CN115305572B - Monocrystalline material GaCuPO 5 Is prepared from monocrystalline material GaCuPO 5 - Google Patents
Monocrystalline material GaCuPO 5 Is prepared from monocrystalline material GaCuPO 5 Download PDFInfo
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
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Abstract
The invention provides a monocrystalline material GaCuPO 5 The preparation method comprises the steps of 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 Adding the precursor solution into deionized water according to a preset proportion, and uniformly mixing and stirring to prepare a precursor solution; transferring the precursor solution into an autoclave, putting the autoclave into a heating box, heating to a preset temperature and keeping the temperature for a preset period of time, and then cooling the temperature to room temperature; washing the reaction product in the autoclave to obtain monocrystalline material GaCuPO 5 。
Description
Technical Field
The invention relates to the technical field of single crystal growth, in particular to a single crystal material GaCuPO 5 Is prepared from monocrystalline material GaCuPO 5 。
Background
Low dimensional magnetic materials may exhibit anomalous physical properties due to the presence of spin quantum effects. As the temperature decreases, the quantum effect of the low dimensional magnetic material gradually increases. Under the limited temperature, the competition between quantum fluctuation and thermal fluctuation will lead the magnetic behavior in the system to lead the material to present ordered state, such as spin disorder and spin liquid at low temperature, etc. These phenomena are involved in abundant physical connotations and have great research value. The physics behind the technology has important significance for guiding the development and the development of spin devices and electronic components of the next generation, and is one of the leading-edge hot spots in the current material science and condensed state physics research fields. Due to the lack of ideal materials, research on spin disorder, spin liquid and other phenomena is greatly restricted. At present, research still depends on more simulation of theoretical calculation, and experimental breakthrough findings are relatively few. In order to seek breakthrough, scientific and engineering technicians gradually focus their eyes on the fields of design, synthesis and preparation of low-dimensional magnetic materials, so as to synthesize ideal single crystal materials for research by a manual method. Phosphate is an important carrier for designing and synthesizing novel magnetic materials because phosphate ions can bridge metal cations with magnetism.
On the other hand, the crystal material can realize magnetic, optical, acoustic, thermal and electric interaction and conversion, and is an important material indispensable in the development of modern science and technology. However, the natural crystals found in nature cannot meet the requirements of the development of modern science and technology in terms of variety, quality, quantity and the like, so that the development of artificial crystals is promoted. In the field of solid microelectronics, along with the continuous improvement of technology, the demands of people on single crystal materials are gradually increased, and particularly in the fields of semiconductor crystals, laser crystals, scintillation crystals, optical crystals, superhard crystals, insulating crystal piezoelectric crystals and the like, the discovery of new materials and the synthesis of new single crystals are possible for the subversion development of technology to a certain extent. Therefore, the design and synthesis of crystalline materials will be in the front of the development of material science for a long time, and the research of single crystal materials has been closely mixed and correlated with the research and development fields of new technologies such as space, electronics, laser, new energy development, biomedicine and the like.
Disclosure of Invention
The application provides a monocrystalline material GaCuPO 5 Is prepared by the preparation method of (1). The preparation method comprises the steps of adding CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 Adding the precursor solution into deionized water according to a preset proportion, and uniformly mixing and stirring to prepare a precursor solution; transferring the precursor solution into an autoclave, and heating in a heating boxTo a preset temperature and for a preset period of time, and then cooling the temperature to room temperature; washing the reaction product in the autoclave to obtain monocrystalline material GaCuPO 5 。
In one embodiment, the predetermined ratio is CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 The molar ratio of Cu, ga and P is (0.8-1.2): (0.4-0.6): (1.2-2.8).
In one embodiment, the molar ratio is 1:0.5:2.
In one embodiment, cuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 The mole ratio of the three to deionized water is (0.5-1.5): (8-30).
In one embodiment, the preset temperature is any temperature value between 180 ℃ and 260 ℃; the preset time period is 2-4 days.
In one embodiment, the preset temperature is 220 ℃ to 230 ℃ and the preset time period is 2.8 to 3.2 days.
