CN105761379A - ATM input device capable of achieving free and quick brightness regulation - Google Patents

Abstract

The invention discloses an ATM input device capable of achieving free and quick brightness regulation.The ATM input device is provided with an electrochromic device, regulation of the light transmittance of the input device is achieved by means of the electrochromic principle.Besides, the ATM input device is further provided with a power module and a control module which are connected with the electrochromic device in series, wherein the power module provides work power for the electrochromic device, and the control module controls the light transmittance of the electrochromic device by regulating current in a circuit.The electrochromic device is of a solid state complementary type structure, and tungsten oxide and nickel oxide serve as electrochromic materials.By optimizing the structure and the material preparation technology, the sensitivity and coloring efficiency of the device are improved, color changing rate and color fading rate are high, so that the light transmittance of the ATM input device in the colored state is reduced greatly, light regulation range is widened, and quick brightness regulation is achieved; besides, using is simple and convenient, and industrial production can be achieved easily.

Description

A kind of ATM input equipment being capable of brightness freely quick regulatory function

Technical field

The present invention relates to ATM field, be specifically related to a kind of ATM input equipment being capable of brightness freely quick regulatory function.

Background technology

ATM and ATM, be the small machines that arranges in different place for the convenience of the user of bank, facilitate user to handle the business such as withdrawal, inquiry.

But, the structure of the typically no adjustable transparent rate of input equipment of existing ATM, it is highly detrimental to the secrecy of user profile.

Summary of the invention

It is an object of the invention to avoid above-mentioned weak point of the prior art to provide a kind of ATM input equipment being capable of brightness freely quick regulatory function.

The purpose of the present invention is achieved through the following technical solutions:

The invention provides a kind of ATM input equipment being capable of brightness freely quick regulatory function, this ATM input equipment is provided with electrochromic device, utilize electrochromic principle to realize light transmittance to regulate, user is facilitated to regulate the brightness of input equipment, light transmittance etc., it is possible to play security information, the convenient purpose used.

Described ATM input equipment is provided with electrochromic device, is additionally provided with the power module connected with electrochromic device in addition and controls module in this ATM input equipment；This power module provides the working power of electrochromic device；This control module is by regulating size of current in circuit, to reach to control the purpose of electrochromic device light transmittance；Described electrochromic device adopts solid-state complementary type electrochromic device structure, electrochromic material respectively tungsten oxide and nickel oxide material；Described electrochromic device through-thickness is made up of following thin film from top to bottom successively: ito glass substrate (1), WO₃Porous membrane (2), MnO₂Horseradish peroxidase thin film (7), WO₃Nano wire film (3), solid electrolyte (4), Au nanoparticulate thin films (5), NiO porous membrane (6) and ito glass substrate (1)；Described Au nanoparticulate thin films thickness is 3nm.

Preferably, the preparation method of described electrochromic device is as follows:

Step one, prepares electrochromic layer WO₃Nano thin-film: a) first, takes certain size ito glass substrate (1), through acetone, ethanol, deionized water ultrasonic cleaning, puts in magnetic control sputtering device, at base vacuum lower than 1.5 × 10^-3When Pa, sputtering current are 1.8A, magnetron sputtering time 20min, obtain the W film of 900nm；B) then, be coated with W film ito glass for anode, platinized platinum is negative electrode, carries out anodized in the NaF solution of 0.7wt.%, and voltage is 50V, and the time is 30min, after anodized with deionized water clean, obtain the W film with loose structure；C) make catalyst at the Ni film of the one layer of 5nm of ito glass surface magnetic control sputtering through anodized, this ito glass is put in CVD tube furnace, under argon and hydrogen effect, 400 DEG C of insulation 5h, grow WO₃Nano wire film (3), porous W film is oxidized to WO simultaneously₃Porous membrane (2)；

Step 2, prepares MnO₂Horseradish peroxidase thin film (7): by stratiform MnO₂Being dispersed in the aqueous solution of Tetramethylammonium hydroxide, centrifugal after stirring under room temperature, the supernatant obtained is MnO₂Nano-film sol；By isopyknic MnO₂After the horseradish peroxidase based sols of nano-film sol and HRP solution 5g/L fully mixes, with micro sample adding appliance by 10 μ LMnO₂Nano-film sol and HRP mixed solution drip in WO₃Porous membrane surface, after drying namely at WO₃Porous membrane surface obtains MnO₂Horseradish peroxidase thin film (7)；

Step 3; preparation ion storage NiO porous membrane (6): a) in 500ml beaker, 0.16mol nickel sulfate, 0.1mol lithium perchlorate, 0.03mol potassium peroxydisulfate are dissolved in 400ml deionized water; form dark green solution; taking certain size ito glass is substrate; ito glass back side adhesive tape seals; vertically put and stand in beaker; under the stirring of 300rpm, 40ml ammonia (25～28%) is poured into; sedimentation time is 10min; rinse well with deionized water after taking-up; in 80 DEG C of baking ovens after drying, heat treatment 2h under 200 DEG C of hydrogen shields, obtain NiO thin film；B) adopting the anodizing in step one b to process NiO thin film, voltage is 30V, and the time is 25min, obtains NiO porous membrane (6)；C) ito glass with loose structure NiO thin film is put in gold spraying instrument, spraying plating Au nanoparticulate thin films (5)；

Step 4, prepare colloidal sol type solid electrolyte (4): under room temperature, first 0.2mol citric acid is dissolved in 100ml dehydrated alcohol, add 0.1mol tetraethyl orthosilicate, it is subsequently adding 5g lithium carbonate and 8g carbamide and fully dissolves, being eventually adding 20g ethylene glycol to promote the carrying out of polyreaction, gained colourless transparent solution is heated to 60O DEG C of held for some time and obtains colloidal sol, the viscosity of colloidal sol increases with the prolongation of temperature retention time；

Step 5, assembling electrochromic device: the ito glass of NiO thin film will be coated with and be coated with WO₃The ito glass of thin film is staggered relatively, and centre insulator separates, and insulation thickness is about 1mm, edge epoxy sealing, stays an aperture for injecting electrolyte；The colloidal sol syringe that then viscosity be about 35cps is injected between two panels ito glass, at 80 DEG C, device is incubated 24h and makes colloidal sol be polymerized and be fully cured, obtain solid-state complementary type electrochromic device.

