CN102943247B - A kind of preparation method of inorganic proton conducting film - Google Patents

Abstract

The invention discloses a kind of preparation method of inorganic proton conducting film, comprising: adopt chemical vapour deposition technique, reaction source is passed in sedimentary system, by adjusting process parameter, substrate is prepared phosphorus doped silicon dioxide inorganic proton conducting film.Present invention also offers a kind of conducting film prepared based on the method, and with the goods that described conducting film is made.Raw material sources of the present invention is abundant, low price; Preparation technology is compatible with existing installation, is suitable for big area continuous seepage; Have a extensive future, of many uses, can be used widely in thin film transistor, polymer dielectric film fuel cell, electrochemical sensor, water/field such as steam electrolytic, biosystem.

Description

A kind of preparation method of inorganic proton conductive membrane

technical field

The invention relates to the field of materials, in particular to a new inorganic proton conductive membrane and its preparation method and application.

Background technique

Proton-conducting and proton-conducting materials play an increasingly important role in batteries, electrochemical sensors, water/steam electrolysis, and biological systems. For example, the proton-conducting membrane is the "heart" of a polymer electrolyte membrane fuel cell. It is different from the diaphragm in general chemical power sources, because it not only plays the role of isolating fuel and oxidant, preventing them from reacting directly, but also plays the role of electrolyte. It responds to proton conduction and electron insulation, and is a selectively permeable functional polymer membrane. Therefore, the output power, cell efficiency, cost and application prospect of polymer electrolyte membrane fuel cells strongly depend on the proton exchange membrane.

Yoshitaka Aoki (Adv. Mater. 2008, 20, 4387-4393) and others have successfully developed a silicon-based double oxide amorphous proton conducting film, which can exhibit the Good proton exchange effect, but in the production, they found that there are some defects in the film, which will restrict its large-scale industrial application. In 2008, French Thomas Berthelot et al. (application number: 2008801108961) prepared proton-conducting membranes for fuel cells through radioactive grafting technology, which belongs to chemical solution synthesis. In addition, Abe et al. found that some phosphate glasses, such as BaO- and SrO-P ₂ O ₅ systems, have protons in the form of OH bond groups, which have higher proton conductivity compared with other glass systems (SiO ₂ glass) , and oxide glass has good chemical stability and is easy to make into various shapes.

Mesoporous silica (SiO ₂ ) has a large specific surface area and can absorb a large amount of water molecules. These water molecules can undergo capillary condensation in the mesoporous channels, so that the channels can store a large amount of water molecules like a "small pool". At the same time, the channel of mesoporous SiO ₂ can also act as a channel for proton movement, as shown in Figure 1, which can avoid the conductivity caused by the addition of a large number of fine particles in the organic composite proton conductive membrane or organic-inorganic hybrid composite proton conductive membrane. drop problem.

Chinese patent application Nos. 200810035587.4 and 200810035586 disclose the method for preparing proton conducting membrane, wherein, by introducing sulfonic acid groups in acidic or basic polymers, inorganic silica hollow microspheres (HSO ₃ -HSS) are prepared, thereby The retention ability of the system to the protonation aid is simultaneously improved in terms of chemical composition and spatial structure. The prepared proton conducting membrane still has excellent proton conducting performance above 100°C, and the prepared proton conducting membrane can be used as a proton exchange membrane and a membrane electrode of a medium temperature (100-200°C) fuel cell. However, the preparation process and performance of the proton conducting membrane are still unsatisfactory.

Haibin Li (Adv.Mater.2002,14(12):912-914) et al. used surfactants such as (CH ₃ (CH ₂ ) ₁₅ N ⁺ (CH ₃ ) ₃ Br ^- ) and C ₁₆ EO ₁₀ as structures Orienting agent, using sol-gel technology to successfully prepare silicon proton conductive film with controllable pore structure on ITO glass, and researched that the channel of the pores in the film is parallel to the substrate and the channel of the pores in the film is perpendicular to the substrate Conductive properties in both cases.

Xiao Kaijun and others successfully prepared mesoporous _SiO2 thin films by sol-gel method, and discussed the relationship between the sol solution formula, the stirring intensity of sol solution preparation and the film-forming time during the preparation of mesoporous films, and their separation and permeation characteristics. It is found that the viscosity of the coating solution is best controlled within the range of 30-40mPa·S, and the mesoporous structure will not be damaged after high-temperature burning, and the mesopore with a pure water flux of 4215L/m ² h is finally obtained. Like SiO ₂ .

