TWI385267B - Method of fabricating patterned metal oxide layer - Google Patents

Description

Patterned metal oxide layer manufacturing method

The present invention relates to a method of fabricating a metal oxide layer, and more particularly to a method of fabricating a patterned metal oxide layer in a low temperature manner.

In general, metal oxide layers are commonly used as materials that resist friction, oxidation, and high impedance. However, in recent years, many documents have revealed that metal oxide layers can be applied to semiconductors and magnetic materials. The conventional metal oxide layer is mainly produced by chemical vapor deposition (CVD) or sputtering. However, these methods of making metal oxide layers generally require the use of high vacuum equipment and require high temperature processing procedures, which results in increased manufacturing costs and increased process complexity.

The process of patterning a metal oxide layer is usually carried out by photolithography, which requires multiple processes such as coating, exposure, development, and etching of high-risk agents, which increases the process. Cost and risk. In addition, the metal oxide pattern layer can also be produced by using a screen printing metal oxide paste and a high-temperature sintering method. Although the process is relatively simple, there is still a procedure requiring high temperature treatment. Although the above two methods have been widely used in the industry, the production of the mask and the screen is still one of the factors that cannot reduce the process cost, and the above process cannot have the flexibility of making the image.

On the other hand, as the need for green environmental protection is raised, the process is simplified, High material utilization and low pollution processes have become the mainstream of the future. Therefore, how to make a patterned metal oxide layer in an environmentally friendly, simple process and cost-saving manner has become one of the important issues in the industry.

In view of the above, the object of the present invention is to provide a method for fabricating a patterned metal oxide layer, which is simpler, more cost-effective and environmentally friendly than conventional methods, and can improve the film properties of the patterned metal oxide layer. .

The invention provides a method for fabricating a patterned metal oxide layer. First, a substrate is provided, and then a surface modification step is performed on the substrate. Next, a substrate is subjected to a one-digit printing step to coat the catalyst in a region where the patterned metal oxide layer is pre-formed. Thereafter, a low temperature electroless plating step is performed to deposit a patterned metal oxide layer on a region of the substrate on which the patterned metal oxide layer is pre-formed.

According to the manufacturing method of the patterned metal oxide layer according to the embodiment of the present invention, the above-mentioned digital printing step is an inkjet method, and the catalyst used is, for example, a metal ion compound, a nano metal particle, a nano alloy metal particle. Or metal oxide particles.

According to the method for fabricating a patterned metal oxide layer according to an embodiment of the present invention, the reaction temperature of the low temperature electroless plating step is less than 100 °C. Further, the reducing agent used in the low temperature electroless plating step is, for example, an alcohol, dimethylamine borane, ascorbic acid, formaldehyde or hydrazine hydrate.

According to a method of fabricating a patterned metal oxide layer according to an embodiment of the invention, the material of the patterned metal oxide layer is, for example, oxidized. Zinc, indium oxide, chromium oxide, tin oxide, manganese oxide, triiron tetroxide, silver oxide, lead oxide, copper oxide, cerium oxide or titanium oxide.

According to the method for fabricating a patterned metal oxide layer according to an embodiment of the invention, the surface modification step is selected from the group consisting of an ultraviolet ozone treatment step, a plasma treatment step, a self-assembled monolayer treatment step, and a polyelectrolyte. A group consisting of molecular membrane processing steps. The plasma processing step is, for example, a normal piezoelectric slurry treatment step, an etching plasma treatment step, or an ion coupling plasma treatment step. The plasma source used in the plasma treatment step includes, for example, ozone (O ₃ ), carbon tetrafluoride (CF ₄ ), sulfur hexafluoride (SF ₆ ), hexafluoroethane (C ₂ F ₆ ), octafluorocarbon. Butane (C ₄ F ₈ ), difluoromethane (CH ₂ F ₂ ) or argon (Ar). In addition, the self-assembled monolayer film processing step forms a monolayer film on the substrate, which is a functional group having a long-chain carbene at one end and -SH, -OH or -NH at the other end. The self-assembled monolayer film processing step is, for example, a soaking method, a spin coating method, an inkjet method, an offset printing method, a letterpress printing method, a gravure printing method, or a microcontact printing method. Further, the polyelectrolyte polymer film treatment step forms a multilayer film on the substrate. The polyelectrolyte polymer film treatment step is, for example, a soaking method, a spin coating method, an inkjet method, an offset printing method, a relief printing method, a gravure printing method, or a microcontact printing method.

