TW202130831A - High-entropy alloy and probe application thereof - Google Patents

Abstract

The present invention relates to a high-entropy alloy and a probe application thereof. The metal elements included by the high-entropy alloy are chosen from a group consisted of specific metal elements and by a specific difference of atomic sizes between any two of these metal elements, the high-entropy alloy has the low resistivity, high toughness and high hardness, the high-entropy alloy can be applied to AFM testing probes or other testing probes, such as four-point probe, thereby solving the problems of abrasion during a probing procedure.

Description

High-entropy alloy and its application in probe

The present invention relates to an alloy and its application, and particularly relates to a high-entropy alloy and its application in probes.

Detection probes can be divided into horizontal and vertical probes according to the detection mode and shape. They are used for semiconductor inspection, printed circuit board inspection, communication products and various electronic products, and measure the electrical characteristics of the products. Determine whether the product has failed. The above-mentioned probe includes a main body substrate and a surface coating. The main body substrate is mostly a single element (>50%) as the main body or an alloy composed of less than three solid solution elements, such as rhenium-tungsten alloy, beryllium copper alloy, palladium gold, palladium Silver or palladium nickel, these alloys suffer from insufficient alloy hardness or poor ductility.

In order to increase conductivity, gold or nickel coatings are usually used on the surface of the probe, but most of the coatings are soft and easy to stick and fall off. The hard coating has better mechanical properties, but it will encounter the problem of excessive resistance. The traditional material of the probe for atomic force microscope is silicon material plated with gold, but its disadvantage is that it will encounter problems such as sticking and abrasion when scanning the surface of the test piece.

Traditionally, the concept of alloy is based on a metal element with an atomic percentage of more than 50%, and a mixture of different elements added. Alloys harden the material, but also reduce its toughness and conductivity.

The conductivity of metal materials and the mobility of free electrons are related to the electron density. However, the movement of electrons at a limited temperature will be affected by the deviation of the nucleus from the ideal position due to thermal shock, causing scattering during the movement, and thus resistance The phenomenon. At the same time, ideal single-crystal metals do not exist in reality. Defects will cause the atomic nuclei around the defects to deviate from the ideal position, and cause scattering of electrons during movement, thereby increasing the resistivity of the metal material. In high-entropy alloys, due to the nature of its structure (a solid solution structure formed by multi-element metals), electrons will encounter more scattering when they move. Since the composition of a high-entropy alloy is a mixture of various elements in approximate proportions, the mobility and electron density of its free electrons cannot be directly determined by the electron mobility and electron density of the main element as in general alloys, and must be based on its solid solution. It depends on the status.

Therefore, although high-entropy alloys have excellent mechanical properties, they must have high electrical conductivity and must have a high degree of solid solution properties between the elements to reduce electron scattering. With the composition of currently known elements, there are more than tens of thousands of high-entropy alloy systems that can be developed, and because the number and types are too large, it will take a long time to develop high-entropy alloys by traditional methods.

In view of this, there is an urgent need to develop a new high-entropy alloy to improve the above-mentioned problems of conventional detection probes and atomic force microscope probes.

In view of the above-mentioned problems, one aspect of the present invention is to provide a high-entropy alloy to solve the problems in the use of detection probes and atomic force microscope probes.

Another aspect of the present invention is to provide a detection probe, wherein the substrate of the detection probe is provided with a coating layer containing a high-entropy alloy, which can improve the conductivity and hardness of the detection probe.

In order to achieve the above objective, the present invention provides a high-entropy alloy. This high-entropy alloy contains four to six metal elements, and these metal elements are selected from silver, gold, copper, chromium, cobalt, iron, hafnium, iridium, manganese, molybdenum, nickel, niobium, osmium, palladium, platinum , Rhodium, rhenium, ruthenium, titanium, tantalum, vanadium, tungsten, zinc and zirconium, and based on the maximum atomic size of these metal elements being 100%, the atomic size of any two of these metal elements The difference is not more than 15%.

According to an embodiment of the present invention, based on the maximum value of the electronegativity of these metal elements being 100%, the difference between the electronegativity of any two of these metal elements is not more than 50%.

According to another embodiment of the present invention, the lattice structure of the high-entropy alloy is a body-centered cubic structure or a face-centered cubic structure.

According to another embodiment of the present invention, the enthalpy of formation (ΔHf) of any two of these metal elements is -199 meV/atom to 37 meV/atom.

According to another embodiment of the present invention, the lattice structure is generated from these metal elements using a molecular simulation program, and the target coordination number of any one of these metal elements is 24% to 26%.

According to another embodiment of the present invention, the weight ratio of any two of the metal elements is 0.2 to 2.0.

According to another embodiment of the present invention, the resistivity of the high-entropy alloy is not more than 400 μΩ-cm.

