CN116375463A - Indium tin cerium oxide target material and preparation method and application thereof - Google Patents
Indium tin cerium oxide target material and preparation method and application thereof Download PDFInfo
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- CN116375463A CN116375463A CN202310412327.9A CN202310412327A CN116375463A CN 116375463 A CN116375463 A CN 116375463A CN 202310412327 A CN202310412327 A CN 202310412327A CN 116375463 A CN116375463 A CN 116375463A
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- 239000013077 target material Substances 0.000 title claims abstract description 58
- PPFXHCAULVWAEC-UHFFFAOYSA-N [Sn+4].[In+3].[O-2].[Ce+3].[O-2].[O-2].[O-2].[O-2] Chemical compound [Sn+4].[In+3].[O-2].[Ce+3].[O-2].[O-2].[O-2].[O-2] PPFXHCAULVWAEC-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 106
- 239000000843 powder Substances 0.000 claims abstract description 95
- 238000005245 sintering Methods 0.000 claims abstract description 80
- 230000008569 process Effects 0.000 claims abstract description 39
- 238000000498 ball milling Methods 0.000 claims abstract description 33
- 239000011812 mixed powder Substances 0.000 claims abstract description 21
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000008187 granular material Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 52
- 239000001301 oxygen Substances 0.000 claims description 52
- 229910052760 oxygen Inorganic materials 0.000 claims description 52
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 16
- 238000009694 cold isostatic pressing Methods 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- 229910003437 indium oxide Inorganic materials 0.000 claims description 12
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 18
- 239000010409 thin film Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 230000008676 import Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 20
- 239000000956 alloy Substances 0.000 description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 15
- 239000007921 spray Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 12
- 238000007580 dry-mixing Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 238000013001 point bending Methods 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- 238000004364 calculation method Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 239000002002 slurry Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000000280 densification Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000011946 reduction process Methods 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 238000000875 high-speed ball milling Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002391 anti-complement effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses an indium tin cerium oxide target material, a preparation method and application thereof, which comprises In 2 O 3 Powder, snO 2 Powder, ceO 2 Mixing the powder to obtain mixed powder, ball milling the mixed powder, granulating to obtain granules, performing near-net forming on the granules to obtain a green body, and sintering the green body in an oxidizing atmosphere to obtain the high-compactness low-resistivity indium tin cerium oxide target. The preparation method of the invention has the advantages of simple process flow, low cost, environmental protection, and capability of preparing the high-density indium tin cerium oxide target material with good conductivity, and the thin film prepared by the indium tin cerium oxide target material has the advantages of simple process flow, environment protection and high conductivityThe TCO film has higher carrier mobility, can solve the problem of free carrier absorption of the TCO film in a near infrared band, meets the performance requirement of the TCO film in the HIT battery industry on high-quality raw materials, greatly reduces the dependence of the raw materials in the solar industry on import, and improves the energy safety level of China.
Description
Technical Field
The invention relates to an indium tin cerium oxide target material, a preparation method and application thereof, and belongs to the technical field of ternary oxide target material preparation.
Background
HIT (Hetero junction with intrinsic thin film) cells, chinese-named crystalline silicon heterojunction solar cells, also known as heterojunction cells, were first developed successfully by the japanese Sanyang company in 1990. The HIT battery is a special PN junction, is formed by amorphous silicon and crystalline silicon materials, is formed by depositing an amorphous silicon film on crystalline silicon, and belongs to one of N-type batteries. In recent years, HIT cells are one of the solar cells having the highest photoelectric conversion efficiency, and have been widely paid attention to and studied by the industry and scientific community.
At present, the HIT battery technology has four working procedures, namely cleaning and texturing, amorphous silicon film deposition, TCO film preparation and screen printing. Wherein, the cleaning texturing and the screen printing are the processes of the traditional silicon crystal battery, and the HIT is unique in amorphous silicon film deposition and transparent conductive layer (TCO film) deposition. Therefore, TCO films are one of the most critical parts in HIT cell structures. The most commonly used transparent conductive film is an ITO thin film. However, ITO thin films greatly limit the spectral response of solar cells in the long wave region due to near infrared band free carrier absorption problems. Therefore, how to improve the carrier mobility of TCO films is one of the important research points in the preparation of high efficiency HIT cells. Mobility is well known as the average drift velocity of carriers (free electrons and vacancies) generated per unit field strength. Mobility represents the magnitude of the carrier conductivity, and its and carrier concentration determine the conductivity of a semiconductor. Mobility is inversely proportional to the effective mass of the carriers and the probability of scattering. The effective mass of the charge carriers is material dependent, with electrons in different materials having different effective masses. Therefore, developing TCO materials with good conductivity is a technical problem to be solved in the field of solar cells.
The target is a core material for producing TCO films, and currently, high-end TCO targets mainly depend on import. On one hand, the preparation process of the target material has a higher technical barrier; on the other hand, since the research and development of China in the TCO target field is late, the intellectual property of the traditional TCO material system is all in foreign countries. Therefore, developing a high-performance TCO target material with independent intellectual property rights is a 'neck-clamping' problem that the HIT battery industry in China needs to break through.
