Tin oxide electronic paste and preparation method and application thereof

Abstract

The present invention belongs to the field of semiconductor material preparation, and specifically relates to a tin oxide electronic paste and its preparation method and application, including mixing tin oxide nanoparticles with metal ion dopants, solvents, and binders and performing dispersion treatment, wherein the molar ratio of the tin oxide nanoparticles to the metal ion dopants is determined according to the electrical properties of the desired tin oxide electronic paste; the binder is used for bonding, pore formation, and dispersion of the paste; the mixture after the dispersion treatment is concentrated to obtain the desired tin oxide electronic paste. The tin oxide film layer is further obtained by coating and sintering, which can be applied to the carrier transport layer or buffer layer in optoelectronic devices such as solar cells, light-emitting diodes, and field effect transistors. The present invention can adjust the semiconductor properties of the tin oxide film layer by performing doping treatment during the paste preparation process to achieve the improvement of device performance, and the process is simple, the conditions are easy to control, and it can be prepared in batches, and has good application prospects.

Description

Technical Field

[0001] The invention belongs to the field of semiconductor material preparation, and more specifically, relates to a tin oxide electronic paste and a preparation method and application thereof. Background Art

[0002] At present, optoelectronic devices are developing rapidly, widely used and diverse, including solar cells, light-emitting diodes, photodetectors and field-effect transistors. Semiconductor materials play a vital role in the performance of these devices, thus giving rise to the semiconductor industry. The semiconductor industry is considered to be a strategic industry that promotes the development of science and technology. Different devices have different requirements for semiconductor performance.

[0003] Among the semiconductor materials, tin oxide has attracted extensive attention due to its high carrier mobility and stability, and has great development potential. For example, in perovskite solar cells, the device efficiency of the tin oxide electron transport layer (ETL) prepared by low-temperature spin coating has reached 25.5%. However, after high-temperature sintering, the problem of semiconductor performance degradation is difficult to solve, which limits its further application, and its performance regulation has become another problem.

[0004] In perovskite solar cells, various electron transport layers, such as TiO 2 SnO 2 、ZnO、PCBM、BaSnO 3 , WO 3 , Nb 2 O 5 、In 2 O 3 However, the only widely used high-temperature sintered mesoporous ETL is TiO 2 . TiO 2 It has low carrier mobility (0.1-4cm 2 V -1 s -1 ) and high UV catalytic activity, limiting the development of TiO-based 2 The performance of perovskite solar cells. SnO with higher mobility and better stability 2 It can be the best substitute. However, at present, mesoporous tin oxide (mp-SnO 2 ) The device efficiency of the ETL is low. For tin oxide as ETL, Li et al. used titanium tetrachloride to treat the surface of tin oxide, reducing the carrier recombination at the interface, and increasing the device efficiency from 6.5% to 10.18%. Bart et al. prepared Ga-doped mp-SnO 2 ETL, which adjusts the electrical performance, increases the efficiency to 16.4%.

[0005] In summary, although the current mp-SnO 2 ETL has been applied in traditional perovskite solar cells, but there are also many problems. On the one hand, the tin oxide film prepared by sintering at high temperature will bring about changes in semiconductor performance, making the carrier recombination at the film interface more serious and the conductivity decreased. On the other hand, the energy level mismatch between the adjacent layer and the tin oxide layer affects the transmission of carriers inside the device. It is necessary to adjust the tin oxide performance according to the actual device structure. In addition, there are also process problems such as complex preparation process, poor film quality and difficulty in large-area preparation. The above problems will limit the application of tin oxide in solar cells. Summary of the invention

[0006] In view of the defects and improvement needs of the prior art, the present invention provides a tin oxide electronic paste and a preparation method and application thereof, the main purpose of which is to prepare a tin oxide semiconductor material with adjustable electrical properties to meet the needs of different devices or scenarios.

