TWI655426B - Structure and manufacturing method of fast screening wafer, and detection method of malachite green concentration using the fast screening wafer - Google Patents

Abstract

The invention provides a structure of a peacock green fast-screening wafer, comprising: a substrate, a first area, a second area and a detection area, wherein the detection area is between the first area and the second area And the detection region forms a plurality of nanometer columns of a predetermined height; a first insulating layer and a second insulating layer are respectively formed in the first region and a second region; and a first electrode and a first electrode a second electrode is formed on the first insulating layer and a second insulating layer, and the first electrode extends a plurality of parallel and equidistant strip electrodes toward the detecting region, and the second electrode faces the detecting region Extending a plurality of parallel and equidistant strip electrodes, the first electrodes and the strip electrodes of the second electrode being parallel and staggered with each other. The invention provides a method for manufacturing a malachite green fast screening wafer and a method for detecting a concentration of malachite green.

Description

Structure and manufacturing method of fast screening wafer, and detection method of malachite green concentration using the fast screening wafer

The invention relates to a structure and a manufacturing method of a fast screening wafer. In particular, the invention relates to a structure and a manufacturing method of a malachite green fast screening wafer, and a method for detecting a concentration of malachite green using the fast screening wafer.

Malachite green (or malachite green) is a triarylmethane compound with a green metallic luster, very soluble in water, and an aqueous solution that is blue-green and has strong resistance to fungi and protozoa. Ability. Malachite green can be divided into two major categories of industry and reagents: industrial malachite green is cheap; reagents use malachite green and oxalate, sulfate, hydrochloride and zinc chloride double salts, among which zinc chloride double salt _{(3C 23 H 25 ClN 2 .2ZnCl} 2 .2H 2 O) is a diamond crystal brass color, type of ion present, can enter the cell, highly toxic (Alderman, 1985).

The Republic of China Invention Patent No. I395949 discloses a prior art malachite green biological monitoring system, the patent specification of which discloses the metabolic mechanism of malachite green: after the malachite green enters the human or animal body, it is first metabolized into fat-soluble by biotransformation. Reductive malachite green (Leucomalachite green), which is then demethylated under thrombopoietin (TPO) catalysis to produce primary and secondary amine metabolites similar in structure to carcinogenic aromatic amines. Since 1993, Malachite Green has been used as an insect repellent, fungicide and preservative, and because of its low price and effectiveness. It has significant advantages and is widely used in the prevention and treatment of aquaculture (Schnick, 1988). However, with the deepening of research, the potential carcinogenicity and degeneration of peacock green have attracted attention (Gouranchat, 2000), and many countries have banned it for aquaculture.

Therefore, the US Food and Drug Administration (FDA) listed malachite green (MG) as a chemical for priority testing of toxicity and carcinogenicity in 1993. In the EU's import and export of aquatic products in 2002, the maximum concentration of malachite green and reduced malachite green was limited to 2 ppb, while Japan specified 5 ppb as the testing standard. In 1989, Taiwan completely banned the use of malachite green, and the Department of Health established the "Animal Residue Standard" to stipulate that the detection standard for malachite green is "not to be tested", but also because the price is not expensive, the treatment effect is good and easy to obtain, resulting in the world Many areas are still commonly used in aquaculture production processes (Schnick, 1988).

Current methods for the detection of malachite green: 1. High Performance Liquid Chromatography (HPLC: High Performance Liquid Chromatography) can be used to detect malachite green and leucomalachite green in organisms and other complex materials. There are basically two ways, one is to measure by indirect method, the method is complicated, and it has been rarely applied. Another method is to use a column (internal filling of lead dioxide, which can reduce reduced malachite green to malachite green), and two substances can be simultaneously determined. 2. High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS-MS): The mass spectrometer is used as a detector to replace the UV detector in high performance liquid chromatography. This method has qualitative function and high sensitivity, but the price is high. expensive. 3. Other detection methods: Spectrophotometry (Safarik et al, 2001) has many detection limits, low sensitivity, and poor accuracy. It cannot be used for the detection of reduced malachite green, and is limited to the detection of water.

