CN115893988A - Evaporation target material for solar cell and preparation method thereof - Google Patents
Evaporation target material for solar cell and preparation method thereof Download PDFInfo
- Publication number
- CN115893988A CN115893988A CN202211580121.9A CN202211580121A CN115893988A CN 115893988 A CN115893988 A CN 115893988A CN 202211580121 A CN202211580121 A CN 202211580121A CN 115893988 A CN115893988 A CN 115893988A
- Authority
- CN
- China
- Prior art keywords
- oxide
- evaporation target
- slurry
- target material
- dispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention discloses an evaporation target material for a solar cell and a preparation method thereof, wherein the evaporation target material comprises the following components in percentage by mass: indium oxide (In) 2 O 3 ) 98.5-99.5 percent of doped oxide, 0.5-1.5 percent of doped oxide, wherein the doped oxide is 2-4 of cerium oxide, tungsten oxide, molybdenum oxide, holmium oxide, yttrium oxide, zirconium oxide and gallium oxide. This schemeThe evaporation target material adopts unique chemical composition, through introducing the doping oxide into the indium oxide base body, can produce higher carrier electron concentration through binary even many first codoping, and carrier electron mobility obtains showing and promotes, and the film that adopts this evaporation target material deposit has high near-infrared transmittance and high electron mobility.
Description
Technical Field
The invention belongs to the technical field of solar cells, and particularly relates to an evaporation target material for a solar cell and a preparation method thereof.
Background
Amorphous silicon/crystalline silicon heterojunction solar cells have been widely researched and developed in the industry in recent years due to their excellent photoelectric conversion efficiency. In order to improve the spectral response of the heterojunction solar cell in an infrared long wave region and further fully utilize solar energy, thereby further improving the photoelectric conversion efficiency of the solar cell, the development of a Transparent Conductive Oxide (TCO) film with high infrared transmittance is significant. However, increasing the ir transmittance of TCO films requires decreasing the electron concentration of the film, and also increases the electron mobility of the film to ensure good conductivity.
To improve the electron mobility of conventional Indium Tin Oxide (ITO) targets, the reduction of SnO needs to be reduced 2 Content (e.g., 3%, 5%). At this time, the electron mobility is slightly increased due to a certain reduction in the carrier concentration, but the conductivity of the thin film tends to be lowered to some extent. And SnO 2 When the content is low, the ITO target with ultrahigh density is difficult to fire, which is not friendly to the actual magnetron sputtering coating process (the nodulation and poisoning phenomenon on the surface of the target is easy to occur), thereby influencing the coating quality and continuous production.
Disclosure of Invention
In order to achieve the purpose and solve the problems in the prior art, the invention prepares a low-density evaporation target material by optimizing the chemical composition of the target material, improving the grinding process and innovating the sintering process, and the target material can be used for preparing TCO films with high electron mobility and high infrared transmittance and is used for meeting the actual requirements in the field of solar cells.
One object of the present invention is to provide a vapor deposition target for a solar cell. The evaporation target comprises the following components: indium oxide (In) 2 O 3 ) 98.5-99.5wt% of doped oxide, 0.5-1.5wt% of doped oxide, wherein the doped oxide is cerium oxide (CeO) 2 ) Tungsten oxide (WO) 3 ) Molybdenum oxide (MoO) 3 ) Holmium oxide (Ho) 2 O 3 ) Yttrium oxide (Y) 2 O 3 ) Zirconium oxide (ZrO) 2 ) Gallium oxide (Ga) 2 O 3 ) 2-4 kinds of them.
The evaporation target for the solar cell provided by the invention has unique chemical composition, the target is not deformed or cracked in the sintering process, the relative density of the target is strictly controlled to be about 60%, and the actual requirement of an evaporation coating process is met. In addition, on the premise of keeping the indium oxide content of 98.5-99.5wt%, oxides such as tungsten oxide, cerium oxide, holmium oxide, gallium oxide and the like are introduced into the indium oxide matrix, and the carrier current mobility is remarkably improved while higher carrier electron concentration is generated through binary or even multi-element co-doping.
The invention further aims to provide a preparation method of the evaporation target material for the solar cell, which comprises the following specific steps: step one, mixing a main oxide, a doped oxide, a dispersing agent and deionized water according to a certain proportion, carrying out primary ball milling and mixing, and finishing ball milling when the D50 of primary ball milling mixed slurry is less than 0.5 mu m; drying and crushing the primary ball-milling mixed slurry, then sieving the dried and crushed primary ball-milling mixed slurry by a 60-80-mesh sieve, and placing the crushed primary ball-milling mixed slurry into a sintering furnace for primary calcination treatment while introducing oxygen; then collecting calcined powder for later use;
step two, mixing the calcined powder, the binder, the dispersant and deionized water according to a certain proportion, carrying out secondary ball milling mixing, firstly adding the dispersant in batches for grinding for more than 4 hours, then adding the binder in batches, and continuously sanding for more than 30min to obtain slurry;
step three, preparing solid spherical particles from the slurry obtained in the step two in a granulation mode, and then sieving the solid spherical particles to obtain the particles for later use;
filling the particles obtained in the step three into a mould, and performing compression molding under the molding pressure of 20-40 MPa to obtain an evaporation target biscuit;
and step five, placing the evaporation target biscuit obtained in the step four into a sintering furnace for sintering, and naturally cooling to room temperature after the sintering process is finished to obtain the evaporation target.