Disclosure of Invention
Aiming at the problem of 'neck' of TCO film raw material in the HIT battery industry, the first aim of the invention is to provide a preparation method of Indium Tin Cerium Oxide (ITCO) target material with good electric conduction performance. By In 2 O 3 、SnO 2 And CeO 2 The powder is used as a raw material, ce is introduced into indium tin oxide, and the electric performance of the target is improved; the yield of the target material is improved through a near net forming technology; and the density of the target material is improved by adopting an oxygen replacement treatment and high-temperature sintering technology. The technical process can prepare the high-performance ITCO target, has important industrial value for solving the problem of 'neck clamping' of TCO film raw materials in the HIT battery industry, and has great significance for energy safety in China.
A second object of the present invention is to provide an Indium Tin Cerium Oxide (ITCO) target material prepared by the above-mentioned preparation method.
The third object of the present invention is to provide an application of the Indium Tin Cerium Oxide (ITCO) target material prepared by the above preparation method.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a preparation method of Indium Tin Cerium Oxide (ITCO) target material, which comprises the following steps of 2 O 3 Powder, snO 2 Powder, ceO 2 Mixing the powder to obtain mixed powder, ball milling the mixed powder, granulating to obtain granules, performing near-net forming on the granules to obtain a green body, and sintering the green body in an oxidizing atmosphere to obtain the indium tin cerium oxide target.
The inventors have found that cerium (Ce) can enhance carrier mobility of oxide targets by employing In 2 O 3 、SnO 2 And CeO 2 The powder is used as a raw material, ce is introduced into indium tin oxide to improve the electrical property of the target, the yield of the target is improved through a near-net forming technology, and the high-purity target is obtained through sinteringAn indium tin cerium oxide target material with dense and excellent conductivity.
Preferably, the In 2 O 3 Powder, snO 2 Powder, ceO 2 The particle size ratio of the powder is (1.0-2.0): (2.0-5.0): 1, ceO 2 The particle size of the powder is 50nm-100nm.
The inventor finds that through the particle size ratio, on one hand, the optimal ball milling dispersibility can be obtained, so that the optimal sintering activity is obtained, and the final product reaches the optimal density, and on the other hand, after the high-dispersion mixed powder slurry is obtained, the distribution uniformity of each powder can be ensured, and the uneven segregation phenomenon is avoided.
Preferably, the In 2 O 3 、SnO 2 、CeO 2 The purity of the powder is above 99.99%.
In a preferred scheme, the atomic percentage of In to Sn to Ce is 90 (10-x) to x, and the value range of x is 0.1-9.9, preferably 1-9.
In the preferable scheme, the ball milling is wet ball milling, zirconia balls with the diameter of 1-3 mm are used as grinding balls, water is used as a ball milling medium, a dispersing agent is added, and the mass ratio of the mixed powder to the grinding balls is controlled to be 1:1 to 5; the mass ratio of the ball milling medium to the mixed powder is 1:0.5 to 4 percent of dispersing agent, and the addition amount of the dispersing agent is 0.1 to 1.0 weight percent of the mass of the mixed powder.
Further preferably, the dispersant is a polyacrylic dispersant.
Further preferably, the rotation speed of the ball milling is 200-1000 r/min, and the ball milling time is 10-180 min.
In can be obtained by the above ball milling 2 O 3 Powder, snO 2 Powder, ceO 2 The powder is fully and uniformly mixed.
Preferably, the granulating mode is spray drying.
Preferably, the particle size of the pellets is 30 to 150. Mu.m, preferably 40 to 100. Mu.m.
In the invention, the granules are controlled in the range, the density of the finally obtained indium tin cerium oxide target material is highest, the performance is optimal, and if the particle size of the granulated powder is too small, the loose packing density of the granulated powder is larger, the fluidity is poorer, the probability of the occurrence of the anisotropy in the molding is increased, and the purpose of near-net molding is difficult to achieve; the granulated powder has the advantages of overlarge particle size, smaller bulk density and better fluidity, but larger pores in a formed blank body can be caused, the compactness of the sintered body can be ensured only by larger shrinkage rate during sintering, the densification burden of the blank body during sintering is increased, and the requirement on the sintering activity of the powder is higher.
In a preferred scheme, the near net forming mode is cold isostatic pressing, and the cold isostatic pressing process is that the pressure is firstly increased to 280-400 MPa, preferably 300-350 MPa, the pressure is firstly maintained, then reduced to 200-300 MPa, preferably 250-300 MPa, the pressure is secondly maintained, the pressure is further reduced to 150-250 MPa, preferably 150-200 MPa, the pressure is third maintained, and finally reduced to 50-120 MPa, preferably 70-100 MPa, and the pressure is fourth maintained.