The current detection method is precise but not fast and portable. The present invention can provide a malachite green fast screening wafer and a detection method thereof, which can be quickly obtained. The test result and the effect of being easy to carry will be applied to the inspection of the residue standard of livestock and poultry aquatic products, so it has industrial applicability.

In view of the problems and application requirements of the prior art, one of the objects of the present invention is to provide a structure of a fast-screening wafer and a manufacturing method thereof, which can utilize the mature process advantages of the semiconductor industry in China to obtain a large number of low-cost manufacturing. .

One of the objects of the present invention is to provide a method for detecting the concentration of malachite green in a fast-screening wafer manufactured by a semiconductor process, which has a rapid test result of malachite green.

In order to achieve the above object of the present invention, the present invention provides a structure for a fast-screening wafer, comprising: a substrate, a first region, a second region, and a detection region, wherein the detection region is between the first Between the region and the second region, and the detection region forms a plurality of nanometer columns of a predetermined height; a first insulating layer and a second insulating layer are respectively formed in the first region and a second region; And a first electrode and a second electrode are respectively formed on the first insulating layer and a second insulating layer, and the first electrode extends a plurality of parallel and equidistant strip electrodes to the detecting region. The second electrode extends a plurality of parallel and equidistant elongated electrodes toward the detection region, and the first electrodes and the elongated electrodes of the second electrode are parallel and staggered with each other.

In order to achieve the above object of the present invention, the present invention further provides a method for manufacturing a fast-screen wafer, comprising the steps of: providing a substrate, and planning a first region, a second region, and a detection region on the substrate; The detection zone is between the first zone and the second zone; a first insulation layer and a second insulation layer are respectively formed in the first zone and the second zone; and a pre-form is formed in the detection zone Having a height of a plurality of nano-pillars; and, at the first insulating layer and the second insulating layer Forming a first electrode and a second electrode respectively, and extending a plurality of parallel and equidistant strip electrodes from the first electrode and the second electrode respectively, and the first electrode and the second electrode The elongated electrodes of the electrodes are parallel and staggered with each other.

In order to achieve the above object of the present invention, the present invention provides a method for detecting the concentration of malachite green, comprising the steps of: using a fast screening wafer, the structure of the fast screening wafer comprising: a substrate having a detection area, wherein The detection area forms a plurality of nanometer columns of a predetermined height; and a first electrode and a second electrode are respectively formed on both sides of the detection area, and the first electrode and the second electrode are respectively The detection area extends a plurality of parallel and equidistant long electrodes, and the first electrodes and the long electrodes of the second electrode are parallel and staggered with each other; a voltage is supplied to the first electrode and the second electrode, and the fast The detection area of the sieve wafer contacts a solution to be tested; and the resistance change between the first electrode and the second electrode is measured to detect the malachite green concentration of the solution to be tested.

The structure of the fast-screening wafer is a metal-oxide-semiconductor field-effect transistor, and the first electrode and the second electrode of the fast-screening wafer are respectively the drain and the source of the metal-oxide-semiconductor field-effect transistor, and The 矽 nano column of the detection area is a gate, and the 矽 nano column contacts the solution to be tested to control the voltage of the gate.

According to the structure and manufacturing method of the fast-screening wafer and the method for detecting the malachite green concentration of the fast-screening wafer, the portable device for detecting small and sensitive malachite green can be developed, and has industrial applicability.

10‧‧‧矽 substrate

11‧‧‧Second District

12‧‧‧Detection area

13‧‧‧First District

14‧‧‧矽奈米柱

151‧‧‧First insulation

152‧‧‧Second insulation

16‧‧‧second electrode

17‧‧‧First electrode

20‧‧‧Detection circuit

21‧‧‧Transition circuit

22‧‧‧ concentration indicator

The first figure is an upper surface view of the crucible substrate structure of the fast screening wafer of the present invention.

2A to 2D are schematic views of the ruthenium column of the fast screening wafer forming detection region of the present invention.

The third figure is an upper surface view of the structure of the fast screening wafer of the present invention.

The fourth A is a cross-sectional view along the section line A-A shown in the third figure.

The fourth B is a cross-sectional view along the section line B-B shown in the third figure.

