TW201606310A - Platinum-silicon composite tip applicable to field sensing and its preparation method - Google Patents

Abstract

Provided is a platinum-silicon composite tip applicable to field sensing and its preparation method, which adopts the use of an electroless template deposition method (or electron beam induced deposition (EBID)) for utilizing partial electrochemical reaction between a metal precursor solution and a silicon tip so as to achieve partially, selectively and precisely controlled platinum nano-structured deposition effect. Further, the invention employs an atmospheric microwave annealing (a-MWA) procedure to form a partial platinum silicide layer between the platinum nano structure and the silicon tip, thereby significantly enhancing tip conductivity and the capability of spatial resolution of field sensing. The invention can be used as a probe for a high field sensitive scanning probe microscope (FS-SPM), not only can avoid stray field effect (SFE), but can have excellent image quality. The probe tip that contains platinum silicide may have effective improvement of interface electron transmission efficiency than that of only having a platinum nano structure, which is applicable to the use of a controllable and high spatial resolution conductive probe.

Description

Platinum-bismuth composite needle tip applied to field sensing and preparation method thereof

The invention relates to a platinum-iridium composite needle tip applied to field sensing and a preparation method thereof, in particular to a method of chemical deposition combined with microwave annealing, which can form partial platinum between the platinum nanostructure and the probe tip body. The telluride layer, in particular, has the ability to have good spatial resolution and sensitivity, and can greatly improve the tip conductivity and field sensing spatial resolution.

One of the most important topics in the study of cutting-edge materials is the two-dimensional optical, electrical, magnetic, and mechanical quality measurements at the nanometer scale. Field Sensitive Scanning Probe Microscopic Technology (FS-SPM), such as Electroforce Force Microscopy (EMM), Magnetic Force Microscope (MFM), and scanning potential Microscopy (Scanning Kelvin Probe Microscopy, SKPM), etc., can provide properties such as local surface potential, electric field and magnetic field of materials; however, when measuring the properties of nanometer scale, it is limited by the limitation of spatial resolution. In general, the spatial resolution and sensitivity of FS-SPM are significantly related to the geometry and size of the tip. The traditional FS-SPM is coated with a conductive metal by the Atomic Force Microscope (AFM) tip. The film is formed, because the field of view of the tip of the needle is too large, and the stray field effect (SFE) cannot be avoided.

In order to reduce SFE, a number of methods for tip modification of probes have been proposed, including US Pat. No. 757,300, which discloses the use of etching to produce high aspect ratio tip nanowires. US5171992 discloses the use of ion beam to assist in the deposition of high aspect ratio nanostructures on carbon substrates. And the European patent EP 1 744 143 discloses the use of an electron beam to focus on a coated probe tip for growing a nanowire. However, the above techniques based on energy beam or dry etching require high vacuum equipment, which is not conducive to mass production. The use of wet chemical processes to modify the tip has the advantages of low cost and large manufacturing advantages, such as the paper presented by HM Lin in 2010 (H.-M. Lin, M.-N. Chang, Y.-S. Lin, And C.-C. Cheng, "The Manufacturing of a Metallic Nano-Cluster at a Tip Apex for Field-Sensitive Microscopy Applications," Journal of Nanoscience and Nanotechnology, vol. 10, pp. 4459-4464, 2010), which discloses The nanoparticle tip is used to reduce the SFE. This method also obtains the Republic of China Patent No. I287089. Other techniques such as electrodeposition chemical modification, such as U.S. Patent No. 7,955,486 and U.S. Patent 7,073,320, require a voltage application at the tip to achieve a metal modification effect. In U.S. Patent No. 1,379,941 to C.-T. Lin et al., a method of electroless plating in a fluorine-containing ion environment to deposit a metal nanostructure on the tip of a probe is proposed. However, each of the foregoing prior art methods, such as electroplating, electroless plating, or Electron Beam Induced Deposition (EBID), has a problem of low electron transfer efficiency between metal-germanium probes, thereby seriously affecting field sensing efficiency.

The prior art has proposed a method for improving the tip of the tip by using metal silicide, such as the titanium telluride (TiSi ₂ ) tip proposed by IBM in US Pat. No. 6,139,759 and US Pat. No. 6,1983,000. Too large, resulting in a stray field phenomenon; a platinum telluride (PtSi) tip structure proposed by IBM in U.S. Patent No. 8,332,692, and a metal telluride read head as claimed in U.S. Patent No. 7,142,449. However, each of the prior art forms a metal telluride by a conventional furnace tube annealing method, and the overall heating has a great influence on the whole of the nano-nano component, and there is little report on the local annealing of the tip. Although the applicant of this case proposed silver (Ag) modified enamel tip in 2013 and combined with microwave annealing (MWA) to enhance the field sensing capability, silver is easily vulcanized or oxidized in the environment, which will seriously affect the service life of the probe. This is not conducive to the practical application of the semiconductor testing industry. Therefore, the user-like users cannot meet the needs of the user in actual use.

