CN107608156B - Flexible tunable visible-near infrared band branch optical waveguide device and preparation method thereof - Google Patents
Flexible tunable visible-near infrared band branch optical waveguide device and preparation method thereof Download PDFInfo
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Abstract
A flexible tunable visible-near infrared band branch optical waveguide device and a preparation method thereof belong to the fields of electrochromic technology and optical waveguide devices. A normal optical waveguide layer and an electrochromic optical waveguide layer are paved on the upper surface of the flexible transparent substrate, the normal optical waveguide layer and the electrochromic optical waveguide layer are arranged on one layer, the normal optical waveguide layer adopts a Y-shaped two-branch structure, namely an A strip before branching, a B strip after branching and a C strip, wherein one side of the A strip before the Y-shaped branching of the normal optical waveguide layer is tightly connected with one side of the electrochromic optical waveguide layer; the electrochromic optical waveguide layer is also led out with a conductive electrode which is partially overlapped with the electrochromic optical waveguide layer, the conductive electrode is used for loading voltage to the electrochromic optical waveguide layer and is flatly paved and fixed on the flexible transparent substrate; the conductive electrode is not in direct contact with the normal optical waveguide layer. The electro-optical modulation effect is utilized to realize the optical modulation by combining the total light reflection and the transmissivity.
Description
Technical Field
The invention belongs to the field of electrochromic technology and optical waveguide devices, and particularly relates to a flexible tunable visible-near infrared band branch optical waveguide device and a preparation method thereof.
Background
Electrochromic refers to the optical properties (absorptivity, transmissivity, or reflectance) of a materialEmissivity, etc.) is stable and reversibly changed under the action of an applied electric field, and the appearance is represented by reversible changes of color and transparency. Electrochromic phenomena are essentially a process of electrochemical reaction, and as an applied voltage changes, the phase of a material changes, resulting in a change in the optical properties (e.g., light transmittance, refractive index, etc.) of the material. The term electrochromic was originally proposed by Piatt in 1961. Deb described tungsten trioxide in detail until 1969 and 1973 (WO 3 ) The film can change the color between colorless and blue under the action of a certain voltage. He uses amorphous WO for the first time 3 The film prepares electrochromic devices and provides a color change mechanism of 'oxygen vacancy color center', which marks the beginning of electrochromic science and technology research. Since then, new color-changing materials have been discovered successively, comprises NiO, co 3 O 4 、TiO 2 、MoO 3 And the transition metal oxides and Polyaniline (PANI), polypyrrole (PPy), polythiophene (Polythiophene) and other organic polymer materials. After the end of the 80 s of the 20 th century, the preparation of novel organic polymer electrochromic materials and the assembly of electrochromic devices become an increasingly active research field. A new energy-saving window based on electrochromic films, namely a Smart window, proposed by swedish scientist c.g. granqvist and american scientist c.m. lamert et al, becomes a milestone for electrochromic technology research. So far, some industrial strong countries in japan, europe and the united states are leading in electrochromic technology application research. The research of electrochromic materials and devices in China is relatively late to start, and has a certain gap with the advanced application research technology in foreign countries. At present, universities of Zhejiang, jilin universities, qinghua universities and other universities of electronics technology and academy of China's academy of sciences of Changchun application chemistry institute, ningbo materials engineering institute and other scientific research institutions have achieved some relatively outstanding results.
The optical waveguide is a light guide channel capable of confining light in or near the surface thereof to guide light waves to propagate in a certain direction, and practical optical waveguides include planar optical waveguides, stripe-shaped optical waveguides and cylindrical optical waveguides. The planar optical waveguide and the strip optical waveguide are mainly used for manufacturing active and passive optical waveguide elements, such as lasers, modulators, optical couplers and the like, and are suitable for manufacturing integrated optical circuits with planar structures by adopting a semiconductor thin film technology. The optical waveguide principle and the device are widely applied to the fields of information acquisition, information transmission, information processing, production and living. In the aspect of information transmission, the active and passive devices can be manufactured, the optical fiber communication trunk line can be formed, the optical switching access network can be formed, and AON, DWDM, OADM, OTDM and FTTC/B/O/H can be realized. The optical branching waveguide device is one of the indispensable passive devices in the optical communication network, and the flexible optical branching waveguide device with tunable optical power is a future development trend.