According to a method of fabricating a patterned metal oxide layer according to an embodiment of the invention, the substrate is, for example, a glass substrate, a polyester substrate, an plexiglass substrate, a flexible plexiglass substrate, a polyimide substrate, A germanium wafer, a polycarbonate resin substrate or an epoxy resin substrate.

According to the method of fabricating the patterned metal oxide layer according to the embodiment of the present invention, the substrate may be subjected to a cleaning step before the surface treatment step.

According to the method for fabricating the patterned metal oxide layer according to the embodiment of the present invention, after the patterned metal oxide layer is formed, a water removal step may be further performed, which utilizes a method of reducing pressure or baking.

According to the method for fabricating a patterned metal oxide layer according to an embodiment of the present invention, the method can be applied to an oxide semiconductor device process, a magnetic material patterning process, a passive device fabrication, or a high dielectric constant material fabrication.

The method of the present invention forms a patterned metal oxide layer by sequentially performing the steps of surface modification treatment, digital printing treatment, and electroless plating treatment, which is mainly manufactured at a low temperature and has a simple process. Compared with the conventional manufacturing method, the present invention does not need to use high-priced equipment such as exposure, development, etching, and high-temperature operation, and can reduce the mask manufacturing process, thereby saving production cost, reducing waste liquid generation, and meeting environmental protection requirements. On the other hand, the method of the present invention can increase the uniformity and adhesion of the metal oxide layer and contribute to the enhancement of the film properties of the metal oxide layer. Moreover, the method of the present invention is also applicable to many different electronic component processes.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

1 is a flow chart showing the fabrication of a patterned metal oxide layer in accordance with an embodiment of the invention. 2A-2D are schematic cross-sectional views showing a process of patterning a metal oxide layer according to an embodiment of the invention.

Referring to FIG. 1 and FIG. 2A simultaneously, the method for fabricating the patterned metal oxide layer is to first provide a substrate 200. This substrate 200 is, for example, a glass base A board, a polyester terephthalate (PET) substrate, a plexiglass fiber (FR-4) substrate, a flexible plexiglass fiber (flexible FR-4) substrate, a polyimide (PI) substrate, a germanium wafer, A polycarbonate (PC) substrate or an epoxy substrate.

Then, referring to FIG. 1 and FIG. 2B, a surface modification step 210 is performed on the substrate 200 (S110) to form a modified portion 212 on the surface of the substrate 200. The surface modification step 210 can adjust the surface properties of the substrate 200 so that the subsequently preformed catalyst can be adsorbed on the surface of the substrate 200 and contribute to uniformity and adhesion during subsequent coating. The surface modification step 210 is selected from the group consisting of a UV-ozone treatment step, a plasma treatment step, a self-assembled monolayer treatment step, and a polyelectrolyte membranes treatment step. The group that makes up. If the surface modification step 210 uses a UV-ozone treatment step or a plasma treatment step, the modified portion 212 is a substrate surface having excellent surface characteristics. If the surface modification step 210 uses a self-assembled monolayer film treatment step or a polyelectrolyte polymer film treatment step, the modified portion 212 on the surface of the substrate 200 is a single layer film or a multilayer film. Of course, the surface modification step 210 can be arbitrarily matched by these processing steps as needed. In addition, for convenience of explanation of the present embodiment, the modified portion 212 is omitted in the subsequent drawings.

In view of the above, the UV-ozone treatment step mainly uses ultraviolet light and ozone to decompose the pollutants on the surface of the substrate to achieve the purpose of cleaning to improve the surface properties of the substrate. The plasma treatment step is, for example, a normal piezoelectric slurry treatment step, an etching plasma treatment step or an inductively coupled plasma (ICP) treatment step, and the plasma source used is, for example, ozone (O ₃ ), four. Carbon fluoride (CF ₄ ), sulfur hexafluoride (SF ₆ ), hexafluoroethane (C ₂ F ₆ ), octafluorobutane (C ₄ F ₈ ), difluoromethane (CH ₂ F ₂ ) or argon Gas (Ar). The plasma treatment step can improve the surface charge and shape of the substrate 200, as well as improve the uniformity and adhesion of the subsequent coating.