According to another embodiment of the present invention, the hardness of the high-entropy alloy is not less than 5 GPa.

Another aspect of the present invention is to provide a detection probe. The detection probe includes a substrate and a cover layer disposed on the substrate, wherein the cover layer includes the aforementioned high-entropy alloy.

The high-entropy alloy and its probe of the present invention can have one or more of the following advantages and applications:

1. The high-entropy alloy with low resistivity (high conductivity), high toughness and high strength can increase the hardness and service life of the probe, and improve the detection yield.

2. In the application of probes for electronic component testing, for example: applied to probes for semiconductor component testing to overcome the stress, reliability and reliability caused by poor electrical contact of the probes for semiconductor component testing during semiconductor testing. The question of longevity.

3. A high-entropy alloy film is formed on the probes for atomic force microscopes to increase the abrasion resistance and mechanical properties of probes for atomic force microscopes (such as silicon probes) and other detection probes (such as four-point probes) Strength, and maintain high conductivity, thereby prolonging the service life.

In order to facilitate the understanding of the technical features, content and advantages of the present invention and the effects that can be achieved, the present invention is combined with the drawings, and detailed descriptions are given in the form of embodiments as follows, and the main purpose of the drawings used therein is only The purpose of the schematic and auxiliary description is not necessarily the true scale and precise configuration of the implementation of the present invention, so the scale and configuration relationship of the accompanying drawings should not be interpreted and/or limited to the scope of rights of the present invention in actual implementation. In addition, for ease of understanding, the same elements in the following embodiments are denoted by the same symbols. Moreover, the size ratios of the components shown in the drawings are only for the convenience of explaining the components and their structures, and are not used to limit the scope of the present invention.

In addition, the terms used in the entire specification and the scope of the patent application, unless otherwise specified, usually have the usual meaning of each term used in this field, in the content disclosed here, and in the special content. Certain terms used to describe the present invention will be discussed later or elsewhere in this specification to provide those with general knowledge with additional guidance on the description of the present invention.

Secondly, the terms "including", "including", "having" and "containing" are used in this article, which are all open terms, which means including but not limited to.

The high-entropy alloy (also known as multi-principal element alloy) of the present invention is a single-phase alloy containing four to six metal elements. The aforementioned metal elements are selected from silver, gold, copper, chromium, cobalt, A group consisting of iron, hafnium, iridium, manganese, molybdenum, nickel, niobium, osmium, palladium, platinum, rhodium, rhenium, ruthenium, titanium, tantalum, vanadium, tungsten, zinc and zirconium. These metal elements exclude metal elements of groups I, II, III, and IV. When the high-entropy alloy contains four metal elements, it is called a quaternary alloy, and the rest is piled up in this way.

In some embodiments, based on the total weight of the high-entropy alloy being 100%, the weight of each metal element contained in the high-entropy alloy ranges from 3% to 40%. The invention uses the enthalpy limit to screen the high-entropy alloy of the solid solution phase. Because of its low resistance, high toughness and high hardness, it can overcome the life reduction of the detection probe caused by wear, adhesion, and peeling of the coating during the test process. And the problem of electrical contact deterioration can also reduce the abrasion problem of the probe used in the atomic force microscope during the scanning process.

In some embodiments, the atomic size of the largest metal element based on the metal elements contained in the high-entropy alloy is 100%, and the difference in atomic size between any two of these metal elements is not more than 15%. When the difference in atomic size is greater than 15%, the composed alloy does not have a stable lattice structure and cannot form a solid solution phase high-entropy alloy. In some preferred embodiments, the aforementioned difference in atomic size may be no more than 10%, and more preferably, no more than 5%.

In some embodiments, based on the maximum value of the electronegativity of the metal elements contained in the high-entropy alloy being 100%, the difference between the electronegativity of any two of these metal elements is not more than 50% . When the difference in electronegativity is in the aforementioned range, the composed alloy has a stable lattice structure and can form a solid solution phase high-entropy alloy. In some preferred embodiments, the difference in electronegativity may be no more than 40%, and more preferably, no more than 20%.

In some embodiments, the lattice structure of the high-entropy alloy is a body-centered cubic (BCC) structure or a face-centered cubic (FCC) structure. When the lattice structure of the high-entropy alloy is a body-centered cubic structure or a face-centered cubic structure, the alloy composed of these metal elements has a stable lattice structure and can form a high-entropy alloy in a solid solution phase.

In one embodiment, the atomic sizes of the Nb, Mo, Ta, and W elements of the body-centered cubic structure of NbMoTaW alloy are 1.45, 1.45, 1.45, 1.35 Å, and the electronegativity is 1.59, 2.16, 1.51, and 2.36, respectively. In another embodiment, the atomic sizes of Cr, Mn, Rh, and Fe in the face-centered cubic structure of CrMnRhFe alloy are 1.40, 1.40, 1.35, 1.40 Å, and the electronegativity is 1.66, 1.55, 2.28, and 1.83, respectively .

