Nbon film, method for producing nbon film, hydrogen generation device, and energy system provided with same

Technical Field

The present invention relates to membrane NbON, NbON film manufacturing method, using the stated NbON film hydrogen generating apparatus, and with the hydrogen generating apparatus of the energy system.

Background Art

In the past, through the are known as optical semiconductor play a role of the light of a semiconductor material for collecting water decomposition of hydrogen and oxygen (for example with reference to Patent document 1). Patent literature 1 in, has the following content, i.e., is disposed in the electrolyte n-type semiconductor electrode and the counter electrode, n-type semiconductor by the irradiating light the surface of the electrode from the surface of the two electrodes gathering hydrogen and oxygen. Specifically, as with the n-type semiconductor electrode TiO₂ the content of the electrode and the like.

However, Patent document 1 disclosed in in the n-type semiconductor electrode, the utilization efficiency of the sunlight is not sufficient. For example TiO₂ electrode because of its band gap in the anatase to 380 nm, therefore can only use about 1% of the sunlight.

In order to solve the problem as stated above, such as the use of a small gap of the optical semiconductor material. For example, in Patent document 2 in, through the use of the proposed Nb₂ O₅ in the high temperature ammonia atmosphere of firing in optical semiconductor NbON the programme. NbON optical semiconductor because pbg small to about 600 nm, thereby improving the utilization efficiency of the sunlight. Furthermore, in Patent document 3 in, can also be used for the photo-decomposition of water, is fixed with a NbON optical semiconductor electrode (electrode catalyst).

Literature of the prior art

Patent literature

Patent literature 1: Japanese opens illustriously especially 51-123779, the

Patent document 2: Japanese opens especially 2002-66333, the

Patent literature 3: Japanese opens especially 2005-161203, the

Content of the invention

The problem to be solved by the invention

However, the optical semiconductor NbON in the past, in order to improve the water decomposition optical semiconductor characteristic gathering hydrogen (quantum efficiency), call for further improvement.

Therefore, the aim of the invention is to, provide a kind of optical semiconductor NbON membraniform, the optical semiconductor NbON compared with the, decomposing water and further improves the optical semiconductor characteristic gathering hydrogen (quantum efficiency).

For a way to solve the problem

The present invention provides a device utilizing light irradiation to generate the photocurrent NbON film.

Effect of the invention

According to the present invention, more simple method can be used to decompose the water, provide enhanced optical semiconductor gathering hydrogen (quantum efficiency) of the characteristic and NbON NbON film.

Description of drawings

Figure 1 is compend diagram of that used for implementing embodiments of the present invention 2 NbON of the manufacturing method of an example of the device.

Figure 2 is diagram of implementation of mode 2 of the method of manufacturing NbON NbON synthesis mechanism.

Figure 3 is compend diagram of that used for implementing embodiments of the present invention 3 NbON film of the manufacturing method of an example of the device.

Figure 4 is plan of note embodiment 3 of the method of manufacturing membrane NbON NbON film synthesis mechanism.

Figure 5 is compend diagram of said embodiment of the invention 4 the composition of the hydrogen generating device.

Figure 6 is compend diagram of said embodiment of the present invention 5 the composition of the hydrogen generating device.

Figure 7 is compend diagram of said embodiment of the present invention 6 of the form of the energy system.

Figure 8 embodiment is 1 used in the raw material for synthesizing NbON TG-DTA (  Analysis   Thermal Thermogravimetry-Differential) data.

Fig. 9 is single-phase powder NbON for comparison 1 XRD of (  diffraction X-ray) XRD data and NbON of analog data.

Fig. 10 is example 1 of the film 1 UV-Vis of (  Spectroscopy   Absorption   Visible Ultraviolet) data.

Figure 11 is a single-phase powder NbON for comparison 1 and example 1 of the film 1 of the, Nb3d of (  Spectroscopy   Photoelectron X-ray) XPS data.

Figure 12 is the implementation of the example 2 membrane 2 UV-Vis of data.

Figure 13 is the implementation of the example 2 membrane 2 Nb3d of the XPS data.

Mode of execution

The use of light irradiation and water decomposition in the technology of gathering hydrogen , made more small light utilizing band gap of the semiconductor material. The inventors in such optical semiconductor material, to the "background technology" in the past recorded in the column of the material to the problems shown below.

For example, in Patent literature 2 and 3 disclose in the case of NbON, in Patent literature 2 and 3 in the synthetic method disclosed in, there is the problem of easy NbON reduction. Therefore, these synthetic method, in addition to other than the generation of the NbON, Nb also vice-production of the stock also of NbN, NbON therefore unable to obtain a single-phase or close to the single-phase material. Therefore, on the use of the Patent literature 2 and 3 is disclosed in the method for synthesizing the purposes NbON, in order to utilize the water decomposition gathering hydrogen light irradiation, it is difficult to play the full NbON optical semiconductor characteristic (high quantum efficiency). By this, from the need of NbN NbON for by-product in the acid dissolves and removed.

Furthermore, even if the utilization of Patent literature 2 and 3 the synthesis of the method disclosed in the in the side products such as NbN NbON for removing dissolved and the acid, and the like, the obtained single-phase or close to the single-phase NbON material, is unable to make use of the same method to obtain a single-phase or close to the single-phase NbON film. For example, even when a single-phase or close to the single-phase NbON material, film-forming method by using the ordinary deposit, because in the film forming process is generated from the new NbON impurity such as NbN, therefore, unable to make single-phase or close to the single-phase NbON film. Specifically, the inventors NbON single-phase or close to the single-phase of the material as the sputtering target, a film using a sputtering method to manufacture. However, as the sputtering target in the sputtering, the energy of the given NbON NbON decomposition, produce by-product from this, could not be single-phase or close to the single-phase NbON film. Furthermore, as other specific example, the inventor, powdery single-phase or close to the single-phase NbON material in the manufacture of the suspension, the suspension formation of a film by the blowing of the base plate, the film firing. However, in sintering in the oxidized NbON, NbON film cannot be obtained.