In one embodiment, after transferring the precursor solution to the autoclave, the ratio of the liquid level of the precursor solution to the height of the liner of the autoclave is 8% to 12%.
In one embodiment, the temperature is reduced to room temperature at a rate of (4-6) DEG C/h.
The application also provides a method for preparing the monocrystalline material GaCuPO by using the preparation method 5 。
In one embodiment, the monocrystalline material GaCuPO 5 Is in the order of millimeters.
The monocrystalline material GaCuPO synthesized by the application 5 The method can meet the requirements of the current scientific research on single crystal materials, and can be used for conventional measurement researches of magnetism, heat, electricity and the like; the monocrystalline material GaCuPO 5 And the material is inert to air and water, and has strong stability. These characteristics indicate that the single crystal material GaCuPO 5 Has certain research value and application prospect in the fields of sound, light, electricity and magnetism.
Drawings
The objects, specific structural features and advantages of the present invention will be further understood from the following description in conjunction with some embodiments of the present invention and the accompanying drawings.
FIG. 1 shows a monocrystalline material GaCuPO according to an embodiment of the invention 5 Is a physical diagram of (a);
FIG. 2 shows a monocrystalline material GaCuPO according to an embodiment of the invention 5 X-ray diffraction pattern of powder;
FIG. 3 shows a monocrystalline material GaCuPO according to an embodiment of the invention 5 An aerial view of the crystal structure along the a-direction;
FIG. 4 shows a monocrystalline material GaCuPO according to an embodiment of the invention 5 An aerial view of the crystal structure along the b-direction;
FIG. 5 shows a monocrystalline material GaCuPO according to an embodiment of the invention 5 An aerial view of the crystal structure in the c-direction;
FIG. 6 shows a monocrystalline material GaCuPO according to an embodiment of the invention 5 Specific heat data map at zero magnetic field.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. While the invention has been illustrated and described with reference to these embodiments, it should be noted that the invention is not limited to only these embodiments. On the contrary, the invention is intended to cover all alternatives, modifications and equivalents as may be included within the spirit and scope of the invention as defined by the appended claims.
In addition, numerous specific details are set forth in the following description in order to provide a better illustration of the invention. It will be understood by those skilled in the art that the present invention may be practiced without these specific details.
The application provides a monocrystalline material GaCuPO 5 Is prepared by the preparation method of (1). The preparation method comprises the following steps:
step (1), cuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 Adding the mixture into deionized water according to a preset proportion, and uniformly mixing and stirring to prepare a precursor solution.
And (2) transferring the precursor solution into an autoclave, putting the autoclave into a heating box, heating to a preset temperature for a preset period of time, and then cooling to room temperature.
Step (3), washing the reaction product in the autoclave to obtain monocrystalline material GaCuPO 5 。
Example 1
According to CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 The molar ratio of Cu, ga and P is 1:0.5:2, and the molar ratio of the mixture to deionized water is 1:10, the mixture was added to 4mL of deionized water, and stirred with a glass rod to dissolve the mixture sufficiently to prepare a precursor solution.
Transferring the precursor solution into an autoclave, keeping the ratio of the liquid level of the precursor solution in the autoclave to the height of the liner of the autoclave to be 10%, heating to 230 ℃ in a muffle furnace, keeping at 230 ℃ for 3 days, and then cooling to room temperature at a cooling rate of 5 ℃ per hour. Wherein, the autoclave is a stainless steel autoclave with 25mL of polytetrafluoroethylene as an inner container. The autoclave used in this example is a stainless steel autoclave with polytetrafluoroethylene as a liner, and may be any other type of autoclave, and is not limited herein.