The inventor finds that the green body formed by granulating the powder generally generates elastic aftereffect due to the organic additive, so that the relative density of the green body is lower, and the probability of occurrence of holes in sintering is increased.
Further preferably, the time of the first pressure maintaining, the second pressure maintaining, the third pressure maintaining and the third pressure maintaining is 1-10 min.
In a preferred scheme, during the near-net forming, the granules are firstly filled into a cold pressing mould, and then are directly subjected to cold isostatic pressing after vibration and vacuumizing operation.
In the prior art, steel die hydroforming and cold isostatic pressing are needed, namely, steel die is adopted in advance to perform the preforming of the granulated powder, and then the preformed blank body is placed in a cold isostatic press to be pressurized again to obtain a green body with higher density. The defect that the uniformity of the density of the steel die molding blank is poor is the biggest defect of the technology, and the distribution mode of granulating powder and the flowability of the powder have great influence on the uniformity of the density of the steel die molding blank. Because the uniformity of the steel die molding blank is poor, the deformation degree of the later-stage sintered body is also large, and the yield of the target is low. Also, the steel die molding blank needs to be carried in the sheath for the second time and then is placed in a cold isostatic press for CIP molding, the blank is damaged due to careless operation, and the damage can generate cracking in the sintering process, so that the yield of the sintered body is affected.
The invention adopts wet ball milling and granulation, then directly carries out cold isostatic pressing molding on the obtained granules, and adopts a mode of firstly boosting and then reducing pressure, thereby obtaining a high-density green body by adopting cold isostatic pressing molding, and solving the problem that the prior art needs to carry out steel die hydraulic molding.
Preferably, the sintering is carried out in a sintering furnace, and before sintering, the sintering furnace is vacuumized until the vacuum degree is less than or equal to 10 -1 Pa, then pure oxygen is injected to the standard atmospheric pressure, and the sintering is carried out by repeatedly introducing oxidizing atmosphere for 3 to 5 times.
Further preferably, the oxidizing atmosphere is oxygen or air.
Preferably, the sintering process is as follows: the temperature is raised to 600-1150 ℃, preferably 650-1000 ℃, the 1 st step sintering is carried out, the time of the 1 st step sintering is controlled to be 4-12 h, preferably 5-6 h, the flow rate of the oxidizing atmosphere is controlled to be 5-20L/min when the 1 st step sintering is carried out, then the temperature is raised to 1200-1500 ℃, preferably 1300-1450 ℃, the 2 nd step sintering is carried out, the time of the 2 nd step sintering is controlled to be 1-10 h, preferably 2-4 h, the flow rate of the oxidizing atmosphere is controlled to be 20-30L/min when the 2 nd step sintering is carried out, then the temperature is raised to 1500-1700 ℃, preferably 1560-1620 ℃, the time of the 3 rd step sintering is controlled to be 0.5-10 h, preferably 1-6 h, the flow rate of the oxidizing atmosphere is controlled to be 30-50L/min when the 3 rd step sintering is carried out, then the temperature is reduced to 1350-1480 ℃, the time of the 4 th step sintering is controlled to be 1-8 h, preferably 2-6 h, the flow rate of the oxidizing atmosphere is controlled to be 20-30L/min when the 4 th step sintering is carried out, and finally the temperature is reduced to room temperature when the 3 step sintering is carried out.
The inventor discovers that by adopting the 4-step sintering process, the indium tin cerium oxide target material with good crystallization, high density and excellent performance can be obtained, and the main functions of the 1 st step are as follows: firstly, organic matters are discharged; secondly, the strength of the blank body is improved, but a closed hole is not formed, so that non-oxidative gas substances such as nitrogen, carbon dioxide and the like in the blank body can be conveniently subjected to substance exchange with oxygen; the main purpose of the step 2 sintering is to ensure that the blank body quickly eliminates pores through volume diffusion, surface diffusion and the like by prolonging the heat preservation time after forming a sintering neck so as to obtain higher density; step 3, the green body is rapidly placed at ultrahigh temperature to obtain the externally given sintering driving force, so that the density of the green body is further improved; after the step 3 sintering, the green body is close to complete densification, but the crystal grains do not complete the growth process, and the invention not only can complete the growth of the crystal grains by reducing the temperature and carrying out high-temperature sintering again, but also can avoid the negative effect of the reverse densification of the green body caused by the decomposition of 3 oxides at high temperature to generate gas.
The invention also provides the Indium Tin Cerium Oxide (ITCO) target material prepared by the preparation method; the main phase of the ITCO target material is indium oxide phase, the relative density is 98-99.5%, the flexural strength is 100-250 MPa, and the resistivity is 1.0 multiplied by 10 -4 ~1.0×10 -3 Omega cm is adjustable.
The invention also provides application of the Indium Tin Cerium Oxide (ITCO) target material prepared by the preparation method, and the ITCO target material is used as a preparation raw material of a transparent conductive layer (TCO film) in the HIT battery.
