CN113372906A - Silicon quantum dot boron slurry and preparation method thereof - Google Patents
Silicon quantum dot boron slurry and preparation method thereof Download PDFInfo
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- CN113372906A CN113372906A CN202110532217.7A CN202110532217A CN113372906A CN 113372906 A CN113372906 A CN 113372906A CN 202110532217 A CN202110532217 A CN 202110532217A CN 113372906 A CN113372906 A CN 113372906A
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- silicon
- silicon quantum
- quantum dot
- boron
- quantum dots
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- 239000010703 silicon Substances 0.000 title claims abstract description 240
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 138
- 239000002002 slurry Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 238000007613 slurry method Methods 0.000 title description 2
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- 239000002904 solvent Substances 0.000 claims abstract description 26
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/63—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
- C09K11/592—Chalcogenides
Abstract
The invention provides silicon quantum dot boron slurry and a preparation method thereof. The silicon quantum dot boron slurry comprises the following components in parts by weight: 1-30 parts of silicon quantum dots, 0-5 parts of additives and 67-99 parts of solvents, wherein the silicon quantum dots are silicon quantum dots with a doped composite structure. The primary structure of the doped composite structure silicon quantum dot comprises a core body and a shell layer coated on the core body, wherein the core body is made of a boron-doped silicon crystal, and the shell layer is made of silicon dioxide. The silicon quantum dot boron paste has good rheological property, belongs to non-Newtonian fluid, and is suitable for a screen printing film forming process. The silicon quantum dot boron slurry has stable dispersion system and long storage time, no carbon residue is left after the solvent is dried in the process of printing and film forming, and the silicon quantum dot particles are kept in good contact. The preparation method of the silicon quantum dot boron slurry has simple process steps and controllable process conditions of each step, thereby ensuring the stable performance of the prepared silicon quantum dot boron slurry.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to silicon quantum dot boron slurry and a preparation method thereof.
Background
The quantum dot is an excellent luminescent material, and has wide application prospect in the fields of light-emitting diodes, flat panel displays and the like; when the lithium ion battery is used for a lithium ion battery, the gram capacity of a negative electrode can be greatly improved, and the battery endurance can be improved; the boron slurry based on the silicon quantum dots can be used for manufacturing high-efficiency solar cells and promoting photoelectric flat networking. The invention belongs to the field of new materials and new energy.
There are also reports on silicon quantum dots, such as japan imperial corporation and suzhou jinzuchen technologies ltd, in addition to the new energy in xin. The former uses silane as raw material to produce spherical nano silicon with diameter of 20 nm; the latter uses silicon powder as raw material to produce spherical nano silicon with diameter about 50 nm.
However, in actual production, it is found that the existing silicon nanoparticle synthesis technology has many places to be improved:
1. the nanometer silicon synthesis technology of Diren takes silane as a raw material, and high-power carbon dioxide laser is used for cracking the silane to form gaseous silicon atom clusters; the nanometer silicon synthesis technology in the Jinruing morning takes silicon powder as a raw material, and the silicon powder is thermally evaporated by high-temperature plasma to form a gaseous silicon cluster; and cooling the silicon atom cluster to generate nano silicon particles. Silane and silicon powder are industrial raw materials produced from quartz sand, and the price is more expensive than that of the quartz sand.
2. The existing synthesis method of the nano silicon core-shell structure is generally completed by two or more steps. The core is typically prepared first and then the shell. The process steps are relatively complicated.
In the application field of quantum dots, the quantum dots are widely applied to the aspects of light emitting diodes and flat panel displays at present. In order to facilitate the formation of quantum dot pattern film layers, quantum dot inks are currently available for flexible printing into the desired quantum dot pattern film layers according to patterns. However, due to the characteristics of the quantum dots, the existing quantum dot ink has the defects that the quantum dots are not uniformly dispersed, the quantum dot agglomeration phenomenon is easy to occur, the poor deposition phenomenon is easy to occur, and the rheological property is not ideal, so that the printing quality of the quantum dot ink is influenced.
Nano silicon boron slurries as presently disclosed generally utilize the dispersing properties of additives to disperse monodisperse nano silicon particles in organic solvents. The existing nano silicon boron paste suitable for screen printing generally has a problem that serious epitaxial expansion often occurs when line patterns are printed on a solar cell silicon chip, lines are irregular, and the line width does not meet the requirement. The main reason is that the extension is caused by the easy flowing of nano silicon particles carried by solvent molecules. And the solar cell is subjected to a texturing process to corrode the sunlight surface of the silicon wafer into pyramids with the size of several microns so as to reduce the sunlight reflection loss. The epitaxial problem is more prominent when the current nano silicon boron slurry is printed during texturing. The printed linewidth is often two or three times the design linewidth. Although the current nano silicon boron slurry is added with a thickening agent and utilizes an organic polymer chain structure to inhibit flowing and reduce epitaxy, the effect is not ideal.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, and provides silicon quantum dot boron paste and a preparation method thereof, so as to solve the technical problems that the quality of a printing film layer is not ideal and especially the printing precision of the boron paste is not ideal due to the unstable dispersion system and the non-ideal rheological property of the existing nano silicon boron paste.
In order to achieve the object of the present invention, in one aspect of the present invention, there is provided a silicon quantum dot boron paste. The silicon quantum dot boron slurry comprises the following components in parts by weight:
1-30 parts of silicon quantum dots
0 to 5 portions of additive
65-99 parts of a solvent;
the silicon quantum dots are silicon quantum dots with a doped composite structure, the silicon quantum dots with the doped composite structure comprise a core body and a shell layer coated on the core body, the core body is made of borosilicate crystals, and the shell layer is made of silicon dioxide.
In another aspect of the invention, a preparation method of the silicon quantum dot boron slurry is provided. The preparation method of the silicon quantum dot boron slurry comprises the following steps:
respectively measuring the components and the content of the silicon quantum dot boron slurry according to the components and the content of the silicon quantum dot boron slurry;
premixing all the components to prepare coarse mortar;
and thinning the coarse mortar.
Compared with the prior art, the silicon quantum dot boron slurry has the following excellent characteristics through the action on the silicon quantum dots and other contained components:
on one hand, the silicon quantum dot boron paste has the characteristic of non-Newtonian fluid, the viscosity of the silicon quantum dot boron paste is sharply reduced by slightly adding shearing force, and then the silicon quantum dot boron paste rapidly tends to be stable, so that the silicon quantum dot boron paste is suitable for printing and film forming, particularly suitable for screen printing. The silicon quantum dots with the core-shell structure, the solvent and the additive have synergistic effect, and the additive molecules and the solvent molecules adsorbed on the shell layer silicon dioxide form stable coating, so that the secondary agglomeration of the silicon quantum dots is effectively prevented; and the components in the silicon quantum dot boron slurry are mutually contained to keep an interaction which cannot be separated, so that the fluidity of the silicon quantum dot boron slurry is inhibited, and particularly, the silicon quantum dot is inhibited from freely flowing along with solvent molecules. Therefore, the problems of epitaxy, expansion and the like which often occur when the silicon quantum dot boron slurry is used for printing the lines on the textured surface of the silicon wafer are solved, and the printing precision is improved;
on the other hand, the silicon quantum dot boron slurry dispersion system is stable, can not generate poor phenomena such as layering and deposition when being stored for a long time, and has the advantage of long effective service cycle;
in the third aspect, after the silicon quantum dot boron slurry is dried by the solvent, no carbon residue is left, and silicon quantum dot particles are kept in good contact with each other to form non-cavity dense packing. And provides an effective continuous channel for substance transfer in subsequent application.