The monolayer film formed by the self-assembled monolayer treatment step contains a long-chain carbene at one end and a functional group of -SH, -OH or -NH at the other end. One end of the functional group containing -SH, -OH or -NH has an adhesion between the substrate and the subsequently preformed plating film. The self-assembled monolayer film processing step can be, for example, using dipping, spin coating, ink-jet printing, flexographic printing, letterpress printing. ), gravure printing or microcontact printing.

Further, the polyelectrolyte polymer film treatment step is carried out, for example, by a dipping method, a spin coating method, an inkjet method, an offset printing method, a relief printing method, a gravure printing method, or a microcontact printing method. Moreover, the polyelectrolyte polymer film processing step is to form a multilayer film by sequentially forming different electrical materials, and the multilayer film can provide a hole structure to increase the adhesion between the substrate and the subsequently preformed plating film. For example, the polyelectrolyte polymer film processing step is performed by a immersion method by first immersing the substrate 200 in a cationic polyelectrolyte solution, and then immersing the substrate 200 in the anionic polyelectrolyte solution, and repeating The above two steps are carried out to form a multilayer film. Wherein, the cationic polyelectrolyte solution is one selected from the group consisting of polypropylene ammonia hydrogen chloride solution (PAH), polyethylpyrazole (PVI ⁺ ), polyethylpyrrolidone (PVP ⁺ ), and polyaniline (PAN); The anionic polyelectrolyte solution is one selected from the group consisting of polyacrylic acid solution (PAA), polymethacrylic acid (PMA), sodium polystyrene sulfonate (PSS), and polycetin-3-acetic acid (PTAA). In addition, the order of immersing the cationic or anionic polyelectrolyte solution may be different for substrates of different materials.

In an embodiment, a cleaning step may be further performed on the substrate 200 prior to performing the surface treatment step 210. This cleaning step is, for example, washing with acetone and deionized water, followed by drying.

Next, please refer to FIG. 1 and FIG. 2C simultaneously, and perform a digital printing step 220 on the substrate 200 (S120). The digital printing step 220 is, for example, an ink jet process that coats the catalyst in a region 230 where the patterned metal oxide layer is pre-formed. The catalyst is, for example, a metal ion compound, a nano metal particle, a nano alloy metal particle or a metal oxide particle, and a metal used in the metal ion compound, the nano metal particle and the nano alloy metal particle is, for example, palladium, platinum or silver. The metal, metal oxide particles are, for example, zinc oxide. That is, the digital printing step 220 is, for example, spraying the ink containing the above-described catalyst on the substrate 200 by digital inkjet printing, and coating only the region 230 in which the patterned metal oxide layer is pre-formed. catalyst. In particular, in the present embodiment, the pattern of FIG. 2C is merely illustrative, and the shape of the region 230 coated with the catalyst is not limited in performing the step of S120, depending on the process requirements or design.

Thereafter, referring to FIG. 1 and FIG. 2D simultaneously, a low temperature electroless plating step (S130) is performed to deposit a patterned metal oxide layer 240 on the region 230 on the substrate 200. The so-called "low temperature" electroless plating step here is The electroless plating step is carried out at a reaction temperature of less than 100 ° C, and preferably at about 60 ° C. In detail, the low-temperature electroless plating step is performed by immersing the catalyst-coated substrate 200 in the step S120 in a plating solution (sometimes referred to as a "plating solution"), and performing a reaction under the condition that the plating solution temperature is less than 100 ° C. Oxide is deposited on the substrate 200. Further, the reducing agent used in the low temperature electroless plating step may be, for example, an alcohol, dimethylamineborane (DMAB), ascorbic acid, formaldehyde or hydrazine hydrate. The material of the patterned metal oxide layer 240 formed is, for example, zinc oxide, indium oxide, chromium oxide, tin oxide, triiron tetroxide, manganese oxide, silver oxide, lead oxide, copper oxide, cerium oxide or titanium oxide. In addition, those skilled in the art will know that when the low temperature electroless plating step is performed, the parameters such as the temperature, pH value, and stirring speed of the plating solution may be related to the film thickness, uniformity, surface type, etc. of the coating film, and Set the parameters depending on the type of coating or the actual conditions of the process.

