TW201712913A - Highly sensitive organic polymer sensor and manufacturing method thereof characterized by generating specific microstructure paths in the organic/polymer active layers to increase sensitivity and reliability under long term use - Google Patents

Abstract

A highly sensitive organic polymer sensor and its manufacturing method utilize specific microstructure paths generated by organic/polymer active layers to allow substances to be sensed to directly reach a passage region via the specific microstructure paths, capable of enhancing the chance of mutual reaction between the organic/polymer active layer of the passage region and the substances to be sensed so as to achieve effective sensitivity. The specific microstructure paths can also reduce the influence caused by exterior impurities and ambient moisture oxygen on the organic/polymer active layer successfully improving the sensitivity of the organic/polymer sensor for 10 times and improving the reliability of the sensor under long term use as well. Accordingly, the invention has features of simplicity, low temperature and low costs, and is highly compatible with a flexible substrate. If the organic/polymer sensor is required to be integrated with other circuit devices such as wearable mobile devices at growing demand, the invention also has high compatibility and absolutely has the potential of business application.

Description

High-sensitivity organic polymer sensor and manufacturing method thereof

The invention relates to a high-sensitivity organic polymer sensor and a manufacturing method thereof, in particular to a special microstructure path in an organic/polymer active layer, in particular to enable a sensing substance to pass through the special microstructure. The path directly reaches the channel region, interacts with the organic/polymer active layer in the channel region to achieve effective sensing, and can reduce the influence of external impurities and environmental water and oxygen on the organic/polymer active layer, and can successfully improve the organic/ The sensitivity of the polymer sensor and the reliability under long-term use.

To check the performance of the sensor, there are two important indicators, one is its sensitivity to the substance to be sensed, and the other is the reliability under long-term use. Generally, organic/polymeric-based transistor-type sensors (OP-TTSs) are affected by foreign substances through the active layer of the organic/polymer semiconductor, and the electrical characteristics of the transistor are changed. The effect of sensing. The transistor type organic/polymer sensor 5 element structure is as shown in FIG. 8, and has an active layer 55 of a gate 51, a dielectric layer 52, a source 53, a drain 54 and an organic/polymer semiconductor. The layer 55 channel region 551 is located inside and connects the source electrode 53 and the drain electrode 54. The organic/polymer semiconductor of the channel region 551 is not easy to interact with the upper sensing substance 6 to achieve effective sensing; Organic/polymer semiconductors usually have some impurities and are susceptible to external impurities and environmental water oxygen. In addition to reducing the sensitivity to the sensing substance 6, the reliability under long-term use is also easy to decline, so nowadays organic / The sensitivity of the polymer sensor 5 is not easy to improve, and the reliability is more difficult to maintain. Therefore, the user-like user cannot meet the needs of the user to effectively improve the sensitivity of the sensor element to the sensing substance in actual use, and to effectively maintain the reliability of the sensor element under long-term use.

