阅读说明：本技术 一种用于玻璃防伪的微纳结构制备方法 (Preparation method of micro-nano structure for glass anti-counterfeiting ) 是由 不公告发明人 于 2019-05-06 设计创作，主要内容包括：本发明涉及一种用于玻璃防伪的微纳结构制备方法。首先将商用聚二甲基硅氧烷(PDMS)混合物浇铸在石英玻璃模板上受热固化后剥离,然后将PDMS软模板浸没在硝酸铈铵乙醇溶液中使其吸收充分并用滤纸滤干。同时在待防伪的玻璃产品表面溅射铬铜种子层,通过硝酸铈铵乙醇溶液与铬铜种子层之间发生反应扩散刻蚀反应,可以在玻璃产品表面的铬铜种子层上制备周期性排列的微纳结构图形,最后通过氢氟酸缓冲溶液对裸露的玻璃进行湿法各向同性刻蚀可得到周期性排列的微纳结构。本发明与传统的光刻、微接触印刷等工艺相比,在满足玻璃产品耐高温且不影响其透光性以及微纳结构规整性的情况下,能够高效低成本地在玻璃产品表面制备所需防伪的微纳结构,适合用于玻璃厂家用于玻璃产品防伪。(The invention relates to a preparation method of a micro-nano structure for glass anti-counterfeiting. Firstly, a commercial Polydimethylsiloxane (PDMS) mixture is cast on a quartz glass template and peeled off after being heated and cured, and then the PDMS soft template is immersed in a ceric ammonium nitrate ethanol solution to be fully absorbed and is filtered to be dry by filter paper. Meanwhile, a chromium-copper seed layer is sputtered on the surface of a glass product to be anti-counterfeit, a periodically arranged micro-nano structure graph can be prepared on the chromium-copper seed layer on the surface of the glass product through a reaction diffusion etching reaction between a ceric ammonium nitrate ethanol solution and the chromium-copper seed layer, and finally, a periodically arranged micro-nano structure can be obtained through wet isotropic etching on exposed glass through a hydrofluoric acid buffer solution. Compared with the traditional photoetching, micro-contact printing and other processes, the method can efficiently prepare the required anti-counterfeiting micro-nano structure on the surface of the glass product at low cost under the condition of meeting the requirements of high temperature resistance of the glass product and not influencing the light transmittance and the regularity of the micro-nano structure, and is suitable for glass manufacturers to be used for anti-counterfeiting of the glass product.)

1. A preparation method of a micro-nano structure for glass anti-counterfeiting is characterized by comprising the following steps:

first, prepare the reactive diffusion etching soft template

(1) Selecting a photoetching template, preparing a quartz glass template through the traditional photoetching, developing and etching technologies, and cleaning the quartz template according to standard steps of standard semiconductor cleaning;

(2) fully mixing a commercial Polydimethylsiloxane (PDMS) mixture, vacuumizing until no bubbles exist, then casting the mixture on the surface of the quartz glass structure, stripping after the PDMS mixture is solidified, completely blowing out nitrogen, soaking the stripped PDMS in a ceric ammonium nitrate ethanol solution, and drying by using filter paper to obtain a reaction diffusion etching template;

(3) placing the stripped and blown-off PDMS soft template in a ceric ammonium nitrate ethanol solution and enabling the reaction etching agent to be absorbed and saturated;

(4) taking out the PDMS soft template in the mixed solution, continuously drying the PDMS soft template by using nitrogen, and then placing the PDMS soft template with the structure surface facing downwards on filter paper for airing for later use;

secondly, cleaning the surface of the anti-counterfeiting glass product, drying and hanging the anti-counterfeiting glass product by using nitrogen, and sputtering a chromium-copper seed layer on the surface of the quartz glass substrate by using a magnetron sputtering machine;

and thirdly, fully contacting the structural surface of the prepared reactive diffusion etching soft template with a chromium-copper seed layer on the surface of the glass product, transferring the pattern structure of the PDMS soft template to the chromium-copper seed layer on the surface of the glass product by using a reactive diffusion etching technology, and then performing wet etching by using a hydrofluoric acid buffer solution to obtain a target structure on the surface of the glass product so as to realize anti-counterfeiting.