Preferably, in the third step, the slurry obtained in the second step is granulated to obtain solid spherical particles, and the solid spherical particles are sieved by a 80-mesh sieve to obtain particles for standby, wherein the specific surface area of the particles is controlled to be 5.0-6.0m in the granulation process 2 /g。
Preferably, in the fifth step, the specific sintering step is as follows:
the first temperature interval: the room temperature is 750 ℃ below zero, the heating rate is 1 ℃/min, and the air flow is controlled to be 10-15L/min;
the second temperature interval: 750-1450 ℃, the heating rate is 2 ℃/min, and the flow rate of the mixed gas is controlled to be 10-15L/min;
the third temperature interval: 1450-1400 ℃, the cooling rate is 2 ℃/min, and the flow rate of the mixed gas is controlled to be 10-15L/min;
a fourth temperature interval: keeping the temperature at 1400 ℃ for 6h, and controlling the flow rate of the mixed gas at 10-15L/min;
a fifth temperature interval: the temperature is reduced at a rate of 3 ℃/min at 1400-800 ℃, and the flow rate of the mixed gas is controlled at 10-15L/min;
sixth temperature interval: the temperature is reduced at the speed of 1 ℃/min at the temperature of 800-100 ℃, the air flow is controlled at 10-15L/min, and the evaporation target material can be prepared by naturally cooling to room temperature after the procedure is finished.
Preferably, the mixed gas consists of nitrogen and hydrogen, wherein the volume of the hydrogen accounts for 3-5%.
Preferably, in the preparation method, the dispersant is ammonium polyacrylate in the primary ball milling process, and the ratio of the mass of the dispersant to the total mass of the oxides is 0.3-0.9%.
Preferably, in the preparation method, the addition amount of the dispersing agent in the secondary ball milling process of calcined powder is ammonium polyacrylate, and the ratio of the mass of the dispersing agent to the total mass of the oxides is 0.3-0.9%; the adhesive is polyvinyl alcohol, and the ratio of the mass of the adhesive to the total mass of the oxides is 1-3%.
Preferably, in the second step, the dispersant is added in batches for grinding for more than 4 hours, and after the D50 of the mixed slurry is less than 0.8 μm, the binder is added in batches.
The invention has the following beneficial effects:
one of the two schemes is that the evaporation target material adopts unique chemical composition, by introducing doped oxide into an indium oxide substrate, binary or even multi-element co-doping can generate higher carrier electron concentration, and meanwhile, the carrier electron mobility is obviously improved, and a film deposited by adopting the evaporation target material has high near-infrared transmittance and high electron mobility, and the electron mobility is higher than that of a conventional ITO target material (In) 2 O 3 /SnO 2 = 90/10) is 8 times higher, which is beneficial to improving the photoelectric conversion efficiency of the solar cell.
Secondly, in the scheme, the grinding process in the preparation process of the evaporation target is optimized, in the secondary ball milling and dispersing process of calcined powder, firstly, the dispersing agent is added in batches to keep the slurry at a proper viscosity so as to realize the high-efficiency grinding of the slurry, and then, the binder is added in batches to continue ball milling, so that the uniformly dispersed nano-scale particles in the slurry are orderly combined, thereby improving the viscosity of the slurry. And then the slurry with the adjusted viscosity is subjected to conventional granulation to obtain solid spherical particles with high compactness. The particles have good fluidity, and in the forming process, the particles are easy to realize tight accumulation and are extruded and crushed under the action of pressure and are completely combined into a compact biscuit, and the bonding strength of the target material can be improved in the sintering process.
Thirdly, the scheme innovates a sintering process, adopts a mixed atmosphere of nitrogen and hydrogen in the sintering process of the evaporation target, and adopts a special variable-temperature sintering temperature system in a high-temperature stage. The nitrogen-hydrogen mixed atmosphere treatment can introduce rich oxygen vacancy defects to further prolong the sintering kinetic process of the target material so as to reduce the sintering density, the variable-temperature sintering temperature system can improve the sintering activity of the surface of the powder so as to improve the sintering density, and the two synergistic effects achieve the purposes of controlling the sintering shrinkage of the target material and improving the bonding strength of the evaporation target material. By accurately controlling the sintering shrinkage of the target material through the mixed atmosphere, the uniformity of the internal tissue of the prepared evaporation target material is obviously improved, the relative density is strictly controlled to be about 60 percent, and the near-net-size preparation of the high-strength evaporation target material is easy to realize. The thermal shock resistance of the evaporation target material obtained by the method is obviously improved, the target material cracking, powder falling and splashing caused by electron beam bombardment in the evaporation process are avoided, the uniformity and density of a deposited film are ensured, the actual requirements of an evaporation coating process are met, and the preparation process is simple and is completely suitable for large-scale production.
Drawings
FIG. 1 shows the results of performance tests of the examples and comparative examples;
Detailed Description
The present invention will be further described with reference to the following detailed description so that the technical means, the characteristics of creation, the objects achieved, and the advantageous effects achieved by the present invention can be clearly understood.
The embodiment provides an evaporation target for a solar cell, which comprises the following components in parts by mass: 98.5-99.5wt% indium oxide (In) 2 O 3 ) And 0.5 to 1.5wt% of a doped oxide; the doped oxide is cerium oxide (CeO) 2 ) Tungsten oxide (WO) 3 ) Molybdenum oxide (MoO) 3 ) Holmium oxide (Ho) 2 O 3 ) Yttrium oxide (Y) 2 O 3 ) Zirconium oxide (ZrO) 2 ) Gallium oxide (Ga) 2 O 3 ) 2-4 kinds of them.
The embodiment provides a preparation method of the evaporation target, which specifically includes the steps of: step one, mixing a main oxide, a doped oxide, a dispersing agent and deionized water, carrying out primary ball milling and mixing, and controlling the solid phase amount of the slurry to be 50wt%, wherein the solid phase amount refers to the mass ratio of the solid mass to the total solid-liquid mass, and the solid mass comprises the total mass of calcined powder, a binding agent and the dispersing agent. Finishing ball milling when the granularity D50 of the mixed slurry is less than 0.5 mu m; putting the primary ball-milling slurry into a 90 ℃ oven for drying and crushing, putting a 60-80 mesh sieve, putting the sieve in a sintering furnace, and calcining at 1400 ℃ for 4-6h while introducing oxygen; and then collecting calcined powder for later use.