The beneficial effects of the invention are as follows:
in the preparation process of the invention, in is adopted firstly 2 O 3 、SnO 2 And CeO 2 Mixing the powder and performing wet ball milling, then obtaining an ITCO blank by using a near net forming technology on the obtained granulated powder, and finally, in the sintering process, improving the density of the target material by combining oxygen replacement with two-step normal-pressure atmosphere sintering, thereby finally obtaining the indium tin cerium oxide target material with high compactness and low resistivity.
The invention proposes to introduce cerium (Ce) into indium tin oxide to improve the carrier mobility of the oxide target. The near-net forming technology is adopted to prepare the Indium Tin Cerium Oxide (ITCO) target, so that the yield of the target is improved, and the production cost is reduced. In order to improve the compactness of the target, an oxygen replacement and step sintering method is adopted. The specific advantages are as follows:
(1) Electrical performance advantages: according to the Indium Tin Cerium Oxide (ITCO) target material prepared by the method, the lanthanide metal element cerium (Ce) is introduced to improve the carrier mobility of the oxide target material, and the conductivity of the ITCO target material is regulated by regulating and controlling the content of Ce, so that the requirements of different HIT batteries on the carrier mobility of the transparent conductive layer are met.
(2) Cost management and control advantages: according to the invention, the near-net forming technology is adopted to prepare the Indium Tin Cerium Oxide (ITCO) target, so that the yield of the target is improved, the production cost is reduced, the use amount of pollutants such as acid and alkali is reduced, and the purpose of environmental protection is achieved.
(3) The process has the following advantages: because the non-oxidizing gas has a great anti-densification effect on the green body in the atmosphere sintering process of the oxide target, particularly the multi-element oxide, the density of the target is often directly influenced. The invention is based on the previous research, and the special process of oxygen replacement is adopted to replace non-oxidizing gas by tin oxide gas, so as to eliminate the anticomplement effect of the non-oxidizing gas on the blank as much as possible.
(4) The density of the target sintered body is ensured by adopting a step-by-step sintering process: step 1, heating to 600-1150 ℃ (preferably 650-1000 ℃) for 4-12 hours (preferably 5-6 hours), wherein the oxygen or air flow is 5-20L/min; step 2, continuously heating to 1200-1500 ℃ (preferably 1300-1450 ℃) for 1-10 h (preferably 2-4 h), wherein the oxygen or air flow is 20-30L/min; step 3, raising the temperature to 1500-1700 ℃ again (preferably 1560-1620 ℃) for 0.5-10 hours (preferably 1-6 hours), wherein the oxygen or air flow is 30-50L/min; step 4, cooling and raising the temperature to 1350-1520 ℃ (preferably 1400-1480 ℃) for 1-8 hours (preferably 2-6 hours), wherein the oxygen or air flow rate is 20-30L/min; then cooling to room temperature; by adopting the 4-step sintering process, the indium tin cerium oxide target material with good crystallization, high density and excellent performance can be obtained, and the main effects of the 1 st step are as follows: firstly, organic matters are discharged; secondly, the strength of the blank body is improved, but a closed hole is not formed, so that non-oxidative gas substances such as nitrogen, carbon dioxide and the like in the blank body can be conveniently subjected to substance exchange with oxygen; the main purpose of the step 2 sintering is to ensure that the blank body quickly eliminates pores through volume diffusion, surface diffusion and the like by prolonging the heat preservation time after forming a sintering neck so as to obtain higher density; step 3, the green body is rapidly placed at ultrahigh temperature to obtain the externally given sintering driving force, so that the density of the green body is further improved; after the step 3 sintering, the green body is close to complete densification, but the crystal grains do not complete the growth process, and the invention not only can complete the growth of the crystal grains by reducing the temperature and carrying out high-temperature sintering again, but also can avoid the negative effect of the reverse densification of the green body caused by the decomposition of 3 oxides at high temperature to generate gas.
The preparation method provided by the invention has the advantages of simple process flow, low cost and environment friendliness, and can be used for preparing the high-density indium tin cerium oxide target material with good conductivity, and the film prepared by using the indium tin cerium oxide target material has higher carrier mobility, so that the problem of free carrier absorption of the TCO film in a near-infrared band is solved, the spectral response of the solar cell in a long-wave region is quickened, the performance requirement of the TCO film of the HIT cell industry on high-quality raw materials can be met, the dependence of the raw materials of the solar energy industry on import is greatly reduced, and the energy safety level of China is improved.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing an indium tin cerium oxide target.
FIG. 2 is a phase XRD pattern of an indium tin cerium oxide target prepared in the present invention, wherein S-1: example 1; s-2: example 2; s-3: example 3; s-4: example 4 corresponds to the phase XRD pattern of the resulting indium tin cerium oxide target.
Fig. 3 is a fracture SEM image of the indium tin cerium oxide target material prepared in example 1.
