CN109930135A - The spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film - Google Patents

The spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film Download PDF

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Publication number
CN109930135A
CN109930135A CN201910245436.XA CN201910245436A CN109930135A CN 109930135 A CN109930135 A CN 109930135A CN 201910245436 A CN201910245436 A CN 201910245436A CN 109930135 A CN109930135 A CN 109930135A
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metal
gradient
dope
spray pyrolysis
metal oxide
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汪福宪
郭鹏然
张芳
梁维新
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Guangdong Institute Of Test And Analysis (guangzhou Analysis And Testing Center China)
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Guangdong Institute Of Test And Analysis (guangzhou Analysis And Testing Center China)
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Priority to CN201910245436.XA priority Critical patent/CN109930135A/en
Priority to PCT/CN2019/083188 priority patent/WO2020191837A1/en
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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material

Abstract

The invention discloses a kind of gradient auto-dope multi-element metal oxide AxByOzThe spray pyrolysis preparation method of semiconductive thin film, using to flow velocity, gradually controller becomes accurate control A, precursor B solution gives liquid speed rate, by adjusting starting to liquid speed rate and to flow velocity fade rates, regulate and control the ratio of metal ion in coating process, under the premise of inhibiting the unitary metal oxide miscellaneous phase of A or B to be precipitated, realize the controllable adjustment of different-thickness film bottom to metal ion A/B ratio gradient between top, preparation A/B ratio gradient from film bottom to top, the all controllable gradient auto-dope multi-element metal oxide AxByOz semiconductive thin film of thickness, the technology needs not rely on high temperature thermal diffusion and assists forming metal ion A/B proportion-controllable gradient, it is possible to prevente effectively from A/B ratio gradient is uncontrollable in high warm assistant spray pyrolysismethod, it is easy to appear the unitary metal oxidation of A or B Object problem of phase separation.

