상온상압 초전도체 LK-99 발명 특허 영문

[최윤남(자유인)]

상온상압 초전도체 LK-99 발명 특허 영문

자료출처

https://patents.google.com/patent/WO2023027537A1/en

Room-temperature and atmospheric-pressure superconducting ceramic compound and preparation method therefor

Abstract

A room-temperature and atmospheric-pressure superconducting ceramic compound and a preparation method therefor are disclosed. The room-temperature and atmospheric-pressure superconducting ceramic compound and the preparation method therefor, according to the present invention, comprise a ceramic compound of chemical formula 1, A10-xBx(PO4)6O (A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag, and x is 0.1-2.0), and the superconducting ceramic compound exhibits superconducting properties at room temperature and at atmospheric pressure.

Images (22)

Classifications

C04B35/447 Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on phosphates, e.g. hydroxyapatite

View 4 more classifications

WO2023027537A1

WIPO (PCT)

Download PDF Find Prior Art Similar

Other languagesFrenchKoreanInventor이석배김지훈권영완

Worldwide applications

2022 WO

Application PCT/KR2022/012774 events

Priority claimed from KR10-2022-0106812

2022-08-25

Application filed by 주식회사 퀀텀에너지연구소

2022-08-25

Priority claimed from KR1020220106812A

2023-03-02

Publication of WO2023027537A1

InfoPatent citations (5) Similar documents Priority and Related ApplicationsExternal linksEspacenetGlobal DossierPatentScopeDiscuss

Description

본 발명은 부분적으로 채워진 SQW 모델로 입증되었으며 상온에서 초전도 퍼즐을 연구하는 데 매우 유용한 재료가 될 것이고, 모든 증거와 설명은 LK-99가 최초의 실온 및 주변 압력 초전도체라는 것을 보여주며, LK-99는 자석, 모터, 케이블, 공중부양열차, 전원 케이블, 양자 컴퓨터용 큐비트, THZ 안테나 등과 같은 다양한 응용 가능성을 가지고 있다 할 수 있다.

Room-temperature, normal-pressure superconducting ceramic compound and its manufacturing method

The present invention relates to a superconducting ceramic compound exhibiting superconducting properties at room temperature and normal pressure and a method for manufacturing the same, and more particularly, to a superconducting ceramic compound exhibiting superconducting properties at room temperature and pressure, and a method for manufacturing the same.

The modern age has made tremendous progress in the technology that handles electrons, enough to be called the age of electricity and electronics. The fundamental aspect is, of course, in the sufficient supply of power based on power generation, transmission, and distribution, and advances to primary and secondary batteries, which are media that can store power, and wireless power transmission and reception technology, making great progress in modern times. It became a driving force.

However, the problems of preparing an alternative to the recently emerging environmental and energy problems and of solving the problem of efficiency reduction caused by high integration/densification of semiconductors are fundamentally solved by using low-resistance materials such as copper and gold. It has come to the point that it is necessary to find a new material to replace/resolve the old method.

The field that has attracted attention as an approach to it is high-temperature superconductivity, which is the field of superconductivity with a critical temperature (Tc) higher than the critical temperature limit of the classical theory, BCS theory, by Bednorz and Muller in 1986. They surprised the solid-state physics community by announcing a new class of materials [Bednorz, et al, ZPhys B 64, 189 (1986)].

These materials are ceramics consisting of copper oxide layers separated by buffer cations. In Bednorz and Muller's original compound (LBCO), the buffer cations are lanthanum and barium. Inspired by their work, Paul Chu synthesized similar materials in which the buffer ions were yttrium and barium.

This material is YBCO, and is the first superconductor with a T exceeding the boiling point of liquid nitrogen (77 K) [Wu, et al, Phys Rev Lett 58, 908 (1987)]

Among reports of similar electricity, the highest critical temperature rise is known to be 203.5K, which hydrogen sulfide exhibits at a pressure of 155 GPa [Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system. Nature 525, 73 (2015).]

Afterwards, related research using similar materials was conducted, and the critical temperature continued to rise, and in 2020, a superconducting material with a critical temperature of 15 ° C, approaching room temperature, was reported, but it requires a very high pressure of 267 GPa, and relatively high pressure As a result of repeated efforts to lower it, in 2021 it was reported that superconductivity was exhibited at about -5°C when a pressure of 186 GPa was applied, but it seems difficult to apply in real life in this way (https://en.Wikipedia.org/wiki/ Room-temperature_superconductor ).

The reason for this is that, due to the experimental results of these hydrogen sulfide series and yttrium superhydride, it is true that there is great expectation for room temperature superconductors in the academic world, but 267 GPa or 186 GPa is a pressure that is about 200,000 times the atmospheric pressure (1 atm), and the weight In terms of , more than 2,700 tons are applied to an area of 1 cm 2 , and it can be seen that it is almost impossible to use it industrially by itself.

Therefore, it is necessary to develop a superconducting material that can be used not only at room temperature but also at normal pressure, and it must be a material that does not require high pressure, not hydrogen sulfide or yttrium superhydride. .

The present inventors have disclosed a material containing a small amount of normal-temperature normal-pressure superconducting material having a critical temperature of 313K in the previously filed invention. Although the fact that the superconducting material was included was confirmed through magnetic properties and MAMMA analysis, the included Due to the small amount, the unique electrical characteristics of superconductivity have been insufficiently confirmed.

Therefore, the first technical problem to be solved by the present invention is to provide a superconducting ceramic compound that exhibits superconducting properties at room temperature and normal pressure.

In addition, the second technical problem to be solved by the present invention is to provide a method for manufacturing a thin film of a superconducting ceramic compound exhibiting superconducting properties at room temperature and normal pressure.

In addition, a third technical problem to be solved by the present invention is to provide a solid-state manufacturing method of a superconducting ceramic compound exhibiting superconducting properties at room temperature and normal pressure.

In order to solve the first technical problem described above, the present invention provides a superconductive ceramic compound comprising a ceramic compound represented by Chemical Formula 1.

<Formula 1>

A 10-x B x (PO 4 ) 6 O

(A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag, x is 0.1 to 2.0)

According to another embodiment of the present invention, B may be substituted at the position of A in Formula 1.

According to another embodiment of the present invention, another location A may be changed by the B.

According to another embodiment of the present invention, the lattice structure of the ceramic compound may be modified by the substitution of B.

According to another embodiment of the present invention, a superconducting quantum well (SQW) may be created between A and (PO 4 ) 6 .

According to another embodiment of the present invention, the distance between the superconducting quantum wells (SQW) may be 3.7 Å to 6.5 Å.

According to another embodiment of the present invention, tunneling may occur between the superconducting quantum wells (SQWs).

According to another embodiment of the present invention, the substitution of B may increase the strength and hardness, thereby reducing the change in heat capacity.

