TWI530688B - Manufacturing micro/nano probes apparatus and method thereof - Google Patents

Description

Micro-nano probe device and method

The present invention relates to a device and method for preparing a micronanoprobe, and more particularly to a device and method for preparing a micronanoprobe which can rapidly and rapidly produce an ultrafine tip probe.

Scanning Probe Microscopy (SPM) is widely used in various fields such as nanolithography, nanoelectronics, electrochemistry, cell biology and electron microscopy. In this technique, the size, shape and composition of the probe tip affect the microscopic resolution. For example, the tip of the probe can provide high resolution, so that the shape of the probe head can be controlled, consistent and reproducible. Whether in the industry or in the academic world is very important.

Among various methods for preparing probes for scanning probe microscopy, electrochemical etching is currently the most commonly used method for preparing ultra-fine needle tips, and is low-cost, fast, and highly reliable. Advantage. However, the surface of the tip after etching has the disadvantage of being rough and unable to effectively control the width and shape of the tip, and the existing electrochemical etching method can only produce one probe at a time, and the preparation process needs to be completed by different equipments and manual cooperation. Not only the limited production capacity, but also the quality of the probes produced are different. Therefore, the industry and academia are in great need of an equipment and method capable of achieving automated batch preparation with extremely sharp probes.

The object of the present invention is to provide a high-efficiency and automated batch preparation apparatus and method having a very sharp micro-nano probe, thereby rapidly mass-producing ultra-fine metal micro-nano probes with high consistency and high reproducibility. needle.

To achieve the above object, the present invention provides a micronanoprobe device comprising an electrochemical etching unit, a transfer unit, a power supply, a vibration unit, a cleaning unit, and a storage unit. The electrochemical etching unit houses an electrochemical etching solution having an etching liquid surface. The conveying unit has a clamping portion, the clamping portion can clamp one end of a metal material, transfer the metal material to the electrochemical etching unit, and immerse the other end of the metal material in the electrochemical etching solution . The power supply has a positive pole of the power source and the clamping part is electrically connected, and a negative pole of the power source and the electrochemical etching liquid are electrically connected. The vibration unit is coupled to the clamping portion such that the other end of the metal material can be displaced up and down with respect to the surface of the etching liquid to form a metal probe by dynamic etching. The cleaning unit has a cleaning liquid, the transfer unit transfers the metal probe to the cleaning unit, and the metal probe is immersed in the cleaning liquid to remove the electrochemical etching remaining on the surface of the metal probe. liquid. The storage unit can receive the metal probe after the electrochemical etching solution is removed.

The invention further provides a method for preparing a micro-nano probe, comprising: providing an electrochemical etching unit for accommodating an electrochemical etching liquid, the electrochemical etching liquid having an etching liquid surface; and clamping one end of a metal material, Transferring the metal material to the electrochemical etching unit, and immersing the other end of the metal material in the electrochemical etching solution; and moving the other end of the metal material up and down with respect to the surface of the etching liquid to dynamically Etching forms a metal probe.

The above objects, technical features and advantages will be apparent to those skilled in the art, and the following detailed description of the preferred embodiments of the invention.

1‧‧‧Preparation of micronano probe equipment

10‧‧‧Power supply

101‧‧‧Power positive

103‧‧‧Power negative

105‧‧‧Negative electrode rod

11‧‧‧Electrochemical etching unit

111‧‧‧Electrochemical etching solution

112‧‧‧etching liquid surface

12‧‧‧Transfer unit

121‧‧‧Capture Department

13‧‧‧Vibration unit

14‧‧‧Control unit

15‧‧‧cleaning unit

151‧‧‧ cleaning solution

16‧‧‧Storage unit

17‧‧‧heating unit

171‧‧‧Cover heating belt

173‧‧‧temperature sensor

2‧‧‧Metal materials

2'‧‧‧Metal probe

21‧‧‧ Main body

23‧‧‧ needle head

25‧‧‧Needle

27‧‧‧Recurve points

a, b‧‧‧ distance

1 is a schematic view showing the preparation of a micro-nano probe by preparing a micro-nano probe device according to an embodiment of the present invention; 2 is a schematic view showing a heating unit for preparing a micro-nano probe device according to an embodiment of the present invention; and FIG. 3(a) and FIG. 3(b) are respectively a preparation of a micro-nano probe device in the embodiment of the present invention; A schematic diagram of one end leaving the liquid surface and immersed in the liquid surface; and FIGS. 4(a) to 4(d) are respectively schematic views of various shapes of the metal probe in the embodiment of the present invention.