The main object of the present invention is to overcome the above problems encountered in the prior art and to provide an opportunity to improve the interaction between the organic/polymer (semiconductor) active layer and the sensing substance at the channel, and to reduce foreign matter and impurities. The effect of environmental water and oxygen on the organic/polymer (semiconductor) active layer, the high sensitivity organic polymer sensor and its manufacturing method that successfully improve the sensitivity of the organic/polymer sensor and the reliability under long-term use. A secondary object of the present invention is to provide a simple, low temperature, low cost feature, and high compatibility with a flexible substrate. If the organic/polymer sensor needs to be integrated with other circuit devices, it also has high compatibility. High sensitivity organic polymer sensor with very commercial application potential and its manufacturing method. For the purpose of the above, the present invention is a high-sensitivity organic polymer sensor and a method of fabricating the same, the method of manufacturing comprising at least the following steps: (A) forming a dielectric layer on a gate, and dielectrically An organic/polymer active layer, a source and a drain are formed on the layer, the organic/polymer active layer is in contact with the source and the drain, and a source is formed between the source and the drain a channel region; and (B) processing the organic/polymer active layer to generate a microstructure path, comprising generating a hollow microstructure path or a solid microstructure path in the organic/polymer active layer to cause sensing The substance can pass directly to the channel region at the bottom of the organic/polymer active layer via the hollow microstructure path or the solid microstructure path. In the above embodiment of the present invention, the organic/polymer active layer is an organic/polymer semiconductor material, and may be a poly(3-hexylthiophene) conjugated polymer, Pentacene and its derivatives, or perylene derivatives. In the above embodiment of the present invention, the step (B) is processing the organic/polymer active layer by mixing, and mixing the semiconductor material, the insulating material, and the ferroelectric material in the organic/polymer active layer. The electrolyte material, or the nano material, causes the organic/polymer active layer to generate a microstructure path by phase separation of the appropriate control material. In the above embodiment of the present invention, the step (B) is to process the organic/polymer active layer in a two-layer stacking manner, to grow a layer of other material on the organic/polymer active layer, or to grow a layer of other materials. The material further grows the organic/polymer active layer, and the organic/polymer active layer generates a microstructure path by appropriately controlling the degree of interpenetration between the organic/polymer active layer and the other material, wherein the other material is a semiconductor Materials, insulating materials, ferroelectric materials, electrolyte materials, or nano materials. In the above embodiment of the present invention, the step (B) is to process the organic/polymer active layer by an interface modification method, and before the organic/polymer active layer is grown, a dielectric layer is formed on the dielectric layer. Graphical nanostructure, or a patterned modified layer, using the organic/polymer active layer and different surface structures or materials to make the organic/polymer active layer grow during the growth process A microstructure path, wherein the material of the modification layer is a semiconductor material, an insulating material, a ferroelectric material, an electrolyte material, or a nano material. In the above embodiment of the present invention, the step (B) is to process the organic/polymer active layer by nanoimprinting, and to produce the organic/polymer active layer by nanoimprinting. The hollow microstructure path, or further backfilling the hollow microstructure path with a semiconductor material, an insulating material, a ferroelectric material, an electrolyte material, or a nano material to form the solid microstructure path. A high-sensitivity organic polymer sensor according to the present invention comprises: a gate; a dielectric layer formed on the gate; a source and a drain formed on the dielectric layer And an organic/polymer active layer formed on the dielectric layer, the organic/polymer active layer being in contact with the source and the drain, and between the source and the drain Forming a channel region, the organic/polymer active layer has a microstructure path, which may be a hollow microstructure path or a solid type microstructure path. In the above embodiment of the present invention, the organic/polymer active layer is an organic/polymer semiconductor material, and may be a poly(3-hexanethiophene) conjugated polymer, a pentacene ring and a derivative thereof, or Anthracene derivatives. In the above embodiment of the present invention, the organic/polymer active layer is mixed with a different material to form a mixed-type microstructure path. In the above embodiment of the present invention, the organic/polymer active layer is interpenetrated with a two-layer stack of other materials to form a two-layer stacked microstructure path. In the above embodiment of the present invention, the organic/polymer active layer and the interface layer are modified to form an interface-modified microstructural path, and the interface layer has a surface patterned nano structure, or A patterned layer is formed on the interface layer by a different material. In the above embodiment of the present invention, the organic/polymer active layer is formed by nanoimprinting to form the hollow microstructure path, and further backfilled with another material to form the solid microstructure path. In the above embodiment of the invention, the other material is a semiconductor material, an insulating material, a ferroelectric material, an electrolyte material, or a nano material.