Li Haibin of Shanghai Jiaotong University and others (Chinese patent application number: 201010134580) used hydrothermal technology to find that the protons in phosphoric acid are more ionic and each phosphorus atom has 3 OH, which can provide more protons as a proton source, thereby Conductive vitreous materials with high proton conductivity are obtained.

At present, most of the existing conventional methods for preparing proton conductive membranes use chemical solution synthesis, ion exchange, sol-gel methods, etc. The common feature of these methods is that the uniformity is relatively poor, and the process is not easy to be used in large-scale production And other shortcomings, especially the prepared mesoporous SiO ₂ due to its too large mesoporous channels and uneven distribution, resulting in limited proton conductivity.

Therefore, there is an urgent need in this field to develop and prepare inorganic proton-conducting membranes with small mesoporous channels, uniform distribution, and excellent proton-conducting properties and corresponding preparation processes.

Contents of the invention

The purpose of the present invention is to provide a method for preparing an inorganic proton conductive membrane which is easy to operate, suitable for large-area continuous production, has small mesoporous channels, uniform distribution, and excellent proton conductivity.

A first aspect of the present invention provides a method for preparing an inorganic proton conductive membrane, comprising the steps of:

Leading the reaction source into the reaction chamber and performing chemical vapor deposition to form a phosphorus-doped silicon dioxide inorganic proton conduction film with a mesoporous structure, wherein the reaction source includes a silicon source, a phosphorus source and an oxygen source.

In another preferred embodiment, the chemical vapor deposition is selected from the group consisting of plasma chemical vapor deposition and atmospheric pressure chemical vapor deposition.

In another preferred example, the chemical vapor deposition is atmospheric pressure chemical vapor deposition.

In another preferred example, the ratio of the silicon source, phosphorus source and oxygen source satisfies the following relationship: phosphorus source: silicon source = 1:100-20:100; silicon source: oxygen source = 1:1-1:6 .

In another preferred example, the method also has one or more of the following features:

The silicon source is selected from the group consisting of trichlorosilane, silicon tetrachloride, disilane, silane, or a combination thereof;

The phosphorus source is selected from the group consisting of phosphorus oxychloride and/or phosphine (such as trihydrogen phosphine PH ₃ );

The oxygen source is selected from the group consisting of nitrogen or argon carrying deionized water and/or oxygen, and the deionized water is in a gaseous state.

In another preferred example, the silane is monosilane (SiH ₄ ).

In another preferred embodiment, the reaction chamber is filled with an inert gas (such as argon, etc.).

In another preferred embodiment, the chemical vapor deposition is deposited on the surface of the substrate, thereby forming an inorganic proton conductive film deposited on the substrate.

In another preferred example, it is characterized in that the substrate is selected from the group consisting of glass substrates, plastic substrates, paper substrates, ceramic substrates, or combinations thereof.

In another preferred example, during the chemical vapor deposition process, the temperature of the substrate is 100-400°C.

In another preferred example, in the plasma chemical vapor deposition technique, the chamber pressure is 20-200Pa.

In another preferred example, when plasma chemical vapor deposition technology is used, the substrate temperature is 0°C to 100°C.

In another preferred example, when the atmospheric pressure chemical vapor deposition technique is used, the pressure of the chamber is 0.1-1.0 atm.

In another preferred example, when the atmospheric pressure chemical vapor deposition technique is used, the substrate temperature is 100-400°C.

In another preferred example, the mixing ratio of phosphorus source and silicon source in the reaction process is 1%-20%.

The second aspect of the present invention provides an inorganic proton-conducting membrane, and the inorganic proton-conducting membrane is formed by chemical vapor deposition.

The third aspect of the present invention provides a kind of inorganic proton conductive membrane, described inorganic proton conductive membrane is phosphorus-doped mesoporous _SiO2 thin film, and described inorganic proton conductive membrane has the following conductive properties: when the ambient humidity is At 80% and room temperature (such as 25°C), its proton conductivity is 1×10 ^-2 S/cm to 10 ^-4 S/cm, and when the ambient humidity is 85% to 100% and 50°C to 80°C, The proton conductivity is 1×10 ^-2 S/cm to 1×10 ^-4 S/cm.