The present invention will be explained by the following examples, but the description of the embodiments is merely illustrative of the technical contents of the present invention and the purpose thereof, and is not intended to limit the scope of the present invention. It is to be noted that in the following embodiments and drawings, elements that are not related to the present invention have been omitted and are not shown, and the dimensional relationships between the elements in the drawings are merely for ease of understanding and are not intended to limit the actual ratio.

As shown in FIGS. 1 and 2, an embodiment of the present invention is a micron probe device 1 for automatically mass-producing a micronanometal probe of a uniform specification from a metal material. The micro-nano probe device 1 comprises a power supply 10, an electrochemical etching unit 11, a transfer unit 12, a vibration unit 13, a control unit 14, a cleaning unit 15, a storage unit 16, and a heating unit. Unit 17 (shown only in Figure 2 for ease of illustration).

The power supply 10 has a power supply positive electrode 101, a power supply negative electrode 103, and a negative electrode rod 105 connected to the power supply negative electrode 103. The negative electrode rod can be made of titanium, platinum or stainless steel, preferably made of platinum. to make. In this embodiment, the power supply 10 is a DC power supply, which provides 5 to 30 volts and 0.2 to 5 amps of DC power from the power supply positive electrode 101 and the power supply negative electrode 103. However, in other implementations, A pulse power supply can be used, and the duty cycle of the pulse voltage value is 0.1 to 1. The negative electrode rod of the present invention is only one of the embodiments. In other embodiments, the use of an electrode mesh or a plate or the like does not affect the scope of the present invention.

The electrochemical etching unit 11 houses an electrochemical etching solution 111. The electrochemical etching liquid 111 has an etching liquid surface 112 and is electrically connected to the power source negative electrode 103. In the present invention, the electrochemical etching solution 111 It may be at least one of sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sodium chloride, potassium chloride, ammonium chloride, potassium hydroxide, sodium hydroxide, calcium hydroxide, aluminum hydroxide, citric acid, oxalic acid and ammonium hydroxide. The mixed solution, and the pH of the electrochemical etching solution 111 is greater than 9. In a preferred embodiment, a mixed electrochemical etching solution 111 of 2 to 30% hydrochloric acid, 2 to 30% nitric acid, 2 to 30% phosphoric acid, 2 to 50% ammonium hydroxide, and 1 to 10% oxalic acid may be used.

The transfer unit 12 has a clamping portion 121 electrically connected to one of the positive electrodes 101 of the power source. The clamping portion 121 can pick up one end of the at least one metal material 2, transfer the metal material 2 to the electrochemical etching unit 11, and the metal material 2 The other end is immersed in the electrochemical etching solution 111. In the present embodiment, the gripping portion 121 can take 2 to 4 metal materials 2 each time to form the micronanometal probe 2', respectively. The metal material 2 may have a cylindrical shape with a diameter ranging from 0.5 to 5 mm. In this embodiment, the metal material 2 may be a beryllium copper wire. In another embodiment, before the metal material 2 is transferred to the electrochemical etching unit 11, a pre-treatment step may be performed to remove the grease on the surface of the metal material 2 by using alcohol, acetone or potassium hydroxide.