Meanwhile, in order to solve the second technical problem, the present invention provides a method for manufacturing a superconducting ceramic compound comprising a step of depositing and synthesizing a ceramic compound according to Chemical Formula 1.

<Formula 1>

A 10-x B x (PO 4 ) 6 O

(A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag, x is 0.1 to 2.0)

According to another embodiment of the present invention, the deposition may be a reaction temperature of 550 ℃ ~ 2000 ℃.

On the other hand, a step of synthesizing a ceramic compound according to Chemical Formula 1 by reacting Lanarkite (L, Lanarkite (Pb 2 SO 5 =PbO PbSO 4 )) and copper phosphide (Cu 3 P) A method for producing a superconducting ceramic compound is provided.

<Formula 1>

A 10-x B x (PO 4 ) 6 O

(A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag, x is 0.1 to 2.0)

According to another embodiment of the present invention, the temperature during the reaction may be 600 ℃ ~ 1000 ℃.

According to another embodiment of the present invention, the lanakite may be heated by mixing and mixing PbO and PbSO 4 in appropriate amounts according to the composition.

According to another embodiment of the present invention, the synthesis of Cu 3 P may be performed by mixing and heating Cu and P in appropriate amounts according to the composition ratio.

Meanwhile, the present invention provides a superconductive ceramic compound characterized in that it is manufactured by the above-described manufacturing method.

According to another embodiment of the present invention, the ceramic compound may exhibit diamagnetism in magnetic susceptibility according to temperature change.

According to another embodiment of the present invention, the ceramic compound may exhibit diamagnetism or ferromagnetism depending on the magnetic susceptibility of the magnetic field change.

According to another embodiment of the present invention, the current-voltage characteristics of the ceramic compound according to temperature change do not follow Ohm's law (V = I × R, V: voltage, I: current, R: resistance) ( V≠I×R).

According to another embodiment of the present invention, the current-voltage characteristics of the ceramic compound according to the magnetic field change may be V=I×R or V≠I×R depending on the magnetic field.

According to another embodiment of the present invention, resistance-temperature characteristics according to temperature change of the ceramic compound may pass through the transition temperature and follow Ohm's law.

According to another embodiment of the present invention, the heat capacity characteristics of the ceramic compound may not follow the heat capacity change law according to the Debye model.

According to the ceramic compound and its manufacturing method according to the present invention, there is an effect of exhibiting superconductive properties at room temperature and normal pressure.

1 and 2 are diagrams schematically illustrating the structure of a ceramic compound according to the present invention, where A represents Pb and B represents Cu, and FIG. 1 shows an a-b plane in a Cartesian coordinate system representing space The structure of the ceramic compound and the unit cell viewed from the orthogonal c-axis direction are shown, and FIG. 2 is a diagram showing the structure of the unit cell of FIG. 1 along the c-axis perpendicular to the a-b plane. is a diagram showing the unit structure of the ceramic chemical of the present invention and the position where a superconducting quantum well (SQW) is created,

3 shows a structure in which A (Pb(II) ion) is substituted with B (Cu(II) ion) at the position of polyhedral Pb(2), and in addition, the volume It is a diagram schematically showing the reduction and the occurrence of stress,

4 is a band diagram showing that the superconducting quantum well (SQW) of FIG. 2 is formed by structural distortion between Pb(1) and phosphate oxygen;

Figure 5 is a photograph taken of the LK-99 sample according to the present invention, dark Shows a gray (light black) color,

6 and 7 are graphs showing a voltage vs. applied current graph and zero resistance measured at 298K to 398K for the sample of Example 1, respectively. ,

8 and 9 are graphs showing the external magnetic field (H) dependence of the applied current for the sample of Example 2 and zero-field cooling, respectively;

10 and 11 are a correlation graph between the critical current and the critical magnetic field and a correlation graph between the critical current and the critical temperature, respectively, for the sample of Example 2;

12 is the result of XRD experiment on the sample of Example 2,

13 is an EPR signal graph of LK-99 according to the present invention;

14 is a graph of the EPR signal obtained after I-V measurement of LK-99,

15 is a graph showing Debye temperature calculated from heat capacity data;

16 is a heat capacity curve of LK-99 according to the present invention;

17 and 18 are graphs showing ferromagnetic behavior through SQUID measurement in VSM mode at 300 K for the sample of Example 2, respectively;

19 is a graph showing the Meissner effect (near 0 Oe, <±100 Oe), ferromagnetic (<±500 Oe), and diamagnetic (>±500 Oe) behaviors by DC magnetic field measurement at 100 K for the sample of Example 2; ,

20 is a graph showing an absorption signal in electron spin resonance measurement of a sample of Example 2;

21 and 22 are photographs of magnetic levitation of the sample of Example 2. FIG. 21 shows that when no current is supplied to the LK-99 sample, the diamagnetic property is very small, so the magnetic levitation phenomenon is not good, and it is just placed on the magnet. 22, it can be seen that diamagnetic properties are enhanced due to the increased Cooper pairs generated by the supplied current, resulting in a magnetic levitation phenomenon.

Hereinafter, the present invention will be described in detail.

However, it should be noted that technical terms used in the present invention are only used to describe specific embodiments and are not intended to limit the present invention.

In addition, technical terms used in the present invention should be interpreted in terms commonly understood by those of ordinary skill in the art to which the present invention belongs, unless specifically defined otherwise in the present invention, and are excessively inclusive. It should not be interpreted in the meaning of, or in an excessively reduced sense, and when the technical terms used in the present invention are incorrect technical terms that do not accurately express the spirit of the present invention, they are technical terms that can be correctly understood by those skilled in the art. It should be replaced and understood, and general terms used in the present invention should be interpreted as defined in advance or according to the context before and after, and should not be interpreted in an excessively reduced sense, and the singular used in the present invention The expression‎ includes a plurality of expressions unless the context clearly indicates otherwise, and in the present invention, the terms 'consisting of' or 'comprising' include all of the various components or steps described in the invention. It should not be construed as such, and some components or some steps of which may not be included, or additional components or steps may be further included, and in describing the present invention, related known technologies If it is determined that the detailed description may obscure the gist of the present invention, the detailed description will be omitted.

The present invention is intended to further disclose the crystal structure of only a small amount of superconducting material that has not been disclosed in the previously filed invention.

The present invention found a method to increase the amount of superconducting material in the form of a thin film through VD (Vapor Deposition) method, and also confirmed the reaction mechanism and crystal structure of the superconducting material through additional analysis. Based on the information, it was possible to synthesize superconducting materials in the form of ingots or powders using general solid-state reactions.

In addition, various energy sources used for deposition are not limited to chemical vapor deposition (CVD) using heat, but atomic layer deposition (ALD), sputtering, and thermal evaporation. , e-beam evaporation, molecular beam epitaxy (MBE), pulsed laser deposition (PLD), etc. are also included without limitation as long as the raw material can be deposited.

The superconducting ceramic compound according to the present invention is characterized in that it includes a ceramic compound represented by Chemical Formula 1.

<Formula 1>

A 10-x B x (PO 4 ) 6 O, x=0.1 to 2.0

(A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag)

Formula 1 has a structural similarity with apatite, but has different physical properties and characteristics, so this patent also distinguishes this structure as 'LK-99'.

The apatite is a mineral in which a phosphoric acid group and a metal are combined and has been commonly used as a dye from the past, and it is an electrical insulator with a large energy gap, whereas the LK-99 structure according to the present invention is a substituent in the compound It has the characteristic of exhibiting electrical conductor, especially superconducting properties, by forming a new energy level with added impurities and defects.

In addition, in Formula 1, A is a metal such as Ca, Ba, Sr, Sn, Pb, etc., and has characteristics of a s-block metal or a p-block metal, or Y, La, Ce, etc., and the metal is a lanthanide series or the like may include a combination of

In addition, B has the characteristics of a d-block metal such as Cu, Cd, Zn, Mn, Fe, Ni, Ag, etc., and B is an element having a d orbital as a kind of substituent or an added impurity, thereby making it a conductor or It has the properties of being a superconductor.

In addition, x = 0.1 to 2.0 is preferable. If it is less than 0.1, spatial distortion due to the structure of the ceramic compound or interparticle stress due to distortion is insignificant, so that a Superconducting Quantum Well (SQW) may not be generated. Conversely, 2.0 If it exceeds, the compound may not be generated or an unstable lattice or other form of lattice may be generated.

1 and 2 are diagrams schematically illustrating the structure of a ceramic compound according to the present invention, where A represents Pb and B represents Cu, and FIG. 1 shows an a-b plane in a Cartesian coordinate system representing space The structure of the ceramic compound and the unit cell viewed from the orthogonal c-axis direction are shown, and FIG. 2 is a diagram showing the structure of the unit cell of FIG. 1 along the c-axis perpendicular to the a-b plane. The inside indicated by a solid line box is a unit structure of the ceramic chemical of the present invention and is a diagram showing the position where the superconducting quantum well (SQW) is created.

3 shows a structure in which A (Pb(II) ion) is substituted with B (Cu(II) ion) at the position of polyhedral Pb(2), and in addition, the volume Figure 4 is a diagram schematically showing the reduction and occurrence of stress, and FIG. 4 is a band diagram showing that the superconducting quantum well (SQW) of FIG. 2 is formed by structural distortion between Pb(1) and phosphate oxygen.

In Formula 1, a polyhedral structure is formed by 6 A (Pb(1)) and channel oxygen (O), that is, 3 A's are planarly arranged in a triangular shape, and 3 A's are arranged above or below it in a triangular shape. The planes are stacked, but each triangle is provided in a staggered arrangement rather than overlapping, and a phosphate ((PO 4 ) 6 ) is disposed adjacent to each A.

Such a polyhedral structure is represented by an asymmetric polyhedron 6Pb(1)-O, for example, A as Pb, and is continued up and down within a unit cell to form a polygonal or cylindrical columnar structure in the entire solid structure.

In more detail, six Pb (1) layers are formed in three layers around four sites where channel oxygen (O) can be located at the center of the triangle made of Pb (1), forming a total of two layers.

When the unit cell is continuous, channel oxygen (O) randomly occupies one of the four sites, and when the 6Pb(1)-O layer in the unit cell thus formed is connected in the c-axis direction, a cylindrical columnar structure is formed. , this structure is surrounded by a three-dimensional structure made of Pb(2)-O-P.

In summary, the LK-99 according to the present invention has a three-dimensional network structure as a whole, and an insulating tetrahedral PO 4 network structure surrounds it, and an asymmetric polyhedron 6Pb (1)-O is arranged inside the surrounded polyhedron 6Pb (1 )-O is characterized in that two triangles (3Pb(1)) are arranged staggered up and down.

Here, B (Cu) is substituted in place of A. Instead of replacing A (Pb (1)) forming the polyhedron earlier, four A (Pb ( 2)), and is marked as Pb(2) to distinguish it from Pb(1) forming the internal column structure.

That is, the polyhedron 4Pb(2) is arranged in the insulating tetrahedral PO 4 network structure of LK-99, and copper ions (Cu 2+ ) are replaced by about one of the four Pb(2) ions, resulting in Pb(1) has a structural feature in which the position of is slightly moved from its original position (before substitution) by the substituted copper, and similarly to that shown in FIG. 3, volume shrinkage in the insulating tetrahedral PO 4 network structure by substituted copper ions and stress), and as a result of this effect, distortion of the arrangement of Pb(1) is generated in the polygonal or cylindrical pillars therein, so that distortion occurs at the interface between the insulating tetrahedral PO 4 network structure and the polygonal or cylindrical pillars, resulting in superconductivity. It can be understood that a quantum well (SQW) is created.

Substitution of copper ions in LK-99 resulted in a volume reduction of 0.48% because copper ions (Cu 2+ , 87 pm) were smaller than lead ions (Pb 2+ , 133 pm), and this volume reduction caused Stress can finally affect the appearance of superconductivity.

Here, the proportion of copper is determined based on the atomic % data of XPS and can be confirmed by a Debye model for heat capacity, which will be described in more detail later.

Each atom % of XPS is the amount or intensity of each atom by summing the respective area of the binding energy peak of the corresponding atom, dividing it by the total number of electrons occupying the measurement orbital of each atom, and then multiplying by the relative sensitivity of the XPS measurement of the corresponding atom ( intensity) can be calculated, the ratio of copper can be determined by calculating the relative amount of Pb and Cu, and the value of Cu can be calculated to be about 0.9 when the value of Pb is set to 10 based on the XPS measurement data.

In addition, the color of the ceramic compound LK-99 of the present invention is contrasted with the ivory color of apatite. It is gray or black (Fig. 5), and unlike apatite, which is an insulator, it is a superconductor.

In addition, according to the present invention, the ceramic compound is characterized by a change in the arrangement position of A due to substitution of B, so that the strength and hardness of the ceramic increase and the change in heat capacity decreases. The reason is that the substituted B (Cu 2 + ) is smaller in size and volume than A (Pb 2+ ), so volumetric shrinkage occurs as a whole.

In other words, the change in heat capacity can be reduced by limiting the normal three-dimensional vibrational movement due to the deformation of the molecular structure by the substitution of B.

When electrons move through tunneling between superconducting quantum wells (SQWs) of the ceramic compound according to the present invention, the resistance value can be zero. It is similar to the effect of flowing current.

Since the distance between the superconducting quantum wells (SQW) of the LK-99 is 3.7 Å to 6.5 Å, tunneling between the superconducting quantum wells is likely to be possible. When this is done, the Coulomb attraction between the nucleus of the neighboring atom and the coulomb force of the electrons of the Cooper pair is greatly reduced, so that they can easily pass through the barrier, and also the kinetic energy required for tunneling is transferred to the movement due to the electron-electron interaction between the Cooper pairs. The energy and the sum of the kinetic energy of the two electrons forming the Cooper pair appear to act as an energy source capable of tunneling between the SQWs.