In other embodiments, after the patterned metal oxide layer 240 is formed, a water removal step may be further performed to remove excess moisture of the patterned metal oxide layer 240. The above water removal step can be carried out by means of reducing the pressure or by baking.

It is worth mentioning that the method of the present embodiment can increase the uniformity and adhesion of the metal oxide layer and contribute to the enhancement of the film properties of the metal oxide layer. In particular, the patterned metal oxide layer of the present embodiment is mainly manufactured at a low temperature and has a simple process, and does not require high-priced equipment such as exposure, development, etching, and high-temperature operation, and can reduce the mask process steps, and the conventional method. Compared with the cost of production, reducing waste generation and meeting environmental requirements begging.

Moreover, the method for fabricating the patterned metal oxide layer of the present embodiment can be applied to many different electronic component processes, such as an oxide semiconductor device process, a magnetic material patterning process, a passive component fabrication, or a high dielectric. Made of electrical constant materials.

Hereinafter, the specific experimental examples will be described in more detail to explain the production method of the present invention and the application of the method of the present invention. In the experimental example, the patterned metal oxide layer was taken as zinc oxide as an example.

Experimental example one

3A is a schematic cross-sectional view showing a semiconductor device fabricated by the method of fabricating the patterned metal oxide layer of the present invention.

Referring to FIG. 3A, a semiconductor element of a top contact structure is fabricated by applying the method of the present invention. First, a surface modification step is performed on the germanium substrate 300, and a modified portion 302 is formed on the substrate 300. A digital inkjet printing step is then performed to spray the catalyst (zinc oxide) onto the area of the subsequently preformed patterned coating. Next, a low temperature electroless plating step is performed to deposit a patterned zinc oxide layer 304 on the substrate 300. Among them, the formulation of the low temperature electroless plating step is: 0.03 mol/L zinc nitrate, 0.01 mol/L DMAB, pH 6.5, and the reaction is carried out at 60 ° C for 30 minutes. Thereafter, the silver electrode 306 is formed by using the inkjet nano silver ink to form a drain and a source to complete the fabrication of the semiconductor device of the upper contact structure.

Experimental example 2

3B is a schematic cross-sectional view showing another semiconductor device fabricated by the method of fabricating the patterned metal oxide layer of the present invention.

Referring to FIG. 3B, a semiconductor element of a bottom contact structure is fabricated by applying the method of the present invention. First, a surface modification step is performed on the germanium substrate 300, and a modified portion 302 is formed on the substrate 300. A digital inkjet printing step is then performed to spray the catalyst (zinc oxide) onto the area of the subsequently preformed patterned coating. Thereafter, the silver electrode 306 is formed using inkjet nano silver ink to form a drain and a source. Next, a low temperature electroless plating step is performed to deposit a patterned zinc oxide layer 304 on the substrate 300 to complete the fabrication of the semiconductor device of the lower contact structure. Among them, the formulation of the low temperature electroless plating step is: 0.03 mol/L zinc nitrate, 0.01 mol/L DMAB, pH 6.5, and the reaction is carried out at 60 ° C for 30 minutes.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope is subject to the definition of the scope of the patent application attached.

200‧‧‧Substrate

210‧‧‧ Surface modification steps

212‧‧‧Modified part

220‧‧‧Digital printing steps

230‧‧‧ Area

240‧‧‧ patterned metal oxide layer

300‧‧‧Substrate

302‧‧‧Modified part

304‧‧‧ patterned zinc oxide layer

306‧‧‧ Silver electrode

S110, S120, S130‧‧‧ steps

1 is a flow chart showing the fabrication of a patterned metal oxide layer in accordance with an embodiment of the invention.

2A-2D are schematic cross-sectional views showing a process of patterning a metal oxide layer according to an embodiment of the invention.