And step two, mixing the calcined powder, the binder, the dispersant and deionized water, performing secondary ball milling and mixing, controlling the solid phase amount of the slurry to be 50wt%, optimizing the feeding mode of the dispersant and the binder, firstly adding the dispersant in batches to keep the slurry at a proper viscosity so as to realize efficient grinding of the slurry for more than 4 hours, and then adding the binder in batches for continuous sanding for more than 30 minutes when the D50 of the mixed slurry is less than 0.8 mu m, so that the uniformly dispersed nano-scale particles in the slurry are orderly combined to improve the viscosity of the slurry.
Step three, preparing the grinding slurry into solid spherical particles with high compactness degree by a conventional granulation mode, taking particles with a 80-mesh sieve for standby application, and controlling the specific surface area of the particles to be 5.0-6.0m in the granulation process 2 /g。
Filling the particles into a steel die, and performing compression molding under the molding pressure of 20-40 MPa to obtain the evaporation target biscuit.
Step five, placing the evaporation target material biscuit subjected to compression molding into a sintering furnace for sintering, wherein the sintering process is as follows:
the first temperature interval: the room temperature is 750 ℃ below zero, the heating rate is 1 ℃/min, and the air flow is controlled to be 10-15L/min;
the second temperature interval: 750-1450 ℃, the heating rate is 2 ℃/min, and the flow rate of the mixed gas is controlled to be 10-15L/min;
the third temperature interval: 1450-1400 ℃, the cooling rate is 2 ℃/min, and the flow rate of the mixed gas is controlled to be 10-15L/min;
a fourth temperature interval: keeping the temperature at 1400 ℃ for 6h, and controlling the flow rate of the mixed gas at 10-15L/min;
a fifth temperature interval: the temperature is reduced at a rate of 3 ℃/min at 1400-800 ℃, and the flow rate of the mixed gas is controlled at 10-15L/min;
sixth temperature interval: the temperature is reduced at the speed of 1 ℃/min at the temperature of 800-100 ℃, the air flow is controlled at 10-15L/min, and the evaporation target material can be prepared by naturally cooling to room temperature after the procedure is finished.
In the preparation method, the evaporation target biscuit after compression molding is placed in a sintering furnace, an air atmosphere is adopted in a low-temperature degreasing stage, a mixed atmosphere is adopted in a sintering stage, the mixed atmosphere is composed of a mixed gas of nitrogen and hydrogen, and the volume of the hydrogen accounts for 3-5%; after the temperature is increased to 750 ℃, the mixed gas is introduced till the temperature is reduced to 800 ℃.
In the first step, the dispersant is ammonium polyacrylate in one ball milling process, but is not limited to the dispersant, and the addition amount of the dispersant is 0.3 to 0.9wt%, wherein the addition amount refers to the mass ratio of the dispersant to total oxides, and the total oxides comprise the total mass of indium oxide and doped oxides. The dispersant is ammonium polyacrylate in the secondary ball milling process of calcined powder, but the dispersant is not limited to the ammonium polyacrylate, and the addition amount of the dispersant is 0.3-0.9 wt%, wherein the addition amount refers to the mass ratio of the dispersant to total oxides, and the total oxides comprise the total mass of indium oxide and doped oxides; the binder is polyvinyl alcohol, but is not limited to this binder, and is added in an amount of 1 to 3wt% in terms of the mass ratio of the binder to the total oxide, including the total mass of indium oxide and doped oxide.
Examples 1 to 3
Mixing 9.9Kg of indium oxide powder, 0.05Kg of tungsten oxide powder, 0.05Kg of cerium oxide powder, a dispersing agent (ammonium polyacrylate) and deionized water, performing primary ball milling and mixing, controlling the solid phase amount of the slurry to be 50wt%, controlling the addition amount of the dispersing agent to be 0.6wt% of the total mass of oxides, and finishing ball milling when the D50 of the mixed slurry is less than 0.5 mu m (namely the proportion of particles with the particle diameter of less than 0.5 mu m in the slurry reaches 50%); and (3) placing the primary ball-milling slurry in a 90 ℃ oven for drying and crushing, sieving the dried and crushed material with a 80-mesh sieve, placing the sieved material in a sintering furnace for primary calcination at 1400 ℃ for 6h, and introducing oxygen. Mixing calcined powder, a binder (polyvinyl alcohol), a dispersant (ammonium polyacrylate) and deionized water, performing secondary ball milling and mixing, controlling the solid phase amount of the slurry to be 50wt%, the addition amount of the dispersant to be 0.8wt% of the total mass of the oxides, and the addition amount of the binder to be 2.5% of the total mass of the oxides, and optimizing the dispersant and the binderThe feeding mode is that firstly, dispersing agent is uniformly added three times at intervals of 15min in the feeding and stirring process to keep the slurry at a proper viscosity, then the slurry is transferred to a sand mill to be efficiently ground for 4h, when the D50 of the mixed slurry is less than 0.8 mu m (namely the proportion of particles with the particle diameter of less than 0.8 mu m in the slurry reaches 50%), then, binding agent is uniformly added five times at intervals of 5min, and the sand mill is continued for 30min (the starting time of the sand mill is that the binding agent is added for the first time and the sand mill is started), so that the uniformly dispersed nano-scale particles in the slurry are orderly combined, and the viscosity of the slurry is improved. The grinding slurry is prepared into solid spherical particles with high compactness degree by a conventional granulation mode, the particles are sieved by a sieve with 80 meshes for standby, and the specific surface area of the particles is controlled to be 5.0-6.0m in the granulation process 2 (ii) in terms of/g. The particles were filled in a steel mold and compression-molded at a molding pressure of 20MPa to obtain evaporation target biscuits (labeled a01, a02, a 03), respectively. Placing the evaporation target biscuit subjected to compression molding into a sintering furnace for sintering, wherein the sintering atmosphere consists of mixed gas of nitrogen and hydrogen, the volume of the hydrogen accounts for 5%, and the sintering process comprises the following steps:
the first temperature interval: the room temperature is 750 ℃ below zero, the heating rate is 1 ℃/min, and the air flow is controlled at 10L/min;
the second temperature interval: 750-1450 ℃, the heating rate is 2 ℃/min, and the flow rate of the mixed gas is controlled at 15L/min;
the third temperature interval: 1450-1400 ℃, the cooling rate is 2 ℃/min, and the flow rate of the mixed gas is controlled at 15L/min;
the fourth temperature interval: keeping the temperature at 1400 ℃ for 6h, and controlling the flow rate of the mixed gas at 15L/min;
a fifth temperature interval: 1400-800 deg.C, cooling rate of 3 deg.C/min, and flow rate of the mixture controlled at 15L/min;
sixth temperature interval: the temperature reduction rate is 1 ℃/min at 800-100 ℃, and the air flow is controlled at 10L/min.