The tunable flexible optical branching waveguide device needs to fulfill three requirements: the tunable, flexible and branched waveguide device needs to be designed and added with two functions on the basis of meeting the requirements of the optical transparent semiconductor material and the thin film technology of the traditional optical branched waveguide. The design idea is as follows: 1. the transparent semiconductor film material with an amorphous-nanocrystalline structure is used, so that the flexible and bendable requirements can be met; 2. the light power of the refraction light is changed by utilizing the transmissivity characteristic of the voltage-tunable electrochromic material, and the reflection light and the refraction light are respectively led out from the two branch channels, so that the requirement of quantitatively controlling the branch light power by the voltage is met.
Disclosure of Invention
The invention aims to invent a flexible tunable visible-near infrared band branch optical waveguide device and a preparation method thereof, and the obtained branch optical waveguide device has better optical power tuning property, stable optical branching effect and lower loss rate under the bending condition of a flexible substrate.
The flexible tunable visible-near infrared band branch optical waveguide device is characterized by comprising a flexible transparent substrate, a conductive electrode, a normal optical waveguide layer and an electrochromic optical waveguide layer, wherein the normal optical waveguide layer and the electrochromic optical waveguide layer are paved on the upper surface of the flexible transparent substrate, the normal optical waveguide layer and the electrochromic optical waveguide layer are in a layer, the normal optical waveguide layer adopts a Y-shaped branch structure, namely an A strip before branching, a B strip after branching and a C strip after branching, and one side edge of the A strip before Y-shaped branching of the normal optical waveguide layer is tightly connected with one side edge of the electrochromic optical waveguide layer; the electrochromic optical waveguide layer is also led out with a conductive electrode which is partially overlapped with the electrochromic optical waveguide layer and is used for loading voltage to the electrochromic optical waveguide layer, and the conductive electrode is tiled and fixed on the flexible transparent substrate; conductive electrode and normal light wave the guiding layer is not in direct contact.
The flexible transparent substrate is PET or PDMS.
The conductive electrode adopts a layered structure and is a metal nanoparticle layer or a graphene film layer.
The normal optical waveguide layer and the electrochromic optical waveguide layer of the present invention may be conventional ones.
Further preferably, the normal optical waveguide layer is a transparent semiconductor thin film material of an amorphous-nanocrystalline composite structure, preferably graphene doped (In 2 O 3 ) x (ZnO) y (Ga 2 O 3 ) z Film material (molar ratio of In, zn and Ga is 0.6-0.9:0.2-0.05:0.2-0.05), electrochromic optical waveguide layer (region) material is preferably amorphous-nanocrystalline composite structure film material, and more preferably (ITO) x (Nb 2 O 5 ) y (Ga 2 O 3 ) z The molar ratio of the thin film material to the indium, the tin, the niobium and the gallium is 0.54-0.81:0.06-0.09:0.05-0.35:0.05-0.35.
Conductive electrode and electrochromic light wave the guiding layer has a partially overlapping portion, the conductive electrode is located between the flexible transparent substrate and the electrochromic optical waveguide layer.
The electrochromic optical waveguide layer is of a strip structure, the long side of the strip structure of the electrochromic optical waveguide layer is the same as the length of the long side of the A strip before Y-shaped branching of the normal optical waveguide layer, and is tightly connected, and the long side of the A strip is parallel to the symmetry axis of the Y-shaped branching structure, as shown in the top view of fig. 1.
The preparation method of the flexible tunable visible-near infrared band branch optical waveguide device is characterized by adopting a conventional preparation method, preparing a single layer, etching a pattern in photoresist by adopting a photoetching technology, preparing a single-layer material film by adopting a sol-gel spin coating method, and removing the photoresist to retain the required material pattern.
