KR102302766B1 - Antibacterial CTSe nano thin film and method for synthesizing the same - Google Patents

Abstract

The present invention relates to an antibacterial CTSe nano-thin film and a method for manufacturing the same, and more particularly, to a method comprising: preparing a copper-tin cation precursor mixed solution in which copper and tin are dissolved in an organic solvent; preparing a mixed solution of a selenium anion precursor in which selenium and anhydrous sodium sulfite are dissolved in an organic solvent; immersing the prepared substrate in the copper tin cation precursor mixture solution; taking out the substrate immersed in the copper tin cation precursor mixed solution and then performing primary cleaning; immersing the first cleaned substrate in the selenium anion precursor mixed solution; and taking out the substrate immersed in the selenium anion precursor mixture solution, and then performing secondary cleaning.

Description

Antibacterial CTSe nano thin film and method for manufacturing the same

The present invention relates to an antibacterial CTSe nano-thin film and a method for manufacturing the same, and more particularly, copper-tin-selenium (CTSe) antibacterial properties exhibiting excellent antibacterial effect even in small or trace amounts by employing a ternary compound having high chemical stability. It relates to a nano-thin film and a method for manufacturing the same.

Antibacterial agents are a kind of product for preparing and removing various germs that cause diseases in the human body. Research on antibacterial products is constantly conducted to protect the human body from tens of thousands of microorganisms that cause diseases and to realize an environmental society. is becoming

While there are microorganisms that help a lot in life, there are also many bacteria that are very harmful to the human body, and these bacteria can cause serious diseases through infection in the human body.

In addition, with the development of antibiotics, bacteria resistant thereto are rapidly appearing, and accordingly, a phenomenon in which the therapeutic effect of antibiotics is reduced worldwide has been reported a lot.

In particular, the development of antibiotics against Gram-negative superbacteria for which there is no suitable treatment and the continuously increasing problem of various resistant bacteria is becoming an urgent problem.

Gram-negative Escherichia coli is a causative bacterium of saccharitis, cystitis, pyelitis, and urinary tract infection, and is present in large numbers in the intestines of humans and animals.

It is widely present outside contaminated with feces, and is known as an indicator when testing whether beverages or food are contaminated with feces.

In addition, Gram-positive Staphylococcus aureus is known as a bacterium causing a lot of food poisoning as one of the bacteria causing suppurative diseases of the skin, otitis media, and cystitis as well as food poisoning.

On the other hand, antibacterial agents can be broadly classified into organic antibacterial agents and inorganic antibacterial agents. In the case of organic antibacterial agents, they exist mainly in liquid form, and are added to products requiring antimicrobial activity in a short time.

Antibacterial agents using organic materials temporarily have higher antibacterial activity than inorganic antibacterial agents, but have a disadvantage in that durability is very short.

In addition, there is a problem that organic antibacterial agents may cause bacterial resistance and may be harmful to the human body due to high acute toxicity.

On the other hand, inorganic antibacterial agents are manufactured using materials such as silver, zinc, copper, and titanium dioxide.

In addition, it is judged to be suitable as a material of antibacterial products for various uses because it has long durability and does not generate bacterial resistance.

However, materials such as silver have excellent antibacterial activity, but are chemically unstable in the atmosphere due to their high reactivity.

Therefore, there is a need for a novel inorganic antibacterial agent that uses a relatively inexpensive material, can be manufactured relatively simply, and is capable of antibacterial activity against Gram-negative bacteria showing high antibacterial activity even with a small amount or trace amount of material.

The antibacterial CTSe nano-thin film and the method for manufacturing the same according to the embodiments of the present invention were created by the above-mentioned problems and needs. An object of the present invention is to provide an antibacterial CTSe nano-thin film capable of simplifying the manufacturing process by manufacturing the thin film and manufacturing the antimicrobial thin film at a lower cost compared to the conventional method, and a manufacturing method thereof.