The fourth C-picture is a cross-sectional view along the section line C-C shown in the third figure, showing the direction of the current between the first electrode and the second electrode.

Fig. 5A is a schematic view showing the amount of current flowing through the column of nanometers when the positive column of the fast-screening wafer of the present invention adsorbs positive ions.

Figure 5B is a schematic diagram showing the amount of current flowing through the column of nanometers when the negative column of the fast-screening wafer of the present invention adsorbs negative ions.

Figure 6 is a graph of the I-V of the fast screening wafer of the present invention.

The seventh figure is a detection circuit diagram of the concentration of malachite green using the fast screening wafer of the present invention.

The eighth graph is a graph showing the measurement of the concentration of malachite green using the fast screening wafer of the present invention.

The ninth drawing is a line graph for detecting the corresponding resistance value of the malachite green concentration using the fast screening wafer of the present invention.

The present invention provides a method for manufacturing a fast-screen wafer, the method comprising: providing a substrate 10, and planning a first region 13, a second region 11, and a detection region 12 on the substrate 10, wherein the detection region 12 is between the first zone 13 and the second zone 11, as shown in the first figure, the upper surface view of the substrate structure of the fast-screening wafer of the present invention. In an embodiment of the invention, cut out A 1.5 cm x 1.5 cm germanium substrate 10, belonging to an N-type germanium wafer, has a planned detection zone 12 having a width of about 8 mm, located in the middle of the germanium substrate 10, and the first region 13 and the second side on both sides of the detecting region 12 The width of the area 11 is equal. Then, using an ultrasonic oscillator, each was washed with acetone, isopropyl alcohol and deionized water for 5 minutes, then washed with a mixture of sulfuric acid and hydrogen peroxide for 3 minutes, and then washed with deionized water, followed by a nitrogen gun. After drying, it is baked at 100 ° C using a baking tray.

After the manufacturing method of the present invention provides a substrate 10, in the embodiment of the present invention, the first region 13 and the second region 11 of the germanium substrate 10 are coated with a photoresist to produce a desired pattern, and the light of the AZ5214e is utilized. The resist is placed on the ruthenium wafer, and then rotated by a spin coater at 500 rpm for 10 seconds and then at 3000 rpm for 50 seconds to distribute the photoresist on the ruthenium substrate 10. Then, the photoresist is fixed by baking at 100 ° C for 5 minutes, and then exposure is performed for 40 seconds by an exposure machine for 30 seconds, and the exposed portion is washed away by the developer, and the detected detection area 12 is Etching is performed, and the first region 13 and the second region 11 covered by the photoresist are then plated with electrodes.

Next, the manufacturing method of the present invention forms a plurality of nanometer columns of a predetermined height in the detection zone 12. In the embodiment of the present invention, there are three types of etching solutions:

(1) 48% HF+DI water=1:5=8%HF

(2) 0.05M AgNO3+DI water=1:9=0.005M AgNO3

(3) 33% H2O2 (2 ml) + DI water (100 ml) = 1:50.

First, 8% HF and 0.005 M AgNO3 were placed in a 1:1 mixture for 90 seconds to adhere silver 1 to the ruthenium substrate 10, and then immersed in a 1:1 mixture of 8% HF and 0.66% H2O2. Etching the nanocolumn for 20 minutes. Finally, the nitric acid deposited in the bottom is removed by nitric acid to form a prototype of the element, and the schematic diagram of the column of the germanium column of the fast screening wafer forming detection region 12 of the present invention is shown in FIGS. 2A to 2D. The diameter of the nano column is between 90-120 nm and the height is 2 μm. The resistivity is 0.008-0.02 (Ω).