Compared to existing technology, there is advantages that

1. configuration aspects: adopting complementary type electrochromic device structure, electrochromic material respectively tungsten oxide and nickel oxide material, at coloured state, light transmission rate is greatly reduced, and increases light range of accommodation；Nickel oxide film, simultaneously as ion storage and photochromic layer, simplifies device architecture；

2.WO₃Electrochomeric films is that loose structure is combined with nano wire, significantly increases the specific surface area of this material, is conducive to reducing painted response time, additionally, at WO₃The preparation of porous membrane surface has MnO₂Horseradish peroxidase thin film, enhances the sensitivity of electrochromic device；

3.NiO thin film be loose structure in conjunction with Au nanoparticle, the painted of NiO thin film is played catalytic action by Au nanoparticle, is greatly improved its coloration efficiency so that this ATM input equipment reaches quickly to regulate the purpose of light transmittance.

Accompanying drawing explanation

Utilize accompanying drawing that invention is described further, but the embodiment in accompanying drawing does not constitute any limitation of the invention, for those of ordinary skill in the art, under the premise not paying creative work, it is also possible to obtain other accompanying drawing according to the following drawings.

Fig. 1 is the structural representation of electrochromic device of the present invention.Wherein, 1-ITO substrate of glass, 2-WO₃Porous membrane, 3-WO₃Nano wire film, 4-solid electrolyte, 5-Au nano thin-film, 6-NiO porous membrane, 7-MnO₂Horseradish peroxidase thin film.

Detailed description of the invention

Electrochromism phenomenon refers to that stable, reversible change phenomenon occurs the optical properties (absorbance, transmitance, reflectance etc.) of material under the effect of extra electric field, shows as the reversible change of color and transparency in appearance.Its essence is the course of reaction that a kind of chemistry is reversible.

Electrochromic material is a kind of novel energy-saving material, provides a kind of new approach for energy-conserving and environment-protective.The fields such as it shows in low energy consumption, Electronic Paper, intelligent window have application potential, and such as in smart window field, according to the situation such as ambient temperature, sunshine, it can regulate the optical property of glass, play the effect saving indoor energy resource consumption.

Many materials being heated, illumination, under the effect such as extra electric field, its color can change, produce coloring as.Inorganic electrochromic material is based on transition metal oxide, and wherein Tungstic anhydride. is a kind of important cathode electrochromic material, has that coloration efficiency height, response time be short, cycle-index advantages of higher.WO 3 film has amorphous state and crystalline state two types, the coloration efficiency of amorphous state WO 3 film is high, color conversion is fast, but it is loosely organized, poor chemical stability, crystalline state Tungstic anhydride. close structure, chemical stability is good, but its coloration efficiency and response time performance are not as amorphous state Tungstic anhydride., but, research finds that the electrochromic property of Tungstic anhydride. is heavily dependent on its surface topography and crystal structure.

Nickel oxide is a kind of typical anode electrochromic material.Nickel oxide is more transparent due to its state of fading, and coloured state has soft neutral color (Lycoperdon polymorphum Vitt), close to the human eye sensitive band to light wave, and as anodic coloration material, and can with the composition complementary type electrochromic device such as tungsten oxide.

The structure of electrochromic device is generally sandwich structure, specifically includes that transparency conducting layer, electrochromic layer, ion conductive layer, ion storage and transparency conducting layer.The effect of transparency conducting layer is the conductor providing electronics in electrochemical reaction for electrochromic material, generally uses tin-doped indium oxide (ITO) thin film or fluorine doped tin oxide (FTO) thin film；Electrochromic layer is the core layer of device, mainly occurs with the form of electrochomeric films, including organic and inorganic electrochromic material；Ion conductor layer is dielectric substrate, it is provided that conduct the passage of ion, electronics during electrochromic device normal operation；Ion storage is also known as to electrode layer, and Main Function is storage and provides the ion needed for electrochromism, plays the effect of balancing charge.

The operation principle of electrochromic device is: plus certain voltage between two transparency conducting layers, under applied voltage effect, electronics and the co-implanted electrochromic layer of ion, and bring it about redox electrochemical reaction and painted, ion storage plays the corresponding counter ion of storage when electrochromic material generation redox reaction, keeping the effect of the charge balance of whole system, when applying backward voltage, electronics and ion are extracted out in painted electrochromic layer and are made it fade.

, the problem such as colouring rate low and cycle life short little for existing electrochromic device light range of accommodation, the present invention is based on tungsten trioxide nano material, in combination with nickel oxide nano design of material complementary type electrochromic device.Using tungsten oxide nano thin film as anode electrochromic material, nickel oxide nano thin film is as cathode electrochromic material, and doping Au nanoparticle, prepares loose structure simultaneously.

The invention provides a kind of ATM input equipment being capable of brightness freely quick regulatory function, this ATM input equipment is provided with electrochromic device, utilize electrochromic principle to realize light transmittance to regulate, user is facilitated to regulate the brightness of input equipment, light transmittance etc., it is possible to play security information, the convenient purpose used.