After the process is finished, the material is naturally cooled to room temperature, and vapor deposition target materials (marked as A11, A12 and A13) can be prepared. Placing the evaporation target material with diameter of 32mm and height of 40mm into a crucible of activated plasma deposition (RPD) equipment, wherein the substrate is Corning glass with thickness of 0.7mm, and argon and oxygen are used as working gases under vacuum condition(Ar:O 2 =100, the flow ratio), controlling the working pressure of the evaporation chamber to 0.353Pa (deposition pressure), starting the electron gun power supply to evaporate and plate the film, and testing the electron mobility and the near-infrared transmittance of the film respectively, the test results are shown in table 1.
Examples 4 to 6
Mixing 9.9Kg of indium oxide powder, 0.05Kg of tungsten oxide powder, 0.05Kg of holmium oxide powder, a dispersing agent (ammonium polyacrylate) and deionized water, performing primary ball milling and mixing, controlling the solid phase amount of the slurry to be 50wt%, controlling the addition amount of the dispersing agent to be 0.6wt%, and finishing ball milling when the D50 of the mixed slurry is less than 0.5 mu m (namely the proportion of particles with the particle diameter less than 0.5 mu m in the slurry is up to 50%); and (3) placing the primary ball-milling slurry in a 90 ℃ oven for drying and crushing, sieving the dried and crushed material by a 80-mesh sieve, placing the sieved material in a sintering furnace for primary calcination at 1400 ℃ for 6h, and introducing oxygen. Mixing calcined powder, a binder (polyvinyl alcohol), a dispersant (ammonium polyacrylate) and deionized water, performing secondary ball milling and mixing, controlling the solid phase amount of slurry to be 50wt%, controlling the addition amount of the dispersant to be 0.8% of the mass of the total oxides, and controlling the addition amount of the binder to be 2.5% of the mass of the total oxides, optimizing the addition modes of the dispersant and the binder, firstly, uniformly adding the dispersant at intervals of 15min for three times in the feeding and stirring process to keep the slurry at a proper viscosity, then transferring the slurry into a sand mill for high-efficiency grinding for 4h, when the D50 of the mixed slurry is less than 0.8 mu m (namely the proportion of particles with the particle diameter less than 0.8 mu m in the slurry reaches 50%), then, uniformly adding the binder at intervals of 5min for five times, and continuing sanding for 30min (the starting time of sanding is the first time of adding the binder and starting sanding), so that nano-scale particles uniformly dispersed in the slurry are orderly combined, thereby improving the viscosity of the slurry. The grinding slurry is prepared into solid spherical particles with high compactness degree by a conventional granulation mode, the particles are sieved by a sieve with 80 meshes for standby, and the specific surface area of the particles is controlled to be 5.0-6.0m in the granulation process 2 (ii) in terms of/g. The particles were filled in a steel mold and compression-molded at molding pressures of 20MPa, 30MPa, and 40MPa to obtain evaporation target blanks (labeled B01, B02, and B03), respectively. Putting the evaporation target biscuit subjected to compression molding into a sintering furnace for sintering, wherein the sintering atmosphere is composed of nitrogen andthe hydrogen consists of hydrogen mixture, wherein the volume of the hydrogen accounts for 5 percent, and the sintering process comprises the following steps:
the first temperature interval: the room temperature is 750 ℃ below zero, the heating rate is 1 ℃/min, and the air flow is controlled at 10L/min;
the second temperature interval: 750-1450 ℃, the heating rate is 2 ℃/min, and the flow rate of the mixed gas is controlled at 15L/min;
the third temperature interval: 1450-1400 ℃, the cooling rate is 2 ℃/min, and the flow rate of the mixed gas is controlled at 15L/min;
a fourth temperature interval: keeping the temperature at 1400 ℃ for 6h, and controlling the flow rate of the mixed gas at 15L/min;
a fifth temperature interval: the temperature is reduced at a rate of 3 ℃/min at 1400-800 ℃, and the flow rate of the mixed gas is controlled at 15L/min;
sixth temperature interval: the temperature reduction rate is 1 ℃/min at the temperature of 800-100 ℃, and the air flow is controlled at 10L/min.
After the procedure is finished, the material is naturally cooled to room temperature, and evaporation target materials (marked as B1, B2 and B3) can be prepared. Placing the above evaporation target material with diameter of 32mm and height of 40mm into crucible of activated plasma deposition (RPD) equipment, wherein the substrate is Corning glass with thickness of 0.7mm, and argon and oxygen are used as working gas (Ar: O) under vacuum condition 2 = 30, flow ratio), the working pressure of the evaporation chamber is controlled to 0.353Pa (deposition pressure), the electron gun power supply is started to evaporate and plate the film, the electron mobility and the near infrared transmittance of the film are respectively tested, and the test results are shown in table 1.