Therefore, the inventors conducted an in-depth research, found can be manufactured by the reduction of the impurity such as the method of the membrane NbON, the use of light irradiation to enhance the water decomposition optical semiconductor gathering hydrogen (quantum efficiency) of the characteristic, NbON film and method of manufacturing the same. Furthermore, the inventors also provides use of the such NbON film of hydrogen generation equipment and energy system.

Of the present invention provide for a 1st using light irradiation to generate the photocurrent NbON film. Moreover, in this specification, the so-called "use of light irradiation to generate photocurrent" means, "use of irradiation of sunlight, to 0.1mA/cm² photocurrent density of the photocurrent produced more than".

1st NbON film due to the reduction of the mixing of the impurities such as by-products, thus can play a used for utilizing the light irradiation of the water decomposition gathering hydrogen , the full NbON optical semiconductor characteristic (high quantum efficiency).

2nd mode of the present invention is provided in the manner as follows by the 1st NbON film, in other words, is single-phase membrane. According to the 2nd mode, can offer single-phase membrane NbON does not exist in the past. Therefore, the film can be more reliably NbON play used for utilizing the light irradiation of the water decomposition gathering hydrogen , the full NbON optical semiconductor characteristic (high quantum efficiency).

Of the present invention that the 3rd 2nd 1st mode or in the mode of membrane NbON is provided, in other words, through the gasification of the R¹ N=Nb (NR² R³)₃ (wherein R¹, R² and R³ are respectively independent hydrocarbyl), and is selected from the group consisting of oxygen and water vapor in at least one of the contact is formed the heated base plate. Film NbON so formed reducing the impurities such as by-products. Therefore, the film can be more reliably NbON play used for utilizing the light irradiation of the water decomposition gathering hydrogen , the full NbON optical semiconductor characteristic (high quantum efficiency).

4th of the present invention is provided in the manner as follows by the 3rd NbON film, in other words, R¹for uncle butyl (-C (CH₃)₃), R² and R³ is their respective independent linear alkyl (n-C_n H_2n+1 (n=1 integer of the above)). The crystallinity of the film has excellent NbON, in addition, can realize more excellent optical semiconductor characteristic.

Of the present invention provide for a 5th NbON film manufacturing method, comprising:

(I) the R¹ N=Nb (NR² R³)₃ (wherein R¹, R² and R³ is independently hydrocarbyl) gasification process;

(II) the gasification of the stated R¹ N=Nb (NR² R³)₃, in oxygen and water vapor and is selected from at least one side of the contact heating process of the substrate.

Method of manufacturing according to the 5th mode, than in the past can be utilized to reduce the number of processes of the method, the synthesis inhibition of the incorporation of impurities such as by-products NbON film. Therefore, according to this manufacturing method, can be used to provide more simple and convenient method and water decomposition gathering hydrogen the optical semiconductor characteristic NbON (quantum efficiency) of the film.

6th of the present invention is in the 5th mode, offering the following method of manufacturing the membrane NbON, in other words, in the process in (II), heating the substrate to the R¹ N=Nb (NR² R³)₃ and is more than the boiling point of the temperature of the below the decomposition temperatures. In such a temperature range by the heating of the base plate, can be the inhibition of the production of the by-product of synthetic NbON at the same time. Therefore, it is easy to synthesize the NbON single-phase membrane. In this way, according to this manufacturing method, the implementation can be used to process and remove the impurities single-phase membrane NbON.

7th of this invention in the manner that in 5th or 6th manner, offering the following method of manufacturing the membrane NbON, in other words, R¹for uncle butyl (-C (CH₃)₃), R² and R³ is their respective independent linear alkyl (n-C_n H_2n+1 (n=1 integer of the above)). R¹for uncle butyl (-C (CH₃)₃), R² and R³ is their respective independent linear alkyl (n-C_n H_2n+1 (n=1 or more an integer)) material is easy to and gasification high heat resistance, therefore can realize more high-temperature synthesis. As a result, to the ease of synthesis of with excellent crystallinity, in addition with more excellent optical semiconductor characteristic single-phase NbON film.

8th of the present invention provide for a hydrogen generating apparatus, which has:

Containing the electric conductor, and is disposed on the electric conductor of the 1st -4th of any way of the membrane NbON optical semiconductor electrode;

Electrically connected with the electric conductor to the electrode;

With the stated NbON film and the pair of electrode contact with the surface of the electrolyte containing water;

Hospices optical semiconductor electrode, wherein the electrode and the electrolyte container,

NbON film by the irradiation of the light to produce hydrogen.

8th manner using the hydrogen generating apparatus has the advantages of excellent light semiconductor characteristics of the 1st -4th of any way NbON film. Therefore, because of the 8th hydrogen generating apparatus can also utilize more long range of wavelengths of light, thereby improving the utilization efficiency of the sunlight.

9th of this invention to provide a energy system, comprising:

8th form of hydrogen generating equipment;

Using 1st piping and the hydrogen generating device is connected with the, stored in the hydrogen generating apparatus to produce the of the bag hydrogen hydrogen ; and

Using said hydrogen piping and 2nd is connected with the bag that is, the hydrogen is in storage bag hydrogen transformation for power and heat of the fuel cell.

9th manner with the energy system using the excellent light semiconductor characteristics of the 1st -4th of any way NbON film hydrogen generating apparatus. Therefore, the energy system of the 9th can also be utilized for a longer range of wavelengths of light, thereby improving the utilization efficiency of the sunlight.

The following, at the same time in the light of the attached drawing, the embodiment of this invention to carry out a detailed description. Moreover, the following embodiment is an example, the invention is not limited to the following embodiments. Furthermore, the following embodiment, the same components use the same symbol, sometimes repeated description is omitted.

(Embodiment 1)

NbON film of the present invention a description of the embodiment of the. NbON film of this embodiment is to utilize the light irradiation to generate the photocurrent NbON film. As mentioned above, so-called photocurrent generated by light irradiation, the use of irradiation of sunlight is to 0.1mA/cm² produce photocurrent density of the photocurrent of the above.

NbON film of this embodiment is a film of impurities, that is, of the proximity of the NbON single-phase film or NbON single-phase membrane , thus can play a used for utilizing the light irradiation of the water decomposition gathering hydrogen , the full NbON optical semiconductor characteristic (high quantum efficiency). In order to more reliably achieving a high quantum efficiency, single-phase membrane NbON film is the best.

