TWI309050B - Azo transparent conducting film with metallic nano particles and method of producing thereof - Google Patents

Description

Ι3〇9〇^οε/ε Nine, invention description: [Technical field of the invention] The present invention relates to a transparent conducting film and a method of manufacturing the same, and in particular to a method having a low electrical resistivity ( A conductive nano-particle of a resistivity-containing aluminum-doped zinc oxide (AZO) transparent conductive film and a method for producing the same.

[Prior Art] Transparent conductive oxide (TCO) thin films are widely used in various optoelectronic products due to their good electrical conductivity, high transparency in the visible range, infrared reflectance, and semiconductor characteristics, such as: Flat panel display, solar cell, photoelectric crystal, touch sensing panel (Wh P_l), light-emitting element, organic light-emitting flat display panel (PDPPanel), automotive heat-resistant defogging glass, optical conversion &, transparent heater anti-static film, infrared Anti (four) use broken glass and so on. Therefore, the material development, nature and process of TC〇9 Wenliang and applied research, etc., are highly valued. The thriving development of the special optoelectronic components has made it possible to make four (4) nucleus plates (4) and (7) film processes. ;S = = = for gas phase process and wet process

The above method requires i to use heat: 疋 is the main one. However, because of the initial conditions and methods of the film, the TCO causes D:: *, the phase structure and the compactness have considerable shadows, and the gamma is Conductive properties and the performance of the first penetration; change: and 5

I309 (Ht film lattice structure tends to be complete and crystal growth becomes larger, which can make the film interface contribute to the improvement of carrier mobility and increase the conductivity. Therefore, the process of 4lTC0 film needs to go through high temperature process or the latter stage. High temperature heat treatment to improve its electrical conductivity (τ > 4 (8). c). However, although the high heat treatment temperature will help crystal growth, it will also reduce = 0 xygenvacancy), but cause Τ [invention] The purpose is to provide the conductivity of the ruthenium film without providing a change in the light transmittance of the nano-metal film containing nano-metal particles. A further object of the present invention is to provide a nano-particle containing nano-particles: transparent ir: an axis-oxidized pen containing nano metal particles) zinc telluride and nano-gold coefficient, including blending °-°1 At.〇/0^ 5 at.% 〇,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The zinc-containing (AZO) transparent conductive ruthenium, the ruthenium granules of the ruthenium granules, and the granules of the emulsified zinc can be blended according to the preferred embodiment of the present invention. 13〇9Q milk doc/e aluminum zinc oxide transparent conductive film,, • gold, platinum, indium, gallium, lithium, the above nano metal particles are selected from the group consisting of silver, _ the invention is good;: copper and bismuth - Aluminium ZnO transparent conductive Λ 掺 掺 例 例 例 例 例 例 例 例 例 例 例 例 例 例 掺 掺 掺 掺 掺 掺 掺 含 含 含 含 含 含 含 含 含 含 含 吕 吕 吕 吕 吕 吕 吕 吕 吕 吕 吕 吕 吕 吕Also, the nano metal-containing particles are doped with nm. The particle size of the above-mentioned nano metal particles is less than about 5 〇. g g x φ (ΑΖΟ) transparent conductive belly f The method for preparing the doped zinc oxide by using the metal oxide particles is to add the metal precursor into the alcohol-containing reaction solution of the zinc sulfide, and the alcohol-based rape Forming! The formation of the lyotropic gel produces a nano-metal colloidal Loose solution. The colloidal solution is a colloidal solution containing nano-sized metal particles t ^ Zn ZnO. Next, the colloidal solution is made into a film, and then The film is subjected to a heat treatment process, the job-transparent conductive film. According to the manufacturing method of the preferred embodiment of the present invention, the heat treatment process comprises a two-stage process, including a first heat treatment: performing calcination; and Heat treatment: heat treatment of hydrogen. According to a preferred embodiment of the present invention, the above heat treatment process may be a hydrogen heat treatment. According to a preferred embodiment of the present invention, the above-described method of forming a colloidal solution into a film Methods include spin coating, dipping, printing, screen printing, stencil printing, spraying (spraying) Or roller coating. 7 I309Q^doc/e The manufacturing method described in the preferred embodiment, the content of the nano metal particles in the transparent electric handle is aG1 at. / to 5 at .%^月金属佳佳例 The manufacturing method described in the above-mentioned nano sharp c including silver, gold, indium, gallium, nickel, steel and granules _) transparent conductive film containing nano gold = Γ Lifting the conductivity of the film. Moreover, the present invention is different from the second process in the preparation of a transparent conductive film by a wet process, so that it can be advanced, which not only has low equipment cost, but also has a large product area. Under the yak, it is easy to be Ϊί;=Ϊ:;卜文m关, and with the accompanying drawings, the details are described. [Embodiment] The invention - the preferred embodiment of the nano-particle-containing metal-containing zinc-containing (yttrium) transparent conductive film preparation