Fig. 4 is an EPMA element distribution diagram of the indium tin cerium oxide target material prepared In the present invention, wherein fig. 4 (a) is an element distribution of In the indium tin cerium oxide target material obtained In example 1, fig. 4 (c) is an element distribution of Sn In the indium tin cerium oxide target material obtained In example 1, and fig. 4 (e) is an element distribution of Ce In the indium tin cerium oxide target material obtained In example 1; wherein fig. 4 (b) shows the elemental distribution of In the indium tin cerium oxide target obtained In example 4, fig. 4 (d) shows the elemental distribution of Sn In the indium tin cerium oxide target obtained In example 4, and fig. 4 (f) shows the elemental distribution of Ce In the indium tin cerium oxide target obtained In example 4.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other.
In the specific implementation method, the In is prepared respectively by a chemical method 2 O 3 And SnO 2 Powder, in 2 O 3 The original grain diameter of the powder is controlled to be 50-200 nm; snO (SnO) 2 The original grain diameter of the powder is controlled between 100nm and 1000nm. CeO (CeO) 2 The powder is commercially available and has a primary particle size of 50nm to 100nm.
Example 1
Weigh 900 grams of In 2 O 3 Powder, 90 g SnO 2 Powder and 10g CeO 2 And transferring the powder into a mixer for dry mixing for 24 hours. Then placing the mixed powder into a high-energy ball mill, and adopting zirconia balls, wherein the mass ratio of the zirconia balls to the powder balls is 1:2; the grinding medium is deionized water, the dispersing agent is ammonium polyacrylate, and the mass ratio of the deionized water to the powder is 1:2, the content of the polyacrylic acid dispersing agent accounts for 0.5wt.% of the mass of the powder, the high-speed ball milling rotating speed is 300r/min, and the ball milling time is 60min. And (3) adding no binder after ball milling to obtain Indium Tin Cerium Oxide (ITCO) slurry.
Then, granulating by a spray method to obtain granulated powder with an average particle diameter of 40-60 mu m for standby. Loading the spray granulation powder into a cold pressing mold, vibrating and vacuumizing, and obtaining an ITCO blank by adopting a near net forming technology, wherein the ITCO blank is pressurized to 280MPa, the pressure is maintained for 5min, then the pressure is reduced, and the pressure reduction process of cold isostatic pressing is as follows: maintaining the pressure for 5min under 200MPa for the 1 st time; the pressure is maintained for 5min under 100MPa for the 2 nd time.
The obtained ITCO green body is firstly subjected to oxygen replacement treatment and then is sintered step by step in an oxygen or air atmosphere. Oxygen displacement treatment processThe method comprises the following steps: before the green body is sintered, the sintering furnace is vacuumized to 10 -1 Pa, then pure oxygen is injected to the standard atmospheric pressure, and the sintering is carried out in the oxygen or air high-temperature atmosphere after the process is repeatedly carried out for 3 to 5 times.
The step sintering process comprises the following steps: step 1, firstly, heating to 850 ℃ for 5 hours, wherein the oxygen or air flow is 5-20L/min; step 2, continuously heating to 1350 ℃ for 4 hours, wherein the oxygen or air flow is 20-30L/min; step 3, raising the temperature to 1580 ℃ again for 2 hours, wherein the oxygen or air flow is 30-50L/min; step 4, cooling and raising the temperature to 1480 ℃ for 4 hours, wherein the oxygen or air flow is 20-30L/min; and then cooling to room temperature.
According to the technical method, the obtained ITCO target is smooth and intact, and has black gray color. The phase structure was an indium oxide single-phase structure as detected by XRD, as shown in FIG. 2 (S-1). The density of the sintered target material measured by adopting an Archimedes drainage method is 7.14 g.cm -3 The relative density was calculated to be 99.7% (theoretical density was 7.16 g.cm) -3 Calculated), the fracture SEM image is shown in figure 3, holes are not seen, the target material density is better, and the cross-section SEM shows the grain size of 5-10 mu m. The distribution of elements in the ITCO target is shown in fig. 4 (a, c, e). The flexural strength of the alloy is 164MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 1.85 multiplied by 10 measured by a four-point probe method -4 Ω·cm。
Example 2
Weigh 900 grams of In 2 O 3 Powder, 70 g SnO 2 Powder and 30 g CeO 2 And transferring the powder into a mixer for dry mixing. The smooth and intact ITCO target material can be obtained according to the preparation flow and the technological parameters in the embodiment 1, and the color is black gray. The phase structure was an indium oxide single-phase structure as detected by XRD, as shown in FIG. 2 (S-2). The density of the sintered target material measured by adopting an Archimedes drainage method is 7.10 g.cm -3 The relative density was calculated to be 99.2% (theoretical density was 7.16 g.cm) -3 Calculation). The flexural strength of the alloy is 134MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 3.75X10 measured by a four-point probe method -4 Ω·cm。
Example 3