Since the LK-99 of the present invention has a SQW between the Pb(1) of the inner column structure and the outer insulating tetrahedral PO 4 network structure, the applied current is transmitted through the SQW present in the cylindrical column through the tunneling process, LK-99 has partially filled SQWs, and the electrons transferred appear to go through pairing, superconducting electrons (Cooper-pair), condensation, etc.

On the other hand, LK-99 according to the present invention exhibits superconductivity at room temperature and pressure, because the stress generated by substitution of B(Cu2 + ) is transmitted to the interface of the cylindrical column without being relieved.

That is, the Pb(1) atoms of the polygonal (or cylindrical) column interface occupy a structurally limited space, and these interface atoms are resistant to stress and strain caused by friendly B, for example, copper ions (Cu 2+ ). It is entirely affected, and since this strain can be maintained even at room temperature and atmospheric pressure (without relaxation where the strain is resolved and restored to its original state), it is determined that SQW is generated and the superconductivity phenomenon is expressed.

On the other hand, the method for manufacturing a ceramic compound according to the present invention is characterized by including a step of synthesizing a ceramic compound according to Chemical Formula 1 by depositing a raw material.

<Formula 1>

A 10-x B x (PO 4 ) 6 O, x=0.1 to 2.0

(A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag)

In addition, the raw materials of Chemical Formula 1 are reacted in an appropriate amount by weight according to the molar ratio at a reaction temperature of 550 ° C. to 2000 ° C. and a reaction time of 1 to 100 hours in a vacuum-adjustable reaction vessel so that the ceramic compound is deposited in the vapor phase. can be synthesized.

In addition, the raw material may be pretreated so that the vapor phase deposition is effectively dense and uniform. In this pretreatment, the total weight of the materials of Chemical Formula 1 is appropriately weighed according to the molar ratio in a reaction vessel capable of controlling vacuum at a reaction temperature of 550 ° C to 1100 ℃, a reaction time of 1 to 100 hours, the pre-treated ceramic precursor can be used as a deposition material.

In the present invention, the process temperature and process time of Thermal Vapor Deposition (TVD), which is a method of physical vapor deposition (PVD), are ① 550 ° C to 1100 ° C for 1 to 100 hours in the case of a ceramic precursor, and ② in the case of a deposition process 550 ℃ ~ 2000 ℃, 0.001 ~ 100 hours can be applied.

For this reason, in the case of ceramic precursors, firstly, stable reaction conditions (550 ° C to 1100 ° C) are established at relatively low temperatures according to the composition ratio so that the reaction proceeds in a well-mixed solid-solution state, which is used for deposition. This is because it is a precursor that is primarily prepared to be used as a raw material.

In the present invention, the process temperature and process time of Thermal Vapor Deposition (TVD), which is a method of physical vapor deposition (PVD), are ① 550 ° C to 1100 ° C for 1 to 100 hours in the case of a ceramic precursor, and ② in the case of a deposition process 550 ℃ ~ 2000 ℃, 0.001 ~ 100 hours can be applied.

For this reason, in the case of ceramic precursors, firstly, stable reaction conditions (550 ° C to 1100 ° C) are established at relatively low temperatures according to the composition ratio so that the reaction proceeds in a well-mixed solid-solution state, which is used for deposition. This is because it is a precursor that is primarily prepared to be used as a raw material.

Here, if the heating temperature of the ceramic precursor is less than 550 ° C, sufficient mixing may not occur, and accordingly, the desired reaction may not sufficiently occur. In addition to the problem that the desired composition is not created by proceeding with another reaction, there is a problem of energy waste, and the heating time requires 10 to 100 hours. If it is less than 10 hours, the problem is that sufficient reaction does not occur, , Conversely, if it exceeds 100 hours, too much energy may be consumed.

The heating temperature of the physical deposition process including thermal evaporation using these precursors may be 550 to 2000 ° C. If it is less than 550 ° C., it may be difficult to uniformly produce a compound because elements are not sufficiently vaporized, and conversely, 2000 ° C. If it exceeds, it may be difficult to produce a superconducting compound, and if the heating time is from 0.001 to 100 hours, if it is less than 0.001 hours, sufficient vaporization will be difficult and it may become very thin to the extent that deposition is almost impossible. On the contrary, if it exceeds 100 hours This can be energy consuming after the deposition is complete.

In addition, another one of the deposition processes is CVD (chemical phosphatase deposition), where a well-prepared sample (including pretreatment material) is placed on a heating unit in a vacuum state and applied as an energy source to raise the temperature and move it to a gas phase. At this time, if it is less than 550 ° C Vaporization of materials to be in a gaseous state does not occur well, and when heated to a temperature exceeding 2000 ° C, the temperature of the deposition surface rises too high, and the desired deposition phase may not be formed well. The heating time is 0.001 to 100 hours, If it is less than 0.001 hours, it is difficult to vaporize enough and it can be very thin enough to hardly deposit. Conversely, if it exceeds 100 hours, it may waste energy after deposition is completed

In the case of chemical vapor deposition (CVD), the reaction in which Larnarkite is primarily formed appears to be formed by vaporizing PbS first and receiving oxygen from the substrate, as shown in Scheme 1.

<Scheme 1>

2PbS (s) + 5/2O 2 (s, from substrate) → Pb 2 SO 5 (s) + S(g)↑

Then, on the Larnarkite (Pb 2 SO 5 =PbO·PbSO 4 ) formed in this way, Cu and P replace Pb and S, respectively, to create 'LK-99', which is a ceramic compound according to the present invention, which is a structure of a superconducting material. there is.

This can be found through the following reasoning.

① Superconducting material is formed in the area where Lanarkite exists, ② Cu and P are detected together in the superconducting material area, ③ Among the compounds formed by Cu and P, the material on the database (COD) is Cu 3 P, ④ Therefore, It can be seen that Lanarkite and Cu 3 P react to produce 'LK-99', which is a structure of a superconducting material, which is a ceramic compound according to the present invention, and can be summarized as shown in Scheme 2 below.

<Scheme 2>

L + Cu 3 P → LK-99

(L: Lanarkite (Pb 2 SO 5 =PbO·PbSO 4 ))

The above reaction formula is the reaction mechanism of the ceramic compound according to the present invention, and the apatite structure does not exist only with sulfate groups, and may exist in the form of a phosphate group alone or a mixture of phosphate groups and sulfate groups. Lanarkite is a sulfate group compound, Cu 3 P It can be seen that some or all of the sulfur reacts with phosphorus to form a phosphoric acid group.

Accordingly, the synthesis of the ceramic compound according to the present invention can be performed by performing a solid-state reaction using the above reaction formula.