Please refer to FIG. 1 to FIG. 7 , which are schematic diagrams of organic polymer sensor elements having a special microstructure path according to the present invention, and a solid type having a function of screening substances in the organic/polymer active layer of the present invention. Schematic diagram of a microstructure path, a schematic diagram of an organic polymer sensor element for generating a special microstructure path by a hybrid method, and a schematic diagram of an organic polymer sensor element for generating a special microstructure path by a two-layer stacking method, and the present invention A schematic diagram of an organic polymer sensor element for producing a special microstructure path by means of interface modification, a schematic diagram of an organic polymer sensor element for producing a hollow microstructure path by nanoimprinting, and a nanometer pressure of the present invention A schematic diagram of an organic polymer sensor element that produces a solid microstructure path. As shown in the figure: the invention is a high-sensitivity organic polymer sensor and a manufacturing method thereof, which can be applied to manufacture various organic/polymer sensors, including a chemical sensor, a biomedical sensor, and a gas sense. Detectors, liquid sensors, etc. In this embodiment, the transistor type organic/polymer sensor 1 includes a gate 11; a dielectric layer 12 is formed on the gate; A source 13 and a drain 14 are formed on the dielectric layer 13; and an organic/polymer active layer 15 is formed on the dielectric layer 12, the organic/polymer active layer 15 Contacting the source 13 and the drain 14 and forming a channel region 151 between the source 13 and the drain 14 , and the organic/polymer active layer 15 is an organic/polymer semiconductor material, and It may be a poly(3-hexylthiophene) conjugated polymer, a pentacene ring and a derivative thereof, or a perylene derivative. In this embodiment, the organic/polymer active layer 15 is formed on the source 13 and the drain electrode 14, but is not limited to this embodiment. In other embodiments, the organic/polymer active layer 15 may also be formed under the source 13 and the drain 14. The invention generates a special microstructure path in the organic/polymer active layer 15 of the transistor type organic/polymer sensor 1, so that the sensing substance 2 can directly reach the organic/high through the special microstructure paths. The channel region 151 at the bottom of the molecular active layer 15 interacts with the organic/polymer semiconductor of the channel region 151 to achieve effective sensing and enhance the sensitivity of the organic/polymer sensor. The special microstructure path types described above include a hollow microstructure path 152 or a solid type microstructure path 153, as shown in FIG. The hollow-type microstructure path 152 allows the sensing substance 2 to directly reach the channel region 151; and the solid-type microstructure path 153 also allows the sensing substance 2 to directly reach the channel region 151, but the solid-type microstructure path 153 can achieve a variety of functions by changing the composition of the path, for example, the substance to be sensed 2 can be screened, as shown in Fig. 2. In addition, the special microstructure path is used to guide the sensing substance to reach the channel, which can effectively reduce the interference of external impurities and environmental water oxygen, especially the solid microstructure path, and the external factor is better, so It can improve the sensitivity of the organic/polymer sensor and improve the reliability of the sensor for long-term use. The method for generating a special microstructure path in the above organic/polymer active layer 15 comprises the following: 1. Mixed type: mixing other materials 3, such as insulating material, iron, in the organic/polymer active layer 15. The organic/polymer active layer 15 is subjected to a special microstructure path by electrical phase separation of the material, electrolyte material, nanomaterial, or other semiconductor material, as shown in FIG. 2. Double-layer stacking type: a layer of other material 3a is grown on the organic/polymer active layer 15, or a layer of other material 3a is grown first and then the organic/polymer active layer 15 is grown. The other materials include insulating materials and ferroelectrics. The organic/polymer active layer 15 generates a special microstructure path by appropriately controlling the degree of interpenetration between the organic/polymer active layer 15 and the other material 3a by appropriately controlling the degree of interpenetration between the organic/polymer active layer 15 and other materials 3a. As shown in Figure 4. 3. Interface modification type: Before growing the organic/polymer active layer 15, a patterned dielectric layer surface nanostructure or modification layer 4 is formed on the dielectric layer 12, and the modification layer material includes an insulating material. , the ferroelectric material, the electrolyte material, the nano material, or other semiconductor material, etc., using the organic/polymer active layer 15 and the difference in compatibility between different surface structures or materials, so that the organic/polymer active layer 15 A special microstructure path is created during growth, as shown in Figure 5. 4. Nanoimprint type: a hollow microstructure path 152 is produced in the organic/polymer active layer 15 by nanoimprinting, as shown in Fig. 6; if further materials 3b are used, including insulating materials The ferroelectric material, the electrolyte material, the nano material, or other semiconductor material, etc., backfilling the hollow microstructure path 152, the solid microstructure path 153 can be formed, as shown in FIG. Thereby, the present invention utilizes a special microstructure path in the organic/polymer (semiconductor) active layer to allow the sensing substance to pass through the special microstructure path to the channel region, thereby improving the organic/polymer (semiconductor) of the channel region. The active layer interacts with the sensing substance to achieve effective sensing, and the special microstructure path can also effectively reduce the influence of external impurities and environmental water oxygen on the organic/polymer (semiconductor) active layer. Therefore, the present invention successfully improves the sensitivity of the organic/polymer sensor and the reliability under long-term use. For example, the use of a poly(3-hexylthiophene) conjugated polymer as an organic/polymer active layer of a sensor element can be introduced into the present invention to increase the sensitivity of the detection gas by at least 10 times and for long-term use. The reliability underneath can also be greatly improved. The invention has the characteristics of simple, low temperature and low cost, and has high compatibility with a flexible substrate. If the organic/polymer sensor needs to be integrated with other circuit devices, for example, a wearable mobile device that is increasingly required, The invention also has high compatibility and therefore the present invention has great potential for commercial application. In summary, the present invention is a high-sensitivity organic polymer sensor and a manufacturing method thereof, which can effectively improve various disadvantages of the conventional use, and can improve the interaction between the active layer of the organic/polymer (semiconductor) at the channel and the sensing substance to be sensed. The opportunity of action, and can reduce the influence of foreign matter and environmental water and oxygen on the organic/polymer (semiconductor) active layer, and successfully improve the sensitivity of the organic/polymer sensor and the reliability under long-term use, so that the present invention has Simple, low temperature, low cost, and high compatibility with flexible substrates. If the organic/polymer sensor needs to be integrated with other circuit devices, the present invention also has high compatibility and has great potential for commercial application. The invention can be made more progressive, more practical, and more in line with the needs of the user. It has indeed met the requirements of the invention patent application, and has filed a patent application according to law. However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto; therefore, the simple equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the invention are modified. All should remain within the scope of the invention patent.