Illustrate that the invention will be further described below in conjunction with accompanying drawing.

Fig. 1 is the structural representation of electrochromic device of the present invention.

Wherein, 1-ITO substrate of glass, 2-WO₃Porous membrane, 3-WO₃Nano wire film, 4-solid electrolyte, 5-Au nano thin-film, 6-NiO porous membrane, 7-MnO₂Horseradish peroxidase thin film.

The invention will be further described with the following Examples.

Embodiment 1:

A kind of ATM input equipment being capable of brightness freely quick regulatory function that embodiments of the invention provide, this ATM input equipment is provided with electrochromic device, utilize electrochromic principle to realize light transmittance to regulate, user is facilitated to regulate the brightness of input equipment, light transmittance etc., it is possible to play security information, the convenient purpose used.

Described ATM input equipment is provided with electrochromic device, is additionally provided with the power module connected with electrochromic device in addition and controls module in this ATM input equipment；This power module provides the working power of electrochromic device；This control module is by regulating size of current in circuit, to reach to control the purpose of electrochromic device light transmittance；Described electrochromic device adopts solid-state complementary type electrochromic device structure, electrochromic material respectively tungsten oxide and nickel oxide material；Described electrochromic device through-thickness is made up of following thin film from top to bottom successively: ito glass substrate (1), WO₃Porous membrane (2), MnO₂Horseradish peroxidase thin film (7), WO₃Nano wire film (3), solid electrolyte (4), Au nanoparticulate thin films (5), NiO porous membrane (6) and ito glass substrate (1)；Described Au nanoparticulate thin films thickness is 3nm.

Preferably, the preparation method of described electrochromic device is as follows:

Step one, prepares electrochromic layer WO₃Nano thin-film: a) first, takes certain size ito glass substrate (1), through acetone, ethanol, deionized water ultrasonic cleaning, puts in magnetic control sputtering device, at base vacuum lower than 1.5 × 10^-3When Pa, sputtering current are 1.8A, magnetron sputtering time 20min, obtain the W film of 900nm；B) then, be coated with W film ito glass for anode, platinized platinum is negative electrode, carries out anodized in the NaF solution of 0.7wt.%, and voltage is 50V, and the time is 30min, after anodized with deionized water clean, obtain the W film with loose structure；C) make catalyst at the Ni film of the one layer of 5nm of ito glass surface magnetic control sputtering through anodized, this ito glass is put in CVD tube furnace, under argon and hydrogen effect, 400 DEG C of insulation 5h, grow WO₃Nano wire film (3), porous W film is oxidized to WO simultaneously₃Porous membrane (2)；

Step 2, prepares MnO₂Horseradish peroxidase thin film (7): by stratiform MnO₂Being dispersed in the aqueous solution of Tetramethylammonium hydroxide, centrifugal after stirring under room temperature, the supernatant obtained is MnO₂Nano-film sol；By isopyknic MnO₂After the horseradish peroxidase based sols of nano-film sol and HRP solution 5g/L fully mixes, with micro sample adding appliance by 10 μ LMnO₂Nano-film sol and HRP mixed solution drip in WO₃Porous membrane surface, after drying namely at WO₃Porous membrane surface obtains MnO₂Horseradish peroxidase thin film (7)；

Step 3; preparation ion storage NiO porous membrane (6): a) in 500ml beaker, 0.16mol nickel sulfate, 0.1mol lithium perchlorate, 0.03mol potassium peroxydisulfate are dissolved in 400ml deionized water; form dark green solution; taking certain size ito glass is substrate; ito glass back side adhesive tape seals; vertically put and stand in beaker; under the stirring of 300rpm, 40ml ammonia (25～28%) is poured into; sedimentation time is 10min; rinse well with deionized water after taking-up; in 80 DEG C of baking ovens after drying, heat treatment 2h under 200 DEG C of hydrogen shields, obtain NiO thin film；B) adopting the anodizing in step one b to process NiO thin film, voltage is 30V, and the time is 25min, obtains NiO porous membrane (6)；C) ito glass with loose structure NiO thin film is put in gold spraying instrument, spraying plating Au nanoparticulate thin films (5)；

Step 4, prepare colloidal sol type solid electrolyte (4): under room temperature, first 0.2mol citric acid is dissolved in 100ml dehydrated alcohol, add 0.1mol tetraethyl orthosilicate, it is subsequently adding 5g lithium carbonate and 8g carbamide and fully dissolves, being eventually adding 20g ethylene glycol to promote the carrying out of polyreaction, gained colourless transparent solution is heated to 60O DEG C of held for some time and obtains colloidal sol, the viscosity of colloidal sol increases with the prolongation of temperature retention time；

Step 5, assembling electrochromic device: the ito glass of NiO thin film will be coated with and be coated with WO₃The ito glass of thin film is staggered relatively, and centre insulator separates, and insulation thickness is about 1mm, edge epoxy sealing, stays an aperture for injecting electrolyte；The colloidal sol syringe that then viscosity be about 35cps is injected between two panels ito glass, at 80 DEG C, device is incubated 24h and makes colloidal sol be polymerized and be fully cured, obtain solid-state complementary type electrochromic device.

The electrochromic property test of device:

By two panels ito glass external wire, make respectively to be coated with WO₃Thin film, the external test circuit anode of ito glass of NiO thin film, negative pole, adopt cyclic voltammetry, and sweep speed is 30mV/s.When device institute making alive is from+3V to-3V, the color of device becomes opaque from transparent, and color increases with negative pressure and deepen；In state of fading, this device transmitance at 550nm place about 80%, in the transmitance about 12% of this device of coloured state, showing good transmitance controllability, its variable color efficiency is 93cm²C^-1；The painted response time of device is about 8s, and the response time that fades is about 11s；By device carrying out long chrono-amperometric test and by contrasting its peak point current, testing its cycle life, after obtaining this device cycle 3000 times, attenuation rate is 12%, good stability.