Electrochromic amorphous-nanocrystalline composite structure (ITO) x (Nb 2 O 5 ) y (Ga 2 O 3 ) z The preparation of the film comprises the following steps:
step 1, indium chloride (InCl) 3 ) Tin tetrachloride (SnCl) 4 ) Niobium pentachloride (NbCl) 5 ) And gallium trichloride (GaCl) 3 ) Adding ammonia water into the mixed aqueous solution, and adjusting the pH value to 8-10 to ensure that cations are completely converted into hydroxide precipitates;
step 2, repeatedly cleaning the mixed hydroxide precipitate by deionized water and an alcohol solvent respectively, and carrying out solid-liquid separation to obtain a hydroxide precursor;
and 3, mixing the hydroxide precursor with ethanol, adding ethanolamine, performing ultrasonic dispersion to obtain a suspension, placing the suspension into an autoclave for heat treatment to obtain an indium tin gallium niobium oxide nanocrystalline dispersion, and performing spin coating to prepare the flexible electrochromic optical waveguide layer film with the amorphous-nanocrystalline composite structure.
Further, the molar ratio of indium ions, tin ions, niobium ions and gallium ions in the step 1 of preparing the electrochromic layer is 0.54-0.81:0.06-0.09:0.05-0.35:0.05-0.35.
Further, the molar ratio of hydroxide precursor to ethanolamine in electrochromic layer preparation step 3 is 1:2, the heat treatment temperature of the autoclave is 200-260 ℃ and the time is 10-40 hours.
The preparation of the normal optical waveguide layer (i.e., transparent optical waveguide layer) includes the steps of:
step 1, carrying out ultrasonic heating reduction on a graphene oxide aqueous solution to obtain graphene nano sheets, controlling the size of the graphene nano sheets by heating temperature and reducing agent proportion, repeatedly centrifuging and washing to obtain a neutral aqueous solution, carrying out ultrasonic scattering, and heating to obtain graphene nano particles for later use;
step 2, inCl 3 、Zn(OAC) 2 、GaCl 3 Dissolving the reagent in glycol solution, heating and stirring until the reagent is colorless and transparent, and obtaining indium gallium zinc oxide sol mixture;
step 3, mixing graphene nano particles with indium gallium zinc oxide sol, and ultrasonically heating and stirring the obtained colorless transparent solution in a water bath to form sol;
and 4, spin-coating the transparent sol obtained in the step 3 through a spin-coating instrument, annealing, and repeating spin-coating and annealing for a plurality of times to prepare the flexible nanoscale transparent optical waveguide film.
Further, in the step of preparing the optical waveguide layer, inCl 3 、Zn(OAC) 2 、GaCl 3 The molar ratio of (2) is 0.6-0.9:0.2-0.05:0.2-0.05; inCl 3 、Zn(OAC) 2 、GaCl 3 The purity of (2) is 99.99%, and the ratio of graphene nanoparticles to the amount of the material of InCl3 is 1:100-1:700.
Further, the ultrasonic reduction heating temperature is 60-95 ℃ and the time is 1-3 hours in the optical waveguide layer preparation step 1; the reducing agent is hydrazine hydrate, and the mass ratio of the hydrazine hydrate to the graphene oxide is 6:10-8:10.
Further, the optical waveguide layer is prepared by InCl described in the step 2 3 、Zn(OAC) 2 、GaCl 3 When dissolved and stirred in glycol solution, the temperature is 20-65 ℃ and the stirring time is 0.5-2 hours;
further, the water bath heating temperature in the optical waveguide layer preparation step 3 is 25-80 ℃ and the heating time is 0.5-4 h.
Further, the annealing temperature of the film in the preparation step 4 of the optical waveguide layer is 50-150 ℃, the annealing time is 0.5-2 h, the spin coating annealing is repeated for 4-18 times, and the thickness of the optical waveguide film is 150-3000 nm.
The tunable branch optical waveguide device has better flexibility and electro-optical modulation branch optical power effect, and utilizes the real electro-optical modulation effect and combines total light reflection and transmittance to realize optical modulation. The invention has the advantages of wide application in passive optical devices, strong expandability, simple manufacturing flow, low cost and the like.
The normal optical waveguide layer has the important effects on the structural change and the appearance of functional performance based on element doping, the indium (In) element doping has the effect of generating a nano crystalline state and improving the light transmittance In a near infrared region, the gallium (Ga) element doping has the effect of keeping an amorphous structure of molecules, and the zinc (Zn) element doping keeps a nano crystal micro-nano covalent structure, so that the film has better mobility and an amorphous-nano crystal mixed structure under a flexible bending condition.