The main object of the present invention is to overcome the above problems encountered in the prior art and to provide a partial deposition of a white gold telluride layer between a platinum nanostructure and a probe tip body by chemical deposition combined with microwave annealing. The spatial resolution and sensitivity can greatly improve the ability of the tip tip conductivity and field sensing spatial resolution.

For the purpose of the above, the present invention is a platinum-iridium composite needle tip applied to field sensing and a preparation method thereof, wherein:

A white gold-platinum telluride-iridium composite field sensing probe tip structure includes: a probe tip; a platinum nanostructure, which grows on the tip of the probe; and a partial platinum telluride The layer is between the tip of the probe probe and the structure of the platinum nanometer, and is used for improving the sensing capability of the needle tip field.

In the above embodiment of the invention, the platinum nanostructure has a particle size of between 25 nm and 35 nm.

A field sensing probe tip modification method comprising at least the steps of: (A) depositing a platinum nanostructure on a probe tip; and (B) operating the probe under microwave heating, A white gold telluride layer is formed between the platinum nanostructure and the tip of the probe.

In the above embodiment of the present invention, the step (A) of depositing the platinum nanostructure on the tip of the probe probe further comprises the steps of: (a1) providing a metal precursor mixed with fluoride ions on a substrate. And (a2) controlling the probe tip of the crucible to perform a limited range scan on the substrate containing the metal precursor solution to reduce the metal on the probe tip of the crucible and to modify the metal by using the surface structure of the substrate The size.

In the above embodiment of the present invention, the microwave heating is performed on an atmospheric microwave annealing (a-MWA) in which a gaseous environmental component is operated in the atmosphere.

In the above embodiment of the invention, the microwave heating is operated at a power of 500 W to 1800 W for a period of 60 seconds to 120 seconds.

In the above embodiment of the invention, the microwave heating is performed by means of segmented microwaves.

In the above embodiment of the invention, the microwave heating is performed by means of a single-stage microwave.

In the above embodiment of the invention, the substrate has a plurality of holes for carrying the metal precursor solution.

In the above embodiment of the invention, the metal precursor solution is composed of hexachloroplatinic acid (H ₂ PtCl ₆ ) and a Buffered Oxide Etchant (BOE).

In the above embodiment of the present invention, the step (a2) is scanning in a tapping mode for 5 seconds to 10 seconds.

In the above embodiment of the present invention, the metal reduction of the step (a2) is performed on the tip of the probe tip by a Localized Fluoride Assisted Galvanic Replacement Reaction (LFAGRR).

1‧‧‧矽 probe

11‧‧‧Needle

12‧‧‧White gold nanostructure

13‧‧‧Local Platinum Telluride Layer

2‧‧‧Substrate

21‧‧‧ holes

3‧‧‧Metal precursor solution

4‧‧‧ microwave oven

S11～S12‧‧‧Steps

S111～S112‧‧‧Steps

Fig. 1 is a flow chart showing the method for modifying the tip of the field sensing probe of the present invention.

Fig. 2 is a flow chart of the present invention for depositing a platinum nanostructure on a probe tip of a crucible.

Figure 3 is a schematic illustration of the process of tip modification of the field sensing probe of the present invention.

Fig. 4 is a view showing the configuration of a probe tip of the present invention before microwave annealing.

Figure 5 is a TEM diffraction diagram of the ruthenium-platinum interface after microwave annealing of the present invention.

Figure 6 is a schematic diagram comparing the field sensing capabilities of the present invention with other probes.

Please refer to FIG. 1 to FIG. 6 , which are schematic diagrams showing the flow of the method for modifying the tip of the field sensing probe of the present invention, and the flow of the invention for depositing a platinum nanostructure on the tip of the probe tip of the present invention. The schematic diagram of the probe tip modification process of the field, the probe tip configuration diagram of the present invention before microwave annealing, the TEM-platinum interface TEM diffraction pattern of the present invention after microwave annealing, and the field of the present invention and other probes A comparison of sensing capabilities. As shown in the figure: the present invention is a platinum-iridium composite tip applied to field sensing and a preparation method thereof, which is subjected to an atmospheric microwave annealing (a-MWA) process, in a platinum nanostructure 12 and a A partial platinum telluride layer (Pt-Si) 13 is formed between the body of the probe 1 tip 11 and the tip of the probe 1 is modified by the local platinum telluride layer 13 to greatly enhance the field sensing capability.