In addition, by employing a ternary compound (copper-tin-selenium) with high chemical stability, excellent antibacterial effects can be exhibited even in trace amounts, and by manufacturing an antibacterial nano-thin film using copper, tin and selenium, silver, zinc oxide and Another object of the present invention is to provide an antibacterial CTSe nano-thin film with excellent price competitiveness and a method for manufacturing the same by reducing production costs compared to the conventional inorganic-based antibacterial nano-thin film manufactured using titanium dioxide.

In addition, another object of the nanoparticles of the present invention is to provide an antibacterial CTSe nano-thin film and a method for manufacturing the same, exhibiting an excellent antibacterial effect against Gram-negative and Gram-positive bacteria.

On the other hand, the technical effects of the present invention are not limited to those mentioned above, and other technical effects not mentioned will be clearly understood by those skilled in the art from the following description.

The method for manufacturing antimicrobial CTSe nano-thin films according to embodiments of the present invention comprises the steps of preparing a copper-tin cation precursor mixed solution in which copper and tin are dissolved in an organic solvent, selenium and anhydrous sodium sulfite to achieve the above objects. Preparing a selenium anion precursor mixed solution dissolved in an organic solvent, immersing the prepared substrate in the copper tin cation precursor mixed solution, taking out the substrate immersed in the copper tin cation precursor mixed solution, first cleaning Step, the step of immersing the firstly cleaned substrate in the selenium anion precursor mixed solution, and taking out the substrate immersed in the selenium anion precursor mixed solution, the secondary cleaning step may include.

Preferably, the copper tin cation precursor mixed solution may include a copper water-soluble salt having a molar concentration of 0.04 to 0.06 and a tin water-soluble salt having a molar concentration of 0.08 to 0.12.

Preferably, the selenium anion precursor mixed solution may be mixed with 4 to 6 g of selenium powder, 90 to 110 g of sodium sulfite and 450 to 550 ml of distilled water.

Preferably, the first and second washing may be performed using deionized water.

Preferably, it may further include the step of heat-treating the substrate in a selenization atmosphere second cleaning.

Preferably, the heat treatment may be performed using 1 to 4 g of selenium powder at a temperature of 250 to 450° C. for 40 to 80 minutes.

The present invention has the following excellent effects.

First, by manufacturing a copper-tin-selenium (CTSe) nano-thin film through the SILAR (Successive ionic layer adsorption and reaction) method, the manufacturing process can be simplified, and the antimicrobial thin film can be manufactured at a lower cost than the conventional method.

In addition, by employing a ternary compound (copper-tin-selenium) with high chemical stability, excellent antibacterial effects can be exhibited even in trace amounts, and by manufacturing an antibacterial nano-thin film using copper, tin and selenium, silver, zinc oxide and Compared to the conventional inorganic-based antibacterial nano-thin film manufactured using titanium dioxide, the production cost can be reduced and the price competitiveness is excellent.

In addition, the nanoparticles of the present invention have an excellent effect of exhibiting an excellent antibacterial effect against Gram-negative and Gram-positive bacteria.

1 is a view showing the overall process of the antimicrobial CTSe nano-thin film manufacturing method according to an embodiment of the present invention.
2 is an image showing a SILAR method for manufacturing an antimicrobial CTSe nano-thin film according to an embodiment of the present invention.
3 is a conceptual diagram illustrating an antimicrobial mechanism of a copper tin selenium (CTSe) nano-thin film according to an embodiment of the present invention.
4 is an image evaluating the antibacterial properties of the copper tin selenium (CTSe) nano-thin film according to an embodiment of the present invention.

The terms used in the present invention have been selected as widely used general terms as possible, but in certain cases, there are also terms arbitrarily selected by the applicant. should be taken into account to understand its meaning.

Hereinafter, the technical configuration of the present invention will be described in detail with reference to preferred embodiments shown in the accompanying drawings.