Weigh 900 grams of In 2 O 3 Powder, 30 g SnO 2 Powder and 70 g CeO 2 And transferring the powder into a mixer for dry mixing. The smooth and intact ITCO target material can be obtained according to the preparation flow and the technological parameters in the embodiment 1, and the color is black gray. The phase structure was an indium oxide single-phase structure as detected by XRD, as shown in FIG. 2 (S-3). The density of the sintered target material measured by adopting an Archimedes drainage method is 7.06 g.cm -3 The relative density was calculated to be 98.6% (theoretical density was 7.16 g.cm) -3 Calculation). The elemental distribution in the ITCO target is shown in fig. 4 (b, d, f). The flexural strength of the alloy is 110MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 6.38X10 measured by a four-point probe method -4 Ω·cm。
Example 4
Weigh 900 grams of In 2 O 3 Powder, 10g SnO 2 Powder and 90 g CeO 2 And transferring the powder into a mixer for dry mixing. The smooth and intact ITCO target material can be obtained according to the preparation flow and the technological parameters in the embodiment 1, and the color is black gray. The phase structure was an indium oxide single-phase structure as detected by XRD, as shown in FIG. 2 (S-4). The density of the sintered target material measured by adopting an Archimedes drainage method is 7.06 g.cm -3 The relative density was calculated to be 98.6% (theoretical density was 7.16 g.cm) -3 Calculation). The elemental distribution in the ITCO target is shown in fig. 4 (b, d, f). The flexural strength of the alloy is 110MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 6.38X10 measured by a four-point probe method -4 Ω·cm。
Comparative example 1
Weigh 900 grams of In 2 O 3 Powder, 90 g SnO 2 Powder and 10g CeO 2 And transferring the powder into a mixer for dry mixing for 24 hours. The mixed powder was then placed in a high energy ball mill, the ball milling process being the same as in example 1. And (3) adding no binder after ball milling to obtain Indium Tin Cerium Oxide (ITCO) slurry.
Then, granulating by a spray method to obtain granulated powder with an average particle diameter of 40-60 mu m for standby. And (3) loading the spray granulation powder into a cold pressing mold, and obtaining an ITCO blank by adopting a near net shaping technology after vibration and vacuumizing operation. The depressurization process for cold isostatic pressing is the same as in example 1.
And (3) directly sintering the obtained ITCO green body step by step under the atmosphere of oxygen or air without oxygen substitution treatment. The step sintering process was the same as in example 1.
According to the technical method, the obtained ITCO target is smooth and intact, and has black gray color. The phase structure was an indium oxide single phase structure as detected by XRD. The density of the sintered target material measured by adopting an Archimedes drainage method is 6.84 g.cm -3 The relative density was calculated to be 95.5% (theoretical density was 7.16 g.cm) -3 Calculation). The flexural strength of the alloy is 88MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 1.84 multiplied by 10 measured by a four-point probe method -3 Ω·cm。
Comparative example 2
Weigh 900 grams of In 2 O 3 Powder, 90 g SnO 2 Powder and 10g CeO 2 And transferring the powder into a mixer for dry mixing for 24 hours. The mixed powder was then placed in a high energy ball mill, the ball milling process being the same as in example 1. And (3) adding no binder after ball milling to obtain Indium Tin Cerium Oxide (ITCO) slurry.
Then, granulating by a spray method to obtain granulated powder with an average particle diameter of 40-60 mu m for standby. And (3) loading the spray granulation powder into a cold pressing mold, and obtaining an ITCO blank by adopting a near net shaping technology after vibration and vacuumizing operation. The depressurization process for cold isostatic pressing is the same as in example 1.
And carrying out oxygen substitution treatment on the obtained ITCO green body, and adopting one-step high-temperature sintering under an oxygen or air atmosphere. The specific sintering process is as follows: directly heating to 1580 ℃, wherein the heat preservation time is 5 hours, and the oxygen or air flow is 30-50L/min; and then cooling to room temperature.
According to the technical method, the obtained ITCO target is smooth and intact, and has black gray color. The phase structure was an indium oxide single phase structure as detected by XRD. The density of the sintered target material measured by adopting an Archimedes drainage method is 6.89 g.cm -3 The relative density was calculated to be 96.2% (theoretical density was 7.16 g.cm) -3 Calculation). The flexural strength of the alloy is 93MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 1.31 multiplied by 10 measured by a four-point probe method -3 Ω·cm。
Comparative example 3
Weigh 900 grams of In 2 O 3 Powder, 90 g SnO 2 Powder and 10g CeO 2 And transferring the powder into a mixer for dry mixing for 24 hours. The mixed powder was then placed in a high energy ball mill, the ball milling process being the same as in example 1. And (3) adding no binder after ball milling to obtain Indium Tin Cerium Oxide (ITCO) slurry.