[0007] To achieve the above object, according to one aspect of the present invention, a method for preparing a tin oxide electronic paste is provided, comprising:

[0008] Tin oxide nanoparticles are mixed with a metal ion dopant, a solvent, and a binder and dispersed to obtain the desired tin oxide electronic paste, wherein the molar ratio of the tin oxide nanoparticles to the metal ion dopant is determined according to the electrical properties of the desired tin oxide electronic paste; the binder is used for bonding, forming pores, and dispersing the paste.

[0009] Furthermore, the solvent is one or more of terpineol, ethanol, diethylene glycol ethyl ether, and n-butanol.

[0010] Furthermore, the binder is one or more of ethyl cellulose, polyvinyl pyrrolidone, PEG8000, PEG6000, PEG4000, PEG1000, and PEG200.

[0011] Furthermore, a dispersant and a leveling agent are added to the mixture in S1, wherein the dispersant is one or more of oleylamine, propionamide, butylamine, quaternary ammonium salt, lauric acid, acetylacetone, BYK110, glacial acetic acid, octylamine, octadecylamine, glucuronamine, polyethyleneimine, polymethacrylic acid, oleic acid, Tween, span, fatty alcohol polyoxyethylene ether, sodium dodecyl sulfate, glutamic acid, diglycylglycine, and hydroxyethylethylenediamine, and the leveling agent is one or more of organic silanes and acrylates.

[0012] Furthermore, the metal ions in the metal ion dopant are metal ions that can be doped into the tin oxide lattice substitutional sites or gaps without segregation.

[0013] The present invention also provides a tin oxide electronic paste, which is prepared by using the above-mentioned method for preparing the tin oxide electronic paste.

[0014] The present invention also provides an application of the tin oxide electronic paste as described above, which is used for a carrier transport layer or a buffer layer in a photoelectric device.

[0015] Furthermore, the optoelectronic devices are solar cells, light emitting diodes, photodetectors and field effect transistors.

[0016] Furthermore, when the optoelectronic device is a solar cell, the metal ion dopant used in the preparation of the tin oxide electronic paste is one or any hydrate of magnesium gluconate, magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium aspartate, magnesium glutamate, magnesium ethoxide, and magnesium phosphate.

[0017] In general, the above technical solutions conceived by the present invention can achieve the following beneficial effects:

[0018] (1) Due to the interaction between the doped metal ions and the tin ions and oxygen vacancies, its semiconductor properties can be regulated. By controlling the ratio of the elements doped into the tin oxide, the film layer of the obtained semiconductor material has different carrier concentrations, band structures and conductivity, so it can meet the needs of optoelectronic devices of different types and kinds. By doping with magnesium elements within a molar ratio of less than 6%, the carrier concentration of the tin oxide layer can be achieved in the range of 9.98×10 19 to 7.75×10 20 cm -3 The conduction band position is continuously adjustable from -4.20eV to -3.94eV.

[0019] (2) The present invention provides a tin oxide slurry that can be doped in one step, which can adjust the semiconductor performance. At present, the semiconductor performance of tin oxide after high-temperature sintering is poor, and the present invention achieves adjustable carrier concentration and band structure by doping elements during a slurry mixing process to meet the requirements for tin oxide performance under different circumstances. From the perspective of technical principles, this is mainly because of the influence of metal ions on the crystal after being doped into the lattice, thereby achieving the purpose of adjusting the semiconductor performance. According to the analysis of the experimental data obtained by the present invention, metal ion doping has two types of occupancy in the lattice: substitutional and interstitial, providing additional donors or acceptors, and being able to adjust the content of oxygen vacancies, thereby performing controllable and continuous adjustment of electrical properties such as band gap and carrier concentration.

[0020] (3) Through this metal ion-doped tin oxide slurry, on the one hand, the doping of metal ions realizes the precise control of the carrier concentration of the tin oxide film layer, which can be adjusted within an order of magnitude, making the conductivity better. On the other hand, after doping, the arrangement and position of the band structure of the oxide film layer are adjusted, so that the tin oxide film layer and other interface layers can be better matched, reducing the obstruction and recombination loss of carrier transmission at the interface. At the same time, since the dopant has been evenly mixed into the tin oxide slurry, the prepared slurry does not need to undergo additional processing, and the doping process can be completed in one step. Applied in solar cells, the original efficiency has been increased from 6% to more than 16%, and the overall device has an excellent photoelectric conversion effect.