Description

The spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film
Technical field:
The present invention relates to the spray pyrolysis preparation methods of gradient auto-dope multi-component metal oxide semiconductor film.
Background technique:
Multi-component metal oxide semiconductor film is one of widely applied film material with function, and photodetachment low efficiency It is the most critical factor for restricting its development, the built in field through entire photoelectricity very thin films can be created by gradient auto-dope, be Promote its photodetachment and promotes the effective way of PhotoelectrocatalytiPerformance Performance.Gradient auto-dope be 2017 by wang et al in state The novel semi-conductor modification technology being put forward for the first time on border is proved that the photoelectric characteristic of semiconductive thin film can be effectively improved.However it is existing Gradient auto-dope technology be to be realized by thermal diffusion assistant spray pyrolysismethod, which has the following deficiencies: that (1) is logical It crosses thermal diffusion to assist forming A/B concentration gradient, however is limited by the thermal diffusion coefficient of A and B, be only capable of preparing thickness < 550nm's Film is difficult to realize the controllable regulation of A/B concentration gradient, and film bottom and top, which are easy to appear, mutually to be separated, and will form carrier Complex centre reduces carrier photodetachment efficiency；(2) thermal diffusion auxiliary inevitably needs to react at high temperature；It is above-mentioned Defect seriously constrains the development and application of existing gradient auto-dope technology.
Summary of the invention:
The object of the present invention is to provide a kind of gradient auto-dope multi-element metal oxide AxByOzThe spraying heat of semiconductive thin film Preparation method is solved, using gradually controller becomes accurate control A, precursor B solution gives liquid speed rate to flow velocity, passes through and adjusts starting To liquid speed rate and flow velocity fade rates are given, the ratio of metal ion is regulated and controled in coating process, in the unitary gold for inhibiting A or B Under the premise of belonging to the precipitation of oxide miscellaneous phase, realize different-thickness film bottom to metal ion A/B ratio gradient between top Controllable adjustment, preparation all controllable gradient auto-dope multi-element metal oxide of A/B ratio gradient, thickness from film bottom to top AxByOz semiconductive thin film, the technology need not rely on high temperature thermal diffusion and assist forming metal ion A/B proportion-controllable gradient, can Effectively to avoid in high warm assistant spray pyrolysismethod, A/B ratio gradient is uncontrollable, is easy to appear the unitary metal oxidation of A or B Object problem of phase separation.
The present invention is achieved by the following technical programs:
The spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film, by accurately controlling metal A, the starting of precursor B solution to flow velocity and gives flow velocity fade rates, and regulation is sprayed at 100~550 DEG C of substrate surface The ratio of metal ion in mist pyrolytic deposition coating process prepares gradient auto-dope multi-element metal oxide (AxByOz, metal A, Metal B, oxygen atom O are with the oxide that chemical dosage ratio is that x:y:z is formed) film, from film bottom to film, gold is formed on top Belong to ion A/B ratio change of gradient.
It is described by accurately controlling the starting of metal A, precursor B solution to flow velocity and to flow velocity fade rates, be Refer to the metal salt solution of preparing metal A and B as precursor solution, the presoma that metal A and B is arranged by ramp control device is molten Liquid spray pyrolysis deposition plating process starting to flow velocity (0.1~10L/min) and to flow velocity fade rates (0.01~ 10L/min2), it is plated according to setting parameter gradual change in 100~550 DEG C of progresss spray pyrolysis depositions to flow velocity in coating process Film, from film bottom to film, the change of gradient of metal ion A/B ratio is formed on top.
Wherein, the precursor solution of metal A, B spray pyrolysis deposition plating process starting to flow velocity be 0.1~ 10L/min is 0.01~10L/min to flow velocity fade rates2。
Metal A, precursor B solution metal salt include but is not limited to the nitrate, acetate, chloride of A and B；Solvent Including but not limited to acetic acid, methanol, ethyl alcohol, acetone, water.
Preferably, metal A, be added stabilizer in precursor B solution, the stabilizer include but is not limited to polyethylene glycol, Trimethyl orthoformate.
Metal A, B ion concentration C of metal A, precursor B solutionA、CBRespectively 1~1000mM.
Preferably, when the multi-element metal oxide is AxByOz, metal A, precursor B solution give liquid speed rate VA、VBIt needs Meet 0 < VA≤ 10L/min, 0 < VB≤ 10L/min, and 0.5 × (x:y) < CBVB/CAVA< 2 × (x:y).
During spray pyrolysis deposition plating, the distance between ultrasonic atomizer nozzle to substrate is 1~100cm, carrier gas Pressure is 0.1~10bar.
Obtained sull is controllable with a thickness of 10nm~10 μm.
The spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film, specifically includes following step It is rapid:
1) precursor solution for preparing metal A, B is respectively placed in fluid reservoir A, B；
2) precursor solution parameter setting: metal A precursor solution is arranged by ramp control device A and flows into rising for mixing device Beginning flow velocity VABegin, final flow rate VAEventually, the threshold speed that metal precursor B solution flows into mixing device is arranged by ramp control device B VBBegin, final flow rate VBEventually and plated film time T, setting ultrasonic atomizatio power is 50~500W, carrier gas pressure be 0.1~ The distance between 10Bar, ultrasonic atomizer nozzle to substrate are 1~100cm and 100~550 DEG C of sample stage heating temperature；
3) specimen heating holder, reach lead to after assigned temperature is stablized carrier gas start it is spraying, metal A, precursor B solution start by Threshold speed according to setting and enter mixing device to flow velocity fade rates, is ejected in through ultrasonic atomizatio with carrier gas after being uniformly mixed The fixed deposition on substrate of sample stage；In spray process, A and B to liquid speed rate respectively according to the fade rates (V of settingA- V eventuallyA Begin)/T, (VB- V eventuallyBBegin)/T variation, the accurate ratio for controlling mixed liquor A and B in atomizer, to realize film bottom (t= 0) it is constructed to the controllable of (t=T) A/B ratio gradient at the top of film；When the time, t reached T, plated film is terminated, and is closed carrier gas and is added Heat collects sample after being cooled to room temperature.
Particularly, it is furnished with radome fairing outside the ultrasonic atomizer nozzle of the ultrasonic atomizatio, can use carrier gas will be after atomization Microlayer model uniformly sprayed with certain speed.
The carrier gas includes but is not limited to compressed air, oxygen, nitrogen, more than one gases in argon gas.
Beneficial effects of the present invention are as follows:
(1) present invention realizes film bottom to A/B ratio change of gradient between top, solution by A, B to liquid speed rate gradual change Heat auxiliary in thermal diffusion assistant spray pyrolysismethod of having determined forms metal A/B ratio gradient, is limited by the thermal diffusion system of metal A and B Number, can be to the film of different-thickness (10nm~10 μm grade) the problem of can not regulating and controlling to metal A/B ratio gradient Created between from bottom to top under the premise of avoiding miscellaneous phase from being precipitated can accuracy controlling metal A/B ratio gradient.