Then, the first insulating layer 151 and the second insulating layer 152 are formed on the first and second electrodes 16 and 16 , and the first electrode 17 extends toward the detecting region 12 . a plurality of parallel and equidistant strip electrodes, the second electrode 16 extending a plurality of parallel and equidistant strip electrodes to the detection region 12, the first electrodes 17 and the strip electrodes of the second electrode 16 being parallel to each other And staggered. In the embodiment of the present invention, the insulating layer of cerium oxide SiO2 and the first electrode 17 and the silver of a second electrode 16 are plated by a sputtering machine, wherein the first electrode 17 and the second electrode 16 respectively The detection zone 12 extends 11 strip electrodes. When using a radio frequency magnetron sputtering machine to deposit ceria and silver for sputtering, first use a mechanical pump with a diffusion pump to reduce the process starting chamber pressure to 5×10-6 torr. Then, argon gas was introduced and the power output was adjusted to 30 W to pulverize the plasma and perform pre-plating; in the pre-plating, a high flow rate of argon gas was introduced in order to make the point not easy to extinguish. After ten minutes of pre-plating, sputtering can be performed.

When cerium oxide SiO2 is plated, the argon gas and oxygen flux are 10 sccm, 1 sccm, and the working chamber in the control chamber is pressed to 6 mtorr, the RF sputtering power is increased to 200 W, and the baffle plate is opened to sputter cerium oxide. Next, the silver pre-plating step is the same as that of argon gas with a flux of 6 sccm and the working chamber of the control chamber is pressed to 6 mtorr. The RF sputtering power is increased to 50 W and the baffle is opened to perform silver sputtering.

Finally, the fabrication method of the present invention utilizes thermal annealing to impart an ohmic contact to the fast-screen wafer, i.e., the I-V curve is more linear as shown in the sixth graph. Annealing is performed by an apparatus for rapid thermal annealing. First, the method of the present invention preheats once to test whether the machine can reach the temperature required for annealing, and then puts the fast screening wafer of the present invention into the machine table and draws 5 mtorr to 30 seconds The temperature is raised to 650 ° C, and then 650 ° C for 60 seconds, then when the temperature is lowered, nitrogen gas is introduced to accelerate the temperature of the gun body cooling, when the temperature is below 70 ° C, the wafer can be taken out, and the invention is completed quickly. The structure of the sieve wafer.

Referring to the third drawing, there is shown an upper surface view of the structure of the fast screening wafer of the present invention. In the embodiment of the present invention, the detection region 12 forms a plurality of columnar nanometer columns, and the first electrode 17 extends a plurality of parallel and equidistant strip electrodes to the detection region 12, and the second electrode 16 faces the detection region 12 A plurality of parallel and equidistant strip electrodes are extended, and the strip electrodes of the first electrode 17 and the second electrode 16 are parallel and staggered with each other. The length of the strip electrode of the first electrode 17 and the second electrode 16 is 6 mm and the width is 0.1 mm, and the strip electrode of the first electrode 17 and the first portion are in the detection region 12 having a width of 8 mm. The long electrodes of the two electrodes 16 are parallel by a distance of 0.4 mm. Therefore, the distance between the two parallel strip electrodes of the first electrode 17 is 0.9 mm, and the distance between the two parallel strip electrodes of the second electrode 16 is also 0.9 mm.

Referring to FIGS. 4A and 4B, cross-sectional views of structural sections A-A and B-B of the fast-screening wafer of the present invention shown in the third figure are respectively shown. In the embodiment of the present invention, the ceria SiO2 of the first insulating layer 151 is formed in the first region 13 of the tantalum substrate 10, and the ceria SiO2 of the second insulating layer 152 is formed in the second region 11 of the tantalum substrate 10. The first electrode 17 and the second electrode 16 are respectively formed on the first and second insulating layers 151 and 152, and the long electrode of the first electrode 17 extends to the plurality of nano columns of the detection region 12, and the second electrode 16 The strip electrodes also extend to the plurality of nano columns of the detection zone 12.

Referring to FIG. 4C, there is shown a cross-sectional view along the structural section line C-C of the fast-screening wafer of the present invention shown in FIG. 3, wherein the dotted arrow indicates the direction of current flow between the first electrode 17 and the second electrode 16. When the first electrode 17 and the second electrode 16 of the fast screening wafer of the present invention are provided When the voltage is detected and the detection zone 12 is in contact with a solution to be tested, the column of nano-bars 14 forms a current path, and the current indicated by the dashed arrow will flow from the columnar column 14 of the first electrode 17 to the second electrode 16 via the substrate 10 .矽 Nano column 14. Among them, the nano-column 14 adsorbs the positive and negative ions of the solution to be tested, which will affect the current change of the current channel in the nano-column 14 .