When the enthalpy of formation of any two of these metal elements is -199 meV/atom to 37 meV/atom, the alloy composed of these metal elements has a stable lattice structure and can form a solid solution phase high-entropy alloy . In some preferred embodiments, the enthalpy of formation may range from -199 meV/atom to 0 meV/atom, and more preferably, it may range from -138 meV/atom to 0 meV/atom.

In some embodiments, molecular simulation programs are used to generate the lattice structure of the high-entropy alloy from these metal elements, and the target value of any one of these metal elements may be 24% to 26%. When the target coordination number is 24% to 26%, the alloy composed of these metal elements has a stable lattice structure and can form a solid solution phase high-entropy alloy. Furthermore, in some preferred embodiments, the target coordination number may be 25%. In addition, in some specific examples, the molecular simulation program may include an inverse Monte Carlo simulation program, and the inverse Monte Carlo simulation program may be performed using an inverse Monte Carlo algorithm.

In some embodiments, the weight ratio of any two of the metal elements contained in the high-entropy alloy is 0.2 to 2.0. When the weight ratio is in the aforementioned range, the alloy composed of these metal elements has a stable lattice structure and can form a high-entropy alloy. In addition, in some preferred embodiments, the weight ratio may be 0.3 to 1.5.

In some embodiments, the resistivity of the high-entropy alloy is not greater than 400 μΩ-cm. When the resistivity of the high-entropy alloy is in the aforementioned range, the alloy can be suitable for the application of detection components. In some specific examples, the detection element may include a probe for atomic force microscopy or other detection probes. In addition, in some preferred embodiments, the resistivity may be not greater than 400 μΩ-cm, and more preferably may be 50 μΩ-cm to 300 μΩ-cm.

In some embodiments, the hardness of the high-entropy composite is not less than 5 GPa. In some specific examples, the hardness of the high entropy compound is 5 GPa to 20 GPa. When the hardness of the high-entropy alloy is in the aforementioned range, the alloy can be suitable for the application of detection components. As described above, specific examples of the detection element may include probes for atomic force microscopy or other detection probes.

Another aspect of the present invention is to provide a detection device, which includes a substrate and a covering layer disposed on the substrate. The covering layer contains the aforementioned high-entropy alloy. In some application examples, the material of the cover layer includes the aforementioned high-entropy alloy. In other application examples, the covering layer is made of the aforementioned high-entropy alloy. When the covering layer contains the aforementioned high-entropy alloy, the physical properties of the covering layer can be improved, thereby improving the service life of the detection element and the detection accuracy. In some applications, the physical properties may include resistivity and hardness.

Please refer to FIG. 1. FIG. 1 is a schematic diagram of the structure of the high-entropy alloy coated probe of the present invention. In the present invention, a high-entropy alloy is applied to the probe, and a high-entropy alloy film 300 is plated on the needle body 110 and the needle tip 120 of the probe. In detail, one of the technical features of the present invention is to propose a material design, process method and application for forming a high-entropy alloy thin film 300 on the probe 100 for semiconductor detection or the probe 200 for atomic force microscope. The semiconductor detection probe of the present invention can be, for example, a horizontal probe (the rhenium tungsten probe shown in Figure 1(a)) or a vertical probe (the spring probe as shown in Figure 1(b)). Needle). The structure of the probe for the atomic force microscope of the present invention can be, for example, the AFM scanning probe shown in (c) of FIG. 1.

The following examples are used to illustrate the application of the present invention, but they are not intended to limit the present invention. Anyone who is familiar with the art can make various changes and modifications without departing from the spirit and scope of the present invention.

Selection of high-entropy alloys

The high-entropy alloys are selected by the selection method described later. The selection method includes the following steps: Define the binary formation enthalpy range for the formation of single-phase high-entropy alloys, thereby finding a plurality of quaternary alloys that meet the binary enthalpy limit Materials; and the database of the software for comparing and calculating the phase diagram, to preliminarily screen out the high-entropy alloys that can form a single-phase solid solution from the combination of multiple alloying elements that meet the binary enthalpy limit. The present invention calculates the phase diagrams of four-element to six-metal high-entropy alloys, and uses the phase diagram software to calculate the binary enthalpy limit. In detail, the present invention takes the annealing temperature (1673K) of the NbMoTaW high-entropy alloy of Senkov et al. in the literature as the criterion, multiplies the temperature by the ideal configuration entropy as the lower limit, and takes the maximum value that can form a single-phase binary alloy The enthalpy of formation (37 meV) is the upper limit, which defines the range of the binary enthalpy of formation that may form a single-phase high-entropy alloy. The above-mentioned calculation phase diagram software can be, for example, but not limited to Pandat software (Pandat software, CompuTherm LLC).