2. The method for preparing a micro-nano structure for glass anti-counterfeiting according to claim 1, wherein the micro-nano structure (1) is a geometric figure which is periodically arranged, the size of the structure is 5-10 μm, and the used material is quartz glass.

3. The method for preparing a micro-nano structure for glass anti-counterfeiting according to claim 1, wherein the cerium ammonium nitrate ethanol solution in the step (2) is cerium ammonium nitrate Ce (NH)₄)(NO₃)₆Perchloric acid HClO₄And absolute ethyl alcohol according to the mass ratio of 9:6: 85.

4. The method for preparing the micro-nano structure for the glass anti-counterfeiting according to claim 1, wherein the time for performing the reactive diffusion etching on the reactive diffusion etching soft template structure surface and the chromium-copper seed layer on the surface of the glass product is as follows: 45-60 min.

5. The method for preparing a micro-nano structure for glass anti-counterfeiting according to claim 2, wherein the hydrofluoric acid buffer solution used in wet etching is (10 wt% -40%) NH₄F and (5 wt% -49 wt%) HF, and the mixing volume ratio of the two is 5: 1.

6. The method for preparing the micro-nano structure for the glass anti-counterfeiting according to claim 4, wherein the etching time is 100-190 s, and the etching temperature is 30 ℃.

7. The method for preparing a micro-nano structure for glass anti-counterfeiting according to claim 1, wherein the commercial Polydimethylsiloxane (PDMS) mixture comprises: polydimethylsiloxane (PDMS), and a curing agent 184 in a mass ratio of 10: 1.

8. The method for preparing the micro-nano structure for glass anti-counterfeiting according to any one of claims 1 to 7, wherein the cleaning of the quartz glass template and the anti-counterfeiting glass product is ultrasonic cleaning of the surface of the quartz glass template or the anti-counterfeiting glass product by sequentially using acetone, ethanol and deionized water.

Technical Field

The invention relates to the fields of micro-nano manufacturing, anti-counterfeiting labels and the like, in particular to a micro-nano structure preparation method for glass anti-counterfeiting.

Background

In recent years, with the rapid development of the economy of China and the improvement of the living standard of people, more and more commodities flow into the market. Counterfeit products sometimes exist in the commodities, the counterfeit can be minimized by using the anti-counterfeit label, the anti-counterfeit label can serve as an identity card of the commodities in the commodity circulation process and can also play an anti-counterfeit role, and a convenient and rapid identification method can be provided for consumers through the anti-counterfeit label.

The micro-nano anti-counterfeiting label is an important achievement combining the nano technology and the anti-counterfeiting field, the micro-nano anti-counterfeiting technology is characterized in that micro charged particles such as atomic nuclei are used as carriers in the micro-nano scale range, random information carried by the carriers is processed and is respectively given to an identification instrument and the anti-counterfeiting label, and authenticity is distinguished by checking whether the information of the two is matched. The Nano anti-counterfeiting label is in a micro-scale range and has a unique physical structure, so that the Nano anti-counterfeiting label is difficult to copy successfully, and the Nano anti-counterfeiting label is widely applied to the fields of currency, credit cards, identity cards, passport visas, commodity trademarks and the like [ Yan Cui, Ravi S.Hegde, InYee Phang, et al.

The nano anti-counterfeiting label is generally required to be installed on a product by methods of manual pasting, machine pasting, online encryption and the like, and the identification of the label is mainly performed by apparent identification or professional arbitration identification by using a professional instrument [ Chuan-hengSun, Wen-yong Li, Chao Zhou, et al.anti-countefect system for acquiring a historical product oriented GPS data and encrypted chip-sensitive Code [ J ]. Computers and Electronics in the agricultural product 2013,92:82-91 ]. However, for glass manufacturers, the nano label is almost opaque, so that the light transmittance of the glass can be affected when the nano label is installed on a product, and the size of the nano anti-counterfeit label is relatively small, so that when the glass with a large layout is cut into small-sized finished products, the anti-counterfeit label of each small-sized product cannot be guaranteed. Also for security labels on glass products, it is often difficult to withstand glass tempering temperatures as high as 690 ℃. The structure in the micro-nano scale range is directly prepared on the surface of the glass product, so that the light transmission of the glass is not influenced, high-temperature impact can be resisted, and the anti-counterfeiting recognition effect is achieved. The micro-nano structure can be obtained by adopting reactive Diffusion Etching patterning and isotropic wet Etching [ Bartosz A.Grzybowski, Kyle J.M.Bishop.micro-and nano-Etching into Solids Using Reaction-Diffusion Etching and Hydrogel stages [ J ] Small.2009,5(1):22-27], and a glass product based on the structure has good anti-counterfeiting recognition effect.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a preparation method of a micro-nano structure for glass anti-counterfeiting. The method provides that a specific micro-nano structure is prepared on the surface of the existing glass product by utilizing reactive diffusion etching, the structure has periodicity and symmetry, has the characteristics of photonic crystals, can be used for glass anti-counterfeiting, does not need complicated equipment such as photoetching, reactive ion etching and the like compared with the traditional micromachining processes such as photoetching, laser direct writing, reactive ion etching and the like, has simple processing steps and low cost, can effectively prevent counterfeiting on the surface of the glass product, and can achieve the aim of appearance identification.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a micro-nano structure for glass anti-counterfeiting comprises the following steps:

first, a reactive diffusion etch template is prepared.

(1) A quartz glass template is selected.

(2) A commercial Polydimethylsiloxane (PDMS) mixture was cast and peeled off to form a periodic arrangement opposite to the hemispherical pore quartz glass template.

(3) And soaking the stripped polydimethylsiloxane PDMS in a ceric ammonium nitrate ethanol solution, and drying the PDMS by using filter paper to obtain the reaction diffusion etching template.

Preferably, the glass template selected in (1) is a hemispherical pore quartz glass template with a period of 5-15 μm and a pore size of 5 μm.

Preferably, the Polydimethylsiloxane (PDMS) incubation temperature in the step (2) is 65-75 ℃. The Polydimethylsiloxane (PDMS) mixture consists of: polydimethylsiloxane (PDMS), and a curing agent 184 in a mass ratio of 10: 1.

Preferably, the cerium ammonium nitrate ethanol solution used in (3) has a composition of: cerium ammonium nitrate Ce (NH)₄)(NO₃)₆Perchloric acid HClO₄And absolute ethyl alcohol in a mass ratio of 9:6: 85.

And secondly, cleaning the surface of the anti-counterfeiting glass product, drying and hanging the anti-counterfeiting glass product by using nitrogen, and sputtering a chromium-copper seed layer on the quartz glass substrate by using a magnetron sputtering machine.

Preferably, the thicknesses of the chromium-copper seed layers sputtered on the surface of the glass product in the second step are respectively as follows: the thickness of the chromium is 30nm, and the thickness of the copper is 170 nm.

And thirdly, contacting the structural surface of the reaction diffusion etching template obtained in the first step with the chromium-copper seed layer obtained in the second step for reaction, taking out the anti-counterfeiting glass product after 50-60 min, and sequentially placing the anti-counterfeiting glass product in a dechroming solution and a hydrofluoric acid buffer solution for etching glass to obtain the glass with the bathtub-shaped micro-pit periodic array structure on the surface.

Preferably, the hydrofluoric acid buffer solution in the step of the third step is (10-40% by mass) NH₄F and (5-49 percent, mass fraction) HF, wherein the mixing volume ratio of the F to the HF is 5:1, and the etching time is 190 s.