Then, granulating by a spray method to obtain granulated powder with an average particle diameter of 40-60 mu m for standby. And (3) loading the spray granulation powder into a cold pressing mold, vibrating and vacuumizing, and obtaining an ITCO blank by adopting a near net forming technology, wherein the pressure is increased to 280MPa in one step, the pressure is maintained for 5min, and then the pressure is directly reduced to normal pressure, so that the step-by-step pressure reduction process in the embodiment 1 is not adopted.
The obtained ITCO green body is subjected to oxygen replacement treatment and then is subjected to step-by-step sintering under the atmosphere of oxygen or air. The oxygen displacement treatment and the step sintering process were the same as in example 1.
According to the technical method, the obtained ITCO target is smooth and intact, and has black gray color. The phase structure was an indium oxide single phase structure as detected by XRD. The density of the sintered target material measured by adopting an Archimedes drainage method is 6.98 g.cm -3 The relative density was calculated to be 97.5% (theoretical density was 7.16 g.cm) -3 Calculation). The flexural strength of the alloy is 105MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 1.04 multiplied by 10 measured by a four-point probe method -3 Ω·cm。
EXAMPLE 5 weighing 900 grams of In 2 O 3 Powder, 90 g SnO 2 Powder and 10g CeO 2 And transferring the powder into a mixer for dry mixing for 24 hours. Then placing the mixed powder into a high-energy ball mill, and adopting zirconia balls, wherein the mass ratio of the zirconia balls to the powder balls is 1:2; the grinding medium is deionized water, the dispersing agent is ammonium polyacrylate, and the mass ratio of the deionized water to the powder is 1:2, the content of the polyacrylic acid dispersing agent accounts for 0.5wt.% of the mass of the powder, the high-speed ball milling rotating speed is 300r/min, and the ball milling time is 60min. And (3) adding no binder after ball milling to obtain Indium Tin Cerium Oxide (ITCO) slurry.
Then, granulating by a spray method to obtain granulated powder with an average particle diameter of 40-60 mu m for standby. And (3) loading the spray granulation powder into a cold pressing mold, and obtaining an ITCO blank by adopting a near net shaping technology after vibration and vacuumizing operation. Firstly, the pressure is increased to 280MPa, the pressure is maintained for 5min, then the pressure is reduced, and the pressure reduction process of cold isostatic pressing is as follows: maintaining the pressure for 5min under 200MPa for the 1 st time; the pressure is maintained for 5min under 100MPa for the 2 nd time.
The obtained ITCO green body is firstly subjected to oxygen replacement treatment and then is sintered step by step in an oxygen or air atmosphere. The oxygen replacement treatment process comprises the following steps: before the green body is sintered, the sintering furnace is vacuumized to 10 -1 Pa, then pure oxygen is injected to the standard atmospheric pressure, and the sintering is carried out in the oxygen or air high-temperature atmosphere after the process is repeatedly carried out for 3 to 5 times.
The step sintering process comprises the following steps: step 1, firstly, heating to 650 ℃ for 5 hours, wherein the oxygen or air flow is 5-20L/min; step 2, continuously heating to 1200 ℃ for 4 hours, wherein the oxygen or air flow is 20-30L/min; step 3, raising the temperature to 1500 ℃ again for 2 hours, wherein the oxygen or air flow is 30-50L/min; step 4, cooling and raising the temperature to 1400 ℃, wherein the time is 4 hours, and the oxygen or air flow is 20-30L/min; and then cooling to room temperature.
According to the technical method, the obtained ITCO target is smooth and intact, and has black gray color. The phase structure was an indium oxide single phase structure as detected by XRD. The density of the sintered target material measured by adopting an Archimedes drainage method is 7.11 g.cm -3 The relative density was calculated to be 99.3% (theoretical density was 7.16 g.cm) -3 Calculation). The flexural strength of the alloy is 142MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 2.27 multiplied by 10 measured by a four-point probe method -4 Ω·cm。
Example 6
Weigh 900 grams of In 2 O 3 Powder, 90 g SnO 2 Powder and 10g CeO 2 And transferring the powder into a mixer for dry mixing for 24 hours. Then placing the mixed powder into a high-energy ball mill, and adopting zirconia balls, wherein the mass ratio of the zirconia balls to the powder balls is 1:2; the grinding medium is deionized water, the dispersing agent is ammonium polyacrylate, and the mass ratio of the deionized water to the powder is 1:2 polyacrylic dispersantsThe content is 0.5wt.% of the powder mass, the high-speed ball milling rotating speed is 300r/min, and the ball milling time is 60min. And (3) adding no binder after ball milling to obtain Indium Tin Cerium Oxide (ITCO) slurry.
Then, granulating by a spray method to obtain granulated powder with an average particle diameter of 40-60 mu m for standby. And (3) loading the spray granulation powder into a cold pressing mold, and obtaining an ITCO blank by adopting a near net shaping technology after vibration and vacuumizing operation. Firstly, the pressure is increased to 280MPa, the pressure is maintained for 5min, then the pressure is reduced, and the pressure reduction process of cold isostatic pressing is as follows: maintaining the pressure for 5min under 200MPa for the 1 st time; the pressure is maintained for 5min under 100MPa for the 2 nd time.