In this regard, first, FIG. 1 is a view showing the entire process of a method for manufacturing an antibacterial CTSe nano-thin film according to an embodiment of the present invention, and FIG. 2 is a SILAR method for manufacturing an antimicrobial CTSe nano-thin film according to an embodiment of the present invention. 3 is a conceptual diagram illustrating the antimicrobial mechanism of a copper tin selenium (CTSe) nano-thin film according to an embodiment of the present invention, and FIG. 4 is a copper tin-selenium (CTSe) nano-thin film according to an embodiment of the present invention. It is an image that evaluates

1 to 4, the antimicrobial CTSe nano-thin film manufacturing method according to an embodiment of the present invention includes preparing a copper-tin cation precursor mixed solution in which copper and tin are dissolved in an organic solvent (S100).

At this time, the copper tin cation precursor mixed solution includes a copper water-soluble salt having a molar concentration of 0.04 to 0.06 and a tin water-soluble salt having a molar concentration of 0.08 to 0.12.

On the other hand, the reason for limiting the molar concentrations of the copper-soluble salt and the tin-soluble salt in the embodiment of the present invention as described above is as follows.

First, when the molar concentration of the copper water-soluble salt is less than 0.04 or exceeds 0.06, the desired crystal phase of copper tin selenium (CTSe) is not formed and an abnormal phase is highly likely to be generated, and the molar concentration of the tin water-soluble salt is less than 0.08 or 0.12 This is because, even when the manufacturing process is carried out in excess of , the desired crystal phase of copper tin selenium (CTSe) is not formed and there is a high possibility of generating an abnormal phase.

Meanwhile, in an embodiment of the present invention, copper chloride (dihydrate) and tin chloride (dihydrate) are used as the copper-soluble salt and the tin-soluble salt.

Meanwhile, in the method for manufacturing an antimicrobial CTSe nano-thin film according to an embodiment of the present invention, a complexing agent for preventing hydrolysis ^{of Sn 2+ ions may be added to the copper tin cation precursor mixed solution.}

At this time, in an embodiment of the present invention, tartaric acid is used as a complexing agent, and tartaric acid is added until the copper tin cation precursor mixed solution is lowered to a predetermined pH or less.

On the other hand, the antimicrobial CTSe nano-thin film manufacturing method according to an embodiment of the present invention includes the step of preparing a selenium anion precursor mixed solution in which selenium and anhydrous sodium sulfite are dissolved in an organic solvent (S200).

At this time, the selenium anion precursor mixed solution is mixed with selenium powder 4 to 6g, sodium sulfite 90 to 110g and distilled water 450 to 550ml At this time, the molar concentration of the selenium anion precursor mixed solution is 0.10 to 0.15.

On the other hand, for uniform mixing and reaction of the anion precursor mixed solution containing selenium, the heating temperature is 70° C. or more, preferably 75° C. or more, and the time is 16 hours or more, preferably 24 hours or more.

On the other hand, if the numerical limitation conditions of the selenium anion precursor mixed solution are described in detail, precipitates can be detected when the solvent (distilled water) of the anion precursor mixed solution is less than 450 ml, and when it is 550 ml or more, a mixed solution of a light concentration is obtained and reacted difficulties may arise.

In addition, if the weight of the selenium is less than 4 g or more than 6 g, and the weight of anhydrous sodium sulfite is less than 90 g or more than 110 g, the anion precursor mixed solution is not formed properly, so the crystalline phase of copper tin selenium (CTSe) is not formed. and this will be discussed again later.

Accordingly, in the selenium anion precursor mixed solution according to an embodiment of the present invention, 4 to 6 g of selenium powder, 90 to 110 g of sodium sulfite, and 450 to 550 ml of distilled water are mixed to solve the above problems, and after mixing, the anion precursor containing selenium The pH of the mixed solution may be 10 to 12.

On the other hand, the antibacterial CTSe nano-thin film manufacturing method according to an embodiment of the present invention comprises the steps of immersing the prepared substrate in the copper tin cation precursor mixed solution (S300), and after taking out the substrate immersed in the copper tin cation precursor mixed solution, First cleaning step (S400), immersing the firstly cleaned substrate in the selenium anion precursor mixed solution (S500), and taking out the substrate immersed in the selenium anion precursor mixed solution, followed by secondary cleaning (S600) is further included.

In this case, the first and second washing steps (S400) (S600) are performed using deionized water.