First, in order to synthesize Lanarkite, PbO powder and PbSO 4 powder were uniformly mixed at a molar ratio of 1:1, placed in an alumina crucible, put into a heating furnace, reacted at 725 ° C for 24 hr, and after the reaction was completed, pulverized to obtain a vial. put in and keep

Next, in order to synthesize Cu 3 P, Cu powder and P powder are mixed in a composition ratio, put in a reaction tube (quartz tube), sealed after forming a vacuum, reacted at 550 ° C. for 48 hr, and after completion of the reaction, Remove from the reaction tube, crush the ingots, put them in a vial, and store.

Next, in order to obtain a ceramic compound according to the present invention, the synthesized Lanarkite and Cu 3 P were uniformly mixed at a molar ratio of 1: 1, put into a reaction tube, sealed after vacuum formation, and 5 hr at 600 ° C to 1000 ° C. After reacting for ~40 hr (if below this temperature range, sufficient reaction energy cannot be supplied, and if this range is exceeded, SO 4 contained in Lanarkite can be decomposed, and unreacted substances below this time range After the reaction, the sample taken out of the reaction tube is in the form of ingots, and if necessary, the ingots are processed or pulverized to can be stored

Example 1 - Evaporation Synthesis

In Formula 1 A 10-x B x (PO 4 ) 6 O, A is Pb and B is Cu, so that Formula 2 Pb 10-x Cu x (PO 4 ) 6 O (x=0.1~2.0) is prepared in a molar ratio 3g of the total weight is appropriately added to the quartz tube, and a vacuum of 10 -5 Torr is created with a vacuum pump. After maintaining for 20 minutes, the total length of the tube is 15cm, and sealed using a torch. A ceramic precursor is synthesized by putting it in a furnace chamber and reacting at a reaction temperature of 550 ℃ ~ 1100 ℃ and a reaction time of 10 ~ 100 hours, loading it on a substrate as a raw material, placing it in a vacuum chamber, and then heating part ( tungsten boat), maintain a vacuum below 10 -5 Torr, maintain the temperature of the heating part at about 550 ℃ ~ 900 ℃ for about 1 to 5 minutes to liquefy, and then raise the temperature to 900 ℃ ~ 2000 ℃ to vaporize, and the gas rises The ceramic compound according to the invention was synthesized by depositing it on the surface of a high-purity glass plate placed on the path.

Example 2 - Solid Phase Synthesis

To synthesize lanarkite, PbO powder and PbSO 4 powder were uniformly mixed at a molar ratio of 1:1, placed in an alumina crucible, put into a heating furnace, reacted at 725 ° C for 24 hr, and pulverized after completion of the reaction, Cu 3 P In order to synthesize, Cu powder and P powder are mixed in a composition ratio, put in a reaction tube (quartz tube), sealed after forming a vacuum, reacted at 550 ° C for 48 hr, and after the reaction is completed, taken out of the reaction tube to form granules (ingot) was pulverized, and the Lanarkite and Cu 3 P were uniformly mixed at a molar ratio of 1: 1, put into a reaction tube, sealed after forming a vacuum of 10 -5 Torr, reacted at 925 ° C for 10 hr, and the reaction was completed. Afterwards, the ceramic compound according to the present invention was synthesized in the form of ingots from the sample taken out of the reaction tube. The materials used for the solid phase reaction here were PbO (JUNSEI, GR), PbSO 4 (KANTO, GR), Cu (DAEJUNG, EP), and P (JUNSEI, EP).

The sample obtained by the solid phase reaction is obtained in the form of a dark gray hard ingot and is slightly proused due to the influence of gas molecules escaping from the synthesis reaction process, and the size of the sample depends on the size of the reaction vessel and the amount of reaction. The measurement of electrical resistance was measured by processing the ingot into a rectangular parallelepiped in the form of a thin plate. XRD, SQUID, and EPR were measured with pulverized powder, and XPS was measured by making powder into a pallet.

Experimental Example 1 - Electrical Characteristics Measurement

The electrical properties of the samples obtained in Example 1 were processed into a thin plate-shaped rectangular parallelepiped were measured using a 4-point probe with an interval of 1.2 mm. Keithley 228A and Keithley 182 were used as voltage/current source and digital voltmeter, respectively. For accurate temperature control and measurement, a self-designed heating device was created using an insulated aluminum mounting plate and a halogen lamp and used as a heat source. A self-made program using LabView software was also used for measurement. All instruments were connected with GPIB interface devices. Temperature measurements were performed with a Keithley 2000 using a FLUKE 80BK-DMM Type K thermocouple probe on the sample surface.

6 is a graph of voltage vs. applied current measured at 298K to 398K, and the DC polarity change was performed every time the temperature increased by 20K in a vacuum of 10 -3 Torr, and the measured resistivity was 10 -6 to 10 -9 Ω It was in the cm range.

The current-voltage characteristic of the ceramic compound according to the present invention does not follow Ohm's law when the magnitude of the external magnetic field is 0 G, there is little change in voltage compared to the supplied current, and the maximum current according to the magnitude of the external magnetic field It shows the characteristic that the amount of decreases, but when it exceeds the maximum amount of current, it shows the current-voltage characteristic that follows Ohm's law.

In addition, the resistance-temperature characteristics of the ceramic compound according to the temperature change show that the superconducting phase is broken by temperature, and as the temperature increases, the amount of current with zero electrical resistance decreases, and eventually the superconducting phase is broken, resulting in the current-voltage characteristics of Ohm's law will show

Figure 7 is a new superconductor international standard ( Y. Wang, Fundamental Elements of Applied Superconductivity in Electrical Engineering . (Wiley, 2013), JW Ekin, Experimental Techniques for Low-Temperature Measurements . (Oxford University Press, New York, 2006)) It is a graph showing the zero resistance of the LK-99 thin film that satisfied the zero resistance of . The voltage measured while the applied current was increased or decreased was obtained in the range of 0.1 μV / cm, and the specific resistance was 10 -10 ~10 -11 Ω cm Calculated in order, the generation of residual resistance decreased according to the thin film due to the decrease in grain boundaries.

It can be seen that the current-voltage characteristics of the ceramic compound according to the present invention do not follow Ohm's law and exhibit superconductive characteristics with little change in voltage compared to the supplied current.

Experimental Example 2 - Measurement of magnetic properties

The degree of magnetization of 45.814 mg of the finely ground sample of Example 2 was measured using a superconducting quantum interference device (SQUID) (setting: dc mode, 30 mm scan length, 10 scans per measurement, 10 sec scan time). In addition, zero field cooling was performed from 400K to 200K without an external magnetic field, then the temperature was raised from 200K to 400K in a 10 Oe magnetic field, and cooled from 400 K to 200K in a 10 Oe magnetic field.