Please take a photo of Fig. 1, first step 1ηΛ by 丨k M with a zinc oxide (AZ0) colloidal solution: this material 104 is added by sol gel method to make C: to Weng Yue ij drive, after step K) 6 mix After the alcohol-containing reaction liquid 102 of the ίί 3, the step (10)%1: reverse 2 is carried out, and the metal precursor is reduced by the alcohol, and the mixture is mixed to form the nano metal particles to form a shim gel. At the same time, the child is selected from the group consisting of silver, gold, Ming, and marriage; one of the above-mentioned nano-metal particles, and the remainder is gold or _(two) gold ^Ϊ ^, copper and Ming among them 8 1309 (3⁄43⁄4^ In step 120, coating is performed to form a film to form a film into a film, and the film forming method is, for example, spin coating, dipping, printing. ), screen printing, stencil printing, spraying (10) mying) or roller spinning (roller (3) also beer); preferably by spin coating or dip coating. Thereafter, in step 130, The film is heat-treated to form a transparent conductive film having a thickness of, for example, 20 Å to 2000 The climbing room preferably has a thickness of 200 _ to i_nm. The heat treatment process of step 13 可以 may be a two-stage process or a direct nitrogen heat treatment. The 'two-stage process includes the first one for calcination. The second heat treatment and the second heat treatment for performing the hydrogen heat treatment. Further, the content of the nano metal particles in the formed transparent conductive film is about 5% to at.〇/〇; preferably at 〇〇5. % to the station%. Moreover, the particle size of the above-mentioned tow particles is less than about 5〇11111. Several examples will be given to illustrate the contents of the present invention in detail, and the scope of the invention is not limited These examples. Consistent example - AZ〇 transparent conductive film containing silver navel green

~ 犯 、 、 视 、 、 、 、 、 、 、 、 、 含 含 含 含 含 含 含 含 含 含 含 含 含 含 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇 乙醇Next, an appropriate amount of zinc acetate (Zn(CJJ3C〇〇)2_2H2〇) and chlorinated (Αΐα3·6Η20) (Α1/Ζη atomic ratio of about ! at.%) were placed in a 3 〇 ml sample bottle. Then, an appropriate amount of 2-methoxypheneethanol (2-meth^yeAanol), the above-mentioned 〇JM silver nitrate and ethanol solution or aqueous solution, and monoethylamine (MEA) (MEA/Zn2+) The molar ratio is 1: 1), and is sequentially added to a sample bottle containing zinc acetate and aluminum chloride to form a mixed solution containing 〇.75M Zn2+ ions. Then, the above mixed solution is placed in a constant temperature water bath, and the temperature is maintained at 60, and the mixture is uniformly stirred to obtain an AZ 〇 colloidal solution containing silver nanoparticles. Then 'take an appropriate amount of AZ0 colloidal solution containing silver nanoparticles on the glass substrate, and then sequentially apply, dry, calcination, hydrogen heat treatment, etc. to obtain - simultaneously with high transparency and conductivity Conductive film. For example, the steps are as follows: 1. The prepared silver-containing lanthanum AZQ was added to a glass substrate, and then spin-coated at about 3000 rpm for 3 seconds. • 2. Place the surface substrate after (4) at 350. (: 10 minutes of drying in a high temperature furnace. Then you can choose to perform the following steps 3a or 3. 3a. Two-stage heat treatment: the first heat treatment is to apply the dried glass substrate to a high temperature furnace for forging After burning for a few hours, the crystallinity and transparency of the test piece are improved. The second heat treatment: the calcined test piece is fed into a tube type having a mixed atmosphere of 3% hydrogen (3⁄4) and 97% argon (10). In the furnace, hydrogen gas heat treatment is carried out for 1 hour to generate oxygen vacancies in the test piece, thereby further improving the conductive properties. 1309·——People's treatment: The glass substrate after drying the cloth is subjected to hydrogen heat treatment for 2 hours, solid 3: In the furnace, the actual oxygen vacancy is carried out to increase the conductive properties. == The resistivity value is lower than the existing lion =; electricity; the particle size range of the rice particles is about 20-30 nm. = The phenomenon of surface crystal agglutination is more obvious. When Ag = 2 3tf), it is a continuous and dense film, and its thickness is about the light transmittance of the visible light range. The AZ is transparent. Method for preparing conductive film based on ethanol, hydrazine: supplement is used to prepare AZ 〇 colloidal solution Methoxy child, due to / in the presence of gold atom precursor is reduced to form the gold particles dagger body wins, two nanoscale particles resulting colloid used. The process of water after ί ^ = Ϊ ^ gold acid (HAUa4) and ethanol or the removal solution as the metal aiMAu3+ ion of ethanol or water from ~, ^' is similar to that of Example 1. The AZO transparent conductive 2 of the film with the different gold content of the second = f = 2, the resistance coefficient of the second heat treatment of the person I Ming is shown in Fig. 2. From the graph resistance (10) transparent conductive film after the completion of heat treatment, the wave = number can be lower than 2Xl〇l, or even close to (four), 丄 卜 关于 贯 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 关于 含 含 含For the .doc/e rate, please refer to Fig. 3, which is the AZ0 transparent conductive yt of different tera-particle content, with uv 2 = length 300_~800_ light penetration property. As can be seen from Fig. 3, the aperture transmittance can be greater than 85%. The above-mentioned metal particles under the axial zinc oxide (AZQ) transparent conductive film of the present invention can improve the conductivity of the film without affecting the light transmittance. Moreover, in the present month, the wet film is prepared by a wet process, which can be carried out under healthy conditions, which not only has low equipment cost = although the present invention has been disclosed in the preferred embodiment as above, 1 The skilled artisan's scope can be changed and (4) without departing from the spirit of the invention, and therefore the scope of the invention is defined by the scope of the patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a process drawing diagram of an aluminum-doped zinc oxide (yttrium) transparent conductive film containing nano metal particles in accordance with a preferred embodiment of the present invention. 2 is a graph showing the relationship between the content of aluminum nano/zinc+ in the two-stage heat treatment of the aluminum-containing zinc oxide containing the nano metal particles of the present invention (%). FIG. A graph of the wavelength and transmittance of the aluminum-doped (yttrium) transparent conductive film of the present invention with different nano gold particle contents. [Main element symbol description] 100, 106, 108, 120, 130: Step 104 ·· Metal precursor (7) 2: Preparation of an alcohol-containing reaction solution of hydrazine by a sol gel method 12