On the other hand, the antibacterial CTSe nano-thin film manufacturing method according to an embodiment of the present invention further comprises the step of heat-treating the second-cleaned substrate in a selenization atmosphere, wherein the heat-treating step is performed using 1-4 g of selenium powder. Heat treatment at a temperature of 250-450°C for 40-80 minutes.

On the other hand, the antimicrobial CTSe nano-thin film manufacturing method according to an embodiment of the present invention uses a SILAR (Successive ionic layer adsorption and reaction) method, which will be described in detail below with reference to FIG. 2 .

First, a copper tin cation precursor mixed solution according to an embodiment of the present invention was prepared using 0.04 to 0.06 M of copper soluble salt and 0.08 to 0.12 M of tin soluble salt, and the mixed solution of selenium anion precursor was 450 to 550 ml of distilled water, 4 to It was prepared with 6 g of selenium powder and 90-110 g of sodium sulfite.

At this time, as shown in FIG. 2 to prepare a copper-tin-selenium nano-thin film, a copper-tin cation precursor mixed solution 11, first washing water 12, selenium anion precursor mixed solution 13, secondary washing Water 14 is received in each vessel 1 , 2 , 3 , 4 .

In more detail, the copper water-soluble salt, the tin water-soluble salt, and tartaric acid as a complexing agent are mixed and accommodated in the first container (1), and selenium dissolved in distilled water and anhydrous sodium sulfite are mixed and accommodated in the third container (3). .

In addition, deionized water, which is washing water, is accommodated in the second container 2 and the fourth container 4 .

In the above process, the copper-soluble salt may be CuCl ₂ ·2H ₂ O, the tin water-soluble salt may be SnCl ₂ ·2H ₂ O, and the anion precursor containing selenium may be _{Na 2} SeSO _{3 .}

The containers (1, 2, 3, 4) containing the solutions (11, 12, 13, 14) are arranged in the same order as in FIG. 2, and the substrate 21 is placed in the first container (1), the second The process of immersion in the container (2), the third container (3), and the fourth container (4) is carried out in this order.

In more detail, it means that the substrate is immersed in the first container (1) to the fourth container (4) for several seconds to several tens of seconds, respectively, and the beam is in detail in the cation solution 11 accommodated in the first container (1). The substrate 21 is immersed in the deionized water 12 accommodated in the second container 2 to first wash the substrate 21, and the anion solution 13 contained in the third container 3 is immersed in the substrate 21 ) is immersed and taken out, and then immersed in deionized water 14 accommodated in the fourth container 4 to undergo a secondary cleaning process.

In this way, each immersion in the first vessel (1) to the fourth vessel (4) in order corresponds to one cycle, and a copper tin selenium (CTSe) nano-thin film 22 formed every time the cycle as described above is repeated. thickness gradually increases, and the cycle can be adjusted as many times as needed.

On the other hand, as described above, the copper tin selenium (CTSe) nano-thin film formed on the substrate 21 exhibits antibacterial properties even when used without a specific post-treatment process, but when heat treatment is performed in a selenization atmosphere as necessary, higher quality copper tin selenium (CTSe) thin film can be obtained.

At this time, when heat treatment is performed in a selenization atmosphere, an appropriate amount of selenium powder is put in a graphite box and carried out in a tube electric furnace.

At this time, the heat treatment temperature is 250 ℃ ~ 450 ℃, preferably 300 ~ 400 ℃, in the case of selenium powder 1 ~ 4g, preferably 2 ~ 3g, the heat treatment time proceeds for 40 ~ 80 minutes.

When performing the selenization heat treatment process as described above, a more purified copper tin selenium (CTSe) nano-thin film can be obtained, and the crystallinity of the copper tin selenium (CTSe) nano-thin film is also increased.

In the process as described above, when the anion precursor mixture solution is prepared or heat treatment is performed in a selenization atmosphere, when the weight range of selenium according to the embodiment is less than or exceeds the occurrence of abnormality and a decrease in crystallinity.