In addition, another magnetization measurement was performed in VSM mode, from -20,000 Oe to +20,000 Oe at 300 K, and a third magnetization measurement was performed in dc mode, 30 mm scan length, 10 scans per measurement, and 10 sec scan time.

Zero field cooling (Zero Field Cooling) was measured at 0 G to 3500 Oe, 3500 Oe to -3500 Oe, and -3500 Oe to 3500 Oe at 100 K after processing from 300 K to 100 K without an external magnetic field.

Fig. 8 shows the dependence of the applied current on the external magnetic field (H). As can be seen in particular in Fig. 9, the DC magnetization values of zero field cooling and field cooling of 10 Oe are still negative even up to 400 K, and these results are consistent with superconductivity. shows that the phase still exists up to 400 K at 10 Oe.

When the magnetic susceptibility rises above the critical temperature (Tc), a transition occurs in which the magnetic susceptibility value suddenly increases. This measurement method is called ZFC, and the method of measuring while lowering the temperature at a high temperature is called FC. When the temperature (Tc) is lowered below, a transition occurs in which the resistance value suddenly decreases (theoretically, it goes to zero '0'). The same data is obtained even if

That is, the magnetic susceptibility of the ceramic compound of the present invention is cooled to 200K according to the temperature change, and then the direct current (DC) magnetic susceptibility is measured while raising the temperature to 400K, and then cooled again to 200K under a magnetic field of 400K to 10 G while direct current ( DC) When the magnetic susceptibility is measured, it can be seen that the negative magnetic susceptibility, that is, the diamagnetism characteristic of superconductors is exhibited.

also. 10 and 11 show that the critical current value is not yet zero at 400 K and 3000 Oe or more, the superconducting phase is maintained even at 400 K, and even at a current of less than 7 mA, it can be seen that it is 400 K or more. Through this, 400 K or less The superconducting transition temperature of cannot be found, and therefore, it can be determined that the critical temperature of LK-99 according to the present invention is 400K or more.

Experimental Example 3 - XRD measurement

A pulverized powder sample of Example 2 was made and measured using an XRD measuring device (Rigaku (Smart Lab, Japan)), and XPS was measured by making the pulverized powder sample into a pellet.

12 is the XRD result of LK-99 consistent with the reference database (Crystallography Open Database (COD)). The original XRD data was only processed with Kα2-strip without any other processing, that is, the X-ray wavelength used in XRD is It is not a single wavelength, but two wavelengths, Kα1 and Kα2, are mixed, and considering that it is technically difficult to separate the two wavelengths due to the similar energy difference, if you look closely at the XRD peak, even one peak is divided by Kα1 and Kα2. It can be seen that it is splitting into two, but since the intensity of Kα2 is about 1/2 smaller than that of Kα1 in the data processing process, the part caused by Kα2 was removed using software and only the peak caused by Kα1 was considered.

The data obtained in this way obtained results very similar to those of apatite on the reference database.

This result indicates that LK-99 according to the present invention is polycrystalline and its main peak is similar to the lead-apatite (AP) structure, and the impurity (Cu 2 S) is small.

The crystal system of conventional lead-apatite is hexagonal (P6 3/m , 176), and the cell parameters are a=9.865 Å and c=7.431 Å. (The volume reduction of 0.48% is the value calculated by substituting the unit cell parameter of lead-apatite into the formula of hexagonal volume V = a 2 c sin (60 o ) and the unit of LK-99) This is the result calculated by entering the cell parameters).

On the other hand, in order to reveal the final influence of the stress due to the volume reduction of the ceramic compound of the present invention, that is, to determine the change in the position of Pb (1), one determination is made through the Fourier transform of the calculated structure factor. One-dimensional electron density calculations along the axis were used.

The electron density was calculated along the z direction θ (c) based on the (00l) reflection intensity of the XRD data using Equation 1 below.

<Equation 1>

Figure PCTKR2022012774-appb-img-000001

Here, l, F(00l), c, and z denote the order of (00l) diffraction peaks, structure coefficient, unit cell parameters along the c-axis, and atomic coordinates along the z-axis, respectively.

Based on the (00l) and (h00) reflection intensities of the XRD data in FIG. 12, the electron density of Pb (1) is calculated along the z-direction and the x-direction ρ (c, rho c) and ρ (a, rho a) For this, the above equation was applied.

The position of Pb(1) constituting the inner cylindrical pillar is slightly shifted from the original position by replacing the substituted copper ion inward or outward, and in the repeating triangular structure of Pb(1) of the cylindrical pillar, Pb in one layer The distance between (1) is reduced to 2.61815 Å, and the next layer is increased from the original distance of 3.03340 Å to 5.23476 Å, but the distance to the c-axis (3.7140 Å) between the triangular layers of Pb (1) of LK-99 is lead-apatite. (3.7153 Å) and little change.

In addition, in the analysis result of XPS data, the binding energy (BE) of lead (Pb(2)) and phosphorus (Phosphor) did not change, but the phosphorus separation value of the tetrahedral PO 4 network structure between 2 p3/2 and 2 p1/2 (Phosphorus splitting value) increased very slightly from 0.68 eV to 0.69 eV, all oxygen BEs increased significantly to 0.21 eV, 0.33 eV, and 0.56 eV, respectively, and the BE value of Pb(1) slightly decreased by 0.03 eV. , From this, it can be seen that the volume decrease due to the substitution of copper ions occurred, and the stress caused by the volume decrease finally caused a change in the position of Pb(1) and a change in the binding energy between oxygen atoms adjacent to Pb(1). there is.

Pb 4f 7/2 , 4f 5/2 P 2P 3/2 2P 1/2 O 1s Cu 2P 3/2 2P 1/2

Lead Apatite Pb(1) 137.42 eV

142.3eV

Pb(2) 138.07eV

142.95eV 131.61eV

132.3eV

Splitting value: 0.69eV O(4) 529.10 eV

O(1) 529.57 eV

O(2) 530.02 eV

O(3) 530.60 eV

LK-99 Pb(1) 137.39eV

142.27eV

Pb(2) 138.07eV

142.94eV 131.62eV

132.3eV

Splitting value: 0.68eV O(4) 529.31 eV

O(1) 529.9 eV

O(2) 530.58 eV

O(3) 531.49 eV Cu(0) 932.05 eV

951.91eV

Cu(II) 933.78 eV

954.03eV

Table 1 above shows the binding energy of lead-apatite and LK-99. Experimental Example 4 - Electron paramagnetic resonance (EPR) spectroscopic measurement

EPR spectroscopic measurements were performed in the temperature range of 3.45 K to 295 K using a JES-FA200 ESR X-band spectrometer (Jeol, Japan), the incident microwave power was 0.9980 mW, the receiver obtained 100 and the sweep time was 1 min. The modulated magnetic field was set to 10G at 100KHz and the swept external magnetic field was set to -100~9,900Oe or 0Oe~10,000Oe.