For possible quaternary high-entropy alloys, the enthalpy of formation of the two-component combination ranges from -199 meV/atom to 37 meV/atom, and there are a total of 27,405 component combinations. However, only 416 quaternary alloy element combinations meet the above-mentioned binary enthalpy limit. Among them, the method of judging whether the combination of quaternary alloy elements meets the above-mentioned binary enthalpy limit can be compared with the data by means of programs or manually. After the above-mentioned 416 kinds of quaternary alloy element combinations that meet the binary enthalpy limit are verified by the existing database of the calculation phase diagram software, 20 body-centered cubic structures and 60 face-centered cubic structures can be found.

The present invention uses the calculation of phase diagram software with binary enthalpy limit calculation to provide a method for selecting element combinations of high-entropy alloys with a high degree of solid solution. A total of 80 quaternary high-entropy alloy element combinations and 73 five-element combinations are screened out. The element combination of high-entropy alloy and the element combination of 36 kinds of six-element high-entropy alloy.

Among them, the element combination of 80 kinds of quaternary high-entropy alloys is NbMoTaW, TiNbTaMo, TiNbWMo, TiMoWTa, VNbTaMo, VMoWTa, TiZrMoNb, TiNbWTa, VNbWMo, VCrCoFe, VZrWNb, TiZrTaNb, VNbNb, TiZrTaNb, VNbNb, TiV, Nb, VZr, VZr, VZr, VZr , TiZrHfAg, CrMnRhFe, CuRhPtIr, CuPdAuPt, MnFeRhCo, MnFeRhNi, MnFeReCo, MnFeOsRh, MnFeIrCo, MnFeIrNi, MnFeIrRh, MnFeIrOs, MnCoRhNi, MnCoReZn, MnCoReRh, MnCoOsRh, MnCoIrNi, MnCoIrRh, MnCoIrOs, MnNiOsRh, MnNiIrCu, MnNiIrRh, MnNiIrOs, MnCuIrRh, MnRuIrRh , MnRhIrOs, NiCuPtRh, NiCuPtPd, NiCuPtIr, CoNiPtRh, CoNiPtPd, FeCoRhNi, FeCoIrNi, FeNiIrRh, CoNiIrRh, CoNiPtIr, FeCoPdNi, FeCoIrRh, CoRhPtIr, NiRhPtIr, PdAgAuPt, CrFeRhNi, CrCoRhNi, CrCoPdNi, MnFeNiCo, CoRhPtOs, NiCuIrRh, CrFeNiCo, CrFeRhCo, CrFePdNi , FeCoOsRh, FeCoIrOs, FeRhIrOs, CoOsPtIr, NiRhIrOs, CrMnNiCo, CrFePdCo, MnFeZnCo, MnFeOsCo, RuRhPtIr and RhOsPtIr.

Wherein the combination of elements 73 kinds of pentasil entropy alloy is TiVZrMoNb, TiVZrHfNb, TiVZrTaMo, TiVZrWNb, TiVNbTaMo, TiVNbWMo, TiVMoWTa, TiZrNbTaMo, TiZrNbWMo, TiZrNbWTa, TiNbMoWTa, VCrNbWTa, VNbMoWTa, CrMnFeOsRe, CrMnFeNiCo, CrMnFeRhCo, CrMnFeRhNi, CrMnCoRhNi, CrMnCoReNi , CrFeCoRhNi, CrFeCoPdNi, CrFeCoReRh, CrFeNiPdRh, CrCoNiPdRh, CrCoNiReRh, MnFeCoRhNi, MnFeCoReNi, MnFeCoReZn, MnFeCoReRh, MnFeCoOsNi, MnFeCoOsZn, MnFeCoOsRh, MnFeCoOsRe, MnFeCoIrNi, MnFeCoIrRh, MnFeCoIrOs, MnFeNiReRh, MnFeNiOsRh, MnFeNiOsRe, MnFeNiIrRh, MnFeNiIrOs, MnFeRhOsRe, MnFeRhIrOs, MnCoNiReRh , MnCoNiOsRh, MnCoNiOsRe, MnCoNiIrRh, MnCoNiIrOs, MnCoRhOsRe, MnCoRhIrOs, MnNiCuIrRh, MnNiRhOsRe, MnNiRhIrOs, MnRuRhIrOs, FeCoNiPdRh, FeCoNiReRh, FeCoNiOsRh, FeCoNiIrRh, FeCoNiIrOs, FeCoRhOsRe, FeCoRhIrOs, FeNiRhOsRe, FeNiRhIrOs, CoNiRhIrOs, CoNiRhPtPd, CoNiRhPtOs, CoNiRhPtIr, CoRhOsPtIr, NiCuRhPtPd , NiCuRhPtIr, NiRhOsPtIr and RuRhOsPtIr.