Here, the so-called in this specification " single-phase membrane NbON film to", refer to the films actually NbON NbON compound phase, or a compound which NbON. The so-called "NbON film consisting substantially of a compound phase NbON", refer to the contained in the membrane NbON NbON compound phase to the compound phase other than 10 atomic % or less, preferably 5 atom % or less, more preferably 3 atomic % the following. However, even in this embodiment the membrane NbON single-phase membrane of the cases, there will also be in the NbON film to doping level in the film-forming of the film containing NbON the initial raw materials used in the alkyl group contained in the element caused by the situation of C, is, however, no particular problem. Moreover, the level of the said doped here, single phase, is that the concentration of the elements of the element other than to 1 atomic % the following. And, whether used for confirming single-phase membrane NbON film is for example a simple way: of the XPS Nd3d in the spectrum, the NbON a single phase can be obtained as the spectrum of a single-phase film. However, even in this case, although the compound is Nb NbON single-phase, also can be detected in the above-mentioned range of from the initial raw materials C.

NbON film of this embodiment can also be, for example, through the gasification of the R¹ N=Nb (NR² R³)₃ (wherein R¹, R² and R³ is independently hydrocarbyl), and is selected from the group consisting of oxygen and water vapor in the at least one contact of the heated substrate to form a film. Under the circumstances, can also be a R¹for uncle butyl (-C (CH₃)₃), R² and R³ to their respective independent linear alkyl (n-C_n H_2n+1 (n=1 integer of the above)).

NbON film of this embodiment there is no particular limitation to the method of manufacturing, however, if the use of the latter manufacturing method can be simply and conveniently.

(Embodiment 2)

NbON of the present invention the mode of execution of the method of manufacturing is described below.

The embodiment of the manufacturing method comprises NbON R¹ N=Nb (NR² R³)₃ (wherein R¹, R² and R³ is independently hydrocarbyl) selected from oxygen and water in the at least one side of the heating of the process atmosphere. As shown in Figure 1 for example can use the device 100 to implement.

Device 100 is provided with: a tubular furnace 111, through tubular furnace 111 the inner tube 112, and is arranged on the tube 112 of the inside of the boat 113. Through to be received in the tube 112 of the boat in 113 of raw materials in (R¹ N=Nb (NR² R³)₃) 101 in the flows in the tube 112 of the oxygen and/or water to be in the inactive gas flow 102 during heating, can synthesize the NbON (NbON powder). According to this method, the can be synthesized by the decrease of the content of such as NbN NbON, NbON single-phase material can also be obtained.

In this embodiment, the heating is used as a raw material R¹ N=Nb (NR² R³)₃ temperature is preferably the R¹ N=Nb (NR² R³)₃ and is more than the boiling point of the following decomposition temperature. If the raw material is heated in this temperature range, it may be the inhibition of the production of the by-product of synthetic NbON at the same time, the single-phase material is easy to synthesize the NbON (single-phase NbON powder). Therefore, implementation of the removal of impurities can be used to obtain NbON the process of the single-phase material. Moreover, the decomposition temperature of the material using the inactive gas flow measuring TG-DTA, sealed in the container to determine such as DSC.

Using as starting material the R¹ N=Nb (NR² R³)₃ in, R¹, R² and R³ is independently hydrocarbyl. Therefore, R¹ N=Nb (NR² R³)₃ in, self-condensation reaction is suppressed. However, as the R¹, from turns into liquid and is easy to dispose of, is easy to gasification, is easy to occur, and the viewpoint of improving the decomposition temperature, is excellent branched chain alkyl radical. The special optimal uncle butyl (tert-butyl yl (-C (CH₃)₃)). Furthermore, for R² and R³, from the considerations of the decomposition temperature, is excellent straight-chain hydrocarbon group, preferably like-CH₃ and C₂ H₅ such a straight-chain alkyl (n-C_n H_2n+1 (n=1 integer of the above)). But, on the contrary, if the carbon chain is too long the decomposition temperature is high, therefore the carbon number is preferably 3 (n≤ 3) below. R¹for uncle butyl (-C (CH₃)₃), R² and R³ to their respective independent linear alkyl (n-C_n H_2n+1 (n=1 integer of the above)) the material is easy to gasification, high heat resistance, therefore can realize more high-temperature synthesis. As a result, to the ease of synthesis of with excellent crystallinity, in addition also has more excellent optical semiconductor characteristic, single-phase NbON. However, because in this embodiment the starting material for the high reactivity of oxygen and water , therefore the starting material containing oxygen in the water content of the starting material as a whole is preferably 1 molar PPM the following, more preferably 0.1 mol PPM the following.

Here, the so-called in this specification "single-phase NbON", refers to the material substantially composed of a compound phase NbON, or this substance comprises NbON compound phase. The so-called "the material substantially composed of a compound phase NbON", means that the substance is contained in the outside of the by-product of NbON compound phase is 10 atomic % or less, preferably 5 atom % or less, more preferably 3 atomic % the following. However, even in this embodiment the substance is obtained in the case of single-phase NbON, there will also be to doping level from the initial raw materials containing alkyl group contained in the element caused by the situation of C, is, however, no particular problem. But, here the so-called doping level of the said, means other than a single-phase of the concentration of the elements of the element is 1 atomic % the following. For recognizes that the utilization of this embodiment of the method for manufacturing of whether NbON a simple way to the single-phase, such as: the XPS Nd3d in the spectrum, the NbON a single phase can be obtained as the spectrum of a single-phase. However, even in this case, although the single-phase NbON Nb compound is, however, also can be detected in the above-mentioned range of from the initial raw materials C.

In addition to the use of the inactive gas is called He of a rare gas, Ne, Ar, other than such as Kr and Xe, also can be nitrogen and the like. Wherein the content of oxygen and water is preferably small gas. Therefore, the inactive gas containing oxygen in the water content is preferably 10 the following PPM volume, more preferably at least 1 volume PPM the following.

The use of tubular furnace 111 of the tube 112 and boat 113 as long as it is able to withstand the temperature and can be of the use environment. However, because the add oxygen and/or water, so the their desorption of quartz attaches few is excellent.

Next, in the with reference to Figure 2 at the same time, the manufacturing method of this embodiment of the mechanism a description of the synthesis of NbON. And, here, in order to will R¹for uncle butyl, R² to and methyl R³ is an ethyl, tert-butyl imino-tri (b yl methyl amino) niobium (Tertialy   Buthylimino   Tris (Ethyl   Methylamino) Niobium (tBuN=Nb (NMeEt)₃)) used for raw materials 101 in the example of a description of the situation. It that, through the raw material (R¹ N=Nb (NR² R³)₃) 101 addition oxygen (O₂) or water (H₂ O) of compounds as initiator, will R¹ N=Nb (NR² R³)₃ addition polymerization. Furthermore, NR² R³ oxygen or water reaction, followed by carrying out condensation polymerization, thereby obtaining powder NbON. Manufacturing method of this embodiment because the course with this kind of reaction, and the therefore Nb₂ O₅ part of the ammonia for compared with the nitride, very little generation of by-products.

According to the manufacturing method of this embodiment, can synthesize very little mixing of the-products, etc., NbON of the by-product is mixed in or not. Therefore, can also be such as not to implement the process of removing the by-product, can also be utilized therefore 1 procedures such a simple method of producing single-phase NbON. As a result, can be simple and low-cost manufacturing and water decomposition gathering hydrogen the optical semiconductor characteristic NbON of (quantum efficiency).

(Embodiment 3)

NbON film of the present invention the mode of execution of the method of manufacturing is described below.

Manufacturing method of this embodiment comprises:

(I) the R¹ N=Nb (NR² R³)₃ (wherein R¹, R² and R³ is independently hydrocarbyl) gasification process;

(II) the gasification of the stated R¹ N=Nb (NR² R³)₃, in oxygen and water vapor and is selected from at least one side of the contact heating process of the substrate. These processes can be used, for example, as shown in Figure 3 the MOCVD (  Deposition   Organic   Vapor   Chemical Metal) device 300 to implement. According to this method, can synthesize the reduced content of impurities such as NbN NbON film, also NbON single-phase membrane can be obtained. Therefore, according to this method, can be made of the embodiment 1 by NbON in the film. Furthermore, according to this method, can be produced on the substrate by the immobilized chemical bond NbON film. For example, in Patent literature 3, as recorded in the electrode catalyst through NbON powder is fixed on the electrode is formed under the condition of NbON film, because the electrode NbON powder is fixed on the contact degree is not full, it is very difficult to obtain the required optical semiconductor characteristic (high quantum efficiency). Different, use of this embodiment is obtained by the method of film because the base plate and NbON NbON the engagement state of a good film, therefore the excellent NbON can play the optical semiconductor characteristic.

In the process (II), preferably the substrate is used as a raw material of heating to R¹ N=Nb (NR² R³)₃ and is more than the boiling point of the temperature of the below the decomposition temperatures. In this temperature range by the heating of the substrate, can be the inhibition of the production of the by-product of synthetic NbON at the same time. Therefore, easy to synthesize the NbON single-phase membrane. In this way, in the past can be obtained by single-phase membrane NbON cannot be obtained. Process (I) in the gasification of the raw material in the raw material is preferably carried out below the decomposition temperature.

For use as a starting raw material R¹ N=Nb (NR² R³)₃, such as embodiment 2 shown in the description, the detailed description is omitted here.

MOCVD device 300 with gasifier 311, supply piping 312, reaction chamber 313, spray head 314, base and 315. Gasifier 311 the raw material is gasified. Reaction chamber 313 is supplied by gasifier 311 gasification of the raw material gas, is used for the treated side of the base plate of the container long crystal. Supply piping 312 from the gasifier 311 to the reaction chamber 313 gas such as the raw material gas is supplied. Spray head 314 and the supply pipe 312 is connected to the end of the reaction chamber 313 internal, used for crystal growth substrate injection raw material gas and the reaction gas and the like. The base 315 support used for crystal growth substrate, the substrate heating.

The use of MOCVD device 300, included in the gasifier to 311 are heated (preferably in the decomposition temperature following heating) and gasification of the raw materials (R¹ N=Nb (NR² R³)₃) 301 inactive gas 302 in, selected from oxygen and water vapor is mixed in at least one side of reaction gas 303. The mixed gas from the spray head 314 to base 315 of the heated base plate 321 injection. At this moment the base plate 321 of the heating temperature as mentioned above, is preferably raw materials 301 and is more than the boiling point of the scope of the below the decomposition temperatures. In this way, can be on the base plate 321 of the crystal precipitation NbON, NbON film is formed. Moreover, the inactive gas 302 with the specific examples of the embodiment of 2 the inactive gas used in the same.

MOCVD device 300 is preferably the pipe wall of the desorption shui Jiyangattaches few of stainless steel. Furthermore, in order to prevent the pipe wall R¹ N=Nb (NR² R³)₃ attachment, can be also R¹ N=Nb (NR² R³)₃ and the organic solvent of the gasification solution. Under the circumstances, as an organic solvent, can be is dissolved R¹ N=Nb (NR² R³)₃, and gasification characteristic and R₁ N=Nb (NR₂ R₃)₃ similar combination of the non-aqueous solvent. For example, ethyl cyclohexane is excellent.

The following, in reference to fig. 4 at the same time, the manufacturing method of this embodiment of the mechanism NbON a description of the synthesis of the film. And, here, in order to will R¹for uncle butyl, R² to and methyl R³ is an ethyl, tert-butyl imino-tri (b yl methyl amino) niobium (Tertialy   Buthylimino   Tris (Ethyl   Methylamino) Niobium (tBuN=Nb (NMeEt)₃)) used for raw materials 301 in the example of a description of the situation. It that, the raw materials through the (R¹ N=Nb (NR² R³)₃) 301 attached to the base plate 321 of the hydroxyl groups on the surface of a the compound generated of initiator, R¹ N=Nb (NR² R³)₃ addition polymerization. Furthermore, NR² R³ oxygen or water reaction, followed by carrying out condensation polymerization, thus NbON film can be obtained. Manufacturing method of this embodiment because the course with this kind of reaction, and the therefore Nb₂ O₅ part of the ammonia for compared with the nitride, very little generation of by-products.

According to the manufacturing method of this embodiment, can synthesize very little mixing of the-products, etc., or not mixins of the by-product film NbON. Therefore, can also be such as not to implement the process of removing the by-product, thus also can utilize the simple method of producing single-phase NbON film. As a result, can be simply and low-cost manufacturing and water decomposition gathering hydrogen the optical semiconductor characteristic NbON (quantum efficiency) of the film. And, under the condition of the film, even if the impurity such as to implement the process of removing the by-product, it is difficult to in addition the removal of film containing by-product. Therefore, even by using the ordinary manufacturing method for forming the film containing NbON, removal of impurities in the film the process of implementation, is also very difficult to obtain can utilize light irradiation to generate the photocurrent, the by-product with little or no mixing of the by-product film NbON.

(Embodiment 4)

In the with reference to Figure 5 at the same time, the hydrogen generating apparatus of this invention the following is a description of the embodiment of the.

The embodiment of a hydrogen generating apparatus 500 with: a suspended with embodiment 2 in the method for manufacturing of the note NbON electrolyte including water of the material 510, and containing electrolyte 510 container 511. The hydrogen generating apparatus 500 through the electrolyte 510 irradiation light to decompose the water, produce hydrogen.

Container 511 at least a portion of the (here is light incident part 512) in order to make such as sunlight to reach container 511 internal, the material of the light such as sunlight. Container 511 also has the advantages of: the container for the 511 of the internally generated hydrogen and oxygen exhaust opening 514, and is used for supplying to the inside of the water for decomposing the supply opening 513. Hydrogen generating apparatus 500 also has the hydrogen separation membrane 515, oxygen exhaust port 516 and hydrogen exhaust outlet 517. Hydrogen separation membrane 515 from the outlet 514 separating hydrogen in the gas discharged. The separated hydrogen by hydrogen exhaust outlet 517 discharge. The oxygen remaining after hydrogen exhaust outlet 516 is discharged.

Next, using fig. 5, in the embodiment of a hydrogen generating apparatus 500 by the action of.

From the hydrogen generating apparatus 500 container 511 the light incident part 512, to the contained in container 511 NbON suspended in a single-phase material of electrolyte including water 510 irradiated sunlight. Under the circumstances, in the electrolyte 510 NbON material in the, produce the electron in the conduction band, the cavity of a valence band. By means of the hole produced at this moment, by using the following equation (1) decomposition of the water, to generate oxygen. On the other hand, electronic use of the following equation (2) to produce hydrogen.

4h⁺ + 2H₂ O <AOX1AAO >O₂ <AOX18AO >+ 4H⁺     (1)

4e^- + 4H⁺ <AOX1AAO >2H₂ <AOX18AO >  (2)

The generated hydrogen and oxygen from the air exhaust port 514 the hydrogen separation membrane in 515 separation, from oxygen air vent 516 discharges the oxygen , hydrogen exhaust outlet 517 discharge. Furthermore, in order to supplement part of the decomposition of the water, from the supply port 513 to container 511 supply the water.

In this embodiment of the optical semiconductor material as NbON with excellent properties, therefore the cavity and the electronic composite probability is low. Therefore, according to this embodiment of a hydrogen generating apparatus 500 by the irradiation of light can be improved by the quantum efficiency of the hydrogen generation reaction. Furthermore, because of the use in this embodiment the band gap of the material NbON small, so to will also be in response to the visible light of the sunlight. As a result, the embodiment of a hydrogen generating apparatus 500 of the use of in the past compared with the case of the optical semiconductor material, can produce more hydrogen.

(Embodiment 5)

In the with reference to Figure 6 at the same time of, in the invention of the embodiment of the hydrogen generation equipment are described below.

The embodiment of a hydrogen generating apparatus 600 with: with embodiment 1 of the described membrane NbON 622 optical semiconductor electrode 620, as with optical semiconductor electrode 620 consisting of a pair of the electrode of the electrode 630, the electrolyte containing water 640, and containing optical semiconductor electrode 620, the electrode 630 and electrolyte 640 container 610.

Optical semiconductor electrode 620 by conductive substrate (electric conductor) 621, and is formed on the conductive substrate 621 NbON film on 622 form.

In the container 610 inner, optical semiconductor electrode 620 NbON film of 622 and the counter electrode 630 is in order to make its surface and the electrolyte 640 contact way to configure. Container 610 the and is disposed on the container 610 of the light in the semiconductor electrode 620 NbON film of 622 part of the face-to-face (hereinafter referred to as light incident part 611) is composed of a material through which light such as sunlight.

Optical semiconductor electrode 620 of the conductive substrate 621 and the electrode 630 by wire 650 is electrically connected. And, here refer to the so-called pair of electrodes with the optical semiconductor electrode via the electrolyte between the electronic transfer to the electrode. Therefore, in this embodiment the electrode 630 as long as the formed optical semiconductor electrode 620 of the conductive substrate 621 can be electrically connected, with the optical semiconductor electrode 620 is no special the position of the defined relationship. Moreover, because this embodiment the NbON film 622 is n-type, so that the electrode 630 from optical semiconductor electrode 620 via the electrolyte in 640 to receive electronic electrode.

As shown in Figure 6, the embodiment of a hydrogen generating apparatus 600 also has a diaphragm 606. Container 610 inside of the diaphragm 606 is configured to separate the optical semiconductor electrode 620 area of one side of, and configuration to the electrode 630 of the region 2 region. Electrolyte 640 is accommodated in the region of the two sides. In the container 610 in, will possess, use for the configuration arimitsu semiconductor electrode 620 generated in the region of of the oxygen dischargesoxygen air vent 613, and is used for the configuration with the electrode 630 produced in the region of of the hydrogen dischargeshydrogen air vent 614. Container 610 also has used for the container 610 inside of the water supply opening of the water supply 612.

Next, using fig. 6, in the embodiment of a hydrogen generating apparatus 600 by the action of.

When the hydrogen generating apparatus 600 container 610 the light incident part 611 to is disposed on the container 610 of the light in the semiconductor electrode 620 NbON film of 622 when the irradiating sunlight, in NbON film 622 of the part of the light to be irradiated, to produce the electron in the conduction band, in producing a hole in the valence band. Because NbON film 622 is n-type semiconductor, therefore NbON film 622 than a surface potential of NbON film 622 of the internal electric potential high. Therefore, along the hole produced at this moment the valence band to the band edge NbON film 622 of the mobile surface. In this way, the membrane NbON 622 surface, will utilize the above-mentioned equation (1) decomposition of the water, to generate oxygen. On the other hand, electronic along from the band edge of the valence band NbON film 622 via NbON the area near the surface of the single-phase film the internal mobile to the conductive substrate 621. Mobile to the conductive substrate 621 electronic via wire 650 to the conductive substrate 621 is electrically connected to the electrode 630 side. In this way, will be on the electrode 630 surface, utilizing the above-mentioned reaction formula (2) to produce hydrogen.

Thereafter, for the generated hydrogen and oxygen, are respectively of oxygen exhaust port 613 discharges the oxygen , hydrogen exhaust port 614 discharge. Furthermore, in order to complement the part of the decomposition of the water, from the supply port 612 to the container 610 supply the water.

Used in this embodiment as the NbON film the characteristics of the optical semiconductor has excellent, therefore the cavity and the electronic composite probability is low. Furthermore, the embodiment of a hydrogen generating apparatus 600 is NbON optical semiconductor play a role in the film used for the electrode, the so-called photoelectric chemical battery. Therefore, according to the hydrogen generating apparatus 600, because the hole and the electron is effective charge separation, caused by the irradiation of light by the reaction of hydrogen generation the quantum efficiency is improved. Furthermore, because the band gap of the single-phase material NbON small, so to will also be in response to the visible light of the sunlight. As a result, the embodiment of a hydrogen generating apparatus 600 with the use of in the past compared with the optical semiconductor material, can produce more hydrogen. Furthermore, according to the hydrogen generating apparatus 600, the separation of the hydrogen and oxygen can be produced, the separation and recovery of hydrogen and oxygen is very easy.

The conductive substrate 621 is not of the part of film NbON 622, for example, the part preferably made of resin or the like covering the insulator. If so provided, can inhibit optical semiconductor electrode 620 is a conductive substrate in 621 in the electrolyte of part 640 is dissolved in.

As the pair of electrodes, it is preferable to use excess voltage small material. For example, as a pair of electrodes by using Pt, Au, Ag, Fe, Ni and other metal catalyst, active will be improved, is thus preferred. Electrolyte 640 as long as they are water-containing solution which can be. Containing water of the electrolyte can be an acidic, can also be alkaline. In the optical semiconductor electrode 620 and the electrode 630 is disposed between the case of the solid electrolyte, the light may also be semiconductor electrode 620 NbON film of 622 and the surface of the electrode 630 contact with the surface of electrolyte 640 as a pure water of the water for electrolysis.

(Embodiment 6)

In the light of the diagram 7 at the same time, the embodiment of the invention 5 a of the explanation of the energy system. Figure 7 is compend diagram of said of this embodiment form of the energy system.

As shown in Figure 7, the energy system of the embodiment 700 have: hydrogen generating equipment 710, hydrogen in the bag 720, fuel cell 730, and 740.

Hydrogen generating equipment 710 is embodiment 4 of the hydrogen generating apparatus 500 or embodiment 5 hydrogen generating apparatus 600, its specific form are respectively as shown in Figure 5 and Figure 6 as shown in. Therefore, detailed description is omitted here.

hydrogen tank 720 using 1st pipe 751 and hydrogen generating equipment 710 is connected. As the hydrogen in the bag 720, can, for example, by the compression in the hydrogen generating equipment 710 hydrogen is generated in the compressor, by utilizing the heat of the compressor and a high-pressure hydrogen is compressed a hydrogen cylinder.

Fuel cell 730 with power generating portion 731, and used for controlling the power generation section 731 of the fuel cell control part 732. Fuel cell 730 using 2nd piping 752 capacity bag 720 is connected. In 2nd piping 752 in, is provided with a cut off valve 753. As fuel cell 730, for example, can use the high molecular solid electrolyte type fuel cell.

Battery 740 using the positive pole and negative pole of the electrical wiring 1st 754 and 2nd wiring 755 of the fuel battery 730 power of 731 is electrically connected with the positive pole and negative pole. In the storage battery 740 in, is used for measuring battery 740 after the residual capacity of photo 756. As accumulator 740, lithium-ion battery for example can be used.

The following, for the energy system of the embodiment 700 action, in order to be regarded as the hydrogen generating equipment 710 using the embodiment 5 of the hydrogen generating apparatus 600 in the case of the example, also with reference to Figure 6 of that at the same time.

When the through the hydrogen generating apparatus 600 the light incident part 611 to is disposed on the container 610 of the light in the semiconductor electrode 620 NbON film of 622 the surface of the irradiated sunlight, will in NbON film 622 generate electron and hole. The hole produced at this moment to NbON film 622 to the surface side of the mobile. In this way, the membrane NbON 622 surface, will utilize the above-mentioned equation (1) decomposition of the water, to generate oxygen.

On the other hand, electronic along NbON film 622 and the conductive substrate 621 of the conduction band in the interface of the bending of the band edge, is moved to the conductive substrate 621. Mobile to the conductive substrate 621 electronic via wire 650 to the electrode 630 side. In this way, will be on the electrode 630 surface, utilizing the above-mentioned reaction formula (2) to produce hydrogen. Such as embodiment 5 shown in the description, according to the hydrogen generating apparatus 600, caused by the irradiation of light by the reaction of hydrogen generation the quantum efficiency is improved.

The generated oxygen from oxygen exhaust port 613 to the hydrogen generating apparatus 600 is discharged outside. On the other hand, the generated hydrogen by way ofhydrogen air vent 614 and 1st pipe 751 to hydrogen the bag 720 supply the.

In the fuel cell 730 when power generation in, from the fuel cell control part 732 of the signal to turn on the stop valve 753, storage in hydrogen tank 720 hydrogen by 2nd piping in 752 to the fuel battery 730 power of 731 supply.

In the fuel cell 730 power of 731 via electrically generated in the 1st wiring 754 and 2nd wiring 755 is accumulated in a battery 740 inner. Accumulated in the storage battery 740 by the 3rd wiring 757 and 4th wiring 758 provided to the family, enterprises.

According to the hydrogen generating apparatus 600, by the irradiation of light can be improved by the quantum efficiency of the hydrogen generation reaction. Therefore, with this kind of hydrogen generation equipment according to the 600 energy system 700, can effectively supply electric power.

Moreover, in this embodiment, the given embodiment of the 5 the hydrogen generating apparatus in 600 examples of the energy system. However, in embodiment 4 the hydrogen generating apparatus in 500 cases, also has the same effect can be obtained of the energy system.

Embodiment

The following, an embodiment of the present invention to carry out a detailed description.

(Embodiment 1)

<NbON 膜的合成 >

As raw materials (R¹ N=Nb (NR² R³)₃), using uncle butyl imino-tri (b yl methyl amino) niobium (Tertialy   Buthylimino   Tris (Ethyl   Methylamino) Niobium ((CH₃)₃ CN=Nb (N (CH₃) C₂ H₅)₃)). The raw materials in the gas stream in Ar TG-DTA data representation in Figure 8 in. Material is about the boiling point of the 181 [...]. Furthermore, residue of the raw material, the raw material of the film is considered to be about the decomposition temperature of the 303 [...].

Furthermore, using the picture 3 is shown in the MOCVD device 300, to synthetic single-phase membrane NbON. In a gasifier 311 inner, will 3.38 × 10^-5 Pa · m³/s (0.2sccm) raw material 301 ethyl cyclohexane solution in 150 the gasified under [...]. As the inactive gas, the use of nitrogen 302. To include raw material gas (gasification of the raw material 301) and nitrogen 302 the, 1.69 × 10^-1 Pa · m³/s (1000sccm) in the mixed gas, mixed 1.69 × 10^-4 Pa · m³/s (1sccm) oxygen 303. The resulting mixed gas from the spray head 314 to base 315 is heated to 300 the substrate [...] 321 (ITO film (film thickness 150 nm)/ glass substrate) injection 6 hours, to obtain film thickness of 160 nm film 1.

< 参照用的 NbON 粉末的合成 >

Graphics 1 the device is shown, with reference to the synthesis of the powder NbON. The tubular furnace 111 inner diameter of 25 mm of quartz pipe 112 of the quartz boat 113 in, substituted R¹ N=Nb (NR² R³)₃, the 2g the Nb₂ O₅ as a raw material 101 is placed. The 1.69 × 10^-1 Pa · m³/s (1000sccm) the NH₃ airflow in the 650 [...] lower heating 4 hours. In from the obtained material, using 1N NbN as sulfuric acid is dissolved impurities. In this way, is powder 1. Figure 9 in, said powder 1 XRD data of the (upper) and NbON XRD of analog data (the lower section). Comparing these XRD data, confirming the results of powder 1 is substantially NbON single-phase powder.

<NbON 单相膜的鉴定 >

Figure 10 in, said film 1 of spectral UV-Vis. It that film 1 is 600 nm. This with various literature reported NbON almost the same of the band. Figure 11 in, said film 1 NbON single-phase material and a powder of urination 1 Nb3d of the XPS spectrum. The two can be known almost unanimously. According to this result, it is possible to confirm, film 1 is roughly single-phase membrane NbON.

Moreover, in this embodiment, synthetic single-phase membrane NbON oxygen flow for 1.69 × 10^-4 Pa · m³/s (1sccm), as (inactive carrier gas) relative to the nitrogen gas concentration is 0.1%. However, the oxygen concentration 0.01-1% range, synthesis of single-phase membrane NbON can be confirmed.

(Embodiment 2)

In addition to the base 315 temperature from 300 the change to [...] the 350 [...] other than this point, with the embodiment 1 the same method of NbON film. Moreover, the resulting NbON film (film 2) the film thickness of 800 nm.

Figure 12 in, said film 2 UV-Vis of the spectrum. In all wavelength range the absorption can be seen in, do not to the band gap.

Figure 13 in, said film 2 Nb3d of the XPS spectrum. With the membrane of 1 (NbON) 206.8V different, film 2 for the binding energy of 203.5eV, it that film 2 containing NbN. However, the membrane 1 binding of 206.8eV also see acromioplasty, it that film 2 also comprises NbON.

(Embodiment 3)

Graphics 1 is shown in the device 100, the synthesis of single-phase powder NbON. The tubular furnace 111 inner diameter of 25 mm of quartz pipe 112 of the quartz boat 113 in, placing the raw material 101. The material 101 in, use with embodiment 1 of the same T-butyl imino-tri (b yl methyl amino) niobium (Tertialy   Buthylimino   Tris (Ethyl   Methylamino) Niobium ((CH₃)₃ CN=Nb (N (CH₃) C₂ H₅)₃)). The raw material 101 in 1.69 × 10^-1 Pa · m³/s (1000sccm) of nitrogen and 1.69 × 10^-4 Pa · m³/s (1sccm) oxygen mixed gas stream, the 300 the heating [...] 4 hours, to obtain powder 2.

Comparing the powder 2 XRD data and embodiment of the 1 powder 1 of the XRD data. As a result, almost the same two can be confirmed. Therefore, recognizing that powder 2 to NbON single-phase.

Moreover, in this embodiment, the synthesis of single-phase powder NbON oxygen flow for 1.69 × 10^-4 Pa · m³/s (1sccm), as relative to the nitrogen (the inactive carrier gas) the gas concentration of 0.1%. However, the oxygen concentration 0.01-1% range, can also be confirmed NbON synthesis of single-phase powder.

(Embodiment 4)

In addition to the embodiment 1 of this point more the oxygen changes other than water vapor, with the embodiment 1 is the same as the method of synthesizing NbON film. The resulting NbON film (film 3) the film thickness is 700 nm.

Determine the film 3 Nb3d of the XPS spectrum, as a result, the membrane 1 is nearly the same. According to the result confirmed, film 3 is single-phase membrane NbON.

Moreover, in this embodiment, in the synthesis of single-phase membrane NbON of the flow rate of the vapor 1.69 × 10^-4 Pa · m³/s (1sccm), as (inactive carrier gas) relative to the nitrogen gas concentration is 0.1%. However, the water-vapor concentration 0.01-1% range, can also be confirmed synthesis of single-phase membrane NbON.

(Embodiment 5)

As raw materials (R¹ N=Nb (NR² R³)₃), using uncle butyl imino three (diethyl amino) niobium (Tertialy   Buthylimino   Tris(di-Ethylamino)Niobium ((CH₃)₃ CN=Nb (N (C₂ H₅)₂)₃)). With the embodiment 1 the same, according to the material in the gas stream in Ar TG-DTA data, recognizes the decomposition temperature of the raw material. As a result, the raw material is about the decomposition temperature of the 410 [...].

Furthermore, using the picture 3 is shown in the MOCVD device 300, the synthesis of single-phase membrane NbON. In a gasifier 311 inner, will 3.38 × 10^-5 Pa · m³/s (0.2sccm) raw material 301 ethyl cyclohexane solution in 150 the gasified under [...]. As the inactive gas, the use of nitrogen 302. To include raw material gas (gasification of the raw material 301) and nitrogen 302 the, 2.87 × 10^-1 Pa · m³/s (1700sccm) in the mixed gas, mixing the 1.69 × 10^-4 Pa · m³/s (1sccm) oxygen 303. The resulting mixed gas from the spray head 314 to base 315 is heated to 400 the substrate [...] 321 (ITO film (film thickness 150 nm)/ glass substrate) injection 6 hours, the film thickness is 300 nm film 4.

Measuring the film 4 Nb3d of the XPS spectrum, as a result, the membrane 1 is nearly the same. According to the result confirmed, film 4 is single-phase membrane NbON.

(Embodiment 6)

As raw materials (R¹ N=Nb (NR² R³)₃), using uncle butyl imino three (dimethyl amino) niobium (Tertialy   Buthylimino   Tris(di-methylamino)Niobium ((CH₃)₃ CN=Nb (N (CH₃)₂)₃)). With the embodiment 1 the same, according to the material in the gas stream in Ar TG-DTA data, recognizes the decomposition temperature of the raw material. As a result, the raw material is about the decomposition temperature of the 250 [...].

Furthermore, using the picture 3 is shown in the MOCVD device 300, the synthesis of single-phase membrane NbON. In a gasifier 311 inner, will 3.38 × 10^-5 Pa · m³/s (0.2sccm) raw material 301 ethyl cyclohexane solution in 150 the gasified under [...]. As the inactive gas, the use of nitrogen 302. To include raw material gas (gasification of the raw material 301) and nitrogen 302 the, 2.87 × 10^-1 Pa · m³/s (1700sccm) in the mixed gas, mixing the 1.69 × 10^-4 Pa · m³/s (1sccm) oxygen 303. The resulting mixed gas from the spray head 314 to base 315 is heated to 240 the substrate [...] 321 (ITO film (film thickness 150 nm)/ glass substrate) injection 6 hours, the film thickness is 300 nm film 5.

Measuring the film 5 Nb3d of the XPS spectrum, as a result, the membrane 1 is nearly the same. According to this structural confirmation, film 5 is single-phase membrane NbON.

(Embodiment 7)

< 氢生成设备的制作 >

As the invention of the embodiment of the hydrogen generating device, having and Figure 6 is shown in the hydrogen generating apparatus 600 is the same as the hydrogen generating equipment. use chart 6, to the hydrogen generating apparatus of the embodiment of a note.

As shown in Figure 6, embodiment 7 of the hydrogen generating apparatus 600 with: the square has an opening in the upper portion of the glass container 610, optical semiconductor electrode 620, to the electrode and 630. The glass container 610 inside, as the electrolyte 640, accommodating a 1mol/L the H₂ SO₄ aqueous solution. As optical semiconductor electrode 620, using the embodiment 1 of the in, on the base plate 321 (ITO film (film thickness 150 nm)/ glass substrate) (equivalent to the conductive substrate 621. ) Is provided with a film thickness of 160 nm film 1 (equivalent to NbON film 622. ) Of 1 cm square electrode. Moreover, optical semiconductor electrode 620 is in order to make the NbON film 622 and the surface of the glass container 610 of the light incidence plane 611 disposed in a manner facing. As the electrode 630, using the procedures completed after clamped once. Optical semiconductor electrode 620 of the conductive substrate 621 with the part of the electrode 630 by wire 650 is electrically connected. With current meter 660 the light for measuring the semiconductor electrode 620-the electrode 630 of the current flowing through.

< 模拟太阳光照射实验 >

Using the simulated sunlight Seric as a sunlight simulator Company system. Through the embodiment 7 of the hydrogen generating apparatus 600 the light incident part 611, optical semiconductor electrode 620 surface irradiation intensity lkW/m² light. The pair of electrodes 630 gas trapping generated on the surface of the of the 60 minutes, using a gas chromatography, the trapping of the composition analysis of the gas and the determination of the formation. With current meter 660 the semiconductor for measuring the flows between the electrode-pair of electrodes of the light current. Using the electrode 630 generation of the gas of apparent quantum efficiency is obtained. From optical semiconductor electrode 620 about generated in the 30 the oxygen   L, from the electrode 630 approximately generated in the 60   L of hydrogen. Observation to about 0.1mA photocurrent, to calculate the apparent quantum efficiency is about 1%.

According to the above results can be recognized, in this embodiment of the single-phase film has NbON using light illuminate the water decomposition optical semiconductor characteristics for the production of hydrogen.

(Embodiment 8)

In addition to the embodiment 1 of the film 1 is changed to embodiment 2 of the film 2 other than this point, and the implementation example 7 preparation of hydrogen producing equipment and the same measuring the photocurrent. Embodiment 2 the film 2 is not single-phase membrane , however, is caused by the NbON 0.1mA/cm² photocurrent density of the photocurrent.

Industrial availability

NbON film of the present invention in the use of light irradiation and water decomposition gathering hydrogen excellent in optical semiconductor characteristic. Therefore, film NbON of this invention in all kind of photocatalyst is very useful in the related technology.