3A and 3B are schematic cross-sectional views showing a semiconductor device fabricated by applying the method of fabricating a patterned metal oxide layer of the present invention, respectively.

S110, S120, S130‧‧‧ steps

Claims (17)

A method for fabricating a patterned metal oxide layer, comprising: providing a substrate; performing a surface modification step on the substrate, wherein the surface modification step is selected from the group consisting of an ultraviolet ozone treatment step, a plasma treatment step, and a self-assembled monolayer a step of a group consisting of a membrane treatment step and a polyelectrolyte polymer membrane treatment step; performing a digital printing step on the substrate, coating a catalyst in a region of the pre-formed patterned metal oxide layer, wherein the catalyst Including a metal ion compound, a nano metal particle, a nano alloy metal particle or a metal oxide particle; and performing a low temperature electroless plating step to deposit a patterned metal oxide layer on the region on the substrate, wherein the patterning The material of the metal oxide layer includes zinc oxide, indium oxide, chromium oxide, tin oxide, triiron tetroxide, manganese oxide, silver oxide, lead oxide, copper oxide, cerium oxide or titanium oxide. The method of fabricating a patterned metal oxide layer according to claim 1, wherein the digital printing step is an inkjet method. The method for producing a patterned metal oxide layer according to claim 1, wherein the reaction temperature of the low temperature electroless plating step is less than 100 °C. The method for producing a patterned metal oxide layer according to claim 1, wherein the reducing agent used in the low temperature electroless plating step comprises an alcohol, dimethylamine borane, ascorbic acid, formaldehyde or hydrazine hydrate. . The patterned metal oxide layer as described in claim 1 The manufacturing method, wherein the plasma processing step comprises a normal piezoelectric slurry treatment step, an etching plasma treatment step or an ion coupling plasma treatment step. The method for fabricating a patterned metal oxide layer according to claim 1, wherein the plasma source used in the plasma treatment step comprises ozone, carbon tetrafluoride, sulfur hexafluoride, hexafluoroethane, Octafluorobutane, difluoromethane or argon. The method for fabricating a patterned metal oxide layer according to claim 1, wherein the self-assembled monolayer film processing step forms a single layer film on the substrate, the single layer film having a long chain carbon at one end An alkane, and the other end contains a functional group of -SH, -OH or -NH. The method for fabricating a patterned metal oxide layer according to claim 1, wherein the self-assembled monolayer film processing step comprises using a dipping method, a spin coating method, an inkjet method, an offset printing method, and a letterpress printing method. , gravure printing or microcontact printing. The method for fabricating a patterned metal oxide layer according to claim 1, wherein the polyelectrolyte polymer film processing step forms a multilayer film on the substrate. The method for fabricating a patterned metal oxide layer according to claim 1, wherein the polyelectrolyte polymer film processing step comprises using a immersion method, a spin coating method, an inkjet method, an offset printing method, and a letterpress printing method. , gravure printing or microcontact printing. The method for fabricating a patterned metal oxide layer according to claim 1, wherein the substrate comprises a glass substrate, a polyester substrate, and an organic A glass fiber substrate, a flexible organic glass fiber substrate, a polyimide substrate, a tantalum wafer, a polycarbonate resin substrate, or an epoxy resin substrate. The method for fabricating a patterned metal oxide layer according to claim 1, wherein before the surface treating step, the substrate is further subjected to a cleaning step. The method for fabricating a patterned metal oxide layer according to claim 1, wherein after the forming the patterned metal oxide layer, further comprising performing a water removal step. The method for fabricating a patterned metal oxide layer according to claim 13, wherein the water removing step comprises using a method of reducing pressure or baking. The method for fabricating a patterned metal oxide layer according to claim 1, wherein the method can be applied to an oxide semiconductor device process, a magnetic material patterning process, a passive device fabrication, or a high dielectric constant material fabrication. The method for producing a patterned metal oxide layer according to claim 1, wherein the metal oxide particles are zinc oxide particles. The method for producing a patterned metal oxide layer according to claim 1, wherein the metal ion compound, the nano metal particles and the metal used in the nano metal particles are palladium, platinum or silver.