Wherein the combination of elements 36 kinds of six yuan high entropy alloy is TiVZrNbMoTa, TiVZrNbMoW, TiVNbMoTaW, CrFeCoNiRhPd, CrFeCoNiRhIr, MnFeCoNiRhRe, MnFeCoNiRhOs, MnFeCoNiRhIr, MnFeCoNiOsIr, MnFeCoZnOsIr, MnFeCoRhOsIr, MnFeCoReOsIr, MnFeNiRhOsIr, MnFeRhReOsIr, MnCoNiRhOsIr, MnCoRhReOsIr, FeCoNiRhPdPt, FeCoNiRhOsIr, FeCoNiRhOsPt , FeCoNiRhIrPt, FeCoRhOsIrPt, FeNiRhOsIrPt, CrMnFeReOsIr, CrMnRuRhReOs, CrMnRuRhOsIr, CrMnRuReOsIr, CrMnRhReOsIr, CrFeCoRhReOs, CrFeCoReOsIr, CrFeRhReOsIr, CrCoNiRhReOs, CrCoNiReOsIr, CrCoRhReOsIr, CrNiRhReOsIr, CrRuRhReOsIr and MnZnRuReOsIr.

In order to verify and explain, take the quaternary alloy NbMoTaW and the quinary alloy NbMoTaWRe in the above-selected material system as an example. Please refer to Figure 2, where Figure 2(a) is the X-ray diffraction diagram of NbMoTaW. By comparing the XRD database of each element of the NbMoTaW film, it can be seen that the β phase of Nb near 2θ=39.5˚ (2θ=38.51˚ ), Mo β phase (2θ=40.51˚), Ta α phase (2θ=38.47˚) and W α phase (2θ=40.26˚) are all (110) BCC structures. In addition, the β phase of Ta (2θ=40.15˚, (411)) is a primitive tetragonal structure, and the β phase of W (2θ=39.88˚, (210)) is a primitive cubic crystal system (Primitive Cubic). ) The structure shows that the NbMoTaW film is a BCC solid solution. Figure 2(b) is the X-ray diffraction diagram of NbMoTaWRe, which is also a BCC solid solution.

In addition, the present invention further compares the X-ray diffraction simulation graph and the experimental graph with respect to the quaternary alloy NbMoTaW and the five-element alloy NbMoTaWRe. For example, the present invention can use the inverse Monte Carlo algorithm to simulate the random scattered structure of high-entropy alloy solid solution atoms. The structure optimization calculation uses VASP software, and the phase stability analysis of high-entropy alloys can be performed through global structure search. To identify trends. The SAS software can be further used to analyze the relationship between variables and energy, predict which atom configuration may have the lowest energy (most stable phase), and find out that NbMoTaW may conform to the experimental atom configuration model. Figure 3 (a)-(b) shows the simulation results of NbMoTaW. Figure 3(a) is the relationship between temperature and phase ratio of the quaternary alloy NbMoTaW. The ☆ curve and the ○ curve in the legend are body-centered cubic ordered lattices, and the ◇ curve in the legend is a disordered lattice, which is represented by the ◇ curve It can be found that at about 690K, there is a 100% disordered body-centered cubic structure. Figure 3(b) is a schematic diagram of the atomic arrangement after stabilization. Figure 3(c) is the X-ray diffraction simulation diagram and experimental diagram of NbMoTaW, and Figure 3(d) is the X-ray diffraction simulation diagram and experimental diagram of NbMoTaWRe. After comparison, it is found that the simulated diagram is very consistent with the experimental diagram, and the accuracy of the comparison is 95%. The aforementioned correct rate is calculated based on the overlap rate of the peak positions of the main peaks in the two patterns.

In the aforementioned inverse Monte Carlo algorithm simulation, the BoltzTrap software was also used to establish a conductivity model, and the Boltzmann transport theory equation under a given electric field, magnetic field or thermal gradient was obtained, and the following table 1 was obtained. The transmission properties of the high-entropy alloy shown are, and the electrical conductivity of the high-entropy alloy is obtained through the conversion of the electronic density of states distribution. In detail, the electronic density of states distribution is optimized using the Vienna Ab initio simulation package (VASP), and the internal stress of the model is optimized to less than 0.06 Kbar to find the equilibrium lattice constant. From the self-consistent field of the electron convergence accuracy, the precise electron density distribution equation is calculated. Then, the electrical conductivity of the high-entropy alloy is obtained through the conversion of the electronic density of states distribution to obtain the electrical conductivity of the high-entropy alloy. The results are shown in Table 1 below. Furthermore, the obtained conductivity is compared with the measured conductivity below. These two conductivity are quite close, so the aforementioned equation of electronic density of states distribution can be used as a simulation evaluation of the conductivity of the alloy. In other words, the alloy found in the aforementioned inverse Monte Carlo simulation has a conductivity consistent with high-entropy alloys, and its conductivity is not greater than 400 μΩ-cm.