Claims (1)

:wf.doc/e X. Patent application scope: - 1. An aluminum-doped zinc oxide (AZO) transparent conductive film containing nano metal particles, which has a resistivity of less than 2χ10_3Ωτιη, including: aluminum-doped zinc oxide; The metal metal particles, wherein the content of the nano metal particles is 0.01 at.% to 5 at.%. 2. The aluminum-doped zinc oxide transparent conductive film containing nano metal particles according to claim 1, which has a light transmittance of 85% or more. 3. The aluminum-doped zinc oxide transparent conductive film containing nano metal particles according to claim 1, wherein the aluminum-doped zinc oxide has an aluminum content of 0.5 at.% to 10 at.%. 4. The aluminum-doped zinc-containing transparent conductive film containing nano metal particles according to claim 1, wherein the nano metal particles are selected from the group consisting of silver 'gold' hook 'indium' gallium 'nickel' palladium 'Copper and one of its t. 5. The aluminum-doped zinc oxide transparent conductive film containing nano metal particles according to claim 1, which has a thickness of from 200 nm to 1000 nm. Φ 6. The aluminum-doped zinc oxide transparent conductive film containing nano metal particles according to claim 1, wherein the nano metal particles have a particle diameter of less than 50 7 nm ° 7. The method for manufacturing an aluminum-doped zinc oxide (AZO) transparent conductive film comprises: adding a metal precursor to an alcohol-containing reaction solution prepared by a melt-gel method to form aluminum-doped zinc oxide, and performing the reduction by alcohol reduction The aluminum zinc oxide sol gel is formed at the same time to produce nano metal particles to form a colloidal solution. The 13 d〇c/e solution of the gel is a ruthenium-containing, zinc-zinc colloid, and a ruthenium film is applied to the tantalum film. Such as Shen Zhi straight ... to ^ to form a transparent conductive film. A method for producing a nanoparticle-containing nanoparticle according to the seventh aspect of the invention, wherein the heat includes: f-man heat treatment·for calcination; and second heat treatment: hydrogen heat treatment. Chain negative ttt Please refer to the manufacturing method of the metal-containing metal particles according to Item 7 of the patent scope, wherein the Lai processing process includes a rolling heat treatment. |0. The method for manufacturing a nano-particle containing nano-particles as described in claim 7 of the patent application, the method for producing a transparent zinc-conducting galvanic method, the method for forming the colloidal solution into a film, including spin coating method (Spin) C〇ating), dip coating, printing, screen printing, stencil printing, spraying or roller coating (r〇ller coating) 11. The method for producing an aluminum-doped zinc oxide transparent conductive film containing a nano metal pole according to claim 7, wherein the content of the nano metal particles in the transparent conductive material is 〇.〇1 at ·% to 5 at.%. 12. The method according to claim 7, wherein the nano metal dipole is selected from the group consisting of silver, gold, platinum, indium, and gallium. , recording, turning, copper and Ming