydro-thermal reaction time is 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned with deionized water immediately.
Embodiment 4：
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing treatment：With 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, absolute ethyl alcohol and deionized water it is each
It is cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, it is standby；
(2) the polishing titanium sheet that will be obtained plates one layer of uniform ZnO Seed Layer as substrate using sol-gel process；Specifically
Method is to prepare the ethanol solution of 0.35mol/L acetic acid dihydrates zinc and 0.35mol/L monoethanolamines, and persistently stirring 4h is obtained afterwards
24h is preserved to water white transparency colloid and at room temperature, treat that colloidal sol is fully aged, that is, obtain precursor solution, use rotary coating
Instrument coats 20 μ L precursor solutions to titanium sheet, and its parameter continues 15 seconds for 500 turns of early stage, and 3000 turns of later stage continues 30 seconds, it
Dried up with nitrogen afterwards, spin coating process is repeated 2 times, the titanium sheet that Seed Layer is coated with afterwards is fired 60 minutes at 400 DEG C, slow drop
To room temperature；
(3) 0.025mol/L zinc nitrate hexahydrates (Zn (NO are prepared first3)2)·6H2) and the methines four of 0.025mol/L six O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettles, scribble ZnO seeds by what step 2 was obtained
The substrate of layer is inverted and is suspended in the solution, and hydrothermal temperature is 90 DEG C, and the hydro-thermal reaction time is 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned with deionized water immediately.
Embodiment 5：
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing treatment：With 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, absolute ethyl alcohol and deionized water it is each
It is cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, it is standby；
(2) the polishing titanium sheet that will be obtained plates one layer of uniform ZnO Seed Layer, tool as substrate using atomic layer deposition method
Body is：Burnett's solution as presoma is prepared as zinc source and oxygen source using diethyl zinc (DEZ) and water, then substrate is carried out
Deposition, depositing temperature be 100 DEG C, deposition pressure is 40Pa, deposition flow be 20 under conditions of, with water flowing pulse 0.1s, height
Purity nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are deposited (H as a circulation2O/N2/DEZ/N2=
0.1:20:0.1:20s), cycle-index is 300, and ZnO Seed Layers are obtained in substrate.
(3) 0.035mol/L zinc nitrate hexahydrates (Zn (NO are prepared first3)2)·6H2) and the methines four of 0.035mol/L six O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettles, scribble ZnO seeds by what step 2 was obtained
The substrate of layer is inverted and is suspended in the solution, and hydrothermal temperature is 90 DEG C, and the hydro-thermal reaction time is 6h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned with deionized water immediately.
Embodiment 6：
(1) titanium sheet (diameter 6mm, thickness 2mm) mechanical polishing treatment：With 240,600,1200 and 2400 mesh on polishing machine
Diamond dust successively by titanium sheet be polishing to surface it is smooth after will polishing titanium sheet be sequentially placed into acetone, absolute ethyl alcohol and deionized water it is each
It is cleaned by ultrasonic 15 minutes, spontaneously dries at room temperature, it is standby；
(2) the polishing titanium sheet that will be obtained plates one layer of uniform ZnO seed as substrate using high vacuum magnetron sputtering method
Layer；Specifically, using rf magnetron sputtering, it is 6.0 × below 10-4Pa first to allow pressure to drop to, it is work gas then to lead to high-purity argon
Body is 2.0Pa to pressure, and sputter temperature is 15 DEG C, and sputtering power is 100W, sputtering time 80s；
(3) 0.015mol/L zinc nitrate hexahydrates (Zn (NO are prepared first3)2)·6H2) and the methines four of 0.015mol/L six O
Amine (C6H12N4) aqueous solution 60ml, and fallen in capacity 100ml water heating kettles, scribble ZnO seeds by what step 2 was obtained
The substrate of layer is inverted and is suspended in the solution, and hydrothermal temperature is 70 DEG C, and the hydro-thermal reaction time is 3h, after reaction, natural cooling
After take out substrate, drying for standby after being cleaned with deionized water immediately.