According to the preparation method of the silicon quantum dot boron slurry, after the components contained in the silicon quantum dot boron slurry are premixed, the silicon quantum dot contained in the silicon quantum dot boron slurry is enabled to have a multi-branch chain structure, the number of branch chains is selectively reduced or the length of the branch chains is shortened through thinning treatment such as a high-energy ball milling process, but the basic structure of the branch chain is maintained, all the components are fully mixed and interacted, the viscosity and rheological property of the slurry are adjusted to form the non-Newtonian fluid, the contained silicon quantum dot is not subjected to secondary agglomeration, so that a stable dispersion system is formed for dispersion, no carbon residue is left after the prepared silicon quantum dot boron slurry is dried, the silicon quantum dot particles are well contacted, and no cavity is formed for dense stacking. In addition, the preparation method of the silicon quantum dot boron slurry has simple process steps and controllable process conditions of each step, thereby ensuring the stable performance of the prepared silicon quantum dot boron slurry.
Drawings
FIG. 1 is a schematic structural diagram of a doped composite structure silicon quantum dot in an embodiment of the present invention;
FIG. 2 is an EDS energy spectrum of the doped composite structure silicon quantum dot of example 11;
FIG. 3 is a TEM photograph of doped composite structure silicon quantum dots in example 11;
FIG. 4 is a process flow diagram of a method for preparing a silicon quantum dot boron slurry according to an embodiment of the present invention;
FIG. 5 is a rheological graph of boron slurry of silicon quantum dots example 21 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In this application, the term "and/or" describes an association relationship of associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the present application, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a, b, c, a-b (i.e., a and b), a-c, b-c, or a-b-c, wherein a, b, and c may be single or plural, respectively.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," or any other variation thereof, as used in this application, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
In various embodiments of the present application, the sequence numbers of the above-mentioned processes do not mean the execution sequence, and some or all of the steps may be executed in parallel or executed sequentially, and the execution sequence of each process should be determined by its function and inherent logic, and should not constitute any limitation to the implementation process of the embodiments of the present application.
The weight of the related components mentioned in the description of the embodiments of the present application may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present application as long as it is scaled up or down according to the description of the embodiments of the present application. Specifically, the mass in the description of the embodiments of the present application may be in units of mass known in the chemical industry, such as μ g, mg, g, and kg.
In one aspect, the embodiment of the invention provides silicon quantum dot boron slurry. The silicon quantum dot boron slurry comprises the following components in parts by weight:
1-30 parts of silicon quantum dots
0 to 5 portions of additive
65-99 parts of a solvent.
The silicon quantum dots contained in the silicon quantum dot boron slurry and the preparation method thereof are the doped composite structure silicon quantum dots and the preparation method thereof described below, and for the sake of saving space, the doped composite structure silicon quantum dots are not described herein again. The silicon quantum dots are doped composite structure silicon quantum dots, and specifically the doped composite structure silicon quantum dots comprise a core body and a shell layer coated on the core body, wherein the core body is made of a boron-doped silicon crystal, and the shell layer is made of silicon dioxide. Thus, the silicon quantum dot is characterized by the shell layer of silicon dioxide, the silicon dioxide has stronger affinity to additive and solvent molecules generally, more stable coating is easier to form, secondary agglomeration of the silicon quantum dot is prevented, a dispersion system is stable for a long time, and deterioration conditions such as layering, deposition and the like are not easy to occur; another characteristic of the silicon quantum dot is its multiple branched chain structure. The synergistic effect among the silicon quantum dots, the solvent and the additive and the thickening effect of the multi-branch chain structure enable the components to be mutually held in a mutually-locked interaction to inhibit the fluidity of the components. In particular, silicon quantum dots are inhibited from free flowing with solvent molecules. This feature is particularly important in improving the printing precision of the silicon quantum dot boron paste. Under the premise of adding no thickening agent or extremely small amount, the silicon quantum dot boron slurry can obtain ideal viscosity and rheological property, has the characteristic of non-Newtonian fluid, and is characterized in that when a shearing force is slightly applied, the viscosity of the silicon quantum dot boron slurry is sharply reduced and then quickly becomes stable. This property makes boron pastes suitable for printing film formation, particularly for screen printing. When fine patterns (such as fine lines, small dots and the like) are printed on the silicon wafer textured surface, no serious stagnation phenomena such as epitaxy, expansion and the like occur. Thereby improving the printing precision of the silicon quantum dot boron paste on the texturing surface of the silicon wafer. When the silicon quantum dot boron paste is used, the silicon quantum dot boron paste is easy to print into a film, carbon residue is not left after a solvent is dried, and the silicon quantum dots are kept in good contact to form dense accumulation. And provides an effective continuous channel for substance transfer in subsequent application. One important application of silicon quantum dot boron slurries is in the area-selective boron doping of silicon wafers. Common doping processes include laser doping and high temperature drive-in. When the solar cell silicon wafer is subjected to boron doping by high-temperature propulsion, boron atoms are smoothly propelled from the silicon quantum dots to the silicon wafer along the continuous channel to realize boron doping of the specified area; meanwhile, the metal pollutants accumulated on the surface of the silicon chip migrate to the silicon quantum dots along the continuous channels and are accumulated in the shell silicon dioxide. Thereby effectively preventing the efficiency reduction caused by the pollution of the metal impurities to the battery piece; when the silicon wafer is doped with boron in a laser doping mode, no high-molecular thickening agent is added into the silicon quantum dot boron slurry, no carbon residue is left after drying and film forming, and no carbon impurity is introduced.
In a specific embodiment, the content of the silicon quantum dots in the silicon quantum dot boron slurry can be 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 23 parts, 26 parts, 30 parts and the like, and preferably 5-25 parts.
In one embodiment, the additive includes at least one of a dispersant, a grinding aid, and a thickener. Wherein the dispersant comprises at least one of Monarden fish oil (oxidized Z-3), oleic acid (Omega-3), sunflower seed oil, corn oil, linseed oil, linoleic acid and stearic acid; in the preferred embodiment, the dispersant is Monarden fish oil (oxidized Z-3), and the selected parts can be 0.2 part, 0.5 part, 0.8 part, 1 part, 2 parts and 3 parts. The grinding aid comprises at least one of glyceryl tristearate (HTG), glyceryl trioleate, phosphate, polyacrylic acid, polyethylene oxide and polypropylene oxide; in a preferred embodiment, the grinding aid is glyceryl tristearate (HTG), and the selected parts can be 0.2 part, 0.5 part, 0.8 part, 1 part, 2 parts and 3 parts; in another preferred embodiment, the grinding aid is polyacrylic acid, and the selected parts can be 0.2 part, 0.5 part, 0.8 part, 1 part, 2 parts and 3 parts. The thickening agent comprises at least one of polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate, cellulose butyrate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyurethane, polyvinylidene fluoride, polymethyl methacrylate and polyethyl methacrylate; in a preferred embodiment, the thickening agent is hydroxyethyl cellulose; in a specific embodiment, the content of the thickener in the silicon quantum dot boron paste may be 0 part, 0.1 part, 0.3 part, 0.5 part, 0.8 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc., preferably 0 to 3 parts.