Table 1 Calculated value of conductivity (S/m) Conductivity measured value (S/m) NbMo _0.35 TaW _0.35 2.46×10 ⁶ 1.54×10 ⁶ 〜2.86×10 ⁶ NbMoTaW 4.40×10 ⁶ 1.28×10 ⁶ 〜1.89×10 ⁶ NbMoTa _0.35 W _0.35 9.62×10 ⁵ 9.43×10 ⁵ 〜1.92×10 ⁶ Note: The conductivity is DC conductivity.

Please refer to FIG. 4, which shows the relationship between the resistivity and the film thickness of the high-entropy alloy. The present invention takes four high-entropy alloy films of NbMoTaW, NbMoTaWRe, CrMnReFe and CrCoFeV as examples. It can be seen from FIG. 4 that the direct current resistivity of these films is between 50-230 μΩ-cm, which shows the application value of the element combination of the high-entropy alloy screened by the screening method of the present invention in electrical conduction.

In addition, the present invention also takes the NbMoTaW high-entropy alloy film in the material system selected as an example to detect its resistivity. The test results show that the test resistance of the NbMoTaW coated probe is 0.60448 Ω, and the test resistance of the bare needle is 0.5285 Ω. The results show that the probe is on the test probe carrier and exhibits good current stability when energized.

Preparation of detection probe

The preparation of the detection probe is to form a high-entropy alloy film on the probe. Among them, the thin film process takes the DC magnetron sputtering method and the RF magnetron sputtering method as examples, the sputtering power is between 50-150 watts, and the substrate temperature is from room temperature to 400 watts. ℃, the film thickness is between 50nm and 1250nm. The experimental results found that the resistivity of the high-entropy alloy mainly decreases with the increase of the thickness. The parameters and conditions for depositing NbMoTaW films by DC magnetron sputtering are as follows: the coating power is 150 W, the grain size is 17 nm, the thickness is 603 nm, and the composition ratio (Nb:Mo:Ta:W) is 26.8: 25.0: 22.4: 25.8, and the resistivity is 53 µΩ-cm. The NbMoTaW film was deposited by the RF magnetron sputtering method. The parameters and conditions are as follows: the coating power is 150 W, the grain size is 12-17 nm, the thickness is 70-570 nm, and the composition ratio of each element (Nb:Mo:Ta : W) is 9.0:7.9:49.7:33.4 to 29.1:25.4:21.5:24.0, and the resistivity is 58~87 µΩ-cm.

Please refer to Figure 5. Figure 5 shows the relationship between the indentation depth and hardness of four high-entropy alloys (NbMoTaW, NbMoTaWRe, CrMnReFe and CrCoFeV). In the present invention, a nanoindenter (model: Agilent, Nanoindenter G200) is used to test the hardness of four high-entropy alloy films of NbMoTaW, NbMoTaWRe, CrMnReFe and CrCoFeV. As shown in Figure 5, the hardness of NbMoTaW and NbMoTaWRe is 20-23GPa, and the hardness of CrMnReFe and CrCoFeV is 10-15GPa. Because the resistivity of the quaternary MoTaWNb film can reach less than 50 μΩ-cm, which is only slightly higher than the film resistivity of the single component elements Nb, Mo, Ta, W (about 30-40 μΩ-cm), but the hardness (1800 HV) But it is much higher than single-component metal film (W (~816 HV), Mo (~612 HV), Nb (~306 HV), Ta (~204 HV)). Because the high-entropy alloy is plated on the probe tip, it can increase its wear resistance twice, so the BCC (body-centered cubic) high-entropy alloy has the potential to develop high stability, high hardness and high electrical conductivity.

Figure 6 shows the scanning electron microscope image (a) of the NbMoTaW high-entropy alloy coating on the rhenium-tungsten (ReW) probe, and the cross-sectional morphology of the rhenium-tungsten alloy probe after being slit through the focused ion beam (FIB) Figure (b). After observing the uniformity, continuity and film thickness of the NbMoTaW film on the probe surface, it can be seen that the NbMoTaW film is deposited with the original surface undulation of the probe. The thickness is approximately uniform and continuous. The average film thickness of sputtering for 10 minutes is about 97.2 nm. .