In another preferred example, the proton conductivity will increase or decrease to varying degrees as the ambient humidity and temperature change.

In another preferred example, the inorganic proton conductive membrane is formed by chemical vapor deposition.

In another preferred example, the inorganic proton conductive membrane is prepared by the preparation method as described in the first aspect of the present invention.

In another preferred example, the inorganic proton conductive membrane has the following components: phosphorus, silicon and oxygen.

In another preferred example, the SiO ₂ thin film has a pore diameter of 2-50 nm.

In another preferred example, the thickness of the thin film is 50 nm˜50 μm.

In another preferred example, the inorganic proton-conducting membrane has the following structural features:

Silica particles stacked to form a mesoporous membrane framework, and

Micro-mesopores that provide channels for the transport of protons.

In another preferred example, the average diameter of the micro-mesoporous channels is ≤20nm.

In another preferred example, the thickness of the inorganic proton conductive film is 100 nm-20 μm.

In another preferred example, the conductive film may further include a substrate material.

The fourth aspect of the present invention provides a product, the product contains the inorganic proton conducting membrane as described in the second aspect and the third aspect of the present invention, or the product is composed of The above-mentioned inorganic proton conductive membrane is made.

In another preferred example, the product is selected from the group consisting of glass plates with the conductive film, glass-based micro-nano components (such as: transparent oxide thin film transistors, fuel cells), plastic-based Substrate micro-nano components (such as flexible thin film transistors, flexible sensors, etc.), paper-based flexible micro-nano components (such as flexible thin film transistors).

It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described in the following (such as embodiments) can be combined with each other to form new or preferred technical solutions. Due to space limitations, we will not repeat them here.

Description of drawings

Fig. 1 is the schematic diagram of the structure of the phosphorus-doped silicon dioxide inorganic proton conductive membrane prepared by the present invention;

Fig. 2 is the scanning electron micrograph example of the phosphorus-doped silicon dioxide inorganic proton-conducting film prepared by the present invention;

3 is an example diagram of the impedance analysis diagram of the phosphorus-doped silicon dioxide inorganic proton conductive film prepared in the present invention, wherein Z' represents the real part in the impedance analysis diagram, and Z" represents the imaginary part in the impedance analysis diagram.

Detailed ways

After long-term and in-depth research, the present inventors unexpectedly found that the chemical vapor deposition method can be used to manufacture high-efficiency and large-scale inorganic proton-conducting membranes with excellent performance. Compatible with electronic processing technology, no need to change other existing production equipment, high repeatability and uniformity, suitable for large-area continuous production; the inorganic proton conductive film prepared by the method of the present invention has high quality and low resistance, and can be used in thin film transistors, polymerization It has been widely used in the fields of bioelectrolyte membrane fuel cells, electrochemical sensors, water/steam electrolysis, and biological systems.

Chemical Vapor Deposition

Chemical Vapor Deposition (CVD) is a technique used to deposit a wide variety of materials, including a wide range of insulating materials, most metallic materials and metal alloy materials. The general operation method of chemical vapor deposition method is as follows: two or more gaseous raw materials are introduced into a reaction chamber, chemical reactions occur between the raw materials, and the formed products are deposited on the surface of the substrate.

In the present invention, the chemical vapor deposition system uses radio frequency glow discharge to make the reaction occur, and controls the process of adsorption, nucleation and growth by controlling the temperature and pressure of the deposition system. Preferably, the chemical vapor deposition method used in the present invention may be a plasma chemical vapor deposition method or an atmospheric pressure chemical vapor deposition method.

Reactor

As used herein, the term "reaction source" refers to the raw materials used in the chemical vapor deposition method, usually in gaseous state, or converted to gaseous state by certain means (such as high temperature, radio frequency glow discharge, etc.) and reacted in the vapor phase deposition system.

The reaction sources used in the preparation of the proton conducting membrane of the present invention include (but are not limited to): silicon sources, oxygen sources and/or phosphorus sources. Reagents for each reaction source can be prepared by conventional methods, or can be obtained commercially.

Wherein, the silicon source includes: trichlorosilane, silicon tetrachloride, disilane, silane, or a combination thereof; the phosphorus source includes: phosphorus oxychloride, phosphine, or a combination thereof; Oxygen sources include: deionized water and/or oxygen carried by the carrier gas. Preferably, the carrier gas is a component that does not chemically react with the reaction source such as inert gas or nitrogen, more preferably, the carrier gas is argon.