As described above, when the manufacturing process of the present invention is performed in excess of the upper limit of the weight of selenium, there is a high possibility of producing a product having an unwanted phase such as _{CuSe, Cu 2} Se and Cu ₃ SnSe _{4 .}

In addition, when the manufacturing process of the present invention is performed using less than the lower limit of the molar concentrations of copper, tin and selenium as described above, there is a high possibility of generating products having undesired phases such as _{SnSe and SnSe 2 .}

On the other hand, sulfur (S) may be added instead of the added selenium (Se), and in this case, a copper-tin-sulfur mixed solution is prepared.

The present invention is not limited to the form of a thin film, and various forms such as nanoparticles can be applied through mechanical scribing and dissolution and separation of the thin film.

Hereinafter, a preferred experimental example (example) is presented to help the understanding of the present invention. However, the following experiments are only for helping understanding of the present invention, and the present invention is not limited by the following experimental examples.

Experimental example

① A copper tin mixed solution was prepared by mixing 0.05 M copper-soluble salt and 0.1 M tin-soluble salt in a beaker of the first container (1) in a volume ratio of 1:1.

^{At this time, hydrolysis of Sn 2+} ions was prevented while lowering the pH by adding a small amount of tartaric acid as a complexing agent.

② 500ml of distilled water was filled in the beaker of the third container (3), 5g of selenium powder and 100g of anhydrous sodium sulfite were added, followed by stirring at 80°C for 24 hours.

③ The first container (1) and the third container (3) accommodated 100 ml of the cation precursor mixed solution and 100 ml of the anion precursor mixed solution, respectively, and the second container (2) and the fourth container (4) contain 100 ml of deionized water was accommodated as a cleaning solution.

④ Referring to FIG. 2, immersion from the first container (1) to the fourth container (4) was carried out for 10, 30, 15, and 30 seconds, respectively, and this process consisting of one cycle was repeated 30 times.

⑤ After the above deposition process, natural drying was performed at room temperature.

⑥ The naturally dried nano-thin film was put in a tube electric furnace with 5 g of selenium in a graphite box and heat-treated for 1 hour at a temperature of 350°C.

On the other hand, referring to FIG. 3 (a), it can be seen that the bacterial cells exhibit a negative charge while the CTSe nano-thin film exhibits a positive charge.

Bacterial cell membranes are composed of thiol, amino and carboxyl groups and are negatively charged.

On the other hand, the copper tin selenium (CTSe) nano-thin film of the present invention has a positive charge.

In other words, while bacterial cells have a negative charge, the CTSe nano-thin film has a positive charge, so electrostatic interaction occurs due to the opposite charge.

On the other hand, referring to Figure 3 (b), it can be seen that the electrostatic interaction between the bacterial cells and the CTSe nano-thin film occurs.

As described above, electrostatic interaction occurs between bacterial cells and copper tin selenium nano-thin films due to opposite charges, and through this, thiol, amino, and carboxyl groups of the copper tin selenium nano-films and bacterial cell membranes are strongly bonded.

On the other hand, referring to Figure 3 (c), it can be seen that the bacterial cell wall is damaged by the CTSe nano-thin film.

As described above, the thiol, amino, and carboxyl groups of the copper tin selenium nano-thin film and the bacterial cell membrane are strongly bound, and as a result, the cell wall of the bacteria is broken down, causing leakage of the cytoplasmic fluid, and the activity that damages the DNA, protein, and lipid of the cell wall to form oxygen

Through this action, the effect of inactivating bacteria can be obtained.

On the other hand, it can be seen that the copper tin sulfur (CTS) nano-thin film according to another preferred embodiment of the present invention also has antibacterial properties against bacteria through the mechanism as described above.

On the other hand, Figure 4 is an image evaluating the antibacterial properties of copper tin selenium (CTSe) nanoparticles according to an embodiment of the present invention, and after 24 hours after injecting the copper tin selenium nano-thin film and nanoparticles into E. coli, the antibacterial properties are evaluated is a result

Referring to FIG. 4, after culturing E. coli, a Gram-negative bacterium, it can be confirmed that CTSe nano-thin films and nanoparticles are injected.

