KR20220094741A - Optical sensor film for dissolved oxygen detection with micro-micro-structure - Google Patents

Abstract

The present invention relates to an optical sensor film for detecting dissolved oxygen having a micro-fine-structure. The present invention relates to the optical sensor film for detecting dissolved oxygen having a micro-fine-structure, and more specifically to the optical sensor film for detecting dissolved oxygen having a micro-fine-structure, which is a functional polymer film based on a micro-pattern structure for fouling resistance and fingerprint prevention according to expansion of touch screen use in smart device displays and for improving a fluorescence gain efficiency of fluorescent sensors. The optical sensor film for detecting dissolved oxygen having a micro-fine-structure according to the present invention includes a step of forming, on a support body, a sensor layer for temperature detection on which CdSeTe(cadmium selenium tellurium) fluorescent dye is fixed, and a sensor layer for dissolved oxygen detection on which tris (4,7-diphenyl-1,10-phenathroline) ruthenium (II) complex (Rudpp) fluorescent dye is fixed.

Description

Optical sensor film for dissolved oxygen detection with micro-micro-structure

The present invention relates to an optical sensor film for detecting dissolved oxygen having a micro-microstructure, and more particularly, a micro-pattern for anti-fouling and fingerprint prevention and fluorescence gain efficiency improvement of a fluorescent sensor according to the expansion of the use of a touch screen in a smart device display. It relates to an optical sensor film for detecting dissolved oxygen having a microstructure, which is a functional polymer film based on a structure.

Dissolved oxygen, temperature and pH are important parameters in environmental monitoring, marine research, food industry, biotechnology and medicine. Optical detection has advantages over other methods because it is possible to measure non-invasively through the glass window of a bioreactor or reaction vessel. In this case, the sensing material is placed on the inner wall of the reaction vessel, and detection by reflection or fluorescence is performed outside the reaction vessel. In addition, the optical sensor has an advantage that an electromagnetic field is not generated because it measures a signal using light instead of an existing electronic device and transmits measurement information through light. In particular, with the development of optical dyes that selectively emit light according to specific substances (dissolved oxygen molecules, carbon dioxide molecules, etc.) or changes in pH, their use in various sensor fields is being highlighted.

Such optical analysis is widely used in various fields because it has sufficient commercial factors such as time and cost reduction. Furthermore, recently, miniaturization of incubators and development of small multi-bioreactors using optical monitoring techniques are being actively conducted. The small multi-bioreactor has the advantage of minimizing the process development cost by enabling the development of process conditions to be achieved in a short time and at low cost in the optimization of pharmaceutical and biological product production processes.

On the other hand, as fluorescent dyes capable of sensing dissolved oxygen, pH and temperature, Rudpp (tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) complex), HPTS (8-hydroxypyrene) -1,3,6-trisulfonic acid trisodium salt) and CdSeTe (cadimium selenium tellurium) are mentioned. Rudpp has a characteristic of emitting fluorescence of 600 nm when excitation light of 480 nm is incident, and fluorescence is generated in inverse proportion to the concentration of dissolved oxygen. In addition, HPTS has a characteristic of emitting fluorescence of 520 nm when excitation light of 410 nm is incident, and the fluorescence intensity tends to increase as the concentration of hydrogen ions decreases. In addition, CdSeTe (cadimium selenium tellurium) is a material used as a fluorescent dye for temperature detection.

Simultaneous measurement of two or more parameters of dissolved oxygen, pH and temperature is required in complex culture and processes. Moreover, knowing the temperature is particularly important in the optical detection of dissolved oxygen because quenching by dissolved oxygen is strongly affected by temperature. Recently, a fluorescent material for simultaneous optical detection of two variables has been reported. For example, in Talanta 47 (1998) 1071-1076, iron and pH are separated by two wavelengths by immobilizing ferrozine, an iron indicator, and HPTS, a pH indicator, to adjacent portions on the same thin film. reported a technique for detection by ATR (attenuated total reflection) spectroscopy. See Chem. Mater. 2006, 18, 4609-4616] reported a sensor capable of simultaneously detecting pH and dissolved oxygen through a single-fiber optical sensor using carboxyfluorescein as a pH probe and Rudpp as a dissolved oxygen probe, respectively. . However, they do not disclose any sensor films made of Rudpp, HPTS, and CdSeTe fluorescent dyes as respective sensor layers.