In the present invention, each reaction source should pass into the chamber in a certain proportion and react. In the present invention, the mixing ratio of the phosphorus source and the silicon source is 1% to 20%, and the ratio of the oxygen source is not particularly limited. Preferably, the amount of the oxygen source introduced is greater than that of the phosphorus source and/or The input amount of silicon source (in moles).

Preparation

The invention provides a preparation method of an inorganic proton conductive film, which adopts chemical vapor deposition technology (such as plasma chemical vapor deposition technology, atmospheric pressure chemical vapor deposition technology).

In order to facilitate the understanding of the present invention, the following mechanism is provided. However, it should be understood that the scope of protection of the present invention is not limited by the mechanism described.

In the present invention, after the reaction source is introduced into the chamber, the reaction can occur under suitable conditions (substrate temperature, pressure), and the conductive film is deposited on the substrate. In the inorganic proton conductive membrane, silicon atoms and phosphorus atoms combine with water molecules to form groups such as Si-OH ⁺ and P-OH ⁺ ; under the action of an electric field, H ⁺ is separated from OH ⁺ groups to provide conductive protons. Pore channels can store water molecules and provide transport pathways for protons.

In the present invention, usually, the reaction source is passed into the chamber in a certain proportion, and chemical vapor deposition is carried out to form a phosphorus-doped silicon dioxide inorganic proton conductive film with a mesoporous structure.

In addition, in order to further improve the quality of the proton conductive membrane, it is advisable to use an inert gas such as argon as the shielding gas.

In a preferred example, among the three reaction sources, the oxygen source should be fed first, and then the silicon source and the phosphorus source (the latter two can be fed simultaneously).

In the present invention, chemical vapor deposition is preferably performed on a substrate. In the present invention, applicable substrates are not particularly limited, and representative substrates include (but are not limited to): silicon wafers, glass, plastics, paper, and ceramics. Utilizing these substrates, the phosphorus-doped silicon dioxide inorganic proton conduction film with the substrate can be prepared by the chemical vapor deposition method of the present invention.

In the present invention, conventional chemical vapor deposition equipment can be used, as well as other production equipment used in microelectronics processing.

In a preferred example, in the plasma chemical vapor deposition technique, the reaction pressure is 20-200 Pa; the substrate temperature is room temperature to 100°C.

In another preferred example, in the pressure chemical vapor deposition technique, the reaction pressure is normal pressure; the substrate temperature is 100-400°C.

The inorganic proton conductive membrane produced by the method of the present invention has the characteristics of small mesoporous channels and uniform distribution. In a preferred example, the film has mesoporous channels with a diameter less than 20 nanometers.

The preparation method provided by the invention is easy to operate and is suitable for large-scale continuous production, so it is very suitable for industrialized large-scale production of phosphorus-doped inorganic proton conductive membranes and products processed based on the conductive membranes with the above characteristics.

Inorganic Proton Conducting Membrane

The inorganic proton conductive membrane provided by the invention is a phosphorus-doped _SiO2 thin film with mesoporous pores. Preferably, the inorganic proton-conducting membrane provided by the present invention has the following structure: a membrane skeleton composed of silica particles with a mesoporous structure, and has micro-mesopores that provide transport channels for protons.

The phosphorus used for doping is an aqueous solution of P ₂ O ₅ , preferably phosphoric acid.

In another preferred embodiment, the inorganic proton conductive membrane of the present invention has the following components: phosphorus, silicon and oxygen.

The mesoporous channel diameter of the inorganic proton conductive membrane of the present invention is ≤50nm, and in a preferred example, the pore diameter of the SiO ₂ thin film is 2-50nm. In another preferred example, the average diameter of the micro-mesoporous channels is ≤20nm.

The conductive thin film of the present invention has a thickness of 50 nm-50 μm, preferably 100 nm-20 μm.

The conductive film of the present invention has excellent proton conductivity. In a preferred example, the proton conductivity of the inorganic proton conductive film can reach 80% humidity and room temperature (such as 25°C). More than 10 ^-4 S/cm.