In another embodiment, the solvent comprises water and/or an organic solvent. The organic solvent includes at least one of amide, carbonate, aromatic hydrocarbon, sulfoxide, cyclic ether, ketone and alcohol. Wherein the amide comprises at least one of N-methyl pyrrolidone, dimethylformamide and dimethylpropionamide; the carbonate includes at least one of ethyl carbonate, propyl carbonate, bis (2,2,2 trifluoroethyl) carbonate, and fluoroethylene carbonate; the sulfoxide comprises at least one of dimethyl sulfoxide and diphenyl sulfoxide; the cyclic ethers include at least one of furan and tetrahydrofuran; the aromatic hydrocarbon includes at least one of benzene, toluene and xylene; the ketones comprise at least one of cyclohexanone, butanone and methyl isobutyl ketone; the alcohols include at least one of terpineol, lauryl alcohol, cyclopentanol, cyclohexanol, cyclododecanol, isobornyl cyclohexanol, palmityl alcohol, ethanol, isopropanol, and propylene glycol. In a preferred embodiment, the solvent is a cyclic compound, and is a mixed solvent of a protic solvent and an aprotic solvent. In a specific embodiment, the mixed solvent is cyclohexanone and isobornyl cyclohexanol, wherein isobornyl cyclohexanol may be a mixture of various isomers. The preferred ratio of cyclohexanone to isobornyl cyclohexanol is 1:10, preferably in the range of 1:2 to 1: 20. The total parts of the solvent can be 60 parts, 70 parts, 80 parts and 90 parts; further preferably, the solvent comprises a mixed solvent of N-methyl pyrrolidone and terpineol, wherein the terpineol can be a natural mixture of three isomers. The preferred ratio of N-methyl pyrrolidone to terpineol is 1:10, preferably in the range of 1:2 to 1: 20. The total parts of the solvent may be 60 parts, 70 parts, 80 parts, 90 parts.
Therefore, through selection and optimization of the types and contents of the solvent, particularly the organic solvent and the high molecular additive, the non-Newtonian fluid property of the silicon quantum dot boron paste can be further improved, the dispersing performance of each component, particularly the silicon quantum dot, can be further improved, the silicon quantum dot boron paste dispersing system is more stable, the long storage time is further prolonged, the adverse phenomena of layering, deposition and the like can not occur during long-time storage, the silicon quantum dot boron paste has the advantage of long effective service cycle, no carbon residue is left after drying, the silicon quantum dot particles are well contacted, and no-hole dense accumulation is formed. And provides an effective continuous channel for substance transfer in subsequent application. In addition, the solid content of the silicon quantum dot boron slurry of each example is 1% to 30%, preferably 10% to 25%, further preferably 15% to 23%, further preferably 18% to 22%, further preferably 19% to 21%; specifically 20%.
Correspondingly, the embodiment of the invention also provides a preparation method of the silicon quantum dot boron slurry. The process flow of the preparation method of the silicon quantum dot boron slurry is shown in figure 4, and comprises the following steps:
s01, measuring component silicon quantum dot boron slurry: respectively measuring the components according to the components and the content of the silicon quantum dot boron slurry;
s02, premixing raw materials to prepare coarse sand: pre-mixing the components to prepare mixed coarse mortar;
s03, grinding and refining the coarse mortar: and refining the mixed coarse mortar.
The silicon quantum dot boron slurry in the step S01 is the above silicon quantum dot boron slurry, and therefore, the components and the content of the silicon quantum dot boron slurry in the step S01 are the components and the content of the above silicon quantum dot boron slurry, and are not described herein again for the sake of brevity.
In a preferred embodiment, the silicon quantum dots are mixed with additives to wet the silicon quantum dots before the premixing treatment, and then a solvent is added to form a mixture.
The premixing process in the step S02 is to homogenize the respective components previously premixed material measured in the step S01.
In an embodiment, the pre-mixing treatment is to mix the components, preferably to mix the silicon quantum dots and the additive to wet the silicon quantum dots and then add the solvent to form a mixture at a revolution speed of 600-; the rotation speed is 300-1000rpm, preferably 300-1000rpm, more preferably 500-800rpm, more preferably 550-650rpm, specifically 600rpm, and the stirring and mixing time is 2-10 minutes, preferably 4-10 minutes. Through the premixing treatment, all the components are fully and uniformly mixed to prepare the coarse mortar easy for pipeline transportation. In addition, the pre-mixing process can be carried out, but not exclusively, in a planetary mixer.
In the step S03, the coarse mortar is refined by selecting a proper grinding process condition and dispersing and agglomerating by utilizing a grinding shearing action, so that the number of branched chains of the silicon quantum dots is controllably reduced or the length of the branched chains is shortened. As the fineness of the mortar is gradually reduced along with the grinding, the viscosity is increased at first and then slowly reduced. If the fineness or the viscosity is abnormal, the grinding process condition is adjusted and the auxiliary agent is replaced. The optimized grinding and refining process plays a decisive role in the viscosity and rheological property of the silicon quantum dot boron slurry, and enables the components to act on the basis of further uniform dispersion of the components, such as organic solvent or additive can be effectively adsorbed on the surface of the silicon quantum dot, and the silicon quantum dot is refined, so that the phenomenon of secondary agglomeration of the silicon quantum dot is avoided, a stable dispersion system is formed, the dispersion system of the silicon quantum dot boron slurry has long storage time, and adverse phenomena such as layering and deposition do not occur in long-time storage, and the silicon quantum dot boron slurry has the advantage of long effective service cycle. In one embodiment, the refining treatment is to grind the mixed coarse mortar until the fineness and viscosity of the coarse mortar reach target values. As in the specific embodiment, the fineness is less than or equal to 1 micron. Preferably, the refining treatment is to add 1 part of silicon nitride beads with a diameter of 2mm and 10 parts of silicon nitride beads with a diameter of 0.2mm into the grinding chamber, and the total volume of the grinding beads accounts for two thirds of the volume of the chamber of the sand mill. The rotation speed of the sand mill is 900-2000rpm, such as 1500 rpm. Pumping the raw material from the material tank into the grinding chamber via a silicone tube by using a peristaltic pump, then returning the raw material tank, and repeatedly circulating for about 60-240 minutes until the fineness of the slurry is less than 1 micron, and stopping grinding.
In one embodiment, the viscosity of the refining treatment is 8000-.
In a further embodiment, after step S03, the following steps shown in fig. 4 are included:
s04, adjusting viscosity: adding a thickening agent or a solvent to adjust the viscosity to a preferable range, and uniformly mixing;
s05, collecting and packaging: and collecting the finished product of the silicon quantum dot boron slurry, and packaging according to requirements to finish quality detection.