Figure 7 shows the change of the tip radius of the coated and uncoated atomic force microscope (AFM) probe, which is the change after scanning the 10.24 mm distance on the standard test piece. The experiment found that the difference of the tip radius of the uncoated AFM probe before and after scanning was 58.44nm (the 11.3 nm in Figure 7 (a1) increased to 69.74 nm in Figure 7 (a2)), and the tip radius of the coated AFM probe (15nm) The difference before and after scanning was 19.74 nm (the 13.65 nm in Fig. 7 (b1) increased to 33.39 nm in Fig. 7 (b2)), and the difference in the tip radius of the coated AFM probe (30 nm) before and after scanning was 10.87 nm (Fig. 7 The 16.06 nm of (c1) increased to 26.93 nm of (c2) in Fig. 7). Two AFM probes with different coating conditions have greatly improved the abrasion resistance of the probes.

Figure 8 shows a graph of current changes in the micro-area, in which Figure 8 (a1) and Figure 8 (a2) are bare needles, Figure 8 (b1) and Figure 8 (b2) are 15nm NbMoTaW coated AFM scanning probes , After scanning 5.12mm (left row) and 10.24mm (right row), the micro-area current change graph. The current values obtained after scanning by the uncoated AFM probe are 0.00289A (as shown in Figure 8 (a1)) and 0.00300A (as shown in Figure 8 (a2)), and the current obtained after scanning with the coated AFM probe The value 0.00285A (shown in (b1) in Figure 8) is close to 0.00312A (shown in (b2) in Figure 8). The data in Figure 8 shows that the NbMoTaW probe current has little effect, that is, it has little effect on image clarity.

In addition, the electrical resistivity of the high-entropy alloy was measured using a test method commonly used by those with ordinary knowledge. The results are shown in Table 2.

Table 2 High entropy alloy Resistivity (μΩ-cm) VCrCoFe 197~229 CrMnReFe 128~140 VZrHfNb 200~260 TiZrHfAg 240~350 MnFeZnCo 244~261

In summary, the high-entropy alloy of the present invention is applied to the electronic component test probe to overcome the problems of stress, reliability and life span caused by poor electrical contact of the probe during the semiconductor probe test. In detail, the present invention forms a high-entropy alloy film on the probe body of the semiconductor element detection probe to form a high-entropy alloy-coated probe. Among them, the probe body of the semiconductor element detection probe includes at least a needle body and a needle tip, and is, for example, a test probe for electronic elements such as semiconductor elements. The material of the probe body is, for example, rhenium-tungsten (ReW) alloy, palladium-gold (Pd-Au) alloy, palladium-silver (Pd-Ag) alloy, palladium-copper-silver (Paliney 7) alloy, and beryllium copper (Be-Cu) alloy, etc. And according to the actual application, the material of the probe body is not limited to the above examples, and other materials can also be used. In addition, the semiconductor device detection probe of the present invention can be applied to, for example, a cantilever probe card (Cantilever Probe Card) or a vertical probe card (Vertical Probe Card). The type of the semiconductor component inspection probe depends on the type of the test pad (Bump & Pad), such as flat head type (Flat) and dot type (Point), but the above type is also only an example, and is not intended to limit the text. The scope of the invention. The high-entropy alloy used in the present invention can be any one of the 80 high-entropy alloy combinations that may form a single-phase solid solution selected by the above-mentioned phase diagram software (Pandat software) with binary enthalpy limit calculation. In detail, the present invention forms a high-entropy alloy film on the probe body of the semiconductor device detection probe, for example. Among them, the high-entropy alloy film is, for example, conformally deposited on the probe body.

Another feature of the present invention is that a high-entropy alloy film is formed on the scanning probe of the atomic force microscope (AFM). The scanning probe of the atomic force microscope is composed of a tip attached to the front end of a cantilever. Increase the anti-wear properties of the scanning probe, maintain high conductivity, extend the service life, and have application value in microscopy technology.

The AFM scanning probe can be, for example, contact mode, non-contact mode, or tapping mode or intermittent contact mode, and for example (1) Silicon Probe: RFESP (Bruker), PPP-NCSTR (Nanosensors), NCSTR (NanoWorld), Tap150Al-G (BudgetSensors), OMCL-AC160/200/240TS (Olympus), HQ: NSC (MikroMasch); (2) Silicon nitride probe (Silicon Nitride Probe): MLCT (Bruker), OMCL-TR400/800PSA (Olympus), XNC12 (MikroMasch); (3) Platinum probe (Pt Probe): 12Pt400B/A (Rocky Mountain); (4) Pt-Ir Probe (Pt-Ir Probe): 12PtIr400B/A (Rocky Mountain). The material of the cantilever beam and/or the tip of the AFM scanning probe is, for example, silicon (Si), silicon nitride (SiN _x ), silicon _{oxide (SiO 2} ) or single crystal alumina (Sapphire), etc. The conductive coating (coating) is for example It is gold (Au), platinum (Pt) or platinum-iridium (Pt-Ir) alloy. The thickness of the high-entropy alloy film can be determined according to actual requirements, for example, between 5 nm and 20 nm. Among them, the ratio of various elements in the high-entropy alloy film (such as the NbMoTaW film) is, for example, 10.7:9.8:48.1:35.5 or 26.8:25.0:22.4:25.8.