Please refer to FIG. 5A and FIG. 5B at the same time, which respectively show the amount of current flowing through the column of nanometers 14 when the nano-column of the fast-screening wafer of the present invention adsorbs positive ions and negative ions. When the nano column 14 adsorbs a large number of positive ions, the amount of current flowing through the current channel in the column 14 is large. When the nano column 14 adsorbs a large number of negative ions, the amount of current flowing through the current channel in the column 14 is small. Therefore, the structure of the fast screening wafer of the present invention is a metal oxide semiconductor field effect transistor (MOSFET), and the first electrode 17 and the second electrode 16 are respectively a drain and a source, and the detection region 12 is a The rice column 14 is a gate, and the nano column 14 is in contact with a solution to be tested to control the voltage of the gate.

Referring to the seventh figure, there is shown a detection circuit diagram of the concentration of malachite green using the fast-screening wafer of the present invention. The invention provides a malachite green concentration detecting circuit 20, comprising: a fast screening wafer, as shown in the third figure, the structure of the fast screening wafer is a metal oxide semiconductor field effect transistor (MOSFET), the first An electrode 17 and a second electrode 16 are respectively a drain and a source, and the column 14 of the detection region 12 is a gate, and the column 14 is in contact with a solution to be tested to control the voltage of the gate. . The first electrode 17 of the fast screening wafer is electrically connected to a positive voltage +V, and the second electrode 16 of the fast screening wafer is electrically connected to a plurality of resistors R1, R2, R3, and R4 in parallel, and the resistance value of each resistor is known and connected. After a switch, the electrical connection is electrically connected to the ground GND, wherein the second electrode 16 of the fast-screening wafer is the measuring contact Vt of the detecting circuit 20. The detection circuit 20 of the malachite green concentration of the present invention further comprises: a conversion circuit 21 and a concentration indicator 22, the conversion circuit 21 is electrically connected to the measurement contact Vt, The analog voltage value of the measurement contact Vt is converted into a digital voltage value and output to the concentration indicator 22, which includes a plurality of LED lamps for displaying the malachite green concentration of the solution to be tested.

In one embodiment of the present invention, the plurality of resistors R1, R2, R3, and R4 provided by the detecting circuit 20 are respectively 270K ohms, 51K ohms, 10K ohms, and 100K ohms, and the ON or OFF of the switches is for paralleling a resistor. The value is close to the initial resistance value of the fast-screening wafer. For example, the initial resistance value of the fast-screening wafer is 30K ohms. The resistance value of the 51K ohm resistor R2 and the 100K ohm resistor R4 may be selected in parallel to connect the resistors in series. 30K ohm fast screening wafer to reduce experimental errors. The switches of the resistors R1, R2, R3, and R4 connected in series can be realized by a dip switch, and the circuit can be modified to automatically adjust the initial resistance value close to the fast-screen wafer.

When the present invention provides a positive voltage +V=5 volts, a test solution is provided to the detection zone 12 of the fast-screen wafer by a micropipette, and 2 ppb of peacock oxalate is sequentially added, and the peacock oxalate is sequentially added. The interval time is mainly considering the alcohol volatilization, and the detection zone 12 waiting for the fast-screening wafer reacts with the measurement contact Vt to have a stable measurement value to calculate the between the first electrode 17 and the second electrode 16 of the fast-screen wafer. The resistance value is measured, and the measurement curve of the malachite green concentration of the fast-screening wafer of the present invention is shown in the eighth figure.