The normal optical waveguide layer adopts the graphene nanostructure doping technology, so that the problem of poor electrical property of the flexible transparent oxide semiconductor film prepared by a chemical method is effectively solved.
Drawings
FIG. 1 is a top view of a flexible tunable visible-near infrared branched optical waveguide device structure;
FIG. 2 is a front view of a flexible tunable visible-near infrared branched optical waveguide device structure;
1 a flexible transparent substrate, 2 a normal optical waveguide layer 3 electrochromic optical waveguide layer, 4 conductive electrode.
Fig. 3 is an X-ray diffraction pattern of an indium tin niobium gallium oxide thin film of an electrochromic optical waveguide zone amorphous-nanocrystalline composite structure of example 1.
Fig. 4 example 1 an X-ray diffraction pattern of an amorphous-nanocrystalline composite structured graphene doped indium gallium zinc oxide transparent conductive film.
Detailed Description
The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the following examples.
Example 1
A flexible tunable visible-near infrared band branch optical waveguide device comprises a flexible substrate, a conductive electrode layer, an optical waveguide layer and a covering layer, and is characterized in that the flexible transparent substrate is PET or PDMS, the conductive electrode layer is a metal nanoparticle layer or a graphene film layer, the optical waveguide layer is divided into a normal optical waveguide area and an electrochromic optical waveguide area, and the structural schematic diagrams of the optical waveguide device are respectively shown in fig. 1 and 2; the normal optical waveguide layer is an amorphous-nanocrystalline graphene doped layer of (In 2 O 3 ) x (ZnO) y (Ga 2 O 3 ) z Thin film material, electrochromic optical waveguide zone material is amorphous-nanocrystalline composite structure (ITO) x (Nb 2 O 5 ) y (Ga 2 O 3 ) z A film material.
The specific embodiment comprises the following steps:
step 1, mixing 0.5 g of standby graphene nano-sheets with 2ml of ethanol, and performing ultrasonic dispersion to obtain suspension dispersion. And spin-coating S1813 photoresist on the flexible transparent substrate, preparing a planar structure by using a maskless direct-writing photoetching system, spin-coating graphene dispersion liquid, and removing the photoresist to obtain a graphene conductive micro-nano structure serving as a conductive electrode.
Step 2, spin-coating S1813 photoresist on the substrate obtained in the step 1, and using maskless direct writing light
Preparing a planar structure by an etching system, spin-coating indium tin gallium niobium oxide nanocrystalline dispersion liquid, and removing photoresist to obtain a flexible electrochromic optical waveguide layer film, wherein the flexible electrochromic optical waveguide layer film is overlapped with end points of the two conductive electrodes; the method specifically comprises the following steps:
(1) 2.633 g of indium chloride (InCl 3 ) 0.354 g tin tetrachloride (SnCl) 4 ) 2.432 g niobium pentachloride (NbCl) 5 ) And 0.176 g of gallium trichloride (GaCl) 3 ) Adding 3ml of ammonia water into the mixed aqueous solution, and adjusting the pH value to be about 9 so that cations are completely converted into hydroxide precipitates;
(2) Repeatedly cleaning with deionized water and alcohol solvent for 4 times, mixing hydroxide for precipitation, and carrying out solid-liquid separation to obtain a hydroxide precursor;
(3) Mixing the precursor with 20ml of ethanol, adding 10ml of ethanol, ultrasonically dispersing to obtain suspension, placing the suspension into an autoclave for heat treatment to obtain indium tin gallium niobium oxide nanocrystalline dispersion, and performing spin coating to prepare the flexible electrochromic optical waveguide layer film with the amorphous-nanocrystalline composite structure.
And 3, preparing a Y-type normal optical waveguide layer on the side edge of the flexible electrochromic optical waveguide layer film on the substrate obtained in the step 2, wherein the Y-type normal optical waveguide layer comprises the following specific steps:
(1) Taking 0.2ml of graphene oxide aqueous solution, carrying out ultrasonic treatment for 0.5 hour, adding 0.3ml of hydrazine hydrate, heating in a water bath at 85 ℃ for 1 hour to reduce the hydrazine hydrate into graphene nano sheets, adding ammonia water to clean the hydrazine hydrate after heating reduction reaction, and repeatedly centrifuging and washing the hydrazine hydrate with deionized water to obtain a neutral aqueous solution, carrying out ultrasonic scattering and heating until the graphene nano powder is ready for use.