In summary, the high-entropy alloy and probe of the present invention can have one or more of the following advantages and applications:

1. The high-entropy alloy with low resistivity (high conductivity), high toughness and high strength can increase the hardness and service life of the probe, and improve the detection yield.

2. In the application of electronic component test probes, such as semiconductor component test probes, to overcome the problems of stress, reliability and lifetime caused by poor electrical contact of semiconductor component test probes during semiconductor testing.

3. A high-entropy alloy film is formed on the AFM probe to increase the abrasion resistance and mechanical strength of the AFM probe (such as silicon probe), and maintain high electrical conductivity, thereby prolonging the service life for the microscopic Technical application value.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various changes and modifications without departing from the spirit and scope of the present invention. Retouching, therefore, the scope of protection of the present invention shall be subject to the scope of the attached patent application.

100: Probes for semiconductor inspection 110: Needle Body 120: Needle tip 200: Probe for Atomic Force Microscope 300: High-entropy alloy film

In order to have a more complete understanding of the embodiments of the present invention and its advantages, please refer to the following description and the corresponding drawings. It must be emphasized that the various features are not drawn to scale and are for illustration purposes only. The contents of the relevant diagrams are described as follows: 1 is a schematic diagram showing the structure of the high-entropy alloy coated probe of the present invention, in which (a) is a horizontal probe, (b) is a vertical probe, and (c) is a schematic diagram of a probe for atomic force microscope. Figure 2 is the X-ray diffraction diagram, where (a) is the X-ray diffraction diagram of the NbMoTaW film, and (b) is the X-ray diffraction diagram of the NbMoTaWRe film. Figure 3 (a) is the temperature and phase rate relationship diagram of the simulated NbMoTaW film, (b) is the atomic structure configuration diagram of NbMoTaW, (c) is the XRD experiment and simulation comparison diagram of the NbMoTaW film, (d) is the NbMoTaWRe film XRD experiment and simulation comparison chart. Figure 4 is a graph showing the relationship between film thickness and resistivity of four high-entropy alloys (NbMoTaW, NbMoTaWRe, CrMnReFe, and CrCoFeV). Figure 5 shows the relationship between the indentation depth and the hardness of four high-entropy alloys (NbMoTaW, NbMoTaWRe, CrMnReFe, and CrCoFeV). Figure 6 is a scanning electron microscope image, in which (a) is a scanning electron microscope image of a coated ReW needle, and (b) is a cross-sectional view of the coating after FIB cutting. Figure 7 is a graph showing the change of the tip radius of the coated and uncoated AFM probes. Fig. 8 is a graph showing the change of micro-area current of the NbMoTaW-coated AFM scanning probe.

100: Probes for semiconductor inspection

110: Needle Body

120: Needle tip

200: Probe for Atomic Force Microscope

300: High-entropy alloy film

Claims (9)

A high-entropy alloy containing: Four to six metal elements, where the metal elements are selected from silver, gold, copper, chromium, cobalt, iron, hafnium, iridium, manganese, molybdenum, nickel, niobium, osmium, palladium, platinum, rhodium, rhenium, A group consisting of ruthenium, titanium, tantalum, vanadium, tungsten, zinc, and zirconium, and based on the maximum atomic size of one of these metal elements being 100%, the difference in one atomic size between any two of these metal elements is Not more than 15%. The high-entropy alloy according to claim 1, wherein the maximum value of electronegativity based on the metal elements is 100%, and the difference in electronegativity between any two of the metal elements is not more than 50%. The high-entropy alloy according to claim 1, wherein a lattice structure of the high-entropy alloy is a unitary-centered cubic structure or a face-centered cubic structure. The high-entropy alloy according to claim 3, wherein an enthalpy of formation (ΔHf) of any two of the metal elements is -199 meV/atom to 37 meV/atom. The high-entropy alloy according to claim 3, wherein the lattice structure is generated from the metal elements using a molecular simulation program, and a target coordination number of any one of the metal elements is 24% to 26% . The high-entropy alloy according to claim 1, wherein the weight ratio of any two of the metal elements is 0.2 to 2.0. The high-entropy alloy according to claim 1, wherein the resistivity of one of the high-entropy alloys is not more than 400 μΩ-cm. The high-entropy alloy according to any one of claims 1 to 7, wherein one of the high-entropy alloys has a hardness of not less than 5 GPa. A detection probe, including: A substrate; and A covering layer is arranged on the substrate, wherein the covering layer comprises the high-entropy alloy according to any one of claims 1 to 8.

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