Korean Patent Registration No. 1493645 (2015.02.09)

The present invention was devised to improve the above problems, and has a micro microstructure, which is a functional polymer film based on a micro pattern structure, so that the stain resistance and fingerprint prevention and fluorescent sensor according to the expansion of the use of touch screens in smart device displays. It aims to improve the fluorescence gain efficiency.

In order to achieve the above object, an optical sensor film for detecting dissolved oxygen having a microstructure according to the present invention includes a sensor layer for temperature detection in which CdSeTe (cadimium selenium tellurium) fluorescent dye is fixed on a support, and tris (4,7-) and forming a sensor layer for detecting dissolved oxygen to which a diphenyl-1,10-phenanthroline)ruthenium(II) complex (Rudpp) fluorescent dye is immobilized.

The optical sensor film for detecting dissolved oxygen having the microstructure includes a) preparing a sensor layer for temperature detection in which CdSeTe (cadimium selenium tellurium) fluorescent dye is fixed on a support, and b) Tris on the sensor layer for temperature detection (4,7-diphenyl-1,10-phenanthroline) ruthenium (II) complex (Rudpp) characterized in that it comprises the step of preparing a sensor layer for detecting dissolved oxygen immobilized with a fluorescent dye.

CdSeTe (cadimium selenium tellurium) of step a) and 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt of step c) (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt, HPTS) Fluorescent dyes are 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate. It is characterized in that it is immobilized using at least one silane coupling agent selected from the group consisting of.

The tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) complex (Rudpp) fluorescent dye in step b) is methyltrimethoxysilane, tetramethoxysilane, dimethyldimethoxysilane, tetra Ethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, decyltrimethoxysilane, isobutyltrimethoxy It is characterized in that it is immobilized using at least one silane coupling agent selected from the group consisting of silane, vinyltrimethoxysilane, vinyltriethoxysilane, glycidooxypropyltrimethoxysilane, and mercaptopropyltrimethoxysilane. .

The optical sensor film for detecting dissolved oxygen having a micro microstructure according to the present invention has a micro microstructure, which is a functional polymer film based on a micro pattern structure. has the effect of improving the fluorescence gain efficiency of

1 shows the configuration of an optical sensor film for detecting dissolved oxygen having a micro-microstructure according to an embodiment of the present invention;
2 is a liquid drop model in the micro pattern structure of the optical sensor film for detecting dissolved oxygen having a micro microstructure according to an embodiment of the present invention;
3 is a design shape structure of an optical sensor film for detecting dissolved oxygen having a microstructure according to an embodiment of the present invention;
4 is a process diagram showing a photomask manufacturing process of an optical sensor film for detecting dissolved oxygen having a microstructure according to an embodiment of the present invention;
5 is a drawing of a photomask for realizing a designed hydrogen surface of an optical sensor film for detecting dissolved oxygen having a microstructure according to an embodiment of the present invention and a manufactured photomask image,
6 is a silicon stamp manufacturing process diagram for imprint for realizing a hydrophobic surface of an optical sensor film for detecting dissolved oxygen having a microstructure according to an embodiment of the present invention;
7 is a micro-patterned silicon stamp image for the fabricated hydrophobic surface structure of the optical sensor film for detecting dissolved oxygen having a microstructure according to an embodiment of the present invention.

Hereinafter, an optical sensor film for detecting dissolved oxygen having a microstructure according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings. Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit or scope of the present invention. In describing each figure, like reference numerals have been used for like elements. With respect to the accompanying drawings, the dimensions of the structures are enlarged than actual for clarity of the present invention.

Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification is present, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having meanings consistent with the meanings in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

1 to 7 show an optical sensor film 10 for detecting dissolved oxygen having a micro-microstructure according to an embodiment of the present invention.

Referring to the drawings, the optical sensor film 10 for detecting dissolved oxygen having a microstructure includes a support 300 , a sensor layer 200 for detecting temperature, and a sensor layer 100 for detecting dissolved oxygen.

The contact angle of the liquid droplet on the flat solid surface of the support 300 is determined by Young's equation.

,

,

는 각각 고체-기체, 고체-액체, 액체-기체간의 계면 에너지를 나타낸다. In Equation 1 above

,

,

denotes the interfacial energy between solid-gas, solid-liquid, and liquid-gas, respectively.