By testing, this ATM input equipment can realize the light transmittance regulatory function of input information, and its sensitivity and coloration efficiency are higher, variable color is fast with fade rates, is greatly reduced at coloured state light transmission rate, and increases light range of accommodation, it is simple, convenient to use, and is beneficial to industrialized production.

Embodiment 2:

A kind of ATM input equipment being capable of brightness freely quick regulatory function that embodiments of the invention provide, this ATM input equipment is provided with electrochromic device, utilize electrochromic principle to realize light transmittance to regulate, user is facilitated to regulate the brightness of input equipment, light transmittance etc., it is possible to play security information, the convenient purpose used.

Described ATM input equipment is provided with electrochromic device, is additionally provided with the power module connected with electrochromic device in addition and controls module in this ATM input equipment；This power module provides the working power of electrochromic device；This control module is by regulating size of current in circuit, to reach to control the purpose of electrochromic device light transmittance；Described electrochromic device adopts solid-state complementary type electrochromic device structure, electrochromic material respectively tungsten oxide and nickel oxide material；Described electrochromic device through-thickness is made up of following thin film from top to bottom successively: ito glass substrate (1), WO₃Porous membrane (2), MnO₂Horseradish peroxidase thin film (7), WO₃Nano wire film (3), solid electrolyte (4), Au nanoparticulate thin films (5), NiO porous membrane (6) and ito glass substrate (1)；Described Au nanoparticulate thin films thickness is 3nm.

Preferably, the preparation method of described electrochromic device is as follows:

Step one, prepares electrochromic layer WO₃Nano thin-film: a) first, takes certain size ito glass substrate (1), through acetone, ethanol, deionized water ultrasonic cleaning, puts in magnetic control sputtering device, at base vacuum lower than 1.5 × 10^-3When Pa, sputtering current are 1.8A, magnetron sputtering time 20min, obtain the W film of 900nm；B) then, be coated with W film ito glass for anode, platinized platinum is negative electrode, carries out anodized in the NaF solution of 0.3wt.%, and voltage is 50V, and the time is 30min, after anodized with deionized water clean, obtain the W film with loose structure；C) make catalyst at the Ni film of the one layer of 7nm of ito glass surface magnetic control sputtering through anodized, this ito glass is put in CVD tube furnace, under argon and hydrogen effect, 400 DEG C of insulation 4h, grow WO₃Nano wire film (3), porous W film is oxidized to WO simultaneously₃Porous membrane (2)；

Step 2, prepares MnO₂Horseradish peroxidase thin film (7): by stratiform MnO₂Being dispersed in the aqueous solution of Tetramethylammonium hydroxide, centrifugal after stirring under room temperature, the supernatant obtained is MnO₂Nano-film sol；By isopyknic MnO₂After the horseradish peroxidase based sols of nano-film sol and HRP solution 5g/L fully mixes, with micro sample adding appliance by 10 μ LMnO₂Nano-film sol and HRP mixed solution drip in WO₃Porous membrane surface, after drying namely at WO₃Porous membrane surface obtains MnO₂Horseradish peroxidase thin film (7)；

Step 3; preparation ion storage NiO porous membrane (6): a) in 500ml beaker, 0.16mol nickel sulfate, 0.1mol lithium perchlorate, 0.03mol potassium peroxydisulfate are dissolved in 450ml deionized water; form dark green solution; taking certain size ito glass is substrate; ito glass back side adhesive tape seals; vertically put and stand in beaker; under the stirring of 300rpm, 40ml ammonia (25～28%) is poured into; sedimentation time is 10min; rinse well with deionized water after taking-up; in 80 DEG C of baking ovens after drying, heat treatment 2h under 200 DEG C of hydrogen shields, obtain NiO thin film；B) adopting the anodizing in step one b to process NiO thin film, voltage is 30V, and the time is 25min, obtains NiO porous membrane (6)；C) ito glass with loose structure NiO thin film is put in gold spraying instrument, spraying plating Au nanoparticulate thin films (5)；

Step 4, prepare colloidal sol type solid electrolyte (4): under room temperature, first 0.2mol citric acid is dissolved in 100ml dehydrated alcohol, add 0.1mol tetraethyl orthosilicate, it is subsequently adding 5g lithium carbonate and 8g carbamide and fully dissolves, being eventually adding 20g ethylene glycol to promote the carrying out of polyreaction, gained colourless transparent solution is heated to 60O DEG C of held for some time and obtains colloidal sol, the viscosity of colloidal sol increases with the prolongation of temperature retention time；

Step 5, assembling electrochromic device: the ito glass of NiO thin film will be coated with and be coated with WO₃The ito glass of thin film is staggered relatively, and centre insulator separates, and insulation thickness is about 1mm, edge epoxy sealing, stays an aperture for injecting electrolyte；The colloidal sol syringe that then viscosity be about 35cps is injected between two panels ito glass, at 80 DEG C, device is incubated 24h and makes colloidal sol be polymerized and be fully cured, obtain solid-state complementary type electrochromic device.

The electrochromic property test of device:

By two panels ito glass external wire, make respectively to be coated with WO₃Thin film, the external test circuit anode of ito glass of NiO thin film, negative pole, adopt cyclic voltammetry, and sweep speed is 30mV/s.When device institute making alive is from+3V to-3V, the color of device becomes opaque from transparent, and color increases with negative pressure and deepen；In state of fading, this device transmitance at 550nm place about 80%, in the transmitance about 14% of this device of coloured state, showing good transmitance controllability, its variable color efficiency is 93cm²C^-1；The painted response time of device is about 6s, and the response time that fades is about 11s；By device carrying out long chrono-amperometric test and by contrasting its peak point current, testing its cycle life, after obtaining this device cycle 3000 times, attenuation rate is 19%, good stability.