The vibrating unit 13 is coupled to the gripping portion 121 such that the other end of the metal material 2 (that is, one end not sandwiched by the gripping portion 121) can be displaced up and down with respect to the etching liquid surface 112, and the other end of the metal material 2 is The electrochemical etching solution 111 is repeatedly immersed and removed, and even if the metal material 2 vibrates away from the liquid surface and immersed in the liquid surface, the metal material 2 is dynamically etched into a metal probe 2'. As shown in FIG. 3(a) and FIG. 3(b), the upper and lower displacements have an amplitude range, wherein the amplitude range includes the displacement of the other end of the metal material 2 onto the etching liquid surface 112 and the etching liquid surface 112 and the displacement to The distance b between the etchant surface 112 and the etchant surface 112. In the present invention, the distance from the displacement onto the etchant surface 112 to the etchant surface 112 is in the range of 3 mm or more, and the displacement to the etchant surface 112 and the etchant surface 112 is in the range of 2-17 mm. The upper and lower displacements of the vibration unit 13 have a vibration frequency of 0.2 to 10 Hz.

The control unit 14 can transmit a control command to the vibration unit 13, wherein the control command can control the vibration unit 13 to be in a vibration mode. In detail, the control command can control the vibration unit 13 to rapidly lower the gripping portion 121 to the amplitude range under the etching liquid surface 112, and then gradually rise to the amplitude range on the etching liquid surface 112. In other implementations, the control command may also be to control the vibration unit 13 to enable the clamping portion 121. The amplitude range is gradually lowered to the surface of the etchant surface 112 and rapidly rises to the amplitude range on the etchant surface 112.

The cleaning unit 15 houses a cleaning liquid 151 which is deionized water and can be a circulating cleaning solution or a fresh cleaning solution. The transfer unit 12 transfers the metal probe 2' to the cleaning unit 15, and immerses the metal probe 2' in the cleaning liquid 151, and shakes for 1 to 3 seconds to remove the residue on the surface of the metal probe 2'. Electrochemical etching solution 111.

The storage unit 16 is used for naturally drying the metal probe 2' after the electrochemical etching solution is removed, and is stored in a batch and placed in a card slot (not shown).

The heating unit 17 is electrically connected to the control unit 14, and as shown in FIG. 2, the heating unit 17 includes a coated heating belt 171 and a temperature sensor 173. The coated heating tape 171 is wrapped around the electrochemical etching unit 11, and the temperature sensor 173 is attached to the surface of the electrochemical etching unit 11. In this embodiment, the temperature sensor 173 is a thermocouple sensor, and senses the temperature of the electrochemical etching unit 11, and after being transmitted to the control unit 14, the control unit 14 calculates and determines the control package. The heating belt 171 heats the temperature of the electrochemical etching unit 11 to adjust the etching reaction rate of the electrochemical etching solution 111 to the metal material 2.

As shown in FIG. 1 , the power supply 10 , the electrochemical etching unit 11 , the cleaning unit 15 , and the storage unit 16 of the embodiment are disposed around the transmission unit 12 , and can be accessed by the robot arm of the transmission unit 12 . Each unit within the range performs a micronano probe method for the preparation of the polar tip metal probe 2'. In other embodiments, the transmitting unit 12 may be mounted on the movable self-propelled power device, or the power supply 10, the electrochemical etching unit 11, the cleaning unit 15, and the storage unit 16 may be disposed on the conveying line. The method of preparing the micronano probe can be carried out smoothly.

In detail, the clamping portion 121 of the transmitting unit 12 of the present embodiment picks up the metal material 2, connects the metal materials 2 to the power source positive electrode 101, and controls the vibration unit 13 with the control command of the control unit 14 to make the clamping portion. 121 at a rate of 1 to 3 cm/sec, at a frequency of 0.2 to 10 Hz, the other of the metal materials 2 The end is displaced upward and downward with respect to the etching liquid surface 112 of the electrochemical etching solution 111, and the other end of the metal material 2 is raised to a height of 2 mm to the etching liquid surface 112, and is immersed in the etching liquid of the electrochemical etching liquid 111 downward. The depth below the surface 112 is 1-17 mm. The metal material 2 is partially immersed in the electrochemical etching solution 111 for a length of time of 10 to 30 seconds, and the sandwiching portion 121 is vertically displaced by sandwiching the metal material 2 for dynamic etching. At this time, the metal material 2 and the negative electrode rod 105 are disposed in parallel, and the vertical distance between the two is 3 to 15 cm. The control command of the control unit 14 stops the vibration unit 13 from vibrating, and causes the clamping portion 121 to be composed of the metal materials. The formed metal probe 2' is displaced upward away from the electrochemical etchant 111. Then, the metal probe 2' is immersed in the cleaning liquid 151 containing deionized water for three seconds, thereby removing and removing the residual electrochemical etching liquid 111, and then placing it in the storage unit 16 to be air-dried and stored. In various embodiments, the micronanoprobe device 1 can be fabricated to produce metal probes 2' of different specifications, depending on the requirements of different probe specifications, with different depth and time control commands.