(2) 5.865 g of InCl 3 0.548 g Zn (OAC) 2 0.44 g of GaCl 3 Dissolving the high-purity reagent in 10ml of glycol solution, heating and stirring to colorless transparent solution at 50 ℃;
(3) Mixing graphene nanosheet powder with an indium gallium zinc oxide solution, and ultrasonically heating and stirring a colorless transparent solution to be sol in a water bath at 30 ℃;
(4) Spin-coating transparent sol at 3000 rpm in spin-coating apparatus, annealing at 100deg.C for 45 min, repeating for 8 times, removing photoresist (removing photoresist after repeated annealing), and making into normal optical waveguide region of symmetrical Y-type two-branch optical waveguide structure on substrate. The normal optical waveguide film thickness is 1500nm-3000nm, and the refractive index of the film to 1550nm laser is 2.4.
According to the flexible tunable visible-near infrared band branch optical waveguide device and the preparation method thereof, provided by the invention, based on the important influence of element doping on the change of molecular structure and the appearance of functional performance, indium (In) element doping has the effect of generating nano crystalline state and improving the light transmittance In a near infrared region, gallium (Ga) element doping has the effect of keeping an amorphous structure of molecules, zinc (Zn) element doping keeps a nano crystalline micro-nano covalent structure, and niobium (Nb) element doping has electrochromic characteristics, so that the device has flexible tunable optical branch waveguide characteristics on visible-near infrared band light under flexible bending conditions.
Claims (4)
1. The flexible tunable visible-near infrared band branch optical waveguide device is characterized by comprising a flexible transparent substrate, a conductive electrode, a normal optical waveguide layer and an electrochromic optical waveguide layer, wherein the normal optical waveguide layer and the electrochromic optical waveguide layer are paved on the upper surface of the flexible transparent substrate, the normal optical waveguide layer and the electrochromic optical waveguide layer are in a layer, the normal optical waveguide layer adopts a Y-shaped branch structure, namely an A strip before branching, a B strip after branching and a C strip after branching, and one side edge of the A strip before Y-shaped branching of the normal optical waveguide layer is tightly connected with one side edge of the electrochromic optical waveguide layer; the electrochromic optical waveguide layer is also led out with a conductive electrode which is partially overlapped with the electrochromic optical waveguide layer and is used for loading voltage to the electrochromic optical waveguide layer, and the conductive electrode is tiled and fixed on the flexible transparent substrate; the conductive electrode is not in direct contact with the normal optical waveguide layer;
the flexible transparent substrate is PET or PDMS;
the conductive electrode adopts a layered structure, and is a metal nanoparticle layer or a graphene film layer;
the normal optical waveguide layer is a transparent semiconductor film material with an amorphous-nanocrystalline composite structure, and the electrochromic optical waveguide layer material is a film material with an amorphous-nanocrystalline composite structure;
the normal optical waveguide layer is graphene doped (In 2 O 3 ) x (ZnO) y (Ga 2 O 3 ) z The mole ratio of In, zn and Ga of the film material is 0.6-0.9:0.2-0.05:0.2-0.05; electrochromic optical waveguide layer Is (ITO) x (Nb 2 O 5 ) y (Ga 2 O 3 ) z The film material has the molar ratio of indium, tin, niobium and gallium of 0.54-0.81:0.06-0.09:0.05-0.35:0.05-0.35;
the conductive electrode and the electrochromic optical waveguide layer are partially overlapped, and the conductive electrode is positioned between the flexible transparent substrate and the electrochromic optical waveguide layer;
the electrochromic optical waveguide layer is of a strip structure, the length of the long side of the strip structure of the electrochromic optical waveguide layer is the same as that of the long side of the A strip before Y-shaped branching of the normal optical waveguide layer, the long side of the A strip is tightly connected with the symmetry axis of the Y-shaped branching structure.