The pulverized powder sample of Example 2 is set in a 5 mm quartz tube (Wilmad Lab Glass, USA), sealed vacuum (5 x 10 -5 torr) for LK-99 before IV measurement, sealed A quartz tube was loaded into a cylinder cavity equipped with a liquid helium cooling (cryostat) system.

After the I-V measurement, the sample whose EPR signal was measured was measured by loading some pieces of the sample whose electrical properties were measured, and was measured in a non-enclosed vacuum state.

In the LK-99 according to the present invention, the superconductivity phenomenon can be explained by the formation of a superconducting quantum well through the EPR test results. FIG. 13 is an EPR signal graph of the LK-99 according to the present invention, and This is an EPR signal graph obtained after I-V measurement, and will be described with reference to this.

The EPR signal of FIG. 13 is the same as that of a heterojunction quantum well such as Si/SiGe, natural DNA in a dry state, and α-Fe 2 O 3 doped with Mg 2+ . It was interpreted as a cyclotron resonance signal of the 2-dimensional electron gas (2-DEG), and it can be seen that it was generated at the interface between Pb(1) and phosphate of LK-99.

In addition, the ceramic compound according to the present invention showed an EPR signal at 3000 Oe by the substituted copper ion, which is the superconductivity reported at 0.3 K and 1 K in the 2-DEG system of GaAs/AlGaAs and DNA, and LaAlO 3 This result is similar to the superconducting properties of a 2-DEG system such as /SrTiO 3 with a heterojunction-like interface structure.

Through this, it was confirmed that a superconducting quantum well (SQW) was generated between Pb (1) and Oxygens of Phosphate by the structural distortion of the molecular structure of the ceramic compound of the present invention, and the SQW band diagram as shown in FIG. 2 can be predicted.

In addition, the superconductivity of LK-99 is closely related to this superconducting quantum well (SQW). Other electrical properties of the SQW of LK-99 include the very low Fermi energy (-9.47 eV) of Pb(1) and the large band of an insulator. It seems to be related to the gap (5~7 eV), and the increase in oxygen B.E. appears to contribute to the strong polarization of the insulating layer and the decrease in B.E. of Pb(1), which contributes to lowering the Fermi energy of Pb(1). It is judged to be

On the other hand, the EPR of FIG. 13 is a signal to which no current is applied, and the EPR of FIG. 14 is a signal to which current is applied. Compared to the former, the signal intensity of the latter is generally reduced, and the signal intensity of cyclotron resonance is relatively reduced.

From the SQW point of view, it can be determined that the LK-99 has a partially filled SQW because there is no charge reservoir to supply the SQW. The EPR signal of the LK-99 can be detected as a cyclotron resonance signal, This is because the cyclotron resonance signal cannot be detected when the SQW is completely filled.

However, as confirmed by YBCO and Bi2212, the absorption signal is obtained at a very low temperature and 1000 Oe external magnetic field (R. Janes, RS Liu, PP Edwards, AD Stevens, MCR Symons, Magnetic-Field Dependent Microwave-Absorption in High-Tc Superconducting Cuprates J Chem Soc Faraday T 87 , 1209-1215 (1991), M. Puri et al. , Microwave-Absorption Characterization of the Yba2cu3o7-Delta High-Temperature Superconductor Prepared by Different Sintering and Oxygen Annealing Times.J Chem Soc Faraday T 87 , 167-174 (1991)), and signals below 1000 Oe external magnetic field can be interpreted as signals by superconducting electrons.

Experimental Example 5 - Measurement of heat capacity

The heat capacity was measured from 5 K to 400 K using 65.26 mg of the sample of Example 2 with a heat capacity measuring system (PPMS: Physical Property Measurement System, PPMS, Quantum Design, USA), and the measurement data (Raw data) was a small amount of impurities. Calibration was performed based on the heat capacity of the included Cu 2 S bulk and nanosheet.

15 is a graph showing the Debye temperature calculated from heat capacity data, and FIG. 16 is a heat capacity curve of LK-99 according to the present invention.

The Debye temperature was calculated based on the heat capacity data using the Pb 10-x Cu x (PO 4 ) 6 O equation (x = 1) through the following Debye heat capacity equation (Equation 2).

<Equation 2>

Figure PCTKR2022012774-appb-img-000002

where Cv is the heat capacity, r is the number of atoms per molecule, N is the number of molecules, k is the Boltzmann constant, T is the measured temperature, θ is the Debye temperature, x = θ/T, and e is a natural constant.

Referring to FIG. 15, it shows that the Debye temperature of LK-99 according to the present invention is continuously changing from about 184 K to 1300 K, so that the transition temperature (Tc) in the conventional electron-phonon prediction model can't count

That is, the Debye model is a model that handles the specific heat of a crystal through phonons, but it is difficult to apply the electron-phonon model because the ceramic compound of the present invention cannot be interpreted by this predictive model.

The heat capacity characteristics of the ceramic compound of the present invention do not show any change in the secondary phase transition characteristics shown by general superconductors in the temperature range from 5K to 400K, and do not follow the law of heat capacity change according to the Debye model, so the internal structural change of the ceramic compound As a material showing the reflected heat capacity characteristics, it can be seen that it exhibits the heat capacity characteristics of normal temperature and normal pressure superconductors.

As can be seen in FIG. 16, the blue line curve (Debye temperature = 280 K) is the heat capacity calculated based on the Debye temperature of typical apatite at 280 K, and the red line curve (Debye temperature = 184.56 K) is LK-99 This is the heat capacity result calculated based on the Debye temperature (184.56 K) at a low temperature (5 K) of LK-99. Since the normal vibration mode is limited by the substitution, it shows that the Debye model is not applied, and through this, it can be seen that it has a distorted structure due to the substitution of copper ions.

Experimental Example 6 - Measurement of magnetic susceptibility

Magnetic susceptibility was measured in VSM mode in the range of -20,000G to +20,000G at 300 K using a sample of 45.814 mg with a Superconducting Quantum Interference Device (SQUID) or Magnetic Property Measurement System (MPMS, Quantum Design, USA). did

LK-99 according to the present invention shows ferromagnetic behavior through SQUID measurement in VSM mode at 300K as shown in FIGS.

Experimental Example 7 - Measurement of magnetic susceptibility

The magnetic susceptibility was measured in DC mode in the range of -3,500G to +3,500G at 100 K using a sample of 45.814 mg with a superconducting quantum interference device.

19 shows Meissner effect (near 0 Oe, <±100 Oe), ferromagnetic (<±500 Oe), and diamagnetic (>±500 Oe) behaviors by DC magnetic field measurement at 100 K.

That is, the ceramic compound of the present invention shows diamagnetism in the low magnetic field range (0 to ±50G), and shows ferromagnetic characteristics in the magnetic field range of ~±50G or more and ~±500G in the magnetic field range of ±500G to ±3500G. Again, it shows diamagnetism (Molecular diamagnetism).