Examples 7 to 9
Mixing 9.85Kg of indium oxide powder, 0.05Kg of tungsten oxide powder, 0.05Kg of cerium oxide powder, 0.05Kg of holmium oxide powder, a dispersing agent (ammonium polyacrylate) and deionized water, performing primary ball milling and mixing, controlling the solid phase amount of the slurry to be 50wt%, wherein the addition amount of the dispersing agent is 0.6% of the mass of the total oxides, and finishing ball milling when the D50 of the mixed slurry is less than 0.5 mu m (namely the proportion of particles with the particle diameter of less than 0.5 mu m in the slurry reaches 50%); and (3) placing the primary ball-milling slurry in a 90 ℃ oven for drying and crushing, sieving the dried and crushed material with a 80-mesh sieve, placing the sieved material in a sintering furnace for primary calcination at 1400 ℃ for 6h, and introducing oxygen. Dispersing calcined powder, binder (polyvinyl alcohol), and dispersingMixing an agent (ammonium polyacrylate) and deionized water, performing secondary ball milling and mixing, controlling the solid phase amount of the slurry to be 50wt%, the addition amount of a dispersing agent to be 0.8% of the mass of the total oxides, and the addition amount of a binder to be 2.5% of the mass of the total oxides, optimizing the addition modes of the dispersing agent and the binder, firstly, uniformly adding the dispersing agent for three times at intervals of 15min in the process of adding and stirring so as to keep the slurry at a proper viscosity, then, transferring the slurry into a sand mill for efficient grinding for 4h, when the D50 of the mixed slurry is less than 0.8 mu m (namely, the proportion of particles with the particle diameter of less than 0.8 mu m in the slurry reaches 50%), then, uniformly adding the binder for five times at intervals of 5min, and continuing for 30min (the starting time of sand milling is that the binder is added for the first time and the sand milling is started), so that the uniformly dispersed nano-scale particles in the slurry are orderly combined, thereby improving the viscosity of the slurry. The grinding slurry is prepared into solid spherical particles with high compactness degree by a conventional granulation mode, and the solid spherical particles are sieved by a 80-mesh sieve for standby, and the specific surface area of the grinding slurry is controlled to be 5.0-6.0m in the granulation process 2 (ii) in terms of/g. Filling the particles into a steel mold, and performing compression molding under molding pressures of 20MPa, 30MPa and 40MPa to obtain evaporation target blanks (labeled as C01, C02 and C03). Placing the evaporation target biscuit subjected to compression molding into a sintering furnace for sintering, wherein the sintering atmosphere consists of mixed gas of nitrogen and hydrogen, the volume of the hydrogen accounts for 5%, and the sintering process comprises the following steps:
first temperature interval: the room temperature is 750 ℃ below zero, the heating rate is 1 ℃/min, and the air flow is controlled at 10L/min;
the second temperature interval: 750-1450 ℃, the heating rate is 2 ℃/min, and the flow rate of the mixed gas is controlled at 15L/min;
the third temperature interval: 1450-1400 ℃, the cooling rate is 2 ℃/min, and the flow rate of the mixed gas is controlled at 15L/min;
a fourth temperature interval: keeping the temperature at 1400 ℃ for 6h, and controlling the flow rate of the mixed gas at 15L/min;
a fifth temperature interval: the temperature is reduced at a rate of 3 ℃/min at 1400-800 ℃, and the flow rate of the mixed gas is controlled at 15L/min;
sixth temperature interval: the temperature reduction rate is 1 ℃/min at the temperature of 800-100 ℃, and the air flow is controlled at 10L/min.
End of the procedureNaturally cooling to room temperature to obtain evaporation target materials (marked as C1, C2 and C3). Placing the above evaporation target material with diameter of 32mm and height of 40mm into crucible of activated plasma deposition (RPD) equipment, wherein the substrate is Corning glass with thickness of 0.7mm, and argon and oxygen are used as working gas (Ar: O) under vacuum condition 2 = 30, flow ratio), the working pressure of the evaporation chamber is controlled to 0.353Pa (deposition pressure), the electron gun power supply is started to evaporate and plate the film, the electron mobility and the near infrared transmittance of the film are respectively tested, and the test results are shown in table 1.