It should be particularly noted that since the metal material 2 of the present invention is not pinched at one end, it is completely left from the etching liquid surface 112 of the electrochemical etching liquid to perform a large oscillation. If the metal material 2 is immersed in the end of the electrochemical etching solution 111 and kept under the etching liquid surface 112, the etching liquid vortex is generated on the etching liquid surface 112 of the electrochemical etching liquid 111 around the immersed metal material 2, and In detail, the etch eddy current is generated at the meniscus level of the etchant surface 112 such that the etch is more intense at the etch vortex. This phenomenon controls the shape of the probe and the aspect ratio of the probe.

Furthermore, since the present invention controls the fluid action of the electrochemical etching solution 111, the tip of the needle is completely removed from the surface 112 of the etching liquid, thereby avoiding the formation of an etching vortex near the liquid surface. Because only the tip of the needle is displaced up and down in the electrochemical etching solution 111, the electrochemical etching solution 111 only etches the tip of the needle, and is etched and etched under the surface of the etchant surface 112, and is in the middle of the metal material. The etching is performed to cause drop off at the back end of the etching. The present invention etches only at the end, so that there is no solid residue of the metal material falling in the electrochemical etching solution, and the metal material is prevented from being wasted.

The post-etched metal probe obtained by the method for preparing a micronanoprobe of the present invention has an aspect ratio which is between 10 and 250. The preparation of the micro-nano probe device of the invention can accurately produce metal probes 2' having various tip shapes, such as flat needle tips, blunt needle tips and sharp needle tips, and the tip radius of curvature is 2-100 μm, which is a flat needle tip and a tip radius of curvature. The tip of the needle is between 200-2000 nm, the radius of curvature of the tip is between 2 and 200 nm, and the tip is sharp. It is also possible to form an inflection point at a specific position of the metal material to produce probes having different needle shapes. As shown in FIGS. 4(a) to 4(d), the metal probes 2' each have a main body portion 21, a needle head portion 23, and a needle tip portion 25, but the metal probes 2' shown in the respective drawings have different shape. In detail, FIG. 4(a) is for explaining that the present invention can produce a metal probe 2' having an elongated needle, and the needle head 23 of such an aspect is elongated near the tip end portion 25, for example, having 4-5 μm. The diameter of the needle head 23 has an inflection point 27 formed at a distance from the tip end portion 25. 4(b) and 4(c), the needle tip 23 of the metal probe has two inflection points 27, respectively, and the difference between FIG. 4(b) and FIG. 4(a) is that The needle head 23 of FIG. 4(b) has a stepwise taper because it has two inflection points 27, and the diameter near the tip end portion 25 is smaller than the diameter of the main body portion 21, and is close to the needle tip portion 25. Figure 4 (c) and Figure 4 (b) are both stepped with two inflection points 27, but the difference is that the needle head 23 of Figure 4 (c) is near the tip 25 It is tapered like a cone. In other embodiments, the number of inflection points 27 of the needle head 23 may be one or more, and the width of the needle head 23 may be prepared as an elongated shape or a plurality of stepwise tapers, depending on different measurement requirements. Design different pin head 23 profiles. Since the metal probe 2' of Fig. 4(d) has no inflection point, the main body portion 21 is directly connected to the tip end portion 25. It should be noted that the above examples are for illustrative purposes only, and the present invention is not limited to the preparation of the above four types of metal probes. The micro-nano probe device and method of the present invention can be controlled according to the actual shape. The parameters are set on unit 14.