Quantum wells with two-dimensional electron gas (2-DEG) systems such as Mg2+ doped α-Fe 2 O 3 and natural dna showed antiferromagnetic or ferromagnetic behavior, and the GaAs/AlGaAs system and the 2-DEG system of dna showed antiferromagnetic or ferromagnetic behavior. Superconductivity has been reported at 0.3K and 1K, and superconductors having an interfacial structure such as a heterojunction of a 2-DEG system such as LaAlO 3 /SrTiO 3 show both superconductivity and magnetism. LK-99 according to the present invention Likewise, it seems to be a system in which both ferromagnetic properties and superconductivity appear.

Experimental Example 8 - Electron Paramagnetic Resonance Spectroscopy (EPR) Measurement

The EPR signal was detected by applying 1 mW of microwave (~9.4 GHz) with AC magnetic field modulation of 100 KHz and passing a current of 200 mA to 100 mA to the sample at 0 G.

When measured with an electron spin resonator at 0 G while increasing the amount of current supplied to the LK-99, an absorption signal as shown in FIG. 20 appears. It can be seen that the absorption signal becomes larger as more current is supplied.

Microwave absorption at 0 G has been known to be a characteristic of superconductors, so the larger and larger signals measured with the magnetic field fixed at 0 G could mean that more Cooper pairs exhibiting superconductivity were created.

Therefore, it can be interpreted that electrons by the current supplied from the superconducting quantum well system of LK-99 are converted into superconducting electrons and more absorption occurs.

Experimental Example 9 - Measurement of adjustable magnetic levitation

The wire was connected to the sample of Example 2, the sample was placed on the magnet, and a video was taken of the magnetic levitation phenomenon generated when current was not flowing and when current was flowing.

21 shows that when no current is supplied to the LK-99 sample, the diamagnetic property is very small, so the magnetic levitation phenomenon is not good, and it is just placed on the magnet. FIG. 22 is a Cooper pair generated and increased by the supplied current As a result, it can be seen that the diamagnetic property is strengthened and the magnetic levitation phenomenon appears.

As a result, the reason why LK-99 according to the present invention exhibits superconductivity at room temperature and ambient pressure is that the stress caused by Cu 2+ substitution of Pb(2) 2+ ions is not relieved due to the structural uniqueness of LK-99 and At the same time, it is because it is properly transferred to the interface of the cylindrical column.

That is, the Pb(1) atoms at the interface of the cylindrical pillars of LK-99 occupy a structurally limited space, and these atoms are entirely affected by the stress and strain generated by the Cu 2+ ions, and thus, the SQWs are free from relaxation. It can be created at the interface with phosphate by a moderate amount of strain at room temperature and ambient pressure.

From this point of view, since CuO and Fe-based superconductor systems cannot constrain the relaxation process due to structural freedom, the stress caused by volume contraction due to temperature and pressure is relaxed and disappears, and therefore, they limit the structural freedom and achieve SQW generation. appropriate temperature or pressure is required.

The present invention has been demonstrated with a partially filled SQW model and will be a very useful material for studying superconducting puzzles at room temperature, all evidence and explanations show that LK-99 is the first room temperature and ambient pressure superconductor, and LK-99 It can be said that has various application possibilities such as magnets, motors, cables, levitation trains, power cables, qubits for quantum computers, and THZ antennas.

A superconductive ceramic compound comprising a ceramic compound according to Chemical Formula 1.

<Formula 1>

A 10-x B x (PO 4 ) 6 O

(A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag, x is 0.1 to 2.0)

According to claim 1,

A superconductive ceramic compound characterized in that B is substituted at the position of A in Formula 1.

According to claim 2,

Superconductive ceramic compound, characterized in that the position of another A is changed by the B.

According to claim 2,

Superconductive ceramic compound, characterized in that the lattice structure of the ceramic compound is deformed by the substitution of B.

According to claim 2,

A superconducting ceramic compound, characterized in that a superconducting quantum well (SQW) is generated between the A and (PO 4 ) 6 .

According to claim 5,

The superconducting ceramic compound, characterized in that the distance between the superconducting quantum well (SQW) is 3.7Å to 6.5 Å.

According to claim 5,

A superconducting ceramic compound, characterized in that tunneling occurs in the superconducting quantum well (SQW).

According to claim 2,

Superconductive ceramic compound, characterized in that the heat capacity change is reduced by the substitution of B.

A method for producing a superconductive ceramic compound comprising a step of synthesizing a ceramic compound according to Chemical Formula 1 by deposition.

<Formula 1>

A 10-x B x (PO 4 ) 6 O

(A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag, x is 0.1 to 2.0)

According to claim 9,

The deposition method for producing a superconductive ceramic compound, characterized in that the reaction temperature of 550 ℃ ~ 2000 ℃.

A superconductive ceramic compound comprising a step of synthesizing a ceramic compound according to Formula 1 by reacting lanarkite (L, Lanarkite (Pb 2 SO 5 =PbO·PbSO 4 )) and copper phosphide (Cu 3 P) Manufacturing method of.

<Formula 1>

A 10-x B x (PO 4 ) 6 O

(A is Ca, Ba, Sr, Sn or Pb, B is Cu, Cd, Zn, Mn, Fe, Ni or Ag, x is 0.1 to 2.0)

According to claim 11,

Method for producing a superconductive ceramic compound, characterized in that the temperature is 600 ℃ ~ 1000 ℃ during the reaction.

According to claim 11,

The method of producing a superconducting ceramic compound, characterized in that the lanakite is heated by mixing PbO and PbSO 4 in appropriate amounts according to the composition.

According to claim 11,

The synthesis of Cu 3 P is a method for producing a superconducting ceramic compound, characterized in that Cu and P are mixed and heated in appropriate amounts according to the composition ratio.

A superconductive ceramic compound produced by the method of any one of claims 9 to 14.

According to claim 15,

The ceramic compound is a superconductive ceramic compound, characterized in that the magnetic susceptibility according to the temperature change exhibits diamagnetism.

According to claim 12,

The ceramic compound is a superconductive ceramic compound, characterized in that the magnetic susceptibility according to the change in the magnetic field exhibits diamagnetism and ferromagnetism.

According to claim 12,

The ceramic compound is a superconductive ceramic compound, characterized in that the current-voltage characteristic according to the temperature change is V≠I×R (V: voltage, I: current, R: resistance).

According to claim 12,

The ceramic compound is a superconductive ceramic compound, characterized in that the current-voltage characteristic according to the magnetic field change is V = I × R or V ≠ I × R depending on the magnetic field.

According to claim 12,

Superconductive ceramic compound, characterized in that the resistance-temperature characteristic according to the temperature change of the ceramic compound follows Ohm's law after passing the transition temperature.

According to claim 12,

A superconductive ceramic compound, characterized in that the heat capacity characteristics of the ceramic compound do not follow the law of heat capacity change according to the Debye model.