[0021] (4) The slurry prepared by the present invention can achieve uniform dispersion of tin oxide nanoparticles in the solvent without obvious agglomeration and sedimentation through the appropriate ratio of binder, dispersant and leveling agent. At the same time, due to its high dispersibility and the thixotropy of the organic binder, a high-quality film layer of any size can be obtained by printing and coating, solving the problem of not being able to prepare high-quality thin films on a large area. At the same time, the shape and pattern of the prepared film layer can be arbitrarily changed to meet more application scenarios and needs.

[0022] (5) The preparation method of the present invention has simple process, low equipment requirements, low cost, and can be mass-produced. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 A flow chart of a method for preparing tin oxide electronic paste provided in an embodiment of the present invention;

[0024] Figure 2 Surface SEM and EDS images of tin oxide nanoparticles provided in an embodiment of the present invention;

[0025] Figure 3 HRTEM image of magnesium-doped tin oxide nanoparticles provided in an embodiment of the present invention;

[0026] Figure 4 A SEM image of a cross section of a solar cell device provided by an embodiment of the present invention;

[0027] Figure 5 This is an efficiency curve diagram of the IV test of the solar cell device provided in an embodiment of the present invention. DETAILED DESCRIPTION

[0028] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0029] In order to meet different application scenarios and performance requirements, the present invention designs a method for preparing a semiconductor material with adjustable performance and easy processing.

[0030] Embodiment 1

[0031] A method for preparing tin oxide electronic paste, such as Figure 1 As shown, including:

[0032] Step 110, mixing tin oxide nanoparticles with a metal ion dopant, a solvent, and a binder and performing a dispersion treatment, wherein the molar ratio of the tin oxide nanoparticles to the metal ion dopant is determined according to the electrical properties of the desired tin oxide electronic paste; the binder is used for bonding, forming pores, and dispersing the paste;

[0033] Step 120: Concentrate the dispersed mixture to obtain the desired tin oxide electronic slurry.

[0034] The above-mentioned tin oxide nanoparticles belong to tin-based oxides, which are represented by Sn 4+ x Sn 2+ y O 2- z , where Sn 4+ For tetravalent tin, Sn 2+ It is divalent tin, x>0, y≥0, z>0, and satisfies 2x+y=z.

[0035] Based on the above preparation method, for example, the preparation of the slurry includes the following steps:

[0036] (1) Tin oxide is mixed with glacial acetic acid and ethanol, and then centrifuged and washed with deionized water.

[0037] (2) Add the above-obtained product into a ball mill, and add a solvent, a dispersant, a binder, a leveling agent and a dopant in proportion, and perform ball milling. The amount of the solvent, the dispersant, the binder and the leveling agent affects the consistency and dispersibility of the prepared slurry, and they are added according to actual needs.

[0038] (3) The ball-milled product is taken out, a dispersant is added again, ultrasonic dispersion treatment is performed, and excess solvent is removed by rotary evaporation to obtain a tin oxide slurry material.

[0039] The optimum mass ratio of tin oxide to acetic acid and ethanol in step (1) is 1:5:80. The optimum mixing time in step (1) is 1-3 hours, and the ball milling time in step (2) is 12-15 hours. The ball milling speed can be selected within the range of 100-400 r / h.

[0040] Preferably, the solvent is one or more of terpineol, ethanol, diethylene glycol ethyl ether, and n-butanol.

[0041] Preferably, the binder is one or more of ethyl cellulose, polyvinyl pyrrolidone, PEG8000, PEG6000, PEG4000, PEG1000, and PEG200.

[0042] Preferably, a dispersant and a leveling agent are further added to the mixture in step 110, wherein the dispersant is one or more of oleylamine, propionamide, butylamine, quaternary ammonium salt, lauric acid, acetylacetone, BYK110, glacial acetic acid, octylamine, octadecylamine, glucuronamine, polyethyleneimine, polymethacrylic acid, oleic acid, Tween, span, fatty alcohol polyoxyethylene ether, sodium dodecyl sulfate, glutamic acid, diglycylglycine, and hydroxyethylethylenediamine, and the leveling agent is one or more of organic silane and acrylate.