The manufacturing process of modified Silicon Tip Apex (MSTA) with a partial platinum telluride layer is shown in Figures 1 to 3:

First, step S11 is performed to deposit a platinum nanostructure 12 on the probe tip 11 of the probe 1 having a particle size of between 25 nm and 35 nm.

The above step S11 further includes a sub-step S111 of providing a metal precursor solution 3 mixed with fluorine ions in a plurality of holes 21 in a substrate 2. Next, sub-step S112 is performed to control the tip 11 of the probe 1 to perform a limited range scan in the tapping mode on the substrate 2 containing the metal precursor solution 3 for 5 seconds to 10 seconds; S111 and S112, the metal is reduced on the tip 11 of the probe 1 and the size of the metal modified by the surface structure of the substrate 2 is used. Wherein, the substrate 2 is alumina, and the metal precursor solution 3 carried in the pores 21 of the substrate 2 is composed of hexachloroplatinic acid (H ₂ PtCl ₆ ) and a buffered oxidizing etchant (Buffered Oxide Etchant, BOE). )composition.

Finally, in step S12, the cymbal probe 1 is placed in a microwave oven 4, and is operated at a power of 500 W to 1800 W for 60 seconds to 120 seconds for microwave heating to make the platinum nanostructure 12 and the 矽 probe 1 tip. A partial platinum telluride layer 13 is formed between the 11 to enhance the analytical ability of the 矽 probe 1 tip 11 field sensing. The microwave heating system can be heated by segmented microwave or single-stage microwave. If so, the new structure and process disclosed above constitute a new platinum-iridium composite tip for field sensing and a preparation method thereof.

In one embodiment, the invention is a mixture of a 16% buffered oxidizing etchant and 0.01 M hexachloroplatinic acid as the metal precursor solution 3. The n-type krypton probe 1 was reacted with the metal precursor solution 3 in a half-contact (ie, tapping mode) scanning mode at room temperature 22 ° C, and deposition was performed for 300 seconds to complete the structure of the platinum nanostructure. The needle is modified to a size of 32 nm. As shown in Fig. 4, (a) and (b) represent SEM images of the tip of the platinum-modified 矽 probe tip, and (c) represents the EDS analysis corresponding to (b), (d) and (e) It represents a TEM image of a white gold nanostructure grown on a planar crucible via a Localized Fluoride Assisted Galvanic Replacement Reaction (LFAGRR). The reaction formula is as follows:

Si+6HF→H ₂ SiF ₆ +4H ⁺ +4e ^-

Pt ⁴⁺ +4e ^- →Pt

It can be seen that the present invention is displayed as platinum in the absence of microwaves, and is measured by different devices, and it is proved that a platinum nanostructure is grown on the tip of the probe. Next, the above-mentioned grown platinum nanostructured probe was placed in a microwave oven 4 for atmospheric annealing, and after annealing conditions of 1800 W for 60 seconds to 90 seconds, a partial platinum telluride layer was obtained. As shown in Fig. 5, (a) and (e) are the SEM images of the local platinum hydrazine layer modified 矽 probe tip, and (b), (d), (f) and (h) are local platinum The TEM image of the tip of the probe is modified by the layer, and the (c) and (g) are derived from the diffraction pattern (SAD) of (b) and (f), respectively, where (a) to (d) and (e) The atmospheric microwave annealing time to (h) was 60 seconds and 90 seconds, respectively. Therefore, in (a) to (h) of Fig. 5, it is shown that the structure of the platinum nanocrystal after annealing in the microwave oven is still formed, forming a local platinum telluride (Pt-Si), which proves that the structure of the platinum nano-structure and the probe tip of the ruthenium A partial platinum telluride layer is formed therebetween.

The improvement of the field sensing capability of the local platinum telluride layer has been verified by scanning potential microscopy (Scanning Kelvin Probe Microscopy, SKPM). The surface potential scanning results shown in Fig. 6 are shown in (a) and ( b) for the SKPM maps obtained from the pure enthalpy, (c) and (d) are the SKPM maps obtained from the probe tip of the Platinum-铱 (Pt-Ir) overlay, and (e) and (f) and (g) And (h) are SKPM patterns obtained by modifying the 矽 probe tip with a partial platinum telluride layer after microwave annealing for 60 seconds and 90 seconds, respectively. From the comparison of SKPM of (a) to (h), the present invention has the best analytical ability for the surface potential of the nano material, and the local platinum telluride layer has better performance than the commercial probe or the probe without modification. The surface electric field resolution capability is sufficient to prove that the present invention forms a local platinum telluride layer between the platinum nanostructure and the probe tip body, which has good spatial resolution and sensitivity, and can greatly improve the field sensing and analysis capability, and is suitable for controllable. Conductive probes with high spatial resolution.