Examples 10 to 12
Mixing 9.85Kg of indium oxide powder, 0.05Kg of tungsten oxide powder, 0.05Kg of cerium oxide powder, 0.025Kg of holmium oxide powder, 0.025Kg of gallium oxide powder, a dispersing agent (ammonium polyacrylate) and deionized water, performing primary ball milling and mixing, controlling the solid phase amount of the slurry to be 50wt%, controlling the addition amount of the dispersing agent to be 0.6% of the mass of the total oxides, and finishing ball milling when the D50 of the mixed slurry is less than 0.5 mu m (namely the proportion of particles with the particle diameter of less than 0.5 mu m in the slurry reaches 50%); and (3) placing the primary ball-milling slurry in a 90 ℃ oven for drying and crushing, sieving the dried and crushed material with a 80-mesh sieve, placing the sieved material in a sintering furnace for primary calcination at 1400 ℃ for 6h, and introducing oxygen. Mixing calcined powder, a binder (polyvinyl alcohol), a dispersant (ammonium polyacrylate) and deionized water, performing secondary ball milling and mixing, controlling the solid phase amount of slurry to be 50wt%, controlling the addition amount of the dispersant to be 0.8% of the mass of the total oxides, and controlling the addition amount of the binder to be 2.5% of the mass of the total oxides, optimizing the addition modes of the dispersant and the binder, firstly, uniformly adding the dispersant at intervals of 15min for three times in the feeding and stirring process to keep the slurry at a proper viscosity, then transferring the slurry into a sand mill for high-efficiency grinding for 4h, when the D50 of the mixed slurry is less than 0.8 mu m (namely the proportion of particles with the particle diameter less than 0.8 mu m in the slurry reaches 50%), then, uniformly adding the binder at intervals of 5min for five times, and continuing sand milling for 30min (the starting time of sand milling is the first time for adding the binder and starting sand milling), so that the uniformly dispersed nano-scale particles in the slurry are orderly combined, thereby improving the viscosity of the slurry. The grinding slurry is prepared into solid spherical particles with high compactness degree by a conventional granulation mode, and the solid spherical particles are sieved by a 80-mesh sieveThe specific surface area of the mixture is controlled to be 5.0-6.0m in the granulation process for standby 2 (ii) in terms of/g. The particles were filled in a steel mold and compression-molded at molding pressures of 20MPa, 30MPa, and 40MPa to obtain evaporation target blanks (labeled D01, D02, and D03), respectively. Placing the evaporation target biscuit subjected to compression molding into a sintering furnace for sintering, wherein the sintering atmosphere consists of mixed gas of nitrogen and hydrogen, the volume of the hydrogen accounts for 5%, and the sintering process comprises the following steps:
the first temperature interval: the room temperature is 750 ℃ below zero, the heating rate is 1 ℃/min, and the air flow is controlled at 10L/min;
the second temperature interval: 750-1450 ℃, the heating rate is 2 ℃/min, and the flow rate of the mixed gas is controlled at 15L/min;
the third temperature interval: 1450-1400 ℃, the cooling rate is 2 ℃/min, and the flow rate of the mixed gas is controlled at 15L/min;
a fourth temperature interval: keeping the temperature at 1400 ℃ for 6h, and controlling the flow rate of the mixed gas at 15L/min;
a fifth temperature interval: the temperature is reduced at a rate of 3 ℃/min at 1400-800 ℃, and the flow rate of the mixed gas is controlled at 15L/min;
sixth temperature interval: the temperature reduction rate is 1 ℃/min at the temperature of 800-100 ℃, and the air flow is controlled at 10L/min.
After the procedure is finished, the material is naturally cooled to room temperature, and evaporation target materials (marked as D1, D2 and D3) can be prepared. Placing the above evaporation target material with diameter of 32mm and height of 40mm into crucible of activated plasma deposition (RPD) equipment, wherein the substrate is Corning glass with thickness of 0.7mm, and argon and oxygen are used as working gas (Ar: O) under vacuum condition 2 =100, the flow ratio), controlling the working pressure of the evaporation chamber to 0.353Pa (deposition pressure), starting the electron gun power supply to evaporate and plate the film, and testing the electron mobility and the near-infrared transmittance of the film respectively, the test results are shown in table 1.
In the embodiment, the mass percent of indium oxide in the evaporation target material is 98.5-99%, and the prepared film has high electron mobility and near-infrared transmittance, thereby being beneficial to improving the photoelectric conversion efficiency of the solar cell.
The invention adopts a Cary5000UV-VIS-NIR spectrophotometer to test the optical characteristics of the sample film in the near infrared region (the wavelength is in the range of 700-1100 nm); the films were tested for electron mobility using a Keithley-4200SCS semiconductor characterization test system.
Comparative example 1
An ITO target having a commercially available composition ratio of 90/10 and a diameter of 6 inches was used. Coating in a DC magnetron sputtering system with a substrate of Corning glass with a thickness of 0.7mm, a sputtering gas of argon, a working gas of oxygen (without introducing water vapor or hydrogen), and an electron mobility of the prepared film of 18.24cm 2 V.s, near infrared transmittance of 80.3%.
Comparative example 2
An ITO target material having an external composition ratio of 97/3 and a diameter of 6 inches was obtained. Coating in a DC magnetron sputtering system with a substrate of Corning glass with a thickness of 0.7mm, a sputtering gas of argon, a working gas of oxygen (without introducing water vapor or hydrogen), and an electron mobility of the prepared film of 26.32cm 2 V.s, the near infrared transmittance was 86.5%.
The results of the performance tests of the examples and comparative examples are shown in table 1 below:
as can be seen from the above table, the photoelectric properties of the thin films in each example are significantly improved compared to those in comparative examples 1 and 2. As can be seen from comparison of various examples, the photoelectric property of the film is closely related to the target material component; the forming pressure can seriously affect the relative density of the sintered evaporation target material, and further can have adverse effect on the evaporation process. On the other hand, when the relative density of the evaporation target is low, the strength of the target itself is also poor. When the electron beam bombards the target material, the target material is easily cracked and cracked by the tiny local thermal expansion, and then the phenomenon of powder falling is generated (A11, B11, C11 and D11 belong to the category). On the other hand, if the relative density is too high, the target cannot absorb the stress and strain applied by the electron beam bombardment, and further cracks and sputtering phenomena (a 13, B13, C13, and D13 belong to the category). Both of these can interrupt the coating process, thereby reducing production efficiency. In order to meet the actual requirements of the evaporation coating process, the relative density of the target material is controlled to be about 60 percent.
Although the present invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the present invention.
Claims (8)
1. An evaporation target for a solar cell is characterized in that: the evaporation target comprises the following components in percentage by mass: indium oxide (In) 2 O 3 ) 98.5-99.5 percent of doped oxide, 0.5-1.5 percent of doped oxide, wherein the doped oxide is 2-4 of cerium oxide, tungsten oxide, molybdenum oxide, holmium oxide, yttrium oxide, zirconium oxide and gallium oxide.