2. A method of making a flexible tunable visible-near infrared band branching optical waveguide device of claim 1, comprising the steps of: preparing a single layer, etching a pattern in the photoresist by adopting a photoetching technology, preparing a single layer material film by adopting a sol-gel spin coating method, and removing the photoresist to reserve the required material pattern;
wherein the electrochromic layer is amorphous-nanocrystalline composite structure (ITO) x (Nb 2 O 5 ) y (Ga 2 O 3 ) z The preparation of the film comprises the following steps:
step 1, indium chloride (InCl) 3 ) Tin tetrachloride (SnCl) 4 ) Niobium pentachloride (NbCl) 5 ) And gallium trichloride (GaCl) 3 ) Adding ammonia water into the mixed aqueous solution, and adjusting the pH value to 8-10 to ensure that cations are completely converted into hydroxide precipitates;
step 2, repeatedly cleaning the mixed hydroxide precipitate by deionized water and an alcohol solvent respectively, and carrying out solid-liquid separation to obtain a hydroxide precursor;
step 3, mixing a hydroxide precursor with ethanol, adding ethanolamine, performing ultrasonic dispersion to obtain a suspension, placing the suspension into an autoclave for heat treatment to obtain an indium tin gallium niobium oxide nanocrystalline dispersion, and performing spin coating to prepare a flexible electrochromic optical waveguide layer film with an amorphous-nanocrystalline composite structure;
the normal optical waveguide layer preparation includes the steps of:
step 1, carrying out ultrasonic heating reduction on a graphene oxide aqueous solution to obtain graphene nano sheets, controlling the size of the graphene nano sheets by heating temperature and reducing agent proportion, repeatedly centrifuging and washing to obtain a neutral aqueous solution, carrying out ultrasonic scattering, and heating to obtain graphene nano particles for later use;
step 2, inCl 3 、Zn(OAC) 2 、GaCl 3 Dissolving the reagent in glycol solution, heating and stirring until the reagent is colorless and transparent, and obtaining indium gallium zinc oxide sol mixture;
step 3, mixing graphene nano particles with indium gallium zinc oxide sol, and ultrasonically heating and stirring the obtained colorless transparent solution in a water bath to form sol;
and 4, spin-coating the transparent sol obtained in the step 3 through a spin-coating instrument, annealing, and repeating spin-coating and annealing for a plurality of times to prepare the flexible nanoscale transparent optical waveguide film.
3. The method according to claim 2, wherein in the step of preparing the optical waveguide layer, inCl 3 、Zn(OAC) 2 、GaCl 3 The molar ratio of (2) is 0.6-0.9:0.2-0.05:0.2-0.05; inCl 3 、Zn(OAC) 2 、GaCl 3 The purity of (2) is 99.99%, and the ratio of the graphene nano particles to the amount of the InCl3 substance is 1:100-1:700; the thickness of the optical waveguide film is 150nm-3000nm;
electrochromic amorphous-nanocrystalline composite structure (ITO) x (Nb 2 O 5 ) y (Ga 2 O 3 ) z Step 1 of film preparation indium chloride (InCl 3 ) Tin tetrachloride (SnCl) 4 ) Niobium pentachloride (NbCl) 5 ) And gallium trichloride (GaCl) 3 ) The molar ratio of (2) is 0.54-0.81:0.06-0.09:0.05-0.35:0.05-0.35.
4. The method according to claim 2, wherein the ultrasonic reduction heating temperature in the optical waveguide layer preparation step 1 is 60 ℃ to 95 ℃ for 1 to 3 hours; the reducing agent is hydrazine hydrate, and the mass ratio of the hydrazine hydrate to the graphene oxide is 6:10-8:10;
InCl described in optical waveguide layer preparation step 2 3 、Zn(OAC) 2 、GaCl 3 When dissolved and stirred in glycol solution, the temperature is 20-65 ℃ and the stirring time is 0.5-2 hours;
the heating temperature of the water bath in the step 3 of preparing the optical waveguide layer is 25-80 ℃ and the heating time is 0.5-4 h;
the annealing temperature of the film in the optical waveguide layer preparation step 4 is 50-150 ℃, the annealing time is 0.5-2 h, and the spin coating annealing times are repeated for 4-18 times;
the molar ratio of hydroxide precursor to ethanolamine in electrochromic layer preparation step 3 is 1:2, the heat treatment temperature of the autoclave is 200-260 ℃ and the time is 10-40 hours.
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