If the solid surface of the support 300 is not flat and there are irregularities in the micro-pattern, the contact angle no longer follows Young's equation, and the contact angle is determined by two models proposed by Wenzel and Cassie.

In the case of Wenzel's model, it is assumed that when a liquid droplet is dropped on a solid surface with irregularities, the liquid droplet completely wets up to the bottom of the irregularity.

는 상기 수학식 2로 표현된다.contact angle at this time

is expressed by Equation 2 above.

)과 상부에서 투영된 면적(

)의 비를 나타내며, 거칠기율로 정의된다.At this time, referring to Equation 3, r is the area where the droplet actually touches the solid surface (

) and the area projected from the top (

), and is defined as the roughness ratio.

Referring to FIG. 3 , the design shape structure of the micro-pattern of the support is shown.

As shown in FIG. 3 , r is calculated by Equation 4 in the square protrusion and depression shapes having shape parameters.

>0), 요철이 있는 고체 표면에서의 접촉각

는

보다 작아지고, 반대로 평평한 고체 표면에서 액체 방울의 접촉각이 90°보다 클 경우 (

<0),

는

보다 커지게 된다.Wenzel's model states that when the contact angle of a liquid droplet is less than 90° on a flat solid surface (

>0), contact angle on an uneven solid surface

Is

If the contact angle of a liquid droplet is greater than 90° on a flat solid surface (

<0),

Is

will get bigger

Cassie's model assumes that when a liquid droplet falls on a solid surface with a micropattern, the droplet is supported by the irregularities and rests on the pattern.

는 액체 방울이 실제로 고체 표면에 닿는 면적(

, 돌출된 면적)과 상부에서 투영된 면적(

)의 비를 나타내며, solid fraction으로 정의한다.The contact angle at this time is calculated by Equation 5 above,

is the area the liquid droplet actually touches the solid surface (

, the projected area) and the projected area from the top (

), and is defined as a solid fraction.

는 수학식 6으로 계산된다.The design of micropatterns in the square protrusion and depression shapes with the same shape parameters as in the shape structure.

is calculated by Equation (6).

에 의해 결정된다.When a droplet falls on a solid surface, which of Wenzel and Cassie's models is determined, the sidewall slope α of the microstructure and the

is determined by

일때, Wenzel의 모델에서 Cassie의 모델로 바뀌는 임계 기울기를

라 하면, 상기 수학식 7 이 성립한다.The contact angle on a flat surface is

, the critical gradient from Wenzel's model to Cassie's model

Then, the above Equation 7 holds.

)를 가지면 Wenzel 모델을, 반대로 미세 구조물의 측벽 기울기가 임계 기울기보다 큰 기울기(

)에서는 Cassie모델을 따른다.Here, the slope in which the side-by-side slope of the microstructure is smaller than the critical slope (

) gives the Wenzel model, conversely, the slope where the sidewall slope of the microstructure is larger than the critical slope (

) follows the Cassie model.

이므로 마이크로 측벽 기울기가 90도인 패턴의 경우는 Cassie 모델을 따르게 된다.Therefore, if there is a microstructure on the film where the surface contact angle of the flat film is 90° or more,

Therefore, in the case of a pattern with a micro-sidewall slope of 90 degrees, the Cassie model is followed.

The micro-pattern shape is designed based on a pattern of protrusion and depression of a square having micro-sized protrusions similar to the surface shape of a lotus leaf.

Structure size

) &
Pore fraction(

)Roughness factor(

) &
Pore fraction(

) Theoritical CAs. a (μm) b (μm) b/a h (μm)

10 50 5 10 1.11111 97.2222 92.2223 166.703 10 100 10 1.03306 99.1736 92.0661 172.759 10 200 20 1.00907 99.7732 92.0181 176.209 10 300 30 1.00416 99.8959 92.0083 177.432 10 500 50 1.00154 99.9616 92.0031 178.439 10 1000 100 1.00039 99.9902 92.0008 179.212

Structure size

) &
Pore fraction(

)Roughness factor(

) &
Pore fraction(

) Theoritical CAs. c (μm) d (μm) CD h (μm)

50 10 5 10 1.55556 69.4444 93.112 134.838 100 10 10 1.33058 82.6446 92.6616 146.357 200 10 20 1.18141 90.7029 92.363 155.543 300 10 30 1.12487 93.6524 92.2499 159.841 500 10 50 1.07689 96.1169 92.1539 164.265 1000 10 100 1.03921 98.0296 92.0785 168.808

Table 1 shows the theoretical contact angle change values according to the micro-pattern pillar structure, and Table 2 shows the theoretical contact angle change values according to the micro-pattern pore structure. To investigate the change in the contact angle, the design dimensions are summarized as in Tables 1 and 2 above, and the pitch was changed while the width a and the height h of the exit structure were fixed to 10 μm, respectively.