In step S04, the viscosity of the system is adjusted to the target range by adding proper amount of thickener or solvent. The grinding cycle is continued for 10-20 minutes to complete the homogenization process.
In the step S05, when the fineness and the viscosity of the silicon quantum dot boron slurry meet the requirements, finished product collection and packaging are carried out, and quality detection is completed.
Therefore, the preparation method of the silicon quantum dot boron slurry carries out mixing refining and pulping treatment according to the components contained in the silicon quantum dot boron slurry, so that the components are fully mixed and interact to form the non-Newtonian fluid, the contained silicon quantum dots are uniformly dispersed, secondary agglomeration is effectively avoided, a stable dispersion system is formed for dispersion, the adverse phenomena of layering, deposition and the like can not occur during long-time storage, and the preparation method has the advantage of long effective service cycle. In addition, the preparation method of the silicon quantum dot boron slurry has simple process steps and controllable process conditions of each step, thereby ensuring the stable performance of the prepared silicon quantum dot boron slurry.
On the other hand, the embodiment of the invention provides a preparation method of the silicon quantum dot, namely the silicon quantum dot with the doped composite structure.
As the existing technology for preparing silicon quantum dots by generally preparing silicon nano particles based on high-temperature plasmas generally utilizes the heat energy of plasmas to generate gaseous Si atomic clusters by thermally cracking silane or thermally evaporating silicon powder, and then the gaseous Si atomic clusters are cooled and solidified into fine silicon crystals to form the silicon nano particlesThe cost of silicon powder and the like is high, so that the cost for preparing the silicon quantum dots is high, and only the first-time silicon quantum dots can be prepared. However, the current high temperature plasma technology is not suitable for quartz Sand (SiO)2) And silicon monoxide (SiO)x) And preparing the silicon quantum dots by using substances with high oxidation states as raw materials.
Based on the problems of the existing technology for preparing silicon nanoparticles by using high-temperature plasma, the embodiment of the invention provides an improved method for preparing silicon nanoparticles by using plasma, so that silicon quantum dots with core-shell structures can be prepared in one step. The preparation method of the doped composite structure silicon quantum dot comprises the following steps:
carrying out plasma treatment on inorganic oxide powder of silicon and boron powder in an environment containing reducing gas, carrying out reduction reaction on part of the inorganic oxide of silicon, and then cooling to generate silicon quantum dots with doped composite structures; wherein the product of the reduction reaction contains elemental silicon.
In this way, the preparation method of the doped composite structure silicon quantum dot directly carries out plasma treatment on the mixed powder of the inorganic oxide powder of silicon and the boron powder in an environment containing reducing gas, so that a plasma system not only has relatively high heat energy, but also has relatively strong chemical reducibility. Under the action of reducing plasma, SiO2A chemical reduction reaction occurs to form Si clusters. By adjusting the proportion of reducing gas, part of the SiO2Participate in chemical reduction, and the rest SiO2Does not participate in the chemical reduction and still exists in the original oxidation valence state. The reaction system can be described as Si atom and boron atom cluster embedded in SiO2In a medium; the size and number of Si atoms and boron atom clusters both increase as the reaction proceeds. When increased to a certain extent, the reaction system rapidly solidifies in contact with the cooling gas: the Si atoms and boron atom clusters solidify to form the nuclei of boron-doped single crystals; SiO around Si and boron clusters2Solidifying to form an amorphous shell; the boron-doped silicon quantum dot with the core-shell structure is synthesized in one step. When the silicon monoxide powder is used as the raw material, SiOxWhen contacted with a reducing plasma, part of the SiOxChemical reduction takes placeReact to form Si atoms and H2An O molecule; partial SiOxDisproportionation reaction at high temperature to generate Si atom and SiO2(ii) a The Si atoms in turn form clusters of silicon atoms. The remainder being SiOxStill in the original oxidation state. The reaction system may be described as boron doped silicon atom clusters embedded in a silicon oxide medium. The size and number of silicon and boron clusters both increase as the reaction proceeds. When increased to a certain extent, the reaction system meets the cooling gas and rapidly solidifies: silicon atom and boron atom cluster solidification forms a core; the surrounding silica solidifies to form a shell; synthesizing the silicon quantum dots with the core-shell structure in one step. Therefore, the preparation method of the silicon quantum dots with the doped composite structure effectively simplifies the preparation method of the silicon quantum dots with the doped composite structure, improves the production efficiency, reduces the production cost, and the particle size of the silicon quantum dots with the doped composite structure is small and uniform.
In one embodiment, a method of plasma treating an inorganic oxide powder of silicon and a boron powder in an environment containing a reducing gas includes the steps of:
conveying powder such as inorganic oxide of silicon, boron powder and the like into a plasma chamber through conveying airflow for plasma treatment; wherein the transport gas stream contains the reducing gas and the transport gas stream is an inert gas.
The inorganic oxide of silicon and the boron powder are conveyed into the plasma chamber along with the conveying airflow, so that the inorganic oxide of silicon and the boron powder are fully contacted with the reducing gas, the dispersibility of the inorganic oxide of silicon and the boron powder in the plasma chamber is improved, the plasma treatment efficiency is improved, the particle size of the generated silicon atomic cluster is reduced, and the doped composite structure silicon quantum dot with small particle size is finally obtained. But also can realize the on-line continuous preparation of the doped composite structure silicon quantum dots with the core-shell structure.
In one embodiment, the flow rate of the transport gas stream is 1-6SLPM, specifically 4 SLPM. The rate at which the inorganic oxide of silicon and boron powder are transported by the transport gas stream is 60-500g/hr, specifically 100 g/hr. The reducing gas may be present in the transport gas stream in an amount of 0.1 to 2% by volume, in particular 1% by volume.
By controlling the conveying airflow, the conveying amount of the inorganic oxide of silicon and the boron powder and the concentration of the reducing gas, the dispersibility of the inorganic oxide of silicon and the boron powder is improved, the plasma treatment efficiency is improved, the particle size of the generated boron-doped silicon atomic cluster is reduced, and the doped composite structure silicon quantum dot with small particle size is finally obtained. In addition, the inorganic oxide of silicon and boron powder, the transport gas flow and the reducing gas can be controlled by a powder feeding device, and the powder feeding device introduces hydrogen and raw material powder into the plasma cavity through a delivery pipe; adjusting the proportion and flow rate of the hydrogen synthesis gas using a Mass Flow Controller (MFC); and the powder feeding device can use a self-feedback loop to maintain the stable operation of the plasma. When power is reduced, the mass flow controller correspondingly reduces the hydrogen flow and vice versa.
In a particular embodiment, the inert gas may be, but is not limited to, argon and the reducing gas may be hydrogen. The hydrogen gas can be ionized in the plasma treatment process to generate various hydrogen ions, hydrogen atoms in a ground state and an excited state and hydrogen molecules, and a plasma atmosphere with strong reducibility is formed. Argon gas has good stability during plasma treatment, thereby improving the stability of the plasma treatment.