Compared with the prior art, the invention has the following beneficial effects:

the method adopts reaction etching liquid diffused inside a commercial Polydimethylsiloxane (PDMS) template to react, diffuse and etch with a Cr/Cu seed layer on the surface of a glass product to realize the patterning of the structure, and then prepares the two-dimensional periodic micro-nano structure on the surface of the glass through isotropic wet etching. Experiments show that: first, microcontact printing, compared to conventional microcontact printing (μ CP), can form a self-assembled monolayer on a metal surface through siloxane chemical bonding, but the self-assembly is mostly limited to the chemical reaction between thiol and gold, and more importantly, the elastic stamp provides little chemical agent at the pattern structure surface and is not effectively supplemented in the reaction process, which limits the microcontact printing method to make it difficult to etch the substrate relatively deeply. The selection range of the technology to the types of the etching agents is relatively wide, and the corresponding substrate materials are more; secondly, compared with the traditional processing technologies such as photoetching, laser direct writing and reactive ion etching, the technologies need expensive equipment investment, and the complex process also increases the processing cost and the production period. The bathtub-shaped micro-pit two-dimensional periodic micro-nano structure is prepared by using a reactive diffusion etching process to realize anti-counterfeiting on a glass product, and the preparation process is simple in operation and low in investment cost.

Drawings

FIG. 1 is a flow chart of a manufacturing process of a bathtub-shaped micro-pit glass two-dimensional periodic array structure.

FIG. 2 Scanning Electron Microscope (SEM) image of chromium copper seed layer after reactive diffusion etching patterning

FIG. 3 is a Scanning Electron Microscope (SEM) image of a bathtub shaped dimple structure formed on a glass surface by wet etching.

FIG. 4 is an atomic force microscope AFM image of a bathtub shaped dimple structure on the surface of a glass product.

FIG. 5A laser beam (650nm) illuminates a diffraction structure image formed by a bathtub shaped dimple structure on a glass product.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that modifications and variations can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention. As shown in figure 1, the preparation method of the glass anti-counterfeiting micro-nano structure mainly comprises the steps of preparing a reactive diffusion etching soft template, carrying out reactive diffusion etching graphical transfer and carrying out wet etching. Part of the process steps of the preparation process are shown in figure 1.

Referring to fig. 1, (a) - (b) are the preparation process of the reactive diffusion etching soft template: firstly, preparing a hemispherical-hole quartz template by using the traditional photoetching, developing and etching technologies, and drying the hemispherical-hole quartz template by using nitrogen for later use; and then casting a commercial Polydimethylsiloxane (PDMS) mixture on a quartz template, heating and curing, carefully peeling and drying by blowing, soaking the PDMS soft template in a ceric ammonium nitrate ethanol solution to obtain a reaction diffusion etching soft template, taking out the PDMS soft template, placing the PDMS soft template on filter paper, washing the surface with deionized water, and blowing by nitrogen for later use.

See (c) - (e) in fig. 1 for the reactive diffusion etching patterning transfer process: firstly, sputtering a chromium-copper seed layer on the surface of a glass product to be anti-counterfeit, then contacting the reaction diffusion etching soft template soaked with the ceric ammonium nitrate ethanol solution with the chromium-copper seed layer under the action of external force to carry out reaction diffusion etching, transferring the soft template structure to the chromium-copper seed layer, and finally, taking copper as a mask and further transferring the pattern to a chromium layer by using a chromium removing liquid.

Referring to fig. 1, (f) is a process for preparing a micro-nano structure by wet etching: and etching the exposed glass outside the chromium-copper seed layer by using a hydrofluoric acid buffer solution by using the chromium-copper seed layer as a mask for wet etching, and removing the chromium-copper seed layer on the surface of the glass product by using a ceric ammonium nitrate aqueous solution after a period of time to obtain the bathtub-shaped micro-pit two-dimensional periodic array structure.