2. The method for preparing an evaporation target material for a solar cell according to claim 1, wherein the method comprises the following steps: the method comprises the following specific steps:
step one, mixing a main oxide, a doped oxide, a dispersing agent and deionized water according to a certain proportion, carrying out primary ball milling and mixing, and finishing ball milling when the D50 of primary ball milling mixed slurry is less than 0.5 mu m; drying and crushing the primary ball-milling mixed slurry, then sieving the dried and crushed primary ball-milling mixed slurry by a 60-80-mesh sieve, and placing the crushed primary ball-milling mixed slurry into a sintering furnace for primary calcination treatment while introducing oxygen; then collecting calcined powder for later use;
step two, mixing the calcined powder, the binder, the dispersant and deionized water according to a certain proportion, carrying out secondary ball milling mixing, firstly adding the dispersant in batches for grinding for more than 4 hours, then adding the binder in batches, and continuously sanding for more than 30min to obtain slurry;
step three, preparing solid spherical particles from the slurry obtained in the step two in a granulation mode, and then sieving the solid spherical particles to obtain particles for later use;
filling the particles obtained in the step three into a mold, and performing compression molding under the molding pressure of 20 to 40MPa to obtain an evaporation target biscuit;
and step five, placing the evaporation target biscuit obtained in the step four into a sintering furnace for sintering, and naturally cooling to room temperature after the sintering process is finished to obtain the evaporation target.
3. The method for preparing an evaporation target material for a solar cell according to claim 2, wherein the method comprises the following steps: in the third step, the slurry obtained in the second step is granulated to obtain solid spherical particles, and the solid spherical particles are sieved by a 80-mesh sieve for standby, wherein the specific surface area of the particles is controlled to be 5.0-6.0m in the granulation process 2 /g。
4. The method for preparing an evaporation target material for a solar cell according to claim 2, wherein the method comprises the following steps: in the fifth step, the concrete sintering steps are as follows:
the first temperature interval: the room temperature is 750 ℃ below zero, the heating rate is 1 ℃/min, and the air flow is controlled to be 10-15L/min;
the second temperature interval: 750-1450 ℃, the heating rate is 2 ℃/min, and the flow rate of the mixed gas is controlled to be 10-15L/min;
the third temperature interval: 1450-1400 ℃, the cooling rate is 2 ℃/min, and the flow rate of the mixed gas is controlled to be 10-15L/min;
a fourth temperature interval: keeping the temperature at 1400 ℃ for 6h, and controlling the flow rate of the mixed gas at 10-15L/min;
a fifth temperature interval: 1400-800 deg.C, cooling rate of 3 deg.C/min, and flow rate of the mixture controlled at 10-15L/min;
sixth temperature interval: the temperature is reduced at the speed of 1 ℃/min at the temperature of 800-100 ℃, the air flow is controlled at 10-15L/min, and the evaporation target material can be prepared by naturally cooling to room temperature after the procedure is finished.
5. The method for preparing the evaporation target material for the solar cell according to claim 2, wherein the method comprises the following steps: the mixed gas consists of nitrogen and hydrogen, wherein the volume of the hydrogen accounts for 3-5%.
6. The evaporation target according to claim 2, wherein in the preparation method, the dispersant is ammonium polyacrylate in one ball milling process, and the ratio of the mass of the dispersant to the total mass of the oxides is 0.3-0.9%.
7. The evaporation target according to claim 2, wherein in the preparation method, the addition amount of the dispersant in the secondary ball milling process of the calcined powder is ammonium polyacrylate, and the ratio of the mass of the dispersant to the total mass of the oxides is 0.3-0.9%; the binder is polyvinyl alcohol, and the ratio of the mass of the binder to the total mass of the oxides is 1~3%.
8. The evaporation target according to claim 2, wherein in the second step, the dispersant is added in batches for grinding for 4 hours or more, and when the D50 of the mixed slurry is less than 0.8 μm, the binder is added in batches.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211580121.9A CN115893988B (en) | 2022-12-07 | 2022-12-07 | Evaporation target material for solar cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211580121.9A CN115893988B (en) | 2022-12-07 | 2022-12-07 | Evaporation target material for solar cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115893988A true CN115893988A (en) | 2023-04-04 |
| CN115893988B CN115893988B (en) | 2023-09-08 |
Family
ID=86476517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211580121.9A Active CN115893988B (en) | 2022-12-07 | 2022-12-07 | Evaporation target material for solar cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115893988B (en) |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0344465A (en) * | 1989-07-13 | 1991-02-26 | Nippon Mining Co Ltd | Production of sputtering target for electrically conductive transparent ito film |
| JPH04160047A (en) * | 1990-10-19 | 1992-06-03 | Sumitomo Metal Mining Co Ltd | Ito sintered body and its production |
| CN101397647A (en) * | 2008-11-03 | 2009-04-01 | 清华大学 | Cu-In-Ga-Se or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof |
| US20110315936A1 (en) * | 2007-03-20 | 2011-12-29 | Idemitsu Kosan Co., Ltd. | Sputtering target, oxide semiconductor film and semiconductor device |
| CN102731068A (en) * | 2012-07-04 | 2012-10-17 | 韶关西格玛技术有限公司 | Method for preparing low-density ITO evaporation target material |
| CN103866253A (en) * | 2014-01-10 | 2014-06-18 | 中国科学院宁波材料技术与工程研究所 | High-carrier concentration ultrathin AZO transparent conducting thin film and preparation method thereof |