Inorganic Proton Conducting Membrane Products

The inorganic proton conductive film provided by the invention can be used to prepare commonly used products prepared by the conductive film, such as micro-nano components with a matrix. Preferred inorganic proton-conducting membrane products include (but are not limited to): glass-based micro-nano components (such as: transparent oxide thin film transistors, fuel cells), plastic-based micro-nano components (such as: flexible film Transistors, flexible sensors, etc.), paper-based flexible micro-nano components (such as flexible thin film transistors).

The main advantages of the present invention include:

1) The preparation method of the inorganic proton conductive membrane of the present invention is simple, the source of raw materials is abundant, the price is cheap, and the obtained proton conductive membrane has high quality and low resistance.

2) The preparation process of the inorganic proton conductive membrane of the present invention is compatible with the microelectronic processing technology, does not need to change other existing production equipment, has high repeatability and uniformity, and is suitable for large-area continuous production;

3) The inorganic proton conductive membrane of the present invention has excellent performance, so it has strong application potential, and can be widely used in thin film transistors, polymer electrolyte membrane fuel cells, electrochemical sensors, water/steam electrolysis, biological systems and other fields.

Below in conjunction with specific embodiment, further illustrate the present invention. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. For the experimental methods without specific conditions indicated in the following examples, the conventional conditions or the conditions suggested by the manufacturer are usually followed. Percentages and parts are by weight unless otherwise indicated.

general method

Raw materials: silane: 99.9% concentration; phosphine: 99.9% concentration; oxygen: 99.95% concentration; argon: 99.95% concentration, 99.95% nitrogen concentration.

In the chemical vapor deposition system, radio frequency glow discharge is used to generate plasma. In a near-vacuum environment, process parameters such as chamber pressure and substrate temperature are controlled to decompose mixed components such as silicon source, phosphorus source, and oxygen source, and A series of chemical reactions such as adsorption, nucleation, and growth occur on the surface of the substrate to grow phosphorus-doped silica inorganic proton conductive film. In order to improve the conductive quality of the inorganic proton conductive film, the inorganic proton conductive film was placed in perchloric acid Soak in lithium solution for more than half an hour.

Determination of electrical conductivity

Use a semiconductor impedance meter to test the impedance characteristics of the product to obtain the proton resistance; use SEM and other equipment to characterize the thickness of the film, and finally use the formula Calculate the proton conductivity of the thin film,

In the formula: l is the thickness of the film; R is the proton resistance of the film, and A is the area of the film.

Embodiment 1: Preparation of conductive film on glass substrate by plasma chemical vapor deposition

1) Strictly clean the glass substrate. Soak the glass substrate in alcohol and deionized water for 10 minutes; then rinse it repeatedly with deionized water; finally dry it with a nitrogen gun.

2) Simultaneously turn on the plasma chemical vapor deposition equipment and open the chamber. In order to prevent the chamber from contaminating the substrate and the growing proton conductive film, first use a vacuum cleaner to extract the fine particles that may exist in the chamber, and then pass through acetone and alcohol in sequence. Wipe around the chamber repeatedly, and finally put the cleaned substrate into the reaction chamber immediately;

3) Turn on the mechanical pump in turn to pump the reaction chamber to a low vacuum of about 1Pa;

4) Introduce argon gas, the flow rate is 45 sccm (standard-state cubic centimeter per minute, standard-state cubic centimeter per minute), adjust the chamber pressure to 30Pa; turn on the radio frequency power supply, set the radio frequency power to 100W;

5) The oxygen source is introduced with a flow rate of 60 sccm; after the pressure is stabilized, silane and phosphine are introduced with a total flow rate of 10 sccm; finally, the reaction pressure is readjusted to 30 Pa;

6) Control the growth time for 50 minutes to prepare phosphorus-doped silicon dioxide inorganic proton conductive film;

7) In order to prevent excessive silane and phosphine from reacting spontaneously to form silica powder and cause pollution, after the reaction, first stop feeding the mixed gas of silane and phosphine, and wait until the mass flow rate of the mixed gas of silane and phosphine shows 0, then wait 2 minutes, stop feeding oxygen;

8) Turn off the radio frequency after the oxygen is exhausted; stop feeding the argon protective gas;

9) Open all the flapper valves between the molecular pump and the chamber, and pump the vacuum of the chamber below the background vacuum before the experiment;

10) Close the flapper valve between the molecular pump and the chamber, feed high-purity nitrogen gas, open the chamber, take out the sample, and store it, or apply it to micro-nano components based on glass.

Results: The schematic diagram of the structure of the prepared inorganic proton conductive membrane is shown in Figure 1, and the photo of the scanning electron microscope is shown in Figure 2. It can be seen from the figure that the thickness of the proton conductive membrane is about 700nm, and its cross-sectional structure presents a vertical The fringes connected in a similar way are caused by the dissection of the micro-mesoporous channel, indicating that there are micro-mesoporous pores inside the proton conducting membrane, and their diameters are below 20nm.

Embodiment 2: Preparation of conductive film on plastic substrate by plasma chemical vapor deposition

1) Strictly clean the plastic substrate. Soak the plastic substrate in alcohol and deionized water for 10 minutes; then rinse it repeatedly with deionized water; finally dry it with a nitrogen gun.

2) Simultaneously turn on the plasma chemical vapor deposition equipment and open the chamber. In order to prevent the chamber from contaminating the substrate and the growing proton conductive film, first use a vacuum cleaner to extract the fine particles that may exist in the chamber, and then pass through acetone and alcohol in sequence. Wipe around the chamber repeatedly, and finally put the cleaned substrate into the reaction chamber immediately;

3) Turn on the mechanical pump in turn to pump the reaction chamber to a low vacuum of about 1Pa;

4) Introduce argon gas with a flow rate of 60sccm; adjust the chamber pressure to 30Pa, turn on the radio frequency power supply, and set the radio frequency power to 50W;

5) Feed oxygen with a flow rate of 45 sccm; after the pressure stabilizes, feed silane and phosphine with a total flow rate of 7 sccm;

6) Control the growth time for 45 minutes to prepare phosphorus-doped silicon dioxide inorganic proton conductive membrane;

7) In order to prevent the excessive silicon source and oxygen source from spontaneously reacting to form silica powder and cause pollution, after the reaction is completed, first stop feeding the mixed gas of silane and phosphine, and wait until the mass flow rate of the mixed gas of silane and phosphine is displayed as 0 , wait for 2 minutes, stop feeding the oxygen source;

8) Turn off the radio frequency after the oxygen is exhausted; stop feeding the argon protective gas;

9) Open all the flapper valves between the molecular pump and the chamber, and pump the vacuum of the chamber below the background vacuum before the experiment;

10) Close the flapper valve between the molecular pump and the chamber, introduce high-purity nitrogen, open the chamber, take out the sample, and store it; or apply it to flexible micro-nano components based on plastic, such as: flexible film Transistors, flexible sensors, etc.

Embodiment 3: Preparation of conductive film on paper substrate by plasma chemical vapor deposition

1) Using paper as a substrate, use a nitrogen gun to blow off the particles attached to the surface.

2) Simultaneously turn on the plasma chemical vapor deposition equipment and open the chamber. In order to prevent the chamber from contaminating the substrate and the growing proton conductive film, first use a vacuum cleaner to extract the fine particles that may exist in the chamber, and then pass through acetone and alcohol in sequence. Wipe around the chamber repeatedly, and finally put the cleaned substrate into the reaction chamber immediately;

3) Turn on the mechanical pumps in turn to pump the reaction chamber to a low vacuum of about 1Pa.

4) Introduce argon gas with a flow rate of 20sccm, adjust the chamber pressure to 35Pa; turn on the RF power supply, and set the RF power to 50W;

5) Introduce nitrogen to carry deionized water, the flow rate is 40 sccm; after the pressure is stabilized, trichlorosilane and phosphorus oxychloride are introduced, the total flow rate is 5 sccm; finally readjust the reaction pressure to 35 Pa;

6) Control the growth time for 60 minutes to prepare phosphorus-doped silicon dioxide inorganic proton conductive film;

7) After the reaction is over, first stop feeding the mixed gas of trichlorosilane and phosphorus oxychloride, wait for the mass flow rate of the mixed gas of trichlorosilane and phosphorus oxychloride to show 0, wait for 2 minutes, and stop feeding nitrogen to carry Deionized water;

8) Turn off the radio frequency after feeding nitrogen and carrying deionized water; stop feeding argon protective gas;

9) Open all the flapper valves between the molecular pump and the chamber, and pump the vacuum of the chamber below the background vacuum before the experiment;

10) Close the flapper valve between the molecular pump and the chamber, introduce high-purity nitrogen, open the chamber, take out the sample, and store it, or apply it to flexible micro-nano components based on paper, such as: flexible film transistor.

Embodiment 4: Preparation of conductive film on glass substrate by atmospheric pressure chemical vapor deposition

1) Strictly clean the glass substrate. Soak the glass substrate in alcohol and deionized water for 10 minutes; then rinse it repeatedly with deionized water; finally dry it with a nitrogen gun.

2) At the same time, turn on the atmospheric pressure chemical vapor deposition equipment and open the chamber. In order to avoid contamination of the substrate and the growing proton conductive film in the chamber, first use a vacuum cleaner to extract the fine particles that may exist in the chamber, and then pass through acetone and alcohol in sequence. Wipe around the chamber, and finally put the cleaned substrate into the reaction chamber immediately;

3) Turn on the mechanical pumps one by one, turn on the mechanical pumps one by one to pump the reaction chamber to a low vacuum of about 1Pa, set the substrate temperature to 300°C, and preheat the substrate for 5 minutes.

4) Introduce argon gas with a flow rate of 60 sccm; under normal pressure, turn on the radio frequency power supply and set the radio frequency power to 300W;

5) Introduce oxygen with a flow rate of 100 sccm; after waiting for the pressure to stabilize, inject silane and phosphine with a total flow rate of 15 sccm;

6) Control the growth time for 30 minutes to prepare a phosphorus-doped silicon dioxide inorganic proton conductive film that can be used for transparent oxide thin film transistors;

7) In order to prevent excessive silane and oxygen from spontaneously reacting to form silicon dioxide powder and cause pollution, after the reaction is over, first stop feeding the mixed gas of phosphine and silane, and wait for 2 Minutes, stop feeding oxygen;

8) Turn off the radio frequency after the oxygen is exhausted; stop feeding the argon protective gas;

9) Open all the flapper valves between the molecular pump and the chamber, and pump the vacuum of the chamber below the background vacuum before the experiment;

10) Close the slide valve between the molecular pump and the chamber, feed high-purity nitrogen, open the chamber, take out the sample, and store it.

Embodiment 5: Preparation of conductive film on ceramic substrate by plasma chemical vapor deposition

1) Strictly clean the ceramic substrate. Submerge the ceramic substrate in deionized water and ultrasonically clean it for 10 minutes; then rinse it repeatedly with deionized water; finally blow dry it with a nitrogen gun.

2) Simultaneously turn on the plasma chemical vapor deposition equipment and open the chamber. In order to prevent the chamber from contaminating the substrate and the growing proton conductive film, first use a vacuum cleaner to extract the fine particles that may exist in the chamber, and then pass through acetone and alcohol in sequence. Wipe around the chamber repeatedly, and finally put the cleaned substrate into the reaction chamber immediately;

3) Turn on the mechanical pumps one by one to evacuate the low vacuum of the reaction chamber to about 1Pa, set the substrate temperature to 100°C, and preheat the substrate for 5 minutes.

4) Introduce argon gas, the flow rate is 60sccm, adjust the chamber pressure to 200Pa; turn on the radio frequency power supply, set the radio frequency power to 300W;

5) Introduce oxygen with a flow rate of 100 sccm; wait for the pressure to stabilize, then inject silane and phosphine with a total flow rate of 15 sccm; finally readjust the reaction pressure to 200 Pa;

6) Control the growth time for 20 minutes to prepare phosphorus-doped silicon dioxide inorganic proton conductive membranes that can be used in electrolyte membrane fuel cells;

7) In order to prevent excessive silane and oxygen from spontaneously reacting to form silicon dioxide powder and cause pollution, after the reaction is over, first stop feeding the mixed gas of phosphine and silane, and wait for 2 Minutes, stop feeding oxygen;

8) Turn off the radio frequency after the oxygen is exhausted; stop feeding the argon protective gas;

9) Open all the flapper valves between the molecular pump and the chamber, and pump the vacuum of the chamber below the background vacuum before the experiment;

10) Close the slide valve between the molecular pump and the chamber, feed high-purity nitrogen, open the chamber, take out the sample, and store it.

The test results of Examples 2-5 are as follows: the calculated proton conductivity in the above examples is 10 ^-2 S/cm to 10 ^-4 S/cm.