The invention adopts an electroless template deposition method (or Electron Beam Induced Deposition (EBID)) to achieve local, selective and precise control by using a local electrochemical reaction between a metal precursor solution and a ruthenium probe tip. The deposition effect of the platinum nanostructure is combined with the atmospheric microwave annealing process to form a local platinum sulphide layer between the platinum nanostructure and the tip of the ruthenium probe tip, which greatly enhances the tip conductivity and the field sensing spatial resolution. The probe of the Field Sensitive Scanning Probe Microscopic Technology (FS-SPM) has better image quality in addition to avoiding stray field phenomenon. The tip of the probe containing platinum telluride will be better than the probe. The probe tip of the platinum nanostructure is more effective in improving the electron transport efficiency of the interface. Therefore, the platinum-iridium composite needle tip applied to the field sensing and the preparation method thereof have the following advantages:

1. Low cost (complete in a home microwave oven).

2. Short time (completed in 2 minutes).

3. Operating at atmospheric conditions.

4. Low temperature process.

5. High uniformity (stable control).

6. Maintain the tip of the probe tip.

7. The interface forms platinum telluride, which greatly increases the conductivity.

8. The formation of the interface platinum telluride allows the platinum to be more closely immobilized on the tantalum substrate.

9. Significantly improve field sensing performance.

10. Compared with the silver tip, it has the advantages of oxidation resistance and vulcanization resistance.

In summary, the present invention is a platinum-iridium composite tip applied to field sensing and a preparation method thereof, which can effectively improve various disadvantages of the conventional use, and can be combined with microwave annealing by chemical deposition method, and can be used in the structure and exploration of platinum. A partial platinum bismuth layer is formed between the needle tip bodies, which has good spatial resolution and sensitivity, and can greatly improve the ability of the tip tip conductivity and the field sensing spatial resolution, thereby making the invention more progressive, practical and more consistent. The user must have met the requirements of the invention patent application and 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.

Claims (12)

[Item 1] A platinum-platinum telluride-iridium composite field sensing probe tip structure includes:
a probe tip;
a platinum nanostructure is grown on the tip of the probe; and a partial platinum telluride layer is interposed between the tip of the probe and the structure of the platinum nanometer for enhancing the sensing capability of the needle tip field . [Item 2] The field sensing probe tip modification method according to claim 1, wherein the platinum nanostructure has a particle diameter of between 25 nm and 35 nm. [Item 3] A method for modifying a field sensing probe tip includes at least the following steps:
(A) depositing a platinum nanostructure on a probe tip; and (B) operating the probe under microwave heating to form a portion of the platinum structure between the platinum nanostructure and the tip of the probe Layer of matter. [Item 4] The field sensing probe tip modification method according to the third aspect of the patent application, wherein the step (A) depositing the platinum nanostructure on the tip of the probe probe further comprises the following steps:
(a1) providing a metal precursor solution mixed with fluoride ions on a substrate; and (a2) controlling the probe tip of the crucible to perform a limited range scan on the substrate containing the metal precursor solution to reduce the metal to The size of the metal modified by the surface of the probe tip is limited by the surface structure of the substrate. [Item 5] The field sensing probe tip modification method according to claim 3, wherein the microwave heating is performed on an atmospheric microwave annealing (a-MWA) in which a gas environment component is operated in the atmosphere. [Item 6] The field sensing probe tip modification method according to claim 3, wherein the microwave heating is operated at a power of 500 W to 1800 W for 60 seconds to 120 seconds. [Item 7] The field sensing probe tip modification method according to claim 3, wherein the microwave heating is performed by segmented microwaves. [Item 8] The field sensing probe tip modification method according to claim 3, wherein the microwave heating is performed by a single-stage microwave. [Item 9] The field sensing probe tip modification method according to claim 4, wherein the substrate has a plurality of holes for carrying the metal precursor solution. [Item 10] The field sensing probe tip modification method according to item 4 of the patent application scope, wherein the metal precursor solution is hexachloroplatinic acid (H ₂ PtCl ₆ ) and Buffered Oxide Etchant (BOE). composition. [Item 11] The field sensing probe tip modification method according to item 4 of the patent application scope, wherein the step (a2) is scanning in a tapping mode for 5 seconds to 10 seconds. [Item 12] The field sensing probe tip modification method according to the fourth aspect of the patent application, wherein the step (a2) metal is reduced on the tip of the probe tip by localized Fluoride Assisted Galvanic Replacement (Localized Fluoride Assisted Galvanic Replacement) Reaction, LFAGRR).