In addition, the effect of the copper tin selenium nano-thin film prepared by the method according to an embodiment of the present invention and the nanoparticles prepared through the thin film on E. coli E. coli can be confirmed.

On the other hand, referring to FIG. 4 , it can be seen that, after 24 hours, a bacterial low-zone was formed in the portion into which the copper tin selenium (CTSe) nanoparticles were injected, thereby inhibiting bacterial growth.

In the case of the CTSe nano-thin film, it can be seen that a bacterial stop zone was formed around the substrate, and when 1 mg of the CTSe nano-thin film was processed into nanoparticles, a stop zone of about 16 mm width was formed.

In addition, the antibacterial properties of copper tin selenium (CTSe) nanoparticles can be confirmed by simultaneously injecting ampicillin, which is used as an antibiotic.

That is, it can be confirmed that the copper tin selenium (CTSe) nano-thin film according to a preferred embodiment of the present invention has an antibacterial effect against Gram-negarive bacteria.

As described above, the antimicrobial nano-thin film according to the present invention is a copper-tin-selenium ternary compound, and by manufacturing a copper-tin-selenium (CTSe) nano-thin film through the SILAR (Successive ionic layer adsorption and reaction) method, the manufacturing process can be simplified. can

In addition, by manufacturing an antibacterial nano-thin film using copper, tin and selenium, it is possible to reduce production costs compared to the conventional inorganic-based antibacterial nano-thin film produced using silver, zinc oxide, and titanium dioxide, and thus has excellent price competitiveness. do.

In addition, it exhibits an excellent antibacterial effect against Gram-negative bacteria.

Therefore, the method for manufacturing a copper tin selenium (CTSe) nano-thin film of the present invention uses a relatively inexpensive material, shows high antibacterial properties even with a small amount of material, and is a novel inorganic antibacterial agent capable of antibacterial activity against Gram-negative bacteria. will be able

As described above, the present invention has been illustrated and described by way of preferred embodiments, but it is not limited to the above-described embodiments, and those of ordinary skill in the art to which the present invention pertains within the scope not departing from the spirit of the present invention Various changes and modifications will be possible.

Claims (7)

preparing a copper tin cation precursor mixed solution in which copper and tin are dissolved in an organic solvent;
preparing a mixed solution of a selenium anion precursor in which selenium and anhydrous sodium sulfite are dissolved in an organic solvent;
immersing the prepared substrate in the copper tin cation precursor mixed solution;
taking out the substrate immersed in the copper tin cation precursor mixed solution and then performing primary cleaning;
immersing the first cleaned substrate in the selenium anion precursor mixed solution; and
After taking out the substrate immersed in the selenium anion precursor mixed solution, including the step of secondary cleaning, wherein the copper tin cation precursor mixed solution has a molar concentration of 0.04 to 0.06 CuCl ₂ ·2H ₂ O and a molar concentration of 0.08 ~0.12 of SnCl ₂ ·2H ₂ O, the selenium anion precursor is Na ₂ SeSO ₃ , and tartaric acid is further added to the copper tin cation precursor mixed solution ^{to prevent hydrolysis of Sn 2+ ions} Method for manufacturing antibacterial CTSe nano-thin film using SILAR method, characterized in that.
The method of claim 1,
The selenium anion precursor mixed solution is a method for producing an antibacterial CTSe nano-thin film, characterized in that 4-6 g of selenium powder, 90-110 g of sodium sulfite, and 450-550 ml of distilled water are mixed.
The method of claim 1,
The first and second washing step is a method of manufacturing an antibacterial CTSe nano-thin film, characterized in that washing using deionized water.
The method of claim 1,
Method for producing an antibacterial CTSe nano-thin film, characterized in that it further comprises the step of heat-treating the second-cleaned substrate in a selenization atmosphere.
5. The method of claim 4,
The heat treatment step is a method of manufacturing an antibacterial CTSe nano-thin film, characterized in that heat treatment for 40 to 80 minutes at a temperature of 250 ~ 450 ℃ using 1-4 g of selenium powder.
[Claim 6] Antimicrobial CTSe nano-thin film, characterized in that it is prepared according to any one of claims 1 to 5. delete

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