(2) present invention does not need the thermal diffusion that high-temperature heating completes metal A and B, it is only necessary to which proper temperature makes metal salt shape At oxide.
(3) applied widely, thermal diffusion assistant spray pyrolysismethod is suitable for preparing binary metal oxide film, this method It can be used for the preparation of gradient auto-dope multi-element metal oxide film.
In short, the present invention is applied widely, to the film of different-thickness (10nm~10 μm grade), can miscellaneous phase avoided to analyse Created under the premise of out between from bottom to top can accuracy controlling metal A/B ratio gradient.Need not rely on high temperature thermal expansion Scattered auxiliary forms metal ion proportion-controllable gradient, it is possible to prevente effectively from metal ion ratio in high warm assistant spray pyrolysismethod Gradient is uncontrollable, is easy to appear the unitary metal oxide problem of phase separation of metal A or B.
Detailed description of the invention:
Fig. 1 is that gradient auto-dope multi-component metal oxide semiconductor film preparation dress is controllably blended in solution of the embodiment of the present invention The structural schematic diagram set；
Wherein, 1, fluid reservoir A；2, fluid reservoir B；3, flow velocity ramp control device A is given；4, flow velocity ramp control device B is given； 5, flow speed controller A；6, flow speed controller B；7, mixing device；8, ultrasonic atomizer；9, ultrasonic power controller；10, radome fairing； 11, spraying area；12, gradient auto-dope AxByOz film；13, substrate；14, sample stage；15, temperature controller.
Fig. 2 is the sample result figure of embodiment 1, wherein (a), scanning electron microscope (SEM) picture；(b), aura is put Electric emission spectrometry (GDOS) test result, wherein ordinate molar ratio refers to A/ (A+B) to A, refers to B/ (A+B), A to B Molar ratio A/B with B is glow discharge optical emission spectrometry (GDOS) test result, and Depth is the distance at the top of film, Scatter plot is test experiments as a result, solid line is linear fit；(c) X-ray diffraction spectrum (XRD) of gradient auto-dope AxByOz Figure.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1:
Gradient auto-dope multi-component metal oxide semiconductor film preparation device, the dress is controllably blended in solution as shown in Figure 1 It sets including spraying area, spraying area is equipped with heatable sample stage, and sample stage is used to fix once purged substrate, the temperature of sample stage It is controlled by temperature controller, the surface of sample stage is equipped with mixing device, ultrasonic atomizer and radome fairing, and described device further includes Fluid reservoir A, fluid reservoir B, ultrasonic power controller, to liquid speed rate ramp control device, flow speed controller, fluid reservoir A, fluid reservoir B It is respectively provided with metal A, precursor B solution, metal A, precursor B solution enter mixing device under the control of flow speed controller and mixes It is atomized into ultrasonic atomizer after uniformly after tiny droplet and is sprayed with carrier gas by radome fairing by nozzle, in spraying area sample The fixed deposition on substrate of sample platform；Metal A, precursor B solution originate in liquid speed rate and sputtering process to liquid fade rates It can be realized by the corresponding setting that links to liquid speed rate ramp control device A and B by coutroi velocity controller；Ultrasonic function Rate controller is used to control the power of ultrasonic atomizer, and the distance between ultrasonic atomizer nozzle to substrate is 1~100cm.
The spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film, specifically includes following step It is rapid:
1) preparing metal A, B ion concentration is respectively CA、CBThe precursor solution of metal A, B be respectively placed in fluid reservoir A, B In；Solute includes but is not limited to the nitrate, acetate, chloride of A and B；Solvent include but is not limited to acetic acid, methanol, ethyl alcohol, Acetone, water.
2) precursor solution parameter setting: metal A precursor solution is arranged by ramp control device A and flows into rising for mixing device Beginning flow velocity VABegin, final flow rate VAEventually, the threshold speed that metal precursor B solution flows into mixing device is arranged by ramp control device B VBBegin, final flow rate VBEventually and plated film time T, setting ultrasonic atomizatio power is 50~500W, carrier gas pressure be 0.1~ The distance between 10Bar, atomizer to substrate are 1~100cm and 100~550 DEG C of sample stage heating temperature；
3) specimen heating holder is opened, logical carrier gas after assigned temperature is stablized is reached and starts by spraying, metal A, precursor B solution are opened Begin to begin to enter mixing device according to the threshold speed vA beginning of setting, vB, is uniformly mixed, tiny mist is atomized into ultrasonic atomizer The fixed deposition on substrate of spraying area sample stage is ejected in carrier gas by nozzle after drop；In spray process, A and B's gives liquid speed Rate is respectively according to the fade rates (V of settingA- V eventuallyABegin)/T, (VB- V eventuallyBBegin)/T variation, it is accurate to control mixed liquor in atomizer The ratio of A and B, to realize that the controllable of (t=T) A/B ratio gradient is constructed at the top of film bottom (t=0) to film；Work as the time When t reaches T, the rate of A and B fade to V respectivelyAEventually, VBEventually, plated film terminates, and carrier gas and warm table is closed, after being cooled to room temperature Collect sample.
Embodiment 1: with the gradient auto-dope ABO of stoichiometric ratio x:y:z=1:1:44For
With reference to specific embodiment, the threshold speed of metal A precursor solution (metal A ion concentration 20mM) is 12ml/ Min, the threshold speed of metal precursor B solution (metal B ion concentration 20mM) are 8ml/min, and metal A precursor solution is to rise Begin on the basis of liquid speed rate, to liquid speed rate with 0.4mL/min2Fade rates gradually successively decrease, B is to originate to liquid speed rate as base Standard, to liquid speed rate with 0.4mL/min2Fade rates be gradually incremented by, plated film time 10min.Setting ultrasonic power is 100W, Atomizer nozzle to the distance between substrate is 20cm, and carrier gas pressure is 0.6Bar, and sample stage heating temperature is 300 DEG C.
Embodiment 2:
Reference implementation example 1, the difference is that: metal A precursor solution gives liquid speed rate to originate on the basis of liquid speed rate With 0.1~1mL/min2Fade rates gradually successively decrease (or be incremented by), metal precursor B solution is to originate to liquid speed rate as base Standard, it is unchanged to liquid speed rate.
Embodiment 3:
Reference implementation example 1, the difference is that: metal A, precursor B solution metal A, B ion concentration be 20~ 1000mM。
Embodiment 4:
Reference implementation example 1, the difference is that: ultrasonic atomizer power is 100~500W.
Embodiment 5:
Reference implementation example 1, the difference is that: the distance between ultrasonic atomizer nozzle to substrate is 20~50cm.
Embodiment 6:
Reference implementation example 1, the difference is that: carrier gas pressure is 0.6~10Bar.
Embodiment 7:
Reference implementation example 1, the difference is that: sample stage heating temperature is 300~550 DEG C.

Claims (10)

1. the spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film, which is characterized in that pass through essence Really control metal A, precursor B solution starting to flow velocity and give flow velocity fade rates, regulation substrate surface 100~ The ratio of metal ion, preparation gradient auto-dope multi-element metal oxide are thin during 550 DEG C of progress spray pyrolysis deposition platings Film, from film bottom to film, the change of gradient of metal ion A/B ratio is formed on top；Obtained sull with a thickness of 10nm~10 μm are controllable；The multi-element metal oxide is AxByOz, wherein A is metal A, and B is metal B, and O is oxygen atom, x, Y, z refers to metal A, metal B, the chemical dose of oxygen atom O.
2. the spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film according to claim 1, It is characterized in that, it is described by accurately controlling the starting of metal A, precursor B solution to flow velocity and to flow velocity fade rates, Refer to that as precursor solution, the presoma of metal A and B are arranged by ramp control device for the metal salt solution of preparing metal A, B Solution to flow velocity and gives flow velocity fade rates in the starting of spray pyrolysis deposition plating process, gives flow velocity in coating process According to setting parameter gradual change, in 100~550 DEG C of progress spray pyrolysis deposition platings, from film bottom to film, gold is formed on top Belong to ion A/B ratio change of gradient.
3. the spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film according to claim 2, It is characterized in that, the precursor solution of metal A, B spray pyrolysis deposition plating process starting to flow velocity be 0.1~10L/ Min is 0.01~10L/min to flow velocity fade rates2。
4. the spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film according to claim 2, It is characterized in that, the metal salt of metal A, precursor B solution include any one of nitrate, acetate, chloride of A, B； Solvent includes any one of acetic acid, methanol, ethyl alcohol, acetone, water.
5. the spray pyrolysis preparation side of gradient auto-dope multi-component metal oxide semiconductor film according to claim 1 or claim 2 Method, which is characterized in that stabilizer is added in metal A, precursor B solution, the stabilizer includes polyethylene glycol, orthoformic acid front three Ester.
6. the spray pyrolysis preparation side of gradient auto-dope multi-component metal oxide semiconductor film according to claim 1 or claim 2 Method, which is characterized in that metal A, precursor B solution the concentration of metal A, B ion be respectively 1~1000mM.
7. the spray pyrolysis preparation side of gradient auto-dope multi-component metal oxide semiconductor film according to claim 1 or claim 2 Method, which is characterized in that when metal A, precursor B solution give liquid speed rate VA、VB0 < V need to be metA≤ 10L/min, 0 < VB≤10L/ Min, and 0.5 × (x:y) < CBVB/CAVA< 2 × (x:y), CA、CBRespectively concentration of metal A, B ion in precursor solution.
8. the spray pyrolysis preparation side of gradient auto-dope multi-component metal oxide semiconductor film according to claim 1 or claim 2 Method, which is characterized in that during spray pyrolysis deposition plating, the distance between ultrasonic atomizer nozzle to substrate be 1~ 100cm。
9. the spray pyrolysis preparation side of gradient auto-dope multi-component metal oxide semiconductor film according to claim 1 or claim 2 Method, which is characterized in that specifically includes the following steps:
1) preparing metal A, B ion concentration is respectively CA、CBThe precursor solution of metal A, B be respectively placed in fluid reservoir A, B；
2) the starting stream that metal A precursor solution flows into mixing device precursor solution parameter setting: is arranged by ramp control device A Fast VABegin, final flow rate VAEventually, the threshold speed V that metal precursor B solution flows into mixing device is arranged by ramp control device BB Begin, final flow rate VBEventually and plated film time T, setting ultrasonic atomizatio power is 50~500W, carrier gas pressure be 0.1~ The distance between 10Bar, ultrasonic atomizer nozzle to substrate are 1~100cm and 100~550 DEG C of sample stage heating temperature；
3) specimen heating holder reaches and leads to carrier gas after assigned temperature is stablized and start spraying, and metal A, precursor B solution start according to setting The threshold speed set and enter mixing device to flow velocity fade rates, is ejected in sample with carrier gas through ultrasonic atomizatio after being uniformly mixed The fixed deposition on substrate of platform；In spray process, A and B to liquid speed rate respectively according to the fade rates (V of settingA- V eventuallyABegin)/ T、(VB- V eventuallyBBegin)/T variation, the accurate ratio for controlling mixed liquor A and B in atomizer, to realize film bottom (t=0) extremely (t=T) A/B ratio gradient controllably constructs at the top of film；When the time, t reached T, plated film is terminated, and closes carrier gas and heating, cold But to collecting sample after room temperature.
10. the spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film according to claim 9, It is characterized in that, being furnished with radome fairing outside the ultrasonic atomizer nozzle of the ultrasonic atomizatio, the carrier gas includes compressed air, oxygen Gas, nitrogen, more than one gases in argon gas, carrier gas pressure are 0.1~10bar.
CN201910245436.XA 2019-03-28 2019-03-28 The spray pyrolysis preparation method of gradient auto-dope multi-component metal oxide semiconductor film Pending CN109930135A (en)

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PCT/CN2019/083188 WO2020191837A1 (en) 2019-03-28 2019-04-18 Spray pyrolysis preparation method for gradient self-doping multi-element metal oxide semiconductor film

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114316637A (en) * 2021-12-28 2022-04-12 南开大学 Controllable preparation method of gradient composite membrane

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103037976A (en) * 2010-06-30 2013-04-10 联邦科学与工业研究组织 Droplet generation system and method
CN107710422A (en) * 2014-12-15 2018-02-16 中国建材国际工程集团有限公司 The method that gradient film is formed by spray pyrolysis

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101203948B (en) * 2005-04-14 2010-06-16 塔林科技大学 Method of preparing zinc oxide nanorods on a substrate by chemical spray pyrolysis
US20120060924A1 (en) * 2010-09-09 2012-03-15 Alion, Inc. Methods and systems for forming functionally graded films by spray pyrolysis
CN104911706B (en) * 2015-06-15 2017-08-25 上海应用技术学院 A kind of preparation method of fast flashing ZnO film

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103037976A (en) * 2010-06-30 2013-04-10 联邦科学与工业研究组织 Droplet generation system and method
CN107710422A (en) * 2014-12-15 2018-02-16 中国建材国际工程集团有限公司 The method that gradient film is formed by spray pyrolysis

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114316637A (en) * 2021-12-28 2022-04-12 南开大学 Controllable preparation method of gradient composite membrane

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Application publication date: 20190625