Embodiment 6 conductive film impedance analysis

Wherein the test result of embodiment 1 is as shown in Figure 3, as can be seen from Figure 3, the composition of phosphorus-doped proton conductive membrane has a semicircle and a straight line to form, and according to impedance analysis theory, its impedance value takes arc and The intersection point of the straight line when the imaginary part is 0, 87.3Ω, according to the formula Calculate the proton conductivity of the film to be 10 ^-4 S/cm, where: l is the thickness of the film; R is the proton resistance of the film, and A is the area of the film.

Example 7 Preparation of Inorganic Proton Conducting Membrane Products

1. On the basis of the above-mentioned preparation of the proton-conducting film, the proton-conducting film is prepared as the gate layer of the transistor by using ITO glass as the substrate.

2. Using self-assembly diffraction technology, the growth of the channel, source and drain of the transistor is completed at one time.

3. Using ALD technology, prepare Al ₂ O ₃ as the passivation layer of the transistor.

All documents mentioned in this application are incorporated by reference in this application as if each were individually incorporated by reference. In addition, it should be understood that after reading the above teaching content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Claims (11)

1. A preparation method for an inorganic proton-conducting membrane, characterized in that it comprises the steps of: Leading the reaction source into the reaction chamber and performing chemical vapor deposition to form a phosphorus-doped silicon dioxide inorganic proton conductive film with a mesoporous structure, wherein the reaction source includes a silicon source, a phosphorus source and an oxygen source; And the oxygen source is selected from the group consisting of nitrogen or argon carrying deionized water and/or oxygen, and the deionized water is in a gaseous state; And among the three reaction sources, the oxygen source is fed first, and then the silicon source and the phosphorus source are fed in, wherein the silicon source and the phosphorus source are fed simultaneously. 2. The method according to claim 1, wherein the chemical vapor deposition is selected from the group consisting of plasma chemical vapor deposition and atmospheric pressure chemical vapor deposition. 3. The method according to claim 1, wherein the ratio of the silicon source, phosphorus source and oxygen source satisfies the following relationship: phosphorus source: silicon source = 1:100-20:100; silicon source: oxygen source =1:1~1:6. 4. The method of claim 1, further comprising one or more of the following features: The silicon source is selected from the group consisting of trichlorosilane, silicon tetrachloride, silane, or a combination thereof; The phosphorus source is selected from the group consisting of phosphorus oxychloride and/or phosphine. 5. The method of claim 4, further comprising one or more of the following features: The silicon source is monosilane or disilane; and/or The phosphorus source is PH ₃ . 6. The method according to claim 1, wherein the chemical vapor deposition is deposited on the surface of the substrate, thereby forming an inorganic proton conductive film deposited on the substrate. 7. The method of claim 6, wherein the substrate is selected from the group consisting of glass substrates, plastic substrates, paper substrates, ceramic substrates, or combinations thereof. 8. An inorganic proton-conducting film, characterized in that, said inorganic proton-conducting film is formed by chemical vapor deposition; Wherein, in the chemical vapor deposition, the oxygen source used is selected from the following group: nitrogen or argon carries deionized water and/or oxygen, and the deionized water is gaseous; And among the three reaction sources, the oxygen source is fed first, and then the silicon source and the phosphorus source are fed in, wherein the silicon source and the phosphorus source are fed simultaneously. 9. An inorganic proton-conducting membrane, characterized in that, said inorganic proton-conducting membrane is prepared by the method as claimed in claim 1, and said inorganic proton-conducting membrane is phosphorus-doped mesoporous _SiO2 thin film, and the inorganic proton conductive film has the following conductive properties: when the ambient humidity is 80% and 25°C, its proton conductivity is 1×10 ^-2 S/cm ~ 10 ^-4 S/cm, and at the ambient humidity When the temperature is 85% to 100% and 50°C to 80°C, the proton conductivity is 1×10 ^-2 S/cm to 1×10 ^-4 S/cm. 10. The inorganic proton conductive membrane according to claim 8, characterized in that, said inorganic proton conductive membrane is prepared by the preparation method as claimed in claim 1. 11. A product, characterized in that the product contains the inorganic proton conductive membrane according to claim 8 or 9, or the product is made of the inorganic proton conductive membrane according to claim 8 or 9.