By testing, this ATM input equipment can realize the light transmittance regulatory function of input information, and its sensitivity and coloration efficiency are higher, variable color is fast with fade rates, is greatly reduced at coloured state light transmission rate, and increases light range of accommodation, it is simple, convenient to use, and is beneficial to industrialized production.

Embodiment 3:

A kind of ATM input equipment being capable of brightness freely quick regulatory function that embodiments of the invention provide, this ATM input equipment is provided with electrochromic device, utilize electrochromic principle to realize light transmittance to regulate, user is facilitated to regulate the brightness of input equipment, light transmittance etc., it is possible to play security information, the convenient purpose used.

Described ATM input equipment is provided with electrochromic device, is additionally provided with the power module connected with electrochromic device in addition and controls module in this ATM input equipment；This power module provides the working power of electrochromic device；This control module is by regulating size of current in circuit, to reach to control the purpose of electrochromic device light transmittance；Described electrochromic device adopts solid-state complementary type electrochromic device structure, electrochromic material respectively tungsten oxide and nickel oxide material；Described electrochromic device through-thickness is made up of following thin film from top to bottom successively: ito glass substrate (1), WO₃Porous membrane (2), MnO₂Horseradish peroxidase thin film (7), WO₃Nano wire film (3), solid electrolyte (4), Au nanoparticulate thin films (5), NiO porous membrane (6) and ito glass substrate (1)；Described Au nanoparticulate thin films thickness is 3nm.

Preferably, the preparation method of described electrochromic device is as follows:

Step one, prepares electrochromic layer WO₃Nano thin-film: a) first, takes certain size ito glass substrate (1), through acetone, ethanol, deionized water ultrasonic cleaning, puts in magnetic control sputtering device, at base vacuum lower than 1.5 × 10^-3When Pa, sputtering current are 1.8A, magnetron sputtering time 20min, obtain the W film of 900nm；B) then, be coated with W film ito glass for anode, platinized platinum is negative electrode, carries out anodized in the NaF solution of 0.2wt.%, and voltage is 50V, and the time is 30min, after anodized with deionized water clean, obtain the W film with loose structure；C) make catalyst at the Ni film of the one layer of 5nm of ito glass surface magnetic control sputtering through anodized, this ito glass is put in CVD tube furnace, under argon and hydrogen effect, 470 DEG C of insulation 4h, grow WO₃Nano wire film (3), porous W film is oxidized to WO simultaneously₃Porous membrane (2)；

Step 2, prepares MnO₂Horseradish peroxidase thin film (7): by stratiform MnO₂Being dispersed in the aqueous solution of Tetramethylammonium hydroxide, centrifugal after stirring under room temperature, the supernatant obtained is MnO₂Nano-film sol；By isopyknic MnO₂After the horseradish peroxidase based sols of nano-film sol and HRP solution 5g/L fully mixes, with micro sample adding appliance by 10 μ LMnO₂Nano-film sol and HRP mixed solution drip in WO₃Porous membrane surface, after drying namely at WO₃Porous membrane surface obtains MnO₂Horseradish peroxidase thin film (7)；

Step 3; preparation ion storage NiO porous membrane (6): a) in 500ml beaker, 0.16mol nickel sulfate, 0.1mol lithium perchlorate, 0.07mol potassium peroxydisulfate are dissolved in 400ml deionized water; form dark green solution; taking certain size ito glass is substrate; ito glass back side adhesive tape seals; vertically put and stand in beaker; under the stirring of 300rpm, 40ml ammonia (25～28%) is poured into; sedimentation time is 10min; rinse well with deionized water after taking-up; in 80 DEG C of baking ovens after drying, heat treatment 2h under 200 DEG C of hydrogen shields, obtain NiO thin film；B) adopting the anodizing in step one b to process NiO thin film, voltage is 30V, and the time is 20min, obtains NiO porous membrane (6)；C) ito glass with loose structure NiO thin film is put in gold spraying instrument, spraying plating Au nanoparticulate thin films (5)；

Step 4, prepare colloidal sol type solid electrolyte (4): under room temperature, first 0.2mol citric acid is dissolved in 100ml dehydrated alcohol, add 0.1mol tetraethyl orthosilicate, it is subsequently adding 5g lithium carbonate and 8g carbamide and fully dissolves, being eventually adding 20g ethylene glycol to promote the carrying out of polyreaction, gained colourless transparent solution is heated to 60O DEG C of held for some time and obtains colloidal sol, the viscosity of colloidal sol increases with the prolongation of temperature retention time；

Step 5, assembling electrochromic device: the ito glass of NiO thin film will be coated with and be coated with WO₃The ito glass of thin film is staggered relatively, and centre insulator separates, and insulation thickness is about 1mm, edge epoxy sealing, stays an aperture for injecting electrolyte；The colloidal sol syringe that then viscosity be about 35cps is injected between two panels ito glass, at 80 DEG C, device is incubated 24h and makes colloidal sol be polymerized and be fully cured, obtain solid-state complementary type electrochromic device.

The electrochromic property test of device:

By two panels ito glass external wire, make respectively to be coated with WO₃Thin film, the external test circuit anode of ito glass of NiO thin film, negative pole, adopt cyclic voltammetry, and sweep speed is 30mV/s.When device institute making alive is from+3V to-3V, the color of device becomes opaque from transparent, and color increases with negative pressure and deepen；In state of fading, this device transmitance at 550nm place about 80%, in the transmitance about 14% of this device of coloured state, showing good transmitance controllability, its variable color efficiency is 93cm²C^-1；The painted response time of device is about 9s, and the response time that fades is about 21s；By device carrying out long chrono-amperometric test and by contrasting its peak point current, testing its cycle life, after obtaining this device cycle 3000 times, attenuation rate is 12%, good stability.

By testing, this ATM input equipment can realize the light transmittance regulatory function of input information, and its sensitivity and coloration efficiency are higher, variable color is fast with fade rates, is greatly reduced at coloured state light transmission rate, and increases light range of accommodation, it is simple, convenient to use, and is beneficial to industrialized production.

Embodiment 4:

A kind of ATM input equipment being capable of brightness freely quick regulatory function that embodiments of the invention provide, this ATM input equipment is provided with electrochromic device, utilize electrochromic principle to realize light transmittance to regulate, user is facilitated to regulate the brightness of input equipment, light transmittance etc., it is possible to play security information, the convenient purpose used.

Described ATM input equipment is provided with electrochromic device, is additionally provided with the power module connected with electrochromic device in addition and controls module in this ATM input equipment；This power module provides the working power of electrochromic device；This control module is by regulating size of current in circuit, to reach to control the purpose of electrochromic device light transmittance；Described electrochromic device adopts solid-state complementary type electrochromic device structure, electrochromic material respectively tungsten oxide and nickel oxide material；Described electrochromic device through-thickness is made up of following thin film from top to bottom successively: ito glass substrate (1), WO₃Porous membrane (2), MnO₂Horseradish peroxidase thin film (7), WO₃Nano wire film (3), solid electrolyte (4), Au nanoparticulate thin films (5), NiO porous membrane (6) and ito glass substrate (1)；Described Au nanoparticulate thin films thickness is 3nm.

Preferably, the preparation method of described electrochromic device is as follows:

Step one, prepares electrochromic layer WO₃Nano thin-film: a) first, takes certain size ito glass substrate (1), through acetone, ethanol, deionized water ultrasonic cleaning, puts in magnetic control sputtering device, at base vacuum lower than 1.5 × 10^-3When Pa, sputtering current are 1.8A, magnetron sputtering time 20min, obtain the W film of 900nm；B) then, be coated with W film ito glass for anode, platinized platinum is negative electrode, carries out anodized in the NaF solution of 0.2wt.%, and voltage is 50V, and the time is 30min, after anodized with deionized water clean, obtain the W film with loose structure；C) make catalyst at the Ni film of the one layer of 5nm of ito glass surface magnetic control sputtering through anodized, this ito glass is put in CVD tube furnace, under argon and hydrogen effect, 400 DEG C of insulation 4h, grow WO₃Nano wire film (3), porous W film is oxidized to WO simultaneously₃Porous membrane (2)；

Step 2, prepares MnO₂Horseradish peroxidase thin film (7): by stratiform MnO₂Being dispersed in the aqueous solution of Tetramethylammonium hydroxide, centrifugal after stirring under room temperature, the supernatant obtained is MnO₂Nano-film sol；By isopyknic MnO₂After the horseradish peroxidase based sols of nano-film sol and HRP solution 5g/L fully mixes, with micro sample adding appliance by 10 μ LMnO₂Nano-film sol and HRP mixed solution drip in WO₃Porous membrane surface, after drying namely at WO₃Porous membrane surface obtains MnO₂Horseradish peroxidase thin film (7)；

Step 3; preparation ion storage NiO porous membrane (6): a) in 500ml beaker, 0.16mol nickel sulfate, 0.1mol lithium perchlorate, 0.03mol potassium peroxydisulfate are dissolved in 400ml deionized water; form dark green solution; taking certain size ito glass is substrate; ito glass back side adhesive tape seals; vertically put and stand in beaker; under the stirring of 300rpm, 40ml ammonia (25～28%) is poured into; sedimentation time is 10min; rinse well with deionized water after taking-up; in 80 DEG C of baking ovens after drying, heat treatment 2h under 200 DEG C of hydrogen shields, obtain NiO thin film；B) adopting the anodizing in step one b to process NiO thin film, voltage is 50V, and the time is 25min, obtains NiO porous membrane (6)；C) ito glass with loose structure NiO thin film is put in gold spraying instrument, spraying plating Au nanoparticulate thin films (5)；

Step 4, prepare colloidal sol type solid electrolyte (4): under room temperature, first 0.2mol citric acid is dissolved in 100ml dehydrated alcohol, add 0.1mol tetraethyl orthosilicate, it is subsequently adding 5g lithium carbonate and 8g carbamide and fully dissolves, being eventually adding 20g ethylene glycol to promote the carrying out of polyreaction, gained colourless transparent solution is heated to 60O DEG C of held for some time and obtains colloidal sol, the viscosity of colloidal sol increases with the prolongation of temperature retention time；

Step 5, assembling electrochromic device: the ito glass of NiO thin film will be coated with and be coated with WO₃The ito glass of thin film is staggered relatively, and centre insulator separates, and insulation thickness is about 1mm, edge epoxy sealing, stays an aperture for injecting electrolyte；The colloidal sol syringe that then viscosity be about 35cps is injected between two panels ito glass, at 80 DEG C, device is incubated 24h and makes colloidal sol be polymerized and be fully cured, obtain solid-state complementary type electrochromic device.

The electrochromic property test of device:

By two panels ito glass external wire, make respectively to be coated with WO₃Thin film, the external test circuit anode of ito glass of NiO thin film, negative pole, adopt cyclic voltammetry, and sweep speed is 30mV/s.When device institute making alive is from+3V to-3V, the color of device becomes opaque from transparent, and color increases with negative pressure and deepen；In state of fading, this device transmitance at 550nm place about 80%, in the transmitance about 19% of this device of coloured state, showing good transmitance controllability, its variable color efficiency is 93cm²C^-1；The painted response time of device is about 6s, and the response time that fades is about 11s；By device carrying out long chrono-amperometric test and by contrasting its peak point current, testing its cycle life, after obtaining this device cycle 3000 times, attenuation rate is 14%, good stability.

By testing, this ATM input equipment can realize the light transmittance regulatory function of input information, and its sensitivity and coloration efficiency are higher, variable color is fast with fade rates, is greatly reduced at coloured state light transmission rate, and increases light range of accommodation, it is simple, convenient to use, and is beneficial to industrialized production.

Embodiment 5:

A kind of ATM input equipment being capable of brightness freely quick regulatory function that embodiments of the invention provide, this ATM input equipment is provided with electrochromic device, utilize electrochromic principle to realize light transmittance to regulate, user is facilitated to regulate the brightness of input equipment, light transmittance etc., it is possible to play security information, the convenient purpose used.

Described ATM input equipment is provided with electrochromic device, is additionally provided with the power module connected with electrochromic device in addition and controls module in this ATM input equipment；This power module provides the working power of electrochromic device；This control module is by regulating size of current in circuit, to reach to control the purpose of electrochromic device light transmittance；Described electrochromic device adopts solid-state complementary type electrochromic device structure, electrochromic material respectively tungsten oxide and nickel oxide material；Described electrochromic device through-thickness is made up of following thin film from top to bottom successively: ito glass substrate (1), WO₃Porous membrane (2), MnO₂Horseradish peroxidase thin film (7), WO₃Nano wire film (3), solid electrolyte (4), Au nanoparticulate thin films (5), NiO porous membrane (6) and ito glass substrate (1)；Described Au nanoparticulate thin films thickness is 3nm.

Preferably, the preparation method of described electrochromic device is as follows:

Step one, prepares electrochromic layer WO₃Nano thin-film: a) first, takes certain size ito glass substrate (1), through acetone, ethanol, deionized water ultrasonic cleaning, puts in magnetic control sputtering device, at base vacuum lower than 1.5 × 10^-3When Pa, sputtering current are 1.8A, magnetron sputtering time 20min, obtain the W film of 900nm；B) then, be coated with W film ito glass for anode, platinized platinum is negative electrode, carries out anodized in the NaF solution of 0.2wt.%, and voltage is 50V, and the time is 30min, after anodized with deionized water clean, obtain the W film with loose structure；C) make catalyst at the Ni film of the one layer of 5nm of ito glass surface magnetic control sputtering through anodized, this ito glass is put in CVD tube furnace, under argon and hydrogen effect, 400 DEG C of insulation 4h, grow WO₃Nano wire film (3), porous W film is oxidized to WO simultaneously₃Porous membrane (2)；

Step 2, prepares MnO₂Horseradish peroxidase thin film (7): by stratiform MnO₂Being dispersed in the aqueous solution of Tetramethylammonium hydroxide, centrifugal after stirring under room temperature, the supernatant obtained is MnO₂Nano-film sol；By isopyknic MnO₂After the horseradish peroxidase based sols of nano-film sol and HRP solution 5g/L fully mixes, with micro sample adding appliance by 10 μ LMnO₂Nano-film sol and HRP mixed solution drip in WO₃Porous membrane surface, after drying namely at WO₃Porous membrane surface obtains MnO₂Horseradish peroxidase thin film (7)；

Step 3; preparation ion storage NiO porous membrane (6): a) in 500ml beaker, 0.16mol nickel sulfate, 0.1mol lithium perchlorate, 0.23mol potassium peroxydisulfate are dissolved in 400ml deionized water; form dark green solution; taking certain size ito glass is substrate; ito glass back side adhesive tape seals; vertically put and stand in beaker; under the stirring of 300rpm, 40ml ammonia (25～28%) is poured into; sedimentation time is 10min; rinse well with deionized water after taking-up; in 80 DEG C of baking ovens after drying, heat treatment 2h under 200 DEG C of hydrogen shields, obtain NiO thin film；B) adopting the anodizing in step one b to process NiO thin film, voltage is 38V, and the time is 25min, obtains NiO porous membrane (6)；C) ito glass with loose structure NiO thin film is put in gold spraying instrument, spraying plating Au nanoparticulate thin films (5)；

Step 4, prepare colloidal sol type solid electrolyte (4): under room temperature, first 0.2mol citric acid is dissolved in 100ml dehydrated alcohol, add 0.1mol tetraethyl orthosilicate, it is subsequently adding 5g lithium carbonate and 8g carbamide and fully dissolves, being eventually adding 20g ethylene glycol to promote the carrying out of polyreaction, gained colourless transparent solution is heated to 60O DEG C of held for some time and obtains colloidal sol, the viscosity of colloidal sol increases with the prolongation of temperature retention time；

Step 5, assembling electrochromic device: the ito glass of NiO thin film will be coated with and be coated with WO₃The ito glass of thin film is staggered relatively, and centre insulator separates, and insulation thickness is about 4mm, edge epoxy sealing, stays an aperture for injecting electrolyte；The colloidal sol syringe that then viscosity be about 35cps is injected between two panels ito glass, at 80 DEG C, device is incubated 24h and makes colloidal sol be polymerized and be fully cured, obtain solid-state complementary type electrochromic device.

The electrochromic property test of device:

By two panels ito glass external wire, make respectively to be coated with WO₃Thin film, the external test circuit anode of ito glass of NiO thin film, negative pole, adopt cyclic voltammetry, and sweep speed is 30mV/s.When device institute making alive is from+3V to-3V, the color of device becomes opaque from transparent, and color increases with negative pressure and deepen；In state of fading, this device transmitance at 550nm place about 80%, in the transmitance about 12% of this device of coloured state, showing good transmitance controllability, its variable color efficiency is 93cm²C^-1；The painted response time of device is about 6s, and the response time that fades is about 11s；By device carrying out long chrono-amperometric test and by contrasting its peak point current, testing its cycle life, after obtaining this device cycle 3000 times, attenuation rate is 16%, good stability.

By testing, this ATM input equipment can realize the light transmittance regulatory function of input information, and its sensitivity and coloration efficiency are higher, variable color is fast with fade rates, is greatly reduced at coloured state light transmission rate, and increases light range of accommodation, it is simple, convenient to use, and is beneficial to industrialized production.

Finally should be noted that; above example is only in order to illustrate technical scheme; but not limiting the scope of the invention; although having made to explain to the present invention with reference to preferred embodiment; it will be understood by those within the art that; technical scheme can be modified or equivalent replacement, without deviating from the spirit and scope of technical solution of the present invention.

Claims (2)

1. the ATM input equipment being capable of brightness freely quick regulatory function, it is characterized in that: described ATM input equipment is provided with electrochromic device, this ATM input equipment is additionally provided with power module in addition that connect with electrochromic device and controls module；This power module provides the working power of electrochromic device；This control module is by regulating size of current in circuit, to reach to control the purpose of electrochromic device light transmittance；Described electrochromic device adopts solid-state complementary type electrochromic device structure, electrochromic material respectively tungsten oxide and nickel oxide material；Described electrochromic device through-thickness is made up of following thin film from top to bottom successively: ito glass substrate (1), WO₃Porous membrane (2), MnO₂Horseradish peroxidase thin film (7), WO₃Nano wire film (3), solid electrolyte (4), Au nanoparticulate thin films (5), NiO porous membrane (6) and ito glass substrate (1)；Described Au nanoparticulate thin films thickness is 3nm.

2. ATM input equipment according to claim 1, it is characterised in that the preparation method of described electrochromic device is as follows:

Step one, prepares electrochromic layer WO₃Nano thin-film: a) first, takes certain size ito glass substrate (1), through acetone, ethanol, deionized water ultrasonic cleaning, puts in magnetic control sputtering device, at base vacuum lower than 1.5 × 10^-3When Pa, sputtering current are 1.8A, magnetron sputtering time 20min, obtain the W film of 900nm；B) then, be coated with W film ito glass for anode, platinized platinum is negative electrode, carries out anodized in the NaF solution of 0.7wt.%, and voltage is 50V, and the time is 30min, after anodized with deionized water clean, obtain the W film with loose structure；C) make catalyst at the Ni film of the one layer of 5nm of ito glass surface magnetic control sputtering through anodized, this ito glass is put in CVD tube furnace, under argon and hydrogen effect, 400 DEG C of insulation 5h, grow WO₃Nano wire film (3), porous W film is oxidized to WO simultaneously₃Porous membrane (2)；

Step 2, prepares MnO₂Horseradish peroxidase thin film (7): by stratiform MnO₂Being dispersed in the aqueous solution of Tetramethylammonium hydroxide, centrifugal after stirring under room temperature, the supernatant obtained is MnO₂Nano-film sol；By isopyknic MnO₂After the horseradish peroxidase based sols of nano-film sol and HRP solution 5g/L fully mixes, with micro sample adding appliance by 10 μ LMnO₂Nano-film sol and HRP mixed solution drip in WO₃Porous membrane surface, after drying namely at WO₃Porous membrane surface obtains MnO₂Horseradish peroxidase thin film (7)；

Step 3; preparation ion storage NiO porous membrane (6): a) in 500ml beaker, 0.16mol nickel sulfate, 0.1mol lithium perchlorate, 0.03mol potassium peroxydisulfate are dissolved in 400ml deionized water; form dark green solution; taking certain size ito glass is substrate; ito glass back side adhesive tape seals; vertically put and stand in beaker; under the stirring of 300rpm, 40ml ammonia (25～28%) is poured into; sedimentation time is 10min; rinse well with deionized water after taking-up; in 80 DEG C of baking ovens after drying, heat treatment 2h under 200 DEG C of hydrogen shields, obtain NiO thin film；B) adopting the anodizing in step one b to process NiO thin film, voltage is 30V, and the time is 25min, obtains NiO porous membrane (6)；C) ito glass with loose structure NiO thin film is put in gold spraying instrument, spraying plating Au nanoparticulate thin films (5)；

Step 4, prepare colloidal sol type solid electrolyte (4): under room temperature, first 0.2mol citric acid is dissolved in 100ml dehydrated alcohol, add 0.1mol tetraethyl orthosilicate, it is subsequently adding 5g lithium carbonate and 8g carbamide and fully dissolves, being eventually adding 20g ethylene glycol to promote the carrying out of polyreaction, gained colourless transparent solution is heated to 60O DEG C of held for some time and obtains colloidal sol, the viscosity of colloidal sol increases with the prolongation of temperature retention time；

Step 5, assembling electrochromic device: the ito glass of NiO thin film will be coated with and be coated with WO₃The ito glass of thin film is staggered relatively, and centre insulator separates, and insulation thickness is about 1mm, edge epoxy sealing, stays an aperture for injecting electrolyte；The colloidal sol syringe that then viscosity be about 35cps is injected between two panels ito glass, at 80 DEG C, device is incubated 24h and makes colloidal sol be polymerized and be fully cured, obtain solid-state complementary type electrochromic device.