[0043] Embodiment 2

[0044] A tin oxide electronic paste is prepared by the method for preparing a tin oxide electronic paste as described in Example 1. The relevant scheme is the same as that in Example 1 and will not be described in detail here.

[0045] Embodiment 3

[0046] An application of the tin oxide electronic paste as described in the second embodiment is used for a carrier transport layer or a buffer layer in a photoelectric device.

[0047] Preferably, the optoelectronic device is a solar cell, a light emitting diode, a photodetector and a field effect transistor.

[0048] Preferably, when the optoelectronic device is a solar cell, the metal ion dopant used in the preparation of the tin oxide electronic paste is one or any hydrate of magnesium gluconate, magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium aspartate, magnesium glutamate, magnesium ethoxide, and magnesium phosphate.

[0049] The dispersant is preferably at least one of oleylamine, propionamide, butylamine, quaternary ammonium salt, lauric acid, acetylacetone, BYK110, glacial acetic acid, octylamine, octadecylamine, glucuronamine, polyethyleneimine, polymethacrylic acid, oleic acid, Tween, span, fatty alcohol polyoxyethylene ether, sodium lauryl sulfate, glutamic acid, diglycylglycine, and hydroxyethylethylenediamine. The leveling agent is preferably at least one of organic silane and acrylate. The binder is preferably at least one of ethyl cellulose, polyvinyl pyrrolidone, PEG8000, PEG6000, PEG4000, PEG1000, and PEG200.

[0050] The doping agent selected includes, but is not limited to, magnesium gluconate, magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium aspartate, magnesium glutamate, magnesium ethoxide, magnesium phosphate or a hydrate of any of the salts thereof.

[0051] According to the above-mentioned method for preparing the doping slurry, a film layer with adjustable performance can be prepared, and its applications include but are not limited to electron transport layer and buffer layer. Applicable optoelectronic devices include solar cells, light-emitting diodes, photodetectors and field effect transistors.

[0052] In order to better illustrate the slurry preparation method of the present invention, the following example is given:

[0053] Example 1

[0054] Slurry preparation method:

[0055] (1) Weigh 1 g of tin oxide powder and disperse it in 80 ml of ethanol and 5 ml of glacial acetic acid. Stir the mixture magnetically and heat it at 50 °C.

[0056] (2) The mixed solution is centrifuged to obtain tin oxide powder, which is washed twice with deionized water and ethanol alternately, and then dried.

[0057] (3) The product was added to a ball mill, and pineneol (the mass ratio of tin oxide powder to pineneol was 1:12) was added at the same time. The dopant was added according to the calculated molar ratio, and 0.05 g of oleylamine, 0.1 g of acetylacetone, and 0.35 g of ethyl cellulose were added. Then, an appropriate amount of ethanol and other dispersants, leveling agents, and binders were added. The mixture was ball milled at a speed of 350 r / h for 12 hours and then taken out.

[0058] (4) Add 0.05 g of acetylacetone and PEG200 to the product taken out in (3) and continue ultrasonic treatment for 4 hours to ensure more uniform dispersion.

[0059] (5) The product obtained in (4) is subjected to rotary evaporation to obtain a tin oxide slurry, which can be prepared by printing to obtain a film layer.

[0060] like Figure 2 The surface SEM image and EDS element distribution of the tin oxide nanoparticles prepared in Example 1 are shown, which have good dispersion, uniform particles, and uniform doping element distribution. Figure 3 Shown is the HRTEM image of the prepared magnesium-doped tin oxide nanoparticles, with clear lattice fringes and good crystallinity.

[0061] Slurry application:

[0062] (1) The device uses conductive glass (such as transparent conductive glass, such as FTO, etc.) as a conductive substrate and deposits a dense titanium dioxide layer with a thickness of 20 nm.