| US20160118254A1 (en) * | 2014-10-28 | 2016-04-28 | Semiconductor Energy Laboratory Co., Ltd. | Oxide and method for forming the same |
| CN106977179A (en) * | 2017-04-07 | 2017-07-25 | 中国船舶重工集团公司第七二五研究所 | A kind of method that two steps multi-steps sintering method prepares high fine and close ITO target |
| CN112645707A (en) * | 2020-12-15 | 2021-04-13 | 株洲火炬安泰新材料有限公司 | Preparation process of high-density ITO target |
| CN114171640A (en) * | 2021-11-25 | 2022-03-11 | 泰州锦能新能源有限公司 | Preparation method of copper indium gallium selenide solar cell |
| CN114524664A (en) * | 2022-02-25 | 2022-05-24 | 洛阳晶联光电材料有限责任公司 | Ceramic target material for solar cell and preparation method thereof |
| CN114620996A (en) * | 2022-02-23 | 2022-06-14 | 洛阳晶联光电材料有限责任公司 | High-efficiency rotary ceramic target for solar cell |
| CN115974530A (en) * | 2022-11-21 | 2023-04-18 | 先导薄膜材料（广东）有限公司 | Preparation method of low-resistivity high-mobility oxide target material |
-
2022
- 2022-12-07 CN CN202211580121.9A patent/CN115893988B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0344465A (en) * | 1989-07-13 | 1991-02-26 | Nippon Mining Co Ltd | Production of sputtering target for electrically conductive transparent ito film |
| JPH04160047A (en) * | 1990-10-19 | 1992-06-03 | Sumitomo Metal Mining Co Ltd | Ito sintered body and its production |
| US20110315936A1 (en) * | 2007-03-20 | 2011-12-29 | Idemitsu Kosan Co., Ltd. | Sputtering target, oxide semiconductor film and semiconductor device |
| CN101397647A (en) * | 2008-11-03 | 2009-04-01 | 清华大学 | Cu-In-Ga-Se or Cu-In-Al-Se solar cell absorption layer target material and preparation method thereof |
| CN102731068A (en) * | 2012-07-04 | 2012-10-17 | 韶关西格玛技术有限公司 | Method for preparing low-density ITO evaporation target material |
| CN103866253A (en) * | 2014-01-10 | 2014-06-18 | 中国科学院宁波材料技术与工程研究所 | High-carrier concentration ultrathin AZO transparent conducting thin film and preparation method thereof |
| US20160118254A1 (en) * | 2014-10-28 | 2016-04-28 | Semiconductor Energy Laboratory Co., Ltd. | Oxide and method for forming the same |
| CN106977179A (en) * | 2017-04-07 | 2017-07-25 | 中国船舶重工集团公司第七二五研究所 | A kind of method that two steps multi-steps sintering method prepares high fine and close ITO target |
| CN112645707A (en) * | 2020-12-15 | 2021-04-13 | 株洲火炬安泰新材料有限公司 | Preparation process of high-density ITO target |
| CN114171640A (en) * | 2021-11-25 | 2022-03-11 | 泰州锦能新能源有限公司 | Preparation method of copper indium gallium selenide solar cell |
| CN114620996A (en) * | 2022-02-23 | 2022-06-14 | 洛阳晶联光电材料有限责任公司 | High-efficiency rotary ceramic target for solar cell |
| CN114524664A (en) * | 2022-02-25 | 2022-05-24 | 洛阳晶联光电材料有限责任公司 | Ceramic target material for solar cell and preparation method thereof |
| CN115974530A (en) * | 2022-11-21 | 2023-04-18 | 先导薄膜材料（广东）有限公司 | Preparation method of low-resistivity high-mobility oxide target material |
Non-Patent Citations (2)
| Title |
|---|
| DENG ZHIQI 等: "Photoelectric Properties of Indium Molybdenum Oxide Thin Films Using Electron Beam Evaporation", PROCEEDINGS OF THE 2019 IEEE EURASIA CONFERENCE ON IOT, COMMUNICATION AND ENGINEERING (ECICE), pages 205 - 207 * |
| 姚远 等: "成型工艺对ITO素胚及靶材的影响", 河南化工, vol. 38, no. 1, pages 25 - 27 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115893988B (en) | 2023-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101935208B (en) | Rare earth aluminate single-phase or complex-phase nanocrystalline transparent ceramic material and preparation method thereof | |
| US11486034B2 (en) | Method of preparing ITO ceramic target with controllable grain size | |
| CN101786885B (en) | Method for controlling grain size to produce ITO target | |
| CN108821777A (en) | Graphene/carbon SiClx composite ceramics and preparation method thereof | |
| CN101775578B (en) | ZnAl target preparation method and prepared ZnAl target | |
| CN105622104A (en) | Preparation method of high-purity AlON transparent ceramic powder | |
| CN114524664B (en) | Ceramic target for solar cell and preparation method thereof | |
| JP2013507526A (en) | Tin oxide ceramic sputtering target and method for producing the same | |
| CN113735565B (en) | Low-tin-content ITO sputtering target material, preparation method and thin-film solar cell | |
| CN102747334A (en) | Zinc-oxide-based transparent conductive film and preparation method thereof | |
| CN106966700A (en) | A kind of short route preparation technology of tin indium oxide sintered body | |
| CN108546109B (en) | Preparation method of large-size AZO magnetron sputtering target with controllable oxygen vacancy | |
| CN114620996A (en) | High-efficiency rotary ceramic target for solar cell | |
| CN105063559A (en) | Zr element-doped AZO target material with enhanced photoelectric property | |
| CN108002428B (en) | Preparation method of ITO (indium tin oxide) particles for evaporation and ITO particles prepared by method | |
| CN102653470B (en) | Cr2AlC ceramic target and preparation method thereof by vacuum hot pressing | |
| CN112813397A (en) | Preparation method of molybdenum-sodium alloy plate-shaped target material | |
| CN115893988B (en) | Evaporation target material for solar cell and preparation method thereof | |
| CN109609099B (en) | High-temperature phase-change heat storage material | |
| CN114436641B (en) | Magnetron sputtering ceramic target material and preparation method thereof | |
| CN109763108A (en) | A kind of ex situ preparation HoB2C2The method of ceramic coating | |
| CN115196964B (en) | Preparation method of sodium-containing molybdenum oxide ceramic sputtering target material | |
| CN1478757A (en) | Method of preparing high pruity block titanium aluminium carbon material using discharge plasma sintering | |
| CN117263671B (en) | IWSO target material, preparation method thereof and film prepared from IWSO target material | |
| CN117285345B (en) | Tin oxide ceramic electrode and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |