阅读说明：本技术 在ito玻璃表面制备纳米结构wo3薄膜的方法 (Nanostructure WO is prepared on ito glass surface3The method of film ) 是由 郭兴伍 高晨璟 聂乐文 彭立明 于 2019-09-27 设计创作，主要内容包括：本发明提供了一种在ITO玻璃表面制备纳米结构WO_3薄膜的方法,涉及薄膜材料制备技术领域；包括在ITO玻璃上依次用电沉积加酸洗的方法制备WO_3种子层和溶剂热法生长纳米结构WO_3薄膜的步骤；制备种子层时,电沉积采用的电镀液包括钨酸盐和无机酸,酸洗所用的溶液为无机酸；本发明在ITO玻璃上依次用电沉积加酸洗的方法制备WO_3种子层,并通过溶剂热法生出纳米结构WO_3薄膜,电沉积种子层既保证了WO_3薄膜与ITO的高结合强度,又克服了传统配制前驱体溶液随后旋涂热分解制备种子层存在的高能耗低效率的问题,为纳米结构WO_3薄膜在调光玻璃、氢气传感器和电致变色等领域的应用提供了技术支持,具有广阔的应用前景。(The present invention provides one kind to prepare nanostructure WO on ito glass surface 3 The method of film is related to technology of thin film material preparation field；Including successively preparing WO with the method that electro-deposition acid adding is washed on ito glass 3 Seed layer and solvent-thermal method grow nanostructure WO 3 The step of film；When preparing seed layer, the electroplate liquid that electro-deposition uses includes tungstates and inorganic acid, and solution used in pickling is inorganic acid；The present invention successively prepares WO with the method that electro-deposition acid adding is washed on ito glass 3 Seed layer, and nanostructure WO is born by solvent-thermal method 3 Film, electro-deposition seed layer both ensure that WO 3 The high bond strength of film and ITO, and the problem that tradition prepares high energy consumption poor efficiency existing for the subsequent spin coating thermal decomposition preparation seed layer of precursor solution is overcome, it is nanostructure WO 3 Application of the film in fields such as dimming glass, hydrogen gas sensor and electrochromism provides technical support, has broad application prospects.)

1. a kind of prepare nanostructure WO on ito glass surface₃The method of film, which comprises the following steps:

A, WO is prepared with electrodeposition process on ito glass₃Seed layer: the ito glass makees cathode, and insoluble anode is used as to electricity Pole makes ito glass electro-deposition in electroplate liquid obtain WO₃Seed layer；

B, pickling；

C, pure water is washed and is dried；

D, solvent-thermal method prepares nanostructure WO₃Film is simultaneously annealed.

2. according to claim 1 prepare nanostructure WO on ito glass surface₃The method of film, which is characterized in that step Electroplate liquid described in rapid A includes the tungstate solution that concentration is 0.01~2.21mol/L.

3. according to claim 2 prepare nanostructure WO on ito glass surface₃The method of film, which is characterized in that step Electroplate liquid described in rapid A further includes the inorganic acid that concentration is 0~0.1mol/L, and the pH of the electroplate liquid is greater than or equal to 7.

4. according to claim 1 prepare nanostructure WO on ito glass surface₃The method of film, which is characterized in that institute The operating condition for stating electrodeposition process is constant current or pulse current, 0.1~10mA/cm of current density², 5~600s of electroplating time.

5. according to claim 1 prepare nanostructure WO on ito glass surface₃The method of film, which is characterized in that institute Stating insoluble anode includes graphite or platinum electrode.

6. according to claim 1 prepare nanostructure WO on ito glass surface₃The method of film, which is characterized in that institute The area ratio for stating insoluble anode and ito glass is greater than or equal to 5:1.

7. according to claim 1 prepare nanostructure WO on ito glass surface₃The method of film, which is characterized in that institute It states step B to specifically include: the ito glass obtained by step A is cleaned in the inorganic acid solution of 0.001~1mol/L.

8. according to claim 3 or 7 prepare nanostructure WO on ito glass surface₃The method of film, which is characterized in that The inorganic acid includes the mixing of one or more of sulfuric acid, hydrochloric acid, nitric acid.

9. according to claim 1 prepare nanostructure WO on ito glass surface₃The method of film, which is characterized in that institute It states step D to specifically include: the ito glass after washing and drying is put into reaction kettle, ethyl alcohol and tungsten source are added in reaction kettle, instead Answer kettle compactedness 60%~70%；Temperature of reaction kettle is more than or equal to 150 DEG C, and taking-up obtains a nanometer WO after keeping the temperature 16~30h_3-XIt is thin Film；Annealing obtains a nanometer WO₃Film, the temperature of the annealing operation are 300~500 DEG C, 2~6h of annealing time.

10. according to claim 9 prepare nanostructure WO on ito glass surface₃The method of film, the tungsten source include The mixing of one or more of the poly- wolframic acid of wolframic acid, tungstates, tungsten carbonyl, tungsten chloride, peroxide.

Technical field

The present invention relates to technology of thin film material preparation fields, and in particular to prepares nanostructure WO on ito glass surface₃It is thin The method of film more particularly to it is a kind of ito glass surface successively use the method for electro-deposition and pickling prepare seed layer, then lead to again Cross solvent-thermal method growth nanostructure WO₃The method of the low-energy-consumption high-efficiency of film.

Background technique

WO₃It is a kind of semiconductor, it has special electrochromism and hydrogen-inducing off-coloring performance, passes in dimming glass, hydrogen It is had broad application prospects in terms of sensor, this is also current WO₃Main direction of studying.A large number of studies show that having nanometer The WO of structure₃The electrochromism of film and hydrogen-inducing off-coloring performance are far superior to block WO₃, this is primarily due to the WO of nanostructure₃ With very big specific surface area, this surface area for allowing to occur chemically and physically to interact increases, and reaction rate obtains It is promoted.

Currently nanostructure WO is prepared on ito glass surface₃The method of film is then revolved presoma with preparing presoma It is coated on ito glass, then seed layer is prepared in thermal decomposition, then with based on solvent-thermal method growth film layer.This method is in order to guarantee The quality of seed layer generally requires to repeat spin coating and thermal decomposition process several times, and the temperature thermally decomposed is mostly 300 Du or more, this method energy consumption height and low efficiency.

Notification number provides a kind of electro-conductive glass matrix tungsten oxide film material for the Chinese invention patent of 106698972A Preparation method, the method pass through the tungsten oxide crystal seed in electro-conductive glass matrix spin coating, arrangement height controllable using hydro-thermal method preparation structure Orderly tungsten oxide laminated structure thin-film material is spent, sample needs are heat-treated at 600 DEG C after spinning, keep the temperature 2h, energy Consumption is high, low efficiency.

Summary of the invention

In view of the deficienciess of the prior art, the object of the present invention is to provide a kind of low-energy-consumption high-efficiencies in ito glass table Wheat flour is for nanostructure WO₃The method of film overcomes the energy of conventional method spin coating thermal decomposition preparation seed layer regrowth nano wire The shortcomings that consumption height, low efficiency, push WO₃The practical application of film.

The purpose of the present invention is what is be achieved through the following technical solutions: a kind of to prepare nanostructure WO on ito glass surface₃ The method of film, comprising the following steps:

A, WO is prepared with electrodeposition process on ito glass₃Seed layer: the ito glass makees cathode, insoluble anode conduct To electrode, ito glass electro-deposition in electroplate liquid is made to obtain WO₃Seed layer；

B, pickling；

C, pure water is washed and is dried；Water, acid is avoided to enter reaction kettle there are also some ions, the ratio of these substances is different, contains Amount is different, influences final experimental result；

D, solvent-thermal method prepares nanostructure WO₃Film is simultaneously annealed.

Preferably, electroplate liquid described in step A includes the tungstate solution that concentration is 0.01~2.21mol/L.Preferably, it walks Electroplate liquid described in rapid A includes the tungstate solution that concentration is 0.01~1mol/L.

Preferably, electroplate liquid described in step A further includes the inorganic acid that concentration is 0~0.1mol/L, the electroplate liquid PH is greater than or equal to 7；The pH of electroplate liquid is still greater than or is equal to 7 after inorganic acid is added, and avoids electroplate liquid pH < 7, leads to sodium tungstate It is unstable, wolframic acid precipitating is generated, subsequent experimental can not be carried out.

Preferably, the operating condition of the electrodeposition process is constant current or pulse current, 0.1~10mA/cm of current density², 5~600s of electroplating time.Current density is lower than 0.1mA/cm²When, WO that electro-deposition obtains₃Seed layer is excessively thin, it is difficult to play and make With, it is difficult to long nanowire, it is difficult to obtain the WO of nanostructure₃Film.When current density is greater than 10mA/cm2, ito glass Conductive film layer will receive to be burnt out because heat is excessively high, is split away off from glass matrix, subsequent operation can not carry out.

When sedimentation time was less than 5 seconds, seed layer can be very thin, so seed layer is difficult to play a role, nano wire is difficult to grow Out.When sedimentation time is greater than 600s, the conductive film layer of ito glass will receive to be burnt out because heat is excessively high, from glass matrix It splits away off, subsequent operation can not carry out.Current density and electrodeposition time are mutually matched, and current density is big, sedimentation time phase It should shorten, current density is small, and sedimentation time accordingly lengthens, if electric current is excessive or overlong time, ito glass will be burnt out, If electric current is too small or the time is too short, seed layer will be too thin, it is difficult to play a role.

Preferably, graphite or platinum electrode can be used in the insoluble anode.

Preferably, the area ratio of the insoluble anode and ito glass is greater than or equal to 5:1.

Preferably, the step B is specifically included: nothing of the ito glass that process step A is obtained in 0.001~1mol/L It cleans, is cleaned to transparent in machine acid solution.

Preferably, the inorganic acid includes the mixing of one or more of sulfuric acid, hydrochloric acid, nitric acid.Preferably, it will wash And the ito glass after drying is put into reaction kettle, is added ethyl alcohol and tungsten source in reaction kettle, the concentration in tungsten source be 1.4g/L~ 1.8g/L, reaction kettle compactedness 60%~70%；Temperature of reaction kettle is more than or equal to 150 DEG C, takes out and is received after 16~30h of heat preservation Rice WO_3-XFilm；Annealing obtains a nanometer WO₃Film, the temperature of the annealing operation are 300~500 DEG C, 2~6h of annealing time.

The concentration in tungsten source increases, and nano wire can grow thicker, and the concentration in tungsten source reduces, and nano wire can grow thin, can be with Obtain the WO of nanostructure₃Film, the optimum concentration in tungsten source are 1.4g/L~1.8g/L.Tungsten source is difficult to decompose when lower than 150 DEG C, In order to guarantee the WO of nanostructure₃Film is preferably grown and energy saving, is preferably 180~220 DEG C by temperature of reaction kettle.Instead Taking-up after 180~220 DEG C of 16~30h of heat preservation of kettle is answered to obtain a nanometer WO_3-XFilm；Annealing obtains a nanometer WO₃Film, in order to save The temperature of annealing operation described in the energy is 300~500 DEG C, 2~6h of annealing time.

Preferably, the tungsten source includes one or more of wolframic acid, tungstates, tungsten carbonyl, tungsten chloride, the poly- wolframic acid of peroxide Mixing.

Compared with prior art, the present invention have following protrusion the utility model has the advantages that

(1) WO is prepared with electrodeposition process on ito glass₃Seed layer is avoided and is spun on after sample again after preparing solution Heating makes solution decompose to obtain seed layer, and long-time heating is avoided to reduce energy consumption, and saving obtains the time of seed layer；

(2) there are one layer of In on ito glass surface₂O₃, In still can be partially reduced out in electrodeposition process, pass through Pickling washes away the In restored in electrodeposition process；Grow the WO of nanostructure₃It is very sensitive to sample surfaces, pass through pure water Remaining impurity washes away when washing pickling, avoids hindering nanostructure WO₃Film grows or to nanostructure WO₃Film morphology produces It is raw to influence；

(3) it grows to obtain the WO of nanostructure by solvent-thermal method_3-xFilm；Annealing obtains a nanometer WO₃Film compares table Area is big, and the surface area for allowing to occur chemically and physically to interact increases, and reaction rate gets a promotion, and product effect is excellent More；

(4) present invention can prepare WO on ito glass surface to low-energy-consumption high-efficiency₃Seed layer then passes through solvent heat Method grows nanostructure WO₃, break it is existing first prepare presoma, then the method preparation WO of spin coating and thermal decomposition is repeated₃ The limitation of the high energy consumption poor efficiency of the method for seed layer is nanostructure WO₃In dimming glass, hydrogen gas sensor and electroluminescent change The application in the fields such as color provides technical support.

Detailed description of the invention

Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention, Objects and advantages will become more apparent upon:

Fig. 1 is the present invention in ito glass surface preparation nanostructure WO₃The process flow chart of film；

Fig. 2 is nanostructure WO prepared by the embodiment of the present invention 1₃The surface microscopic topographic photo of film；

Fig. 3 is nanostructure WO prepared by the embodiment of the present invention 2₃The surface microscopic topographic photo of film；

Fig. 4 is the WO of comparative example 3 of the present invention preparation₃The surface microscopic topographic photo of film.

Specific embodiment

Following embodiment will be helpful to those skilled in the art and further understand the present invention, but not limit in any form The present invention.To those skilled in the art, without departing from the inventive concept of the premise, several changes can also be made Change and improve, these are all within the scope of protection of the present invention.The present invention is described in detail combined with specific embodiments below:

Following embodiments provide a kind of in ito glass surface preparation nanostructure WO₃The method of film, the method packet It includes and successively prepares WO with the method that electro-deposition acid adding is washed on ito glass₃Seed layer and solvent-thermal method grow nanostructure WO₃It is thin The step of film.

The electroplate liquid used when the preparation seed layer can be added for the tungstate solution of 0.01~2.21mol/L H2SO4 adjusts pH value of solution, and the pH of final solution is not less than 7.

The electroplating technology is constant current or pulse, and current density is 0.1~10mA/cm², 5~600s of electroplating time.

The electroplating technology is used as using insoluble anode to electrode, and ito glass makees cathode, the area ratio of anode and sample At least 5:1.

The insoluble anode uses graphite or platinum electrode.

Solution used in pickling is 0.001~1mol/L inorganic acid when the preparation seed layer.

The inorganic acid includes the mixing of one or more of sulfuric acid, hydrochloric acid, nitric acid.

Raw material used in solvent-thermal method growth nanostructure includes ethyl alcohol and tungsten source, the concentration in tungsten source be 1.4g/L~ 1.8g/L, reaction kettle compactedness 60%~70%；200 DEG C of reaction kettle heat preservations are taken out afterwards for 24 hours obtains a nanometer WO_3-XFilm；It anneals To nanometer WO₃Film, the temperature of the annealing operation are 300~500 DEG C, 2~6h of annealing time；Tungsten source includes wolframic acid, wolframic acid The mixing of one or more of the poly- wolframic acid of salt, tungsten carbonyl, tungsten chloride, peroxide.