[0063] (2) A magnesium-doped tin oxide layer, a mesoporous spacer layer, and a mesoporous back electrode are prepared from top to bottom by coating or the like.

[0064] (3) Sintering at high temperature (e.g. 500°C), then cooling, filling with perovskite solution and drying.

[0065] The particle size of nano-tin oxide is, for example, 20 nm, and the thickness is about 0.5-1 μm. The mesoporous spacer layer is, for example, zirconium dioxide, silicon dioxide, aluminum oxide, etc., and the thickness is 2 μm. The mesoporous back electrode is a thin film of a mesoporous porous structure made of graphite or carbon black, and the thickness is about 10 μm. A certain amount, for example, 3 μL of iodine lead methylammonium (CH 3 NH 3 PbI 3 ) Precursor solution (30% wt) was dripped onto the mesoporous back electrode, left to stand for 15 minutes until it was completely infiltrated, and then dried at 57°C. Tests showed that at 100mW*cm -2 Under sunlight, the efficiency of the device using a tin oxide electron transport layer but not magnesium doped (ie, no dopant was added in the above slurry preparation step) was 6.62%, and the efficiency of the device using a magnesium-doped tin oxide electron transport layer was 16.10%.

[0066] like Figure 4 The SEM image of the device cross section is shown in Figure 5 This is the efficiency curve of the IV test of the device. It can be seen that the efficiency of the device is significantly improved after Mg doping.

[0067] It will be easily understood by those skilled in the art that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing tin oxide electronic paste, characterized in that: include: Tin oxide nanoparticles are mixed with a metal ion dopant, a solvent, and a binder, and then dispersed to obtain the desired tin oxide electronic paste, and element doping is achieved through the paste mixing process, wherein the molar ratio of the tin oxide nanoparticles to the metal ion dopant is determined according to the band gap and carrier concentration of the desired tin oxide electronic paste; the binder is used for bonding, pore formation, and dispersion of the paste; The tin oxide electronic paste is used for preparing the mesoporous ETL; the metal ions in the metal ion dopant are metal ions that can be doped into the tin oxide lattice substitution or gap without segregation, thereby controlling and continuously adjusting the band gap and carrier concentration.

2. The method for preparing a tin oxide electronic paste according to claim 1, characterized in that: The solvent is one or more of terpineol, ethanol, diethylene glycol ethyl ether and n-butanol.

3. The method for preparing a tin oxide electronic paste according to claim 1, characterized in that: The binder is one or more of ethyl cellulose, polyvinyl pyrrolidone, PEG8000, PEG6000, PEG4000, PEG1000, and PEG200.

4. The method for preparing a tin oxide electronic paste according to claim 1, characterized in that: A dispersant and a leveling agent are further added to the mixture obtained after performing the mixing operation, wherein the dispersant is one or more of oleylamine, propionamide, butylamine, quaternary ammonium salt, lauric acid, acetylacetone, BYK110, glacial acetic acid, octylamine, octadecylamine, glucuronamine, polyethyleneimine, polymethacrylic acid, oleic acid, Tween, span, fatty alcohol polyoxyethylene ether, sodium dodecyl sulfate, glutamic acid, diglycylglycine, and hydroxyethylethylenediamine, and the leveling agent is one or more of organic silane and acrylate.

5. A tin oxide electronic paste, characterized in that: The tin oxide electronic paste is prepared by the method for preparing the tin oxide electronic paste according to any one of claims 1 to 4.

6. An application of the tin oxide electronic paste as claimed in claim 5, characterized in that: Used as carrier transport layer or buffer layer in optoelectronic devices.

7. The use according to claim 6, characterized in that: The photoelectric devices are solar cells, light emitting diodes, photoelectric detectors and field effect tubes.

8. The use according to claim 7, characterized in that: When the optoelectronic device is a solar cell, the metal ion dopant used in the preparation of the tin oxide electronic paste is one or any hydrate of magnesium gluconate, magnesium acetate, magnesium chloride, magnesium nitrate, magnesium sulfate, magnesium aspartate, magnesium glutamate, magnesium ethoxide, and magnesium phosphate.

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