In one embodiment, the plasma gas used in the plasma treatment is argon at a flow rate of 10-40SLPM, specifically 25 SLPM. The plasma sheath gas of the plasma treatment is argon gas and hydrogen gas, wherein the flow rate of the argon gas is 30-60SLPM, specifically 50SLPM, and the flow rate of the hydrogen gas is 0.5-3SLPM, specifically 2 SLPM. By optimizing the plasma treatment control, the plasma treatment efficiency is improved, and the particle size of the generated boron-doped silicon atomic cluster is reduced, so that the doped composite structure silicon quantum dot with small particle size is finally obtained. Under the above plasma treatment conditions, the temperature in the chamber for plasma treatment was 1 ten thousand ℃ or more. The plasma treatment, as described above in particular, may be accomplished by conventional commercial plasma equipment, such as the TekNano 40 system. The maximum temperature of the system can reach more than ten thousand degrees according to the simulation calculation, and the common solid can be vaporized instantly.
During the cooling process after the plasma treatment is finished, as described above, the reaction system of the plasma treatment is rapidly solidified in the cooling process as meeting the cooling gas: the Si atoms and the boron atom clusters are solidified to form a single crystal nucleus; SiO around Si atom cluster2Solidifying to form an amorphous shell; the boron-doped silicon quantum dot with the core-shell structure is synthesized in one step. In addition to the above embodiments, in an embodiment, the cooling treatment is to introduce a cooling inert gas into the environment after the reduction reaction is completed, specifically, the cooling inert gas may be argon, and the flow rate may be 200-450SLPM, and specifically, 350 SLPM. By optimally controlling the cooling treatment conditions, the stability of the core-shell structure of the silicon quantum dots with the doped composite structure and the particle size of the silicon quantum dots with the doped composite structure are improved.
In addition, based on the preparation method of the doped composite structure silicon quantum dot in each of the above embodiments, the inorganic oxide powder of silicon includes at least one powder of quartz sand, silicon dioxide, and silica, and in a further embodiment, the average particle size of the inorganic oxide powder of silicon and the boron powder is 4N to 5N in purity, specifically, the purity of quartz sand and silicon dioxide is 5N, and the purity of silica and boron powder is 4N. The inorganic oxide powder and boron powder of silicon have a particle size of 0.3-5 μm, specifically 1 μm. The inorganic oxide powder and the boron powder of the silicon can be subjected to plasma treatment in a reducing atmosphere to generate the silicon quantum dots with the doped composite structure. Further, it was found by examination that Silica (SiO) still remains in the doped composite structure silicon quantum dots produced by subjecting the inorganic oxide powder in which silica is selected as silicon to reduction plasma treatment. There are many methods of treating silica, the most common of which is to convert silica to silica by heat treatment in an oxygen atmosphere. The conversion proceeds according to the following reaction equation:
2SiO+O2→2SiO2
i.e., 2 moles of Silica (SiO) with 1 mole of oxygen (O)2) Oxidation reaction takes place to 2 mol of silicon dioxide (SiO)2). However, since the core of the silicon quantum dot is a fine silicon crystal, it is easily oxidized to form silicon dioxide, and the structure of the silicon quantum dot is damaged. Therefore, in an embodiment, after the step of cooling, the method further includes a step of post-treating the generated doped composite structure silicon quantum dots:
and carrying out thermal oxidation treatment on the generated doped composite structure silicon quantum dots in a protective atmosphere.
By carrying out thermal oxidation treatment in the protective atmosphere of the silicon quantum dots with the doped composite structure, the conversion is carried out according to the following reactions when the boron-doped silicon quantum dots are subjected to thermal treatment at a lower temperature by virtue of the quantum confinement effect of the boron-doped silicon quantum dots:
2SiO→Si+SiO2
that is, 2 moles of silicon monoxide undergo an auto-redox reaction to produce 1 mole of silicon (Si) and 1 mole of silica. The silica is quantitatively converted to silica. Thereby effectively ensuring the stability of silicon contained in the doped composite structure silicon quantum dots, and simultaneously converting all contained shell layer materials into SiO2Thereby improving the photoelectric property of the silicon quantum dots with the doped composite structure.
Therefore, the preparation method of the doped composite structure silicon quantum dot in each embodiment can generate the doped composite structure silicon quantum dot in one step, effectively simplifies the preparation method of the doped composite structure silicon quantum dot, improves the production efficiency, and reduces the generation cost. In addition, the preparation method provided by the embodiment of the invention can generate the doped composite structure silicon quantum dots in one step, the conditions are easy to control, the stable luminescent performance of the generated doped composite structure silicon quantum dots can be ensured, and the generated doped composite structure silicon quantum dots have small particle size and uniform particles and are of a core-shell composite structure.
Through detection, the structure of the doped composite structure silicon quantum dot prepared by the preparation method of the doped composite structure silicon quantum dot is shown in fig. 1, and the doped composite structure silicon quantum dot comprises a core body 1 and a shell layer 2 coated on the core body, wherein the core body 1 is made of a boron-doped silicon crystal, and the shell layer 2 is made of silicon dioxide. Wherein, the core body 1 is the core of boron doped silicon single crystal, the morphology can be spherical, and the particle size is 2-5 nm. The shell layer 2 forms a coating layer, and the thickness of the coating layer is 2-3 nm. The particle diameter of the silicon quantum dots with the doped composite structure is 8-10nm, and the overall appearance of the silicon quantum dots is in a multi-branch chain structure. Therefore, the doped composite structure silicon quantum dot provided by the embodiment of the invention has a core-shell composite structure, small particle size, strong photoelectric property and stability.
In the doped composite structure silicon quantum dot of the embodiment of the invention, the core is the core body 1, namely the boron doped silicon quantum dot, and the physical properties and the basic functions of the doped composite structure silicon quantum dot are determined by the core body. For example, quantum confinement effects cause the spectrum of the quantum dot emission to be determined by the size of the core; the capacity of the lithium battery cathode based on the silicon quantum dots is improved from the core. The silica of shell 2 has little, if any, effect, although it is some ancillary effect. The shell 2 silicon dioxide is a passivation layer. The method has the effects of passivating crystal defects such as dangling bonds on the surface of silicon, enabling the light-emitting spectrum to be narrower and the color to be more bright, and enhancing the photoelectric effect of the silicon quantum dots with the doped composite structure; on the other hand, the shell 2 silicon dioxide is a protective layer. The doped composite structure silicon quantum dots are prevented from spontaneous combustion caused by air oxidation, the actual use value is improved, and the use cost is reduced; also sometimes, shell 2 silica is a gettering layer. Since the solid solubility of metal impurities is much higher in silica than in silicon, shell 2 silica can be used to absorb metal impurities. When the method is properly applied, the problem of pollution of metal impurities to solar cells or semiconductor devices in the production process can be effectively solved.
Because the doped composite structure silicon quantum dot in the embodiment of the invention has a core-shell composite structure, and the core body is doped with boron, the conductivity of silicon, namely the rising resistivity is reduced, and the Fermi level is shifted down, so that the doped composite structure silicon quantum dot has high conductivity and low Fermi level. In the application aspect, the doped composite structure silicon quantum dot can be used as a boron source in the form of ink or boron slurry to carry out area selective doping on a silicon wafer, so that the production and manufacturing process of a solar cell or a semiconductor device can be effectively simplified. And the particle size is small, the photoelectric property is strong and stable, and the applicability of the doped composite structure silicon quantum dot is effectively enhanced and expanded. In one embodiment, the doped composite structure silicon quantum dots in the above embodiments can be applied to the preparation of silicon quantum dot ink, silicon quantum dot boron paste, light emitting diodes, optical fiber communication, semiconductor triodes, lithium ion batteries or solar batteries.
The silicon quantum dot boron slurry and the preparation method thereof according to the embodiment of the invention are illustrated by a plurality of specific examples.
1. Doped composite structure silicon quantum dot and preparation method embodiment thereof
Example 11
The embodiment provides a doped composite structure silicon quantum dot and a preparation method thereof. The structure of the doped composite structure silicon quantum dot is shown in figure 1 and is a core-shell mechanism, wherein the core is Si and is a boron-doped silicon crystal with the size of about 2-5 nm; the shell being SiO2It is amorphous and has a thickness of about 3 nm.
The preparation method comprises the following steps:
s11: 19 parts of white quartz sand with the particle size of 1 mu m and 1 part of boron powder with the purity of 4N are conveyed into a plasma chamber through argon conveying airflow to carry out plasma treatment; wherein the argon-conveying gas stream contains a hydrogen reducing gas;
s12: and after plasma treatment, introducing cooling argon gas into the environment in the plasma chamber for cooling, and collecting the silicon quantum dots with the boron-doped composite structure, wherein the silicon quantum dots are fine powder, are brown and have the weight of about 125g/hr and the boron content of about 3% (w/w).
Wherein, the corresponding conditions in step S11 and step S12 are as follows:
the raw materials are white quartz sand powder and brown boron powder, and the particle sizes are both 1 mu m. Fully mixing until the color is uniform and consistent and the particle size is 1 mu m;
the powder feeding speed is 300g/hr, the argon synthetic gas for powder feeding contains 1% of hydrogen, and the flow rate is 4 SLPM;
the powder feeder pressure was 15.2 psi;
the system pressure is 14.9psi (the equipment operates at pressure, and the tail pump maintains the equipment to operate under micro negative pressure);
the plasma gas is argon, and the flow rate is 35 SLPM;
the plasma sheath gas is argon and hydrogen, and the flow rates are respectively 50SLPM and 0.5 SLPM;
the cooling gas was argon at a flow rate of 350 SLPM;
the plasma equipment is a TekNano 40 system, and the temperature in the cavity is more than 1 ten thousand ℃.
The detection shows that the collected doped composite structure silicon quantum dot product of the present embodiment is a fine powder, and is brown. The brown product was analyzed for composition. As shown in fig. 2, the EDS spectrum is mainly composed of two elemental peaks, i.e., a silicon peak and an oxygen peak, and boron is not detected by EDS due to its small atomic number and low content. According to the GDMS inspection result, the silicon quantum dots contain 3% (w/w) of boron, namely, silicon and oxygen and boron. TEM observation is carried out on the boron-doped composite structure silicon quantum dots, the overall morphology of the powder is in a multi-branch chain structure, and the primary particle size is about 12 nm. Fig. 3 is a representative high resolution TEM image. Careful observation revealed that the boron doped silicon had lattice diffraction fringes that were approximately spherical in shape and were approximately 2-5nm in size. Because the size dimension is close to the Bohr radius of silicon, the quantum dots are called silicon quantum dots. The quantum dots are independently dispersed in amorphous silica. Therefore, the structure of the doped composite structure silicon quantum dot of the present embodiment can be described as a core-shell structure as shown in fig. 1: the core is Si, is boron-doped silicon crystal and has the size of about 2-5 nm; the shell being SiO2It is amorphous and has a thickness of about 3 nm.
Example 12
The embodiment provides a doped composite structure silicon quantum dot and a preparation method thereof. The structure of the doped composite structure silicon quantum dot is shown in fig. 1, which is prepared according to the first embodiment, wherein 19 parts of quartz sand in the step S11 of the embodiment is replaced by 50 parts of silica.
The preparation method comprises the following steps:
s11: conveying 50 parts of white 4N-silicon oxide with the particle size of 9 mu m and 1 part of 4N-boron powder with the particle size of 1 mu m into a plasma chamber through argon conveying airflow for plasma treatment; wherein the argon-conveying gas stream contains a hydrogen reducing gas;
s12: refer directly to example step S12;
wherein, the corresponding conditions in step S11 and step S12 are as follows:
the raw materials are mixed powder containing 50 parts of gray silicon oxide and 1 part of brown boron, and the grain diameters are respectively 9 and 1 mu m. Fully mixing until the color is uniform;
the powder feeding speed is 60g/hr, the argon synthetic gas for powder feeding contains 0.5 percent of hydrogen, and the flow rate is 1 SLPM;
the powder feeder pressure was 15.2 psi;
system pressure was 14.9 psi;
the plasma gas was argon, the flow rate was 40 SLPM;
the plasma sheath gas is argon and hydrogen, and the flow rates are respectively 30SLPM and 0.5 SLPM;
the cooling gas was argon at a flow rate of 250 SLPM;
the plasma equipment is a TekNano 40 system, and the temperature in the cavity is more than 1 ten thousand ℃.
S13: placing the doped composite structure silicon quantum dots collected in the step S12 in a quartz crucible, and transferring the crucible to a quartz tube furnace; setting the argon flow as 10SLPM, and starting a nitrogen flow meter; flushing the hearth for 10 minutes by using nitrogen to drive out air; then opening the tube furnace, heating to 600 ℃ at 10 ℃ per minute and keeping the temperature for 10 minutes; cooling to room temperature, taking out the crucible, and performing heat treatment to obtain fine powder (brown color, about 40 g/hr).
Through detection, the doped composite structure silicon quantum dots collected in the second embodiment are fine powder and brown. And analyzing the components of the collected silicon quantum dots with the doped composite structure. Essentially the same as in fig. 2, the EDS spectrum is composed of two elemental peaks, namely a silicon peak and an oxygen peak. Boron was not detected by EDS because of its smaller atomic number and lower content. According to the GDMS inspection result, the silicon quantum dots contain 0.5% (w/w) of boron, namely, silicon and oxygen and boron. The TEM photograph is substantially the same as fig. 3.
Example 13
The third embodiment provides a composite-structure silicon quantum dot and a preparation method thereof. The structure of the composite-structured silicon quantum dot is shown in fig. 1, which is prepared according to example one, wherein 19 parts of quartz sand in example step S11 is replaced with 5 parts of silica.
S11: 5 parts of white silicon dioxide powder with the particle size of 0.3 mu m and the purity of 5N and 1 part of brown boron powder with the particle size of 3 mu m and the purity of 4N are uniformly mixed and then are conveyed into a plasma chamber through argon conveying airflow for plasma treatment; wherein the argon-conveying gas stream contains a hydrogen reducing gas;
s12: and after plasma treatment, introducing cooling argon gas into the environment in the plasma chamber for cooling, and collecting the silicon quantum dots with the composite structure, wherein the silicon quantum dots are fine powder and brown and are about 90 g/hr.
Wherein, the corresponding conditions in step S11 and step S12 are as follows:
the raw material comprises 2 parts of white silicon dioxide powder and 1 part of brown boron powder, the grain diameters are respectively 0.3 mu m and 3 mu m, and the mixture is mixed until the color is uniform;
the powder feeding speed is 120g/hr, the argon synthetic gas for powder feeding contains 2% of hydrogen, and the flow rate is 2 SLPM;
the powder feeder pressure was 15.2 psi;
system pressure was 14.9 psi;
the plasma gas was argon, the flow rate was 25 SLPM;
the plasma sheath gas is argon and hydrogen, and the flow rates are respectively 55SLPM and 2 SLPM;
the cooling gas was argon at a flow rate of 450 SLPM;
the plasma equipment is TekNano 40, and the temperature in the cavity is more than 1 ten thousand ℃.
Through detection, the doped composite structure silicon quantum dots collected in the third embodiment are fine powder and brown. And analyzing the components of the collected silicon quantum dots with the doped composite structure. The EDS spectrum found a boron peak in addition to a silicon peak and an oxygen peak similar to those of FIG. 2. According to the GDMS measurement result, the silicon quantum dots contain 9% (w/w) of boron, namely, silicon and oxygen and boron. The TEM photograph is substantially the same as fig. 3.
2. Silicon quantum dot boron slurry containing silicon quantum dots with doped composite structures and preparation method embodiment thereof
Example 21
The embodiment provides silicon quantum dot boron slurry and a preparation method thereof. The silicon quantum dot boron slurry comprises 15 parts of doped composite structure silicon quantum dots, 1 part of Monarden fish oil (oxidized Z-3), 1 part of glyceryl tristearate (HTG), 7 parts of cyclohexanone and 70 parts of isobornyl cyclohexanol; wherein the doped composite structure silicon quantum dot is the silicon quantum dot powder containing 3 wt% of boron doped composite structure provided in example 11; the Monarden fish oil (oxidized Z-3) is a mixed nonionic surfactant, has a good wetting effect on silicon quantum dot powder, promotes the silicon quantum dots to be dispersed in a solvent and forms mortar easy for pipeline transportation.
The silicon quantum dot boron slurry is prepared by the method comprising the following steps:
s21, measuring component wet silicon powder:
according to the components contained in the silicon quantum dot boron slurry, 1 part of Monarden fish oil (oxidized Z-3) and 1 part of glyceryl tristearate (HTG) are dripped into 15 parts of silicon quantum dot powder with a doped composite structure, and after the silicon quantum dot powder is fully wetted, 7 parts of cyclohexanone and 70 parts of isobornyl cyclohexanol are poured;
s22, raw material premixing and coarse mortar preparation:
placing the container filled with the raw materials into a planetary stirrer, and setting the following stirrer parameters for premixing: the revolution speed is 2000rpm, the rotation speed is 1400rpm, and the running time is 5 minutes;
s23, grinding and refining the mortar: adding 1 part of silicon nitride grinding beads with the diameter of 2mm and 10 parts of silicon nitride grinding beads with the diameter of 0.2mm into a grinding cavity, wherein the total volume of the grinding beads accounts for about two thirds of the volume of the cavity of the sand mill; the rotation speed of the sand mill is 1000rpm, the mortar premixed in the step S22 is pumped into the grinding cavity from the charging bucket through the silicone tube by a peristaltic pump, and the circulation is repeated for about 90-120 minutes. Cooling to room temperature, measuring fineness and viscosity of less than 1 micrometer and 9500cps, and stopping grinding;
s24, adjusting viscosity: because the viscosity and the fineness are both in a target range, no thickening agent is required to be additionally added for adjusting the viscosity;
s25, collecting and packaging: and collecting the slurry subjected to the refining treatment in the step S23, and packaging the slurry according to requirements.
Through detection, the silicon quantum dot boron slurry of the embodiment is brown paste; viscosity of 9500 cps; the fineness is less than 1 micron; the content of the silicon quantum dots is 15.9 percent.
The viscosity of the silicon quantum dot boron slurry provided in example 21 was measured: the viscosity of the silicon quantum dot boron slurry is measured under the condition of constant temperature of 20 ℃, and the rheological curve is shown in figure 5. Under a static state, the viscosity of the silicon quantum dot boron slurry is very high and hardly flows; when a slight shearing force is applied, the viscosity is rapidly reduced; as the shear force continues to increase, the viscosity quickly stabilizes and reaches a steady value of about 5000 cps. Therefore, the rheological characteristics of the silicon quantum dot boron paste are very suitable for screen printing. After the silicon quantum dot boron paste is used for screen printing, the surface of a printed pattern is uniform and flat, and the edge is neat and clear. The phenomena of printing missing, accumulation, flow stagnation and the like are not easy to occur.
Example 22
The embodiment provides silicon quantum dot boron slurry and a preparation method thereof. The silicon quantum dot boron slurry comprises 5 parts of doped composite structure silicon quantum dots, 1 part of Monarden fish oil (oxidized Z-3), 0.5 part of polyacrylic acid, 2.5 parts of hydroxyethyl cellulose with the viscosity of 5 ten thousand, 30 parts of N-methyl pyrrolidone and 60 parts of terpineol; the doped composite structure silicon quantum dot is the silicon quantum dot powder containing 3 wt% of boron doped composite structure provided in embodiment 12.
The silicon quantum dot boron slurry is prepared by the method comprising the following steps:
s21, measuring component wet silicon powder: referring to step S21 of example 21, 1 part of a mongolian maytansine fish oil (oxidized Z-3) and 0.5 part of polyacrylic acid were dropped into 5 parts of a silicon quantum dot powder, and 30 parts of N-methyl pyrrolidone and 60 parts of terpineol were poured after wetting;
s22, raw material premixing and coarse mortar preparation: step S22 of reference example 21;
s23, grinding and refining the mortar: referring to step S23 of example 21, the mill rotation speed was set at 2000rpm, and the cycle was repeated for 90 to 120 minutes. The measured fineness and viscosity are respectively 1 micron and 6500 cps;
s24, adjusting viscosity: 2.5 parts of hydroxyethyl cellulose with the viscosity of 5 ten thousand is added into a charging bucket, and the circulation is continued for 10 to 15 minutes, so that the homogenization treatment is completed;
s25, collecting and packaging: referring to step S25 of example 21, the slurry refined in step S23 was collected and packaged as required.
Through detection, the silicon quantum dot boron slurry of the embodiment is brown paste; viscosity 11000 cps; the fineness is less than 1 micron; the content of the silicon quantum dots is 5.0 percent.
The rheological curve and the screen printing effect of the silicon quantum dot boron paste provided by the embodiment 22 are basically the same as those of the silicon quantum dot boron paste provided by the embodiment 21.
Example 23
The embodiment provides silicon quantum dot boron slurry and a preparation method thereof. The silicon quantum dot boron slurry comprises 25 parts of doped composite structure silicon quantum dots, 2 parts of Monarden fish oil (oxidized Z-3), 2 parts of glyceryl tristearate (HTG), 5 parts of cyclohexanone and 70 parts of isobornyl cyclohexanol; wherein the doped composite structure silicon quantum dot is the silicon quantum dot powder containing 3 wt% of boron doped composite structure provided in example 13;
the silicon quantum dot boron slurry is prepared by the method comprising the following steps:
s21, measuring component wet silicon powder: according to the components contained in the silicon quantum dot boron slurry, 2 parts of Monarden fish oil (oxidized Z-3) and 2 parts of glyceryl tristearate (HTG) are dropwise added into 25 parts of silicon quantum dot powder with a doped composite structure, and after the powder is fully wetted, 5 parts of cyclohexanone and 70 parts of isobornyl cyclohexanol are poured;
s22, raw material premixing and coarse mortar preparation: step S22 of reference example 21
S23, grinding and refining the mortar: referring to step S23 of example 21, the rotation speed of the mill was set at 1000rpm, and the cycle was repeated for 150 and 180 minutes. The measured fineness and viscosity are respectively 1 micron and 17000 cps;
s24, adjusting viscosity: adding 5 parts of isobornyl cyclohexanol, and continuously grinding for 5-10 minutes to finish homogenization treatment;
s25, collecting and packaging: and collecting the slurry subjected to the refining treatment in the step S24, and packaging the slurry according to requirements.
Through detection, the silicon quantum dot boron slurry of the embodiment is brown paste; viscosity of 15000 cps; the fineness is less than 1 micron; the content of the silicon quantum dots is 24.0 percent.
The rheological curve and the screen printing effect of the silicon quantum dot boron paste provided by the embodiment 23 are basically the same as those of the silicon quantum dot boron paste provided by the embodiment 21.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The silicon quantum dot boron slurry comprises the following components in parts by weight:
1-30 parts of silicon quantum dots
0 to 5 portions of additive
65-99 parts of a solvent;
the silicon quantum dots are silicon quantum dots with a doped composite structure, the silicon quantum dots with the doped composite structure comprise a core body and a shell layer coated on the core body, the core body is made of borosilicate crystals, and the shell layer is made of silicon dioxide.
2. The silicon quantum dot boron paste of claim 1, wherein: the grain size of the doped composite structure silicon quantum dots is 8-10nm, and the grain size of the core body is 2-5 nm; and/or
The overall particle morphology of the doped composite structure silicon quantum dots is in a multi-branch chain structure; and/or
The morphology of the nucleus is spherical.
3. The silicon quantum dot boron paste of claim 1 or 2, wherein: the silicon quantum dot is prepared by the following steps:
carrying out plasma treatment on inorganic oxide powder of silicon and boron powder in an environment containing reducing gas, carrying out reduction reaction on part of the inorganic oxide of silicon, and then cooling to generate silicon quantum dots with doped composite structures; wherein the product of the reduction reaction contains elemental silicon.
4. The silicon quantum dot boron paste of claim 3, wherein the method of plasma treating the inorganic oxide of silicon and boron powder in an environment containing a reducing gas comprises the steps of:
conveying inorganic oxide powder and boron powder of silicon into a plasma chamber through conveying airflow for plasma treatment; wherein the transport gas stream contains the reducing gas and the transport gas stream is an inert gas.
5. The silicon quantum dot boron slurry of claim 4, wherein the flow rate of the transport gas stream is 1-6 SLPM; and/or
The total rate of conveying the silicon inorganic oxide powder and the boron powder by the conveying gas flow is 60-500 g/hr; and/or
The volume content of the reducing gas in the conveying gas flow is 0.1-2%; and/or
The plasma gas of the plasma treatment is argon, and the flow rate is 10-40 SLPM; and/or
The plasma sheath gas of the plasma treatment is argon and hydrogen, wherein the flow rate of the argon is 30-60SLPM, and the flow rate of the hydrogen is 0.5-3 SLPM; and/or
The inorganic oxide powder of silicon and the boron powder are subjected to the plasma treatment in an environment containing the reducing gas at a weight ratio of (50-1): 1.
6. The silicon quantum dot boron paste of claim 3, wherein: the cooling treatment is to introduce cooling inert gas into the environment after the reduction reaction is finished; and/or
The inorganic oxide powder of silicon comprises at least one powder of quartz sand, silicon dioxide and silicon monoxide; and/or
The average grain diameter of the inorganic oxide powder of silicon and/or the boron powder is 0.1-10 mu m; and/or
After the step of cooling treatment, the method also comprises the step of post-treating the generated silicon quantum dots with the doped composite structure:
and carrying out thermal oxidation treatment on the generated doped composite structure silicon quantum dots in a protective atmosphere.
7. The silicon quantum dot boron paste of any one of claims 1, 2, 4-6, wherein: the additive comprises at least one of a dispersant, a grinding aid and a thickener; and/or
The solvent comprises water and/or an organic solvent; the organic solvent comprises at least one of amide, carbonate, aromatic hydrocarbon, sulfoxide, cyclic ether, ketone and alcohol; and/or
The fineness of the silicon quantum dot boron slurry is less than or equal to 1 micron; and/or
The viscosity of the silicon quantum dot boron slurry is 8000-15000 cps; and/or
The solid content of the silicon quantum dot boron slurry is 1-30%.
8. The silicon quantum dot boron paste of claim 7, wherein: the dispersant comprises at least one of Monarden fish oil, oleic acid, sunflower seed oil, corn oil, linseed oil, linoleic acid and stearic acid;
the grinding aid comprises at least one of glyceryl tristearate, glyceryl trioleate, phosphate, polyacrylic acid, polyethylene oxide and polypropylene oxide;
the thickening agent comprises at least one of polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate, cellulose butyrate, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, polyurethane, polyvinylidene fluoride, polymethyl methacrylate and polyethyl methacrylate;
the amide comprises at least one of N-methyl pyrrolidone, dimethylformamide and dimethylpropionamide;
the carbonate includes at least one of ethyl carbonate, propyl carbonate, bis (2,2,2 trifluoroethyl) carbonate, and fluoroethylene carbonate;
the aromatic hydrocarbon comprises at least one of benzene, toluene and xylene;
the sulfoxide comprises at least one of dimethyl sulfoxide and diphenyl sulfoxide;
the cyclic ether comprises at least one of furan and tetrahydrofuran;
the ketone comprises at least one of cyclohexanone, butanone and methyl isobutyl ketone;
the alcohol comprises at least one of terpineol, lauryl alcohol, cyclopentanol, cyclohexanol, cyclododecanol, isobornyl cyclohexanol, palmityl alcohol, ethanol, isopropanol, and propylene glycol.
9. A preparation method of silicon quantum dot boron slurry comprises the following steps:
the silicon quantum dot boron slurry according to any one of claims 1 to 8, wherein the components and the content thereof are measured respectively;
premixing all the components to prepare coarse mortar;
and thinning the coarse mortar.
10. The method of claim 9, wherein: the premixing treatment is to mix the measured components in a planetary stirrer at the revolution speed of 600-; stirring and mixing for 2-10 min; and/or
The thinning treatment is to grind the coarse mortar until the fineness and the viscosity of the coarse mortar reach target values; wherein the fineness is less than or equal to 1 micron, and the viscosity is 8000-.
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