(Part of the Invention) Transistor Organic/Polymer Sensor 1 Gate 11 Dielectric Layer 12 Source 13 Deuterium 14 Organic/Polymer Active Layer 15 Channel Region 151 Hollow Microstructure Path 152 Solid Microstructure Path 153 To Sensitive Substance 2 Other Materials 3, 3a, 3b Patterned Dielectric Layer Surface Nanostructure or Modification Layer 4 (Conventional Part) Transistor Organic/Polymer Sensor 5 Gate 51 Dielectric Layer 52 Source Pole 53 bungee 54 active layer 55 channel zone 551 to sense substance 6

Fig. 1 is a schematic view showing an organic polymer sensor element having a special microstructure path according to the present invention. Fig. 2 is a schematic diagram showing the physical microstructure path of the organic/polymer active layer of the present invention having the function of screening substances. Fig. 3 is a schematic view showing the organic polymer sensor element of the present invention which produces a special microstructure path by mixing. Figure 4 is a schematic view of an organic polymer sensor element for producing a special microstructure path in a two-layer stacking manner. Fig. 5 is a schematic view showing the organic polymer sensor element of the present invention which produces a special microstructure path by means of interface modification. Figure 6 is a schematic view of an organic polymer sensor element for producing a hollow microstructure path by nanoimprinting in the present invention. Figure 7 is a schematic view of an organic polymer sensor element for producing a solid microstructure path by nanoimprinting in the present invention. Fig. 8 is a schematic view showing the structure of a conventional transistor type organic/polymer sensor element.