In the present embodiment, the transfer unit 12 takes 2 minutes to grasp 2 metal materials 2, and the metal material 2 is dynamically etched in the electrochemical etching solution 111 for 15 minutes, and then the formed metal probe 2' is used as a cleaning liquid. The 151 was cleaned for 3 minutes, and finally left in the storage unit 16 for 3 minutes to dry. The single preparation method took a total of 25 minutes to complete two micronano metal probes 2', with an average of 12.5 minutes per working hour.

The micronanoprobe device of the present invention can determine the morphology of the probe, such as radius of curvature, probe tip and aspect ratio, and the metal probes of the present invention can have an aspect ratio greater than 250. In other words, the present invention can efficiently and efficiently produce micro-nano metal probes of a specific shape according to requirements, and these probes have extremely high consistency and reproducibility, and are more convenient and stable in providing various micro-nano fields. Test tool for efficiency.

The invention has been described above in terms of the preferred embodiments, and it should be understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that variations and permutations equivalent to those of the embodiments are intended to be included within the scope of the present invention. Therefore, the scope of protection of the present invention is defined by the scope of the patent application.

1‧‧‧Preparation of micronano probe equipment

10‧‧‧Power supply

101‧‧‧Power positive

103‧‧‧Power negative

105‧‧‧Negative electrode rod

11‧‧‧Electrochemical etching unit

111‧‧‧Electrochemical etching solution

112‧‧‧etching liquid surface

12‧‧‧Transfer unit

121‧‧‧Capture Department

13‧‧‧Vibration unit

14‧‧‧Control unit

15‧‧‧cleaning unit

151‧‧‧ cleaning solution

16‧‧‧Storage unit

2‧‧‧Metal materials

2'‧‧‧Metal probe

Claims (10)

A micro-nano probe device comprises: an electrochemical etching unit, accommodating an electrochemical etching solution, the electrochemical etching liquid having an etching liquid surface; a conveying unit having a clamping portion, the clamping portion Capturing one end of a metal material, transferring the metal material to the electrochemical etching unit, and immersing the other end of the metal material in the electrochemical etching solution; a power supply having a positive electrode and the power supply The clamping portion is electrically connected, a negative electrode of the power source and the electrochemical etching liquid are electrically connected; a vibration unit is coupled to the clamping portion, so that the other end of the metal material can be vertically displaced relative to the surface of the etching liquid for dynamic etching Forming a metal probe; a cleaning unit having a cleaning liquid, the transfer unit transferring the metal probe to the cleaning unit, and immersing the metal probe in the cleaning liquid to remove the metal probe An electrochemical etching solution remaining on the surface; and a storage unit for accommodating the metal probe after the electrochemical etching solution is removed. The micro-nano probe device according to claim 1, wherein the upper and lower displacements have an amplitude range, wherein the amplitude range includes a displacement of the other end of the metal material onto the surface of the etching liquid and a distance and displacement of the etching liquid surface. The distance from the surface of the etchant to the surface of the etchant. The micro-nano probe device according to claim 2, wherein the distance from the surface of the etching liquid to the surface of the etching liquid is 2 mm or more. A micronanoprobe device as claimed in claim 2, wherein the distance from the surface of the etchant to the surface of the etchant is from 1 to 17 mm. The micro-nano probe device according to claim 2, wherein the up-and-down displacement has a vibration frequency of 0.2 to 10 Hz. The micro-nano probe device according to claim 2, wherein the electrochemical etching solution is sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, sodium chloride, potassium chloride, ammonium chloride, potassium hydroxide, sodium hydroxide, a mixture of at least one of calcium hydroxide, aluminum hydroxide and ammonium hydroxide, and the pH of the electrochemical etching solution is greater than 9. The micro-nano probe device according to claim 2, wherein the metal material has a cylindrical shape, and the cylindrical shape has a diameter ranging from 0.5 to 5 mm. The micro-nano probe device according to claim 2, wherein the metal probe after etching has an aspect ratio, and the aspect ratio is between 10 and 250. The preparation of the micro-nano probe device as claimed in claim 2 further comprises a heating unit. A micronanoprobe device as claimed in claim 9 wherein the heating unit is a coated heating strip.