Washing the reaction product in the autoclave with distilled water to obtain monocrystalline material GaCuPO 5 。
FIG. 1 shows a single crystal material GaCuPO synthesized in this example 5 Is a real image of (a). Wherein, in FIG. 1, each small square is 1mm 2 . As can be seen from FIG. 1, the single crystal material GaCuPO 5 Is dark green in color. Through practical measurement, the monocrystalline material GaCuPO 5 Up to 1mm in length, i.e. in the order of millimeters in size. Dimensionally, the single crystal material GaCuPO 5 The method can meet the requirements of the current scientific research on single crystal materials, and can be used for conventional magnetic, thermal, electric and other measurement researches. In addition, in practical application, the monocrystalline material GaCuPO 5 And the material is inert to air and water, and has strong stability. This isSome characteristics indicate that the monocrystalline material GaCuPO 5 Has certain research value and application prospect in the fields of sound, light and electricity.
Measurement of monocrystalline material GaCuPO using monocrystalline x-ray diffractometer 5 To obtain diffraction data. Analyzing the diffraction data by using ShellxL software to obtain the monocrystalline material GaCuPO 5 Is a crystal structure and a crystallographic data of the same. The crystallographic data are shown in tables 1 and 2. Wherein U (eq) in Table 2 is orthogonalization U ij One third of the tensor trajectory. The crystal structure is shown in fig. 3-5. As can be seen from the contents of tables 1 and 2, the chemical formula of the synthesized single crystal material is GaCuPO 5 . The monocrystalline material GaCuPO is compared with a chemical database 5 Is synthesized for the first time. The crystal structure of the single crystal material is an orthogonal structure, and the space group is P nnm The unit cell parameters areAccording to the data, an XRD standard peak position card can be obtained through theoretical simulation.
TABLE 1 GaCuPO 5 Crystallographic data of single crystal material
TABLE 2 GaCuPO 5 Atomic coordinates and equivalent isotropic displacement parameters of (a)
The monocrystalline material GaCuPO 5 Grinding into powder, and measuring the powder by a powder X-ray diffractometer to obtain an X-ray diffraction pattern, as shown in FIG. 2. As can be seen from FIG. 2, the X-ray diffraction pattern is well matched with the XRD standard peak position card obtained by the theoretical simulationGood, thereby further verifying that the parsing result of the shellxl software is correct.
Next, the monocrystalline material GaCuPO was measured 5 Specific heat data at zero magnetic field as shown in fig. 6. As can be seen from FIG. 6, the single crystal material GaCuPO when the temperature T is above and below 17K 5 Exhibits two different evolution trends with respect to specific heat behavior. This indicates that the single crystal material GaCuPO 5 Lattice or magnetic interactions may exist near 17K, macroscopically causing thermal perturbations.
In addition, gaCuPO 5 Is Cu as the magnetic ion 2+ The magnetic ion Cu 2+ By cations O 2- Bridging, edge [001 ]]The crystal planes form one-dimensional magnetic chains as shown in fig. 3 and 4. The magnetic ion Cu 2+ The chain structure is relatively simple (one-dimensional features), and may exhibit rich physical properties at low temperatures. Furthermore, cu 2+ Low spin ions, s=1/2, have a more pronounced quantum effect. Thus, the monocrystalline material GaCuPO 5 Is also an important candidate material for researching quantum magnetism.
Example 2
According to CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 The molar ratio of Cu, ga and P is 0.8:0.5:1.2, 1:0.4:2.2, 0.9:0.6: 1.1: 0.6:1.2, 1.1:0.45:2.8, and the like, and according to the mole ratio of the mixture to deionized water of 1:10, adding the mixture into deionized water with corresponding amount, and stirring uniformly by using a glass rod to enable the mixture to be fully dissolved so as to prepare a precursor solution.
The precursor solution was transferred to an autoclave, heated to 230 ℃ in a muffle furnace, maintained at 230 ℃ for 3 days, and cooled to room temperature at a cooling rate of 5 ℃ per hour. Wherein, the autoclave is a stainless steel autoclave with 25mL of polytetrafluoroethylene as an inner container.
Washing the reaction product in the autoclave with distilled water to obtain monocrystalline material GaCuPO 5 。
The reaction product synthesized in this example was also confirmed by the verification method in example 1 to beMonocrystalline material GaCuPO 5 . Is different from the monocrystalline material GaCuPO in example 1 5 In comparison, the monocrystalline material GaCuPO in example 2 5 The size of the crystal obtained by the proportion of partial raw materials is small and even the crystal is indistinguishable to naked eyes.
Example 3
According to CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 The molar ratio of Cu, ga and P is 1:0.5:2, and the molar ratio of the mixture to deionized water is 0.5: 9. 1: 5. 1.2: 15. 0.6: 20. 0.8: 25. or 1.3:30, and the like, adding the mixture into deionized water with corresponding amount, and uniformly stirring by using a glass rod to fully dissolve the mixture so as to prepare a precursor solution.
The precursor solution was transferred to an autoclave, heated to 230 ℃ in a muffle furnace, maintained at 230 ℃ for 3 days, and cooled to room temperature at a cooling rate of 5 ℃ per hour. Wherein, the autoclave is a stainless steel autoclave with 25mL of polytetrafluoroethylene as an inner container.
Washing the reaction product in the autoclave with distilled water to obtain monocrystalline material GaCuPO 5 。
The reaction product synthesized in this example was also confirmed to be monocrystalline material GaCuPO by the verification method in example 1 5 . Is different from the monocrystalline material GaCuPO in example 1 5 In comparison, the monocrystalline material GaCuPO in example 3 5 Is smaller in size.
Example 4
According to CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 Preparing a mixture according to the molar ratio of Cu to Ga to P of 1:0.5:2, adding the mixture into deionized water with a corresponding amount according to the proportion relation of the molar ratio of the mixture to deionized water of 1:10, and uniformly stirring by using a glass rod to fully dissolve the mixture to prepare a precursor solution.
Transferring the precursor solution into an autoclave, putting into an oven, heating to different temperatures of 180 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃ and the like, keeping at the corresponding temperatures for 3 days, and naturally cooling to room temperature. Wherein, the autoclave is a stainless steel autoclave with 25mL of polytetrafluoroethylene as an inner container.
Washing the reaction product in the autoclave with distilled water to obtain monocrystalline material GaCuPO 5 。
The reaction product synthesized in this example was also confirmed to be monocrystalline material GaCuPO by the verification method in example 1 5 . Is different from the monocrystalline material GaCuPO in example 1 5 In comparison, the monocrystalline material GaCuPO in example 4 5 Is smaller in size.
Example 5
According to CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 Preparing a mixture according to the molar ratio of Cu to Ga to P of 1:0.5:2, adding the mixture into deionized water with a corresponding amount according to the proportion relation of the molar ratio of the mixture to deionized water of 1:10, and uniformly stirring by using a glass rod to fully dissolve the mixture to prepare a precursor solution.
The precursor solution was transferred to an autoclave, placed in an oven and heated to 230 ℃, kept at 230 ℃ for 2 days, 2.5 days, 2.8 days, 2.9 days, 3.1 days, 3.2 days, 3.5 days or 4 days, and then naturally cooled to room temperature. Wherein, the autoclave is a stainless steel autoclave with 25mL of polytetrafluoroethylene as an inner container.
Washing the reaction product in the autoclave with distilled water to obtain monocrystalline material GaCuPO 5 。
The reaction product synthesized in this example was also confirmed to be monocrystalline material GaCuPO by the verification method in example 1 5 . Is different from the monocrystalline material GaCuPO in example 1 5 In comparison, the monocrystalline material GaCuPO in example 5 5 Is smaller in size.
Example 6
According to CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 The molar ratio of Cu, ga and P is 1:0.5:2, and the mixture is prepared according to the proportion relation of the molar ratio of the mixture to deionized water of 1:10The mixture was added to a corresponding amount of deionized water, and stirred with a glass rod to dissolve the mixture sufficiently to prepare a precursor solution.
Transferring the precursor solution into an autoclave, putting the autoclave into a muffle furnace, heating to 230 ℃, keeping the autoclave at the temperature of 230 ℃ for 3 days, and then cooling to room temperature at different cooling rates of 4 ℃/h, 4.5 ℃/h, 5.5 ℃/h, 6 ℃/h and the like. Wherein, the autoclave is a stainless steel autoclave with 25mL of polytetrafluoroethylene as an inner container.