,

는 각각 거칠기율과 상부에서 투영된 전체 면적 대비 바닥 면적이 차지하는 비율로 정의되는 함몰비율을 나타내며, 이론적으로 b/a 값이 커질수록 함몰비율이 커지고, 그에 따라 접촉각도 증가하게 된다. 하지만 더 큰 접촉각을 얻기 위해 b/a 를 무한정 늘여가다 보면, 구조물 사이의 간격이 접촉각 측정시의 물방울 직경에 가까워지거나 더 커져, 실제 접촉각은 이론 접촉각과는 사뭇 다른 양상을 보이게 된다. In Table 1 above

,

represents the roughness ratio and the dent ratio defined as the ratio of the floor area to the total area projected from the top, respectively. However, if b/a is increased indefinitely to obtain a larger contact angle, the spacing between structures approaches or becomes larger than the diameter of the water droplet measured when the contact angle is measured, and the actual contact angle shows a different aspect from the theoretical contact angle.

The concave shape of the square is the reverse of the protrusion of the square, and has a major difference from the protrusion. In the case of the protrusion, a network-type channel is formed between the square microstructures, so that the water droplets are easy to spread or move. However, the recessed microstructure follows Cassie's model even when the surface is hydrophilic because it is relatively difficult to move water droplets due to the rising network-type barrier ribs, and thus exhibits greater hydrophobicity.

The optical sensor film for detecting dissolved oxygen having a micro-structure of the present invention described above has a micro-structure, which is a functional polymer film based on a micro-pattern structure. There is an effect of improving the fluorescence gain efficiency of the fluorescent sensor.

The description of the presented embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the scope of the invention. Thus, the present invention is not to be limited to the embodiments presented herein, but is to be construed in the widest scope consistent with the principles or novel features presented herein.

10: Optical sensor film for detecting dissolved oxygen having a microstructure
100: sensor layer for detecting dissolved oxygen
200: sensor layer for temperature detection
300: support
400: Wenzel's model
410: Cassie's model

Claims (4)

A sensor layer for temperature detection in which CdSeTe (cadimium selenium tellurium) fluorescent dye is fixed on the support;
A tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) complex (Rudpp) fluorescent dye comprising the step of forming a sensor layer for detecting dissolved oxygen
An optical sensor film for detecting dissolved oxygen with a microstructure.
The method of claim 1,
The optical sensor film for detecting dissolved oxygen having the microstructure is
a) preparing a sensor layer for temperature detection in which CdSeTe (cadimium selenium tellurium) fluorescent dye is fixed on a support;
b) preparing a sensor layer for detecting dissolved oxygen in which tris (4,7-diphenyl-1,10-phenanthroline) ruthenium (II) complex (Rudpp) fluorescent dye is fixed on the sensor layer for temperature detection; containing
An optical sensor film for detecting dissolved oxygen with a microstructure.
3. The method of claim 2,
CdSeTe (cadimium selenium tellurium) of step a) and 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt of step c) (8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt, HPTS) Fluorescent dyes are 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate. Characterized in that it is immobilized using at least one silane coupling agent selected from the group consisting of
An optical sensor film for detecting dissolved oxygen with a microstructure.
3. The method of claim 2,
The tris(4,7-diphenyl-1,10-phenanthroline)ruthenium(II) complex (Rudpp) fluorescent dye in step b) is methyltrimethoxysilane, tetramethoxysilane, dimethyldimethoxysilane, tetra Ethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, decyltrimethoxysilane, isobutyltrimethoxy Characterized in that immobilization using at least one silane coupling agent selected from the group consisting of silane, vinyltrimethoxysilane, vinyltriethoxysilane, glycidooxypropyltrimethoxysilane, and mercaptopropyltrimethoxysilane
An optical sensor film for detecting dissolved oxygen with a microstructure.

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