Embodiment 7：
(1) by clean sheet glass (1 × 1cm2) be sequentially placed into acetone, absolute ethyl alcohol and deionized water and be respectively cleaned by ultrasonic
15min, spontaneously dries at room temperature, standby；
(2) specific method with the sol-gel in embodiment 1 is consistent；
(3) with embodiment 1.
Embodiment 8：
(1) with embodiment 1；
(2) with the specific method of the sol-gel in embodiment 1 (2), only spin coating process number of repetition is changed to three times；
(3) with embodiment 1.
Corresponding Analysis of test results is carried out to embodiment 1-3：The ZnO Seed Layers of three kinds of method preparations are all evenly distributed on
Titanium-based basal surface, in addition, the sol-gal process that compares, by hydrothermal growth after atomic layer deposition method, high vacuum magnetron sputtering
ZnO nano-rod array is almost vertical with substrate, and distribution is more uniform, the diameter about 100nm of ZnO nanorod, about 2 μm of length, with
ZnO Seed Layers compare, and the ZnO nano-rod array of preparation has a more excellent antibacterial effect, ZnO Seed Layers as shown in Figure 1 and
, to the antibacterial OD column comparison diagrams of staphylococcus aureus, to being analyzed in figure, pure Ti is almost without antibiotic property, ALD- for nanometer rods
The antibiotic property of ZnOs is 90.2%, Sol-ZnO for the antibiotic property that the antibiotic property of 45.5%, ALD-ZnO is 97.0%, Sol-ZnOs
Antibiotic property for 96.4%, Spu-ZnOs antibiotic property for 45.0%, Spu-ZnO antibiotic property be 98.2%.
Analysis of Surface Topography is carried out to prepared ZnO Seed Layers and nanometer rods, as illustrated in figs. 2 through 8, can through sem analysis
Know, the ZnO Seed Layers of three kinds of method preparations are all evenly distributed on titanium-based basal surface, in addition, the sol-gal process that compares, by original
The ZnO nano-rod array of hydrothermal growth is almost vertical with substrate after sublayer sedimentation, high vacuum magnetron sputtering, is distributed more equal
It is even, the diameter about 100nm of ZnO nanorod, about 2.5 μm of length；The SEM with glass as substrate is carried out to embodiment 7,8 to test simultaneously
The analysis of testing result is carried out, as shown in Figure 16,17, titanium substrate is contrasted, on the glass substrate by hydro-thermal after sol-gel process
The ZnO nanorod of growth is more vertical, more dense；The analysis of testing result is carried out to embodiment 8：Contrast spin coating process is repeated 2 times,
The ZnO nano-rod array surface for being repeated 3 times growth becomes more out-of-flatness.
Hydrophobic type test is carried out to ZnO nanorod, contact angle of the liquid on solid material surface is to weigh the liquid pair
The important parameter of material surface wettability, and and then acquisition material surface solid-liquid, many letters of solid-air interface interaction
Breath, as shown in Fig. 9-15, tests through the analysis of contact angle figure, and the contact angle figure for polishing titanium sheet is 78.3 ± 1.1 ° (such as Fig. 9 institutes
Show), the contact angle figure of the ZnO Seed Layers that sol-gel process is obtained is 43.3 ± 4.8 ° (as shown in Figure 10), atomic layer deposition method
The contact angle figure of the ZnO Seed Layers for obtaining is 80.7 ± 1.5 ° (as shown in figure 11), the ZnO seeds that high vacuum magnetron sputtering is obtained
The contact angle figure of layer is 93.8 ± 1.4 ° (as shown in figure 12), and the contact angle figure of hydro-thermal is 95.0 ± 1.7 ° after sol-gel process
(as shown in figure 13), the contact angle figure of hydro-thermal is 140.2 ± 1.2 ° (as shown in figure 14), high vacuum magnetic control after atomic layer deposition method
The contact angle figure of hydro-thermal is 141.2 ± 3.7 ° (as shown in figure 15) after sputtering.Be can be seen that from contact angle map analysis prepared
ZnO nanorod has good hydrophobic performance, and by sol-gel process hydro-thermal process, atomic layer deposition method, high vacuum magnetic
The hydrophobic effect of the ZnO nanorod after control sputtering method treatment is best.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. the preparation method of antibacterial hydrophobic ZnO nanorod, its feature mainly comprises the following steps：
Step one, titanium sheet mechanical polishing treatment
Titanium sheet is polished successively with 240,600,1200 and 2400 mesh diamond dust on polishing machine, it is smooth to surface, by polishing titanium
Piece is respectively cleaned by ultrasonic 10-15 minutes in being sequentially placed into acetone, absolute ethyl alcohol and deionized water, spontaneously dries at room temperature, standby；
Step 2, prepares ZnO Seed Layers
The polishing titanium sheet that step one is obtained as substrate, using sol-gel process or atomic layer deposition method or high vacuum magnetic control
Sputtering method plates one layer of uniform ZnO Seed Layer；
Step 3, prepares ZnO nanorod
By step 2 obtain scribble ZnO Seed Layers substrate be inverted be suspended in zinc nitrate hexahydrate containing 0.015-0.025mol/L,
In the aqueous solution of 0.015-0.025mol/L hexamethylenetetramines, hydrothermal temperature is 70-90 DEG C, and the hydro-thermal reaction time is 3-
6 hours, natural cooling after reaction was ZnO nanorod after being dried after being cleaned with deionized water after taking-up substrate.
2. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, it is characterised in that described in step 2
Sol-gel process, concretely comprise the following steps：
1) ethanol solution of 0.35-0.85mol/L acetic acid dihydrates zinc and 0.35-0.85mol/L monoethanolamines is prepared, is continued afterwards
Stirring obtains water white transparency colloid for 2-4 hours and preserves 20-24 hours at room temperature, treats that colloidal sol is fully aged, that is, obtain forerunner
Liquid solution；
2) 20-30 μ L precursor solutions are coated to titanium sheet using rotary coating instrument, early stage 500-1000 turns to continue 10-15 seconds,
Later stage 3000-5000 turns to continue 20-30 seconds, is dried up with nitrogen afterwards, and spin coating process is repeated 2 times；
3) titanium sheet that Seed Layer is coated with after is fired 40-60 minutes at 400-500 DEG C, is slowly dropped to room temperature.
3. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, it is characterised in that for atomic layer
Sedimentation, specific method is：
1) burnett's solution as presoma is prepared as zinc source and oxygen source using diethyl zinc and water, then substrate is sunk
Product, is 80-100 DEG C specially in depositing temperature, and deposition pressure is 20-40Pa, under conditions of deposition flow is 10-20, with logical
Water
Pulse 0.1s, High Purity Nitrogen cleaning 20s, diethyl zinc pulse 0.1s, High Purity Nitrogen cleaning 20s are sunk as a circulation
Product, cycle-index is 200-300, and ZnO Seed Layers are obtained in substrate.
4. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, it is characterised in that for high vacuum
Magnetron sputtering method, specific method is：
1) rf magnetron sputtering is utilized, first allows pressure to drop to 6.0 × 10-4Below Pa, then leads to high-purity argon and is arrived as working gas
Pressure is 2.0-3.0Pa, and sputter temperature is 15-25 DEG C, and sputtering power is 100-120W, sputtering time 80-120 seconds.
5. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 2, it is characterised in that step 1) two
Acetate hydrate zinc concentration is 0.75mol/L, the concentration of monoethanolamine is 0.75mol/L.
6. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 2, it is characterised in that step 2) rotation
It is that 1000 turns of early stage continues 15s to apply parameter, and 5000 turns of later stage continues 30s.
7. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 2, it is characterised in that step 3) burning
Parameter processed is 60 minutes at 500 DEG C.
8. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 3, it is characterised in that step 1) it is anti-
Depositing temperature is answered to be 40Pa, deposit flow for 20, reaction cycle number of times is 300 for 100 DEG C, deposition pressure.
9. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 4, it is characterised in that step 1) splash
Temperature is penetrated for 25 DEG C, sputtering power are 120W, sputtering time 120s.
10. the preparation method of antibacterial hydrophobic ZnO nanorod according to claim 1, it is characterised in that step 3) six
Water nitric acid zinc concentration is 0.025mol/L, the concentration of hexamethylenetetramine is 0.025mol/L.
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