1‧‧‧Transistor type organic/polymer sensor

11‧‧‧ gate

12‧‧‧Dielectric layer

13‧‧‧ source

14‧‧‧汲polar

15‧‧‧Organic/Polymer Active Layer

151‧‧‧Channel area

152‧‧‧ Hollow microstructure path

153‧‧‧Solid microstructural path

2‧‧‧Sensitive substance

Claims (10)

A method for manufacturing a high-sensitivity organic polymer sensor, comprising at least the following steps: (A) forming a dielectric layer on a gate, and forming an organic/polymer active layer, a source on the dielectric layer a pole and a drain, the organic/polymer active layer is in contact with the source and the drain, and forms a channel region between the source and the drain; and (B) processing the organic/high The molecular active layer generates a microstructure path, and comprises generating a hollow microstructure path or a solid type microstructure path in the organic/polymer active layer, so that the sensing substance can pass through the hollow type microstructure path or the entity type micro The structural path is directly to the channel region at the bottom of the organic/polymer active layer. The method for manufacturing a high-sensitivity organic polymer sensor according to claim 1, wherein the organic/polymer active layer is an organic/polymer semiconductor material, and may be a poly(3-hexane group). Poly(3-hexylthiophene) conjugated polymer, pentacene and its derivatives, or perylene derivatives. The method for manufacturing a high-sensitivity organic polymer sensor according to claim 1, wherein the step (B) is processing the organic/polymer active layer by mixing, in the organic/ The polymer active layer is mixed with a semiconductor material, an insulating material, a ferroelectric material, an electrolyte material, or a nano material, and the organic/polymer active layer is subjected to a microstructure path by phase separation of the appropriate control material. The method for manufacturing a high-sensitivity organic polymer sensor according to the first aspect of the patent application, wherein the step (B) is processing the organic/polymer active layer in a two-layer stacking manner, in the organic / growing a layer of other material on the active layer of the polymer, or growing a layer of other material to grow the organic/polymer active layer, and appropriately controlling the degree of interpenetration between the organic/polymer active layer and the other material to make the organic/ The active layer of the polymer generates a microstructure path, wherein the other material is a semiconductor material, an insulating material, a ferroelectric material, an electrolyte material, or a nano material. The method for manufacturing a high-sensitivity organic polymer sensor according to the first aspect of the patent application, wherein the step (B) is processing the organic/polymer active layer by an interface modification method, and growing the organic / Before the active layer of the polymer, a patterned nanostructure is formed on the dielectric layer, or a patterned modified layer is grown, and the compatibility between the organic/polymer active layer and different surface structures or materials is utilized. Differently, the organic/polymer active layer generates a microstructure path during the growth process, wherein the modified layer material is a semiconductor material, an insulating material, a ferroelectric material, an electrolyte material, or a nano material. The method for manufacturing a high-sensitivity organic polymer sensor according to the first aspect of the patent application, wherein the step (B) is processing the organic/polymer active layer by a nanoimprint method, and In the manner of embossing, the hollow microstructure path is generated in the organic/polymer active layer, or the hollow microstructure path is further backfilled by a semiconductor material, an insulating material, a ferroelectric material, an electrolyte material, or a nano material. The solid microstructure path is formed. A high-sensitivity organic polymer sensor includes: a gate; a dielectric layer formed on the gate; a source and a drain formed on the dielectric layer; An organic/polymer active layer is formed on the dielectric layer, the organic/polymer active layer is in contact with the source and the drain, and a channel region is formed between the source and the drain The organic/polymer active layer has a microstructure path, which may be a hollow microstructure path or a solid type microstructure path. The high-sensitivity organic polymer sensor according to claim 7 , wherein the organic/polymer active layer is an organic/polymer semiconductor material and may be a poly(3-hexanethiophene) A conjugated polymer, a pentacene ring and a derivative thereof, or an anthracene derivative. The high-sensitivity organic polymer sensor according to claim 7, wherein the organic/polymer active layer is mixed with a other material to form a mixed-type microstructure path. The high-sensitivity organic polymer sensor according to claim 7 , wherein the organic/polymer active layer is interpenetrated with a double layer of another material to form a double-layer stacked microstructure path.