Washing the reaction product in the autoclave with distilled water to obtain monocrystalline material GaCuPO 5 。
The reaction product synthesized in this example was also confirmed to be monocrystalline material GaCuPO by the verification method in example 1 5 . Is different from the monocrystalline material GaCuPO in example 1 5 In comparison, the monocrystalline material GaCuPO in example 6 5 Is smaller in size.
The foregoing detailed description and drawings are merely typical examples of the invention. It will be evident that various additions, modifications and substitutions may be made therein without departing from the spirit and scope of the invention as defined in the accompanying claims. It will be appreciated by those of skill in the art that the invention can be varied in form, construction, arrangement, proportions, materials, elements, components and otherwise, used in the practice of the invention, which are particularly adapted to specific environments and operative requirements without departing from the principles of the present invention. Accordingly, the embodiments disclosed herein are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the appended claims and any and all legal equivalents thereof.
Claims (6)
1. Monocrystalline material GaCuPO 5 Is characterized in that the preparation method comprises the following steps:
CuCl is added 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 Adding the precursor solution into deionized water according to a preset proportion, and uniformly mixing and stirring to prepare a precursor solution, wherein the preset proportion is CuCl 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 According to the mole ratio of Cu, ga and P, the mole ratio is (0.8-1.2): 0.4-0.6): 1.2-2.8;
transferring the precursor solution into an autoclave, then placing the autoclave into a heating box to heat to a preset temperature for a preset period of time, and then cooling the autoclave to room temperature, wherein the preset temperature is any temperature value between 180 ℃ and 260 ℃; the preset time period is 2-4 days, wherein after the precursor solution is transferred to the autoclave, the ratio of the liquid level of the precursor solution to the height of the liner of the autoclave is 8-12%, and the temperature is reduced to room temperature according to the cooling rate of (4-6) DEG C/h; and washing the reaction product in the autoclave to obtain monocrystalline material GaCuPO 5 。
2. The monocrystalline material GaCuPO according to claim 1 5 Characterized in that the molar ratio is 1:0.5:2.
3. The monocrystalline material GaCuPO according to claim 1 5 The preparation method of (2) is characterized in that 2 ·2H 2 O、Ga(NO 3 ) 3 ·xH 2 O、K 2 HPO 4 The mol ratio of the three to the deionized water is (0.5-1.5): (8-30).
4. The monocrystalline material GaCuPO according to claim 1 5 The preparation method is characterized in that the preset temperature is 220-230 ℃, and the preset time period is 2.8-3.2 days.
5. A single crystal material GaCuPO as claimed in any one of claims 1 to 4 5 Is used for preparing the monocrystalline material GaCuPO by the preparation method of (a) 5 。
6. The monocrystalline material GaCuPO of claim 5 5 Characterized in that the monocrystalline material GaCuPO 5 Is in the order of millimeters.
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CN101619495A (en) * | 2008-07-01 | 2010-01-06 | 南京理工大学 | Method for thermally preparing single-crystal bismuth trisulfide nano-wires from mixed solvent |
CN104058461A (en) * | 2014-07-04 | 2014-09-24 | 武汉理工大学 | Low-temperature preparation method for CuFeO2 crystal material of delafossite structure |
CN107098401A (en) * | 2017-06-02 | 2017-08-29 | 武汉理工大学 | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method |
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Patent Citations (4)
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GB1485398A (en) * | 1974-11-22 | 1977-09-08 | Matsushita Electric Ind Co Ltd | Method of making fibrous alkali metal titanates |
CN101619495A (en) * | 2008-07-01 | 2010-01-06 | 南京理工大学 | Method for thermally preparing single-crystal bismuth trisulfide nano-wires from mixed solvent |
CN104058461A (en) * | 2014-07-04 | 2014-09-24 | 武汉理工大学 | Low-temperature preparation method for CuFeO2 crystal material of delafossite structure |
CN107098401A (en) * | 2017-06-02 | 2017-08-29 | 武汉理工大学 | A kind of delafossite structure CuCoO2Crystalline material and its low temperature preparation method |
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