According to the experimental results shown in the eighth figure, when the peacock oxalate increases by 2 ppb, the resistance between the first electrode 17 and the second electrode 16 of the fast-screen wafer is significantly increased, indicating a low concentration ( 2-14 ppb) Regularly increasing the value of the detected resistance to obtain a line graph showing the corresponding resistance value of the malachite green concentration using the fast-screening wafer of the present invention as shown in FIG. From the numerical analysis, the peacock oxalate concentration is 13.5±0.26kΩ at 2ppb, and the resistance value will increase slightly with the concentration difference of 2ppb. The polynomial formula is y=-23.317x3+533.12x2-674.16x +11500) (x is the concentration, the unit is ppb; y is the resistance value of the nano column). Therefore, the present invention is peacock green The detection circuit 20 of the degree corresponds to the malachite green concentration contacted by the fast screening wafer reaction detection area 12, and the voltage value of the measurement contact Vt is indicated by the LED of the concentration indicator 22 via the conversion circuit 21 to indicate the concentration of the malachite green contained in the solution to be tested. .

Therefore, the detection circuit 20 of the malachite green concentration of the present invention has a test result which can be quickly obtained and which facilitates realization of a portable device. The device of the invention can be applied to the inspection of the residue standard of livestock and poultry aquatic products, and therefore has industrial applicability.

Claims (10)

The structure of a fast screening wafer comprises: a substrate, a first area, a second area and a detection area, wherein the detection area is between the first area and the second area, and the detection area Forming a predetermined height of the plurality of nano-columns; a first insulating layer and a second insulating layer are respectively formed in the first region and a second region; and a first electrode and a second electrode are respectively The first insulating layer is formed on the second insulating layer, and the first electrode extends a plurality of parallel and equidistant strip electrodes toward the detecting region, and the second electrode extends a plurality of parallel and equidistant directions to the detecting region. The long electrode, the first electrode and the long electrode of the second electrode are parallel to each other and staggered. The structure of the fast-screening wafer of claim 1, wherein the length of the long electrode of the first electrode and the second electrode is at least half of the width of the detection zone. The structure of the fast-screening wafer according to claim 1, wherein the preset height of the nano-column columns is 2 μm. The structure of the fast-screening wafer according to claim 1, wherein the diameter of the nano-column is between 90 and 120 nm. The structure of the fast-screening wafer according to claim 1, wherein the detection zone contacts the malachite green concentration of 2-14 ppb, which is proportional to the resistance value between the first electrode and the second electrode. The structure of the fast screening wafer according to claim 1 is a metal oxide semiconductor field effect transistor, wherein the first electrode and the second electrode are respectively a drain and a source, and the detection area is The meter column is a gate, and the column of the nanometer column contacts a solution to be tested to control the voltage of the gate. A method for manufacturing a fast-screen wafer includes: providing a substrate, and planning a first region, a second region, and a detection region on the substrate, wherein the detection region is between the first region and the second region Forming a first insulating layer and a second insulating layer respectively in the first region and the second region; forming a plurality of nanometer columns of a predetermined height in the detecting region; and in the first insulating layer Forming a first electrode and a second electrode respectively on the second insulating layer, and extending a plurality of parallel and equidistant strip electrodes from the first electrode and the second electrode respectively to the detecting region, and the first electrode An electrode and the elongated electrodes of the second electrode are parallel and staggered with each other. The method for manufacturing a fast-screen wafer according to claim 7, wherein the first electrode and the second electrode are respectively a drain and a source of a metal oxide semiconductor field effect transistor, and the detection region is germanium. The nano column is the gate. A method for detecting concentration of malachite green comprises: using a fast screening wafer, the structure of the fast screening wafer comprising: a substrate having a detection area, wherein the detection area forms a plurality of nanometer columns of a predetermined height; a first electrode and a second electrode are respectively formed on both sides of the detection area, and a plurality of parallel and equidistant long electrodes are respectively extended from the first electrode and the second electrode to the detection area, and The first electrode and the long electrode of the second electrode are parallel and staggered with each other; a voltage is supplied to the first electrode and the second electrode, and the detection area of the fast-screen wafer is contacted with a solution to be tested; and the measurement is performed The electrical resistance between the first electrode and the second electrode is changed to detect the malachite green concentration of the solution to be tested. The method for detecting the concentration of malachite green according to claim 9, wherein the structure of the fast-screening wafer is a metal oxide semiconductor field effect transistor, and the first electrode and the second electrode are respectively a drain and a source. And the 矽 nano column of the detection area is a gate, and the 矽 nano column contacts the solution to be tested to control the voltage of the gate.