The obtained ITCO green body is firstly subjected to oxygen replacement treatment and then is sintered step by step in an oxygen or air atmosphere. The oxygen replacement treatment process comprises the following steps: before the green body is sintered, the sintering furnace is vacuumized to 10 -1 Pa, then pure oxygen is injected to the standard atmospheric pressure, and the sintering is carried out in the oxygen or air high-temperature atmosphere after the process is repeatedly carried out for 3 to 5 times.
The step sintering process comprises the following steps: step 1, firstly, heating to 1150 ℃ for 2 hours, wherein the oxygen or air flow is 5-20L/min; step 2, continuously heating to 1500 ℃ for 2 hours, wherein the oxygen or air flow is 20-30L/min; step 3, raising the temperature to 1700 ℃ again for 0.5h, wherein the oxygen or air flow is 30-50L/min; step 4, cooling and raising the temperature to 1520 ℃, wherein the time is 1h, and the oxygen or air flow is 20-30L/min; and then cooling to room temperature.
According to the technical method, the obtained ITCO target is smooth and intact, and has black gray color. The phase structure was an indium oxide single phase structure as detected by XRD. The density of the sintered target material measured by adopting an Archimedes drainage method is 7.10 g.cm -3 The relative density was calculated to be 99.2% (theoretical density was 7.16 g.cm) -3 Calculation). The flexural strength of the alloy is 138MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 5.24 multiplied by 10 measured by a four-point probe method -4 Ω·cm。
Example 7
Weigh 900 grams of In 2 O 3 Powder, 90 g SnO 2 Powder and 10g CeO 2 And transferring the powder into a mixer for dry mixing for 24 hours. However, the method is thatThen placing the mixed powder into a high-energy ball mill, wherein zirconia balls are adopted, and the mass ratio of the zirconia balls to the powder balls is 1:1, a step of; the grinding medium is deionized water, the dispersing agent is ammonium polyacrylate, and the mass ratio of the deionized water to the powder is 1:4, the content of the polyacrylic acid dispersing agent accounts for 0.5wt.% of the mass of the powder, the high-speed ball milling rotating speed is 600r/min, and the ball milling time is 120min. And (3) adding no binder after ball milling to obtain Indium Tin Cerium Oxide (ITCO) slurry.
Then, granulating by a spray method to obtain granulated powder with an average particle diameter of 40-60 mu m for standby. And (3) loading the spray granulation powder into a cold pressing mold, and obtaining an ITCO blank by adopting a near net shaping technology after vibration and vacuumizing operation. Firstly, the pressure is increased to 280MPa, the pressure is maintained for 5min, then the pressure is reduced, and the pressure reduction process of cold isostatic pressing is as follows: maintaining the pressure for 5min under 200MPa for the 1 st time; the pressure is maintained for 5min under 100MPa for the 2 nd time.
The obtained ITCO green body is firstly subjected to oxygen replacement treatment and then is sintered step by step in an oxygen or air atmosphere. The oxygen replacement treatment process comprises the following steps: before the green body is sintered, the sintering furnace is vacuumized to 10 -1 Pa, then pure oxygen is injected to the standard atmospheric pressure, and the sintering is carried out in the oxygen or air high-temperature atmosphere after the process is repeatedly carried out for 3 to 5 times.
The step sintering process comprises the following steps: step 1, firstly, heating to 650 ℃ for 5 hours, wherein the oxygen or air flow is 5-20L/min; step 2, continuously heating to 1200 ℃ for 4 hours, wherein the oxygen or air flow is 20-30L/min; step 3, raising the temperature to 1500 ℃ again for 2 hours, wherein the oxygen or air flow is 30-50L/min; step 4, cooling and raising the temperature to 1400 ℃, wherein the time is 4 hours, and the oxygen or air flow is 20-30L/min; and then cooling to room temperature.
According to the technical method, the obtained ITCO target is smooth and intact, and has black gray color. The phase structure was an indium oxide single phase structure as detected by XRD. The density of the sintered target material measured by adopting an Archimedes drainage method is 7.07 g.cm -3 The relative density was calculated to be 98.7% (theoretical density was 7.16 g.cm) -3 Calculation). The flexural strength of the alloy is 102MPa measured by a three-point bending resistance method, and the resistivity of the alloy is 4.37X10 g measured by a four-point probe method -4 Ω·cm。
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the indium tin cerium oxide target material is characterized by comprising the following steps of: in is to 2 O 3 Powder, snO 2 Powder, ceO 2 Mixing the powder to obtain mixed powder, ball milling the mixed powder, granulating to obtain granules, performing near-net forming on the granules to obtain a green body, and sintering the green body in an oxidizing atmosphere to obtain the indium tin cerium oxide target.
2. The method for preparing the indium tin cerium oxide target material according to claim 1, wherein the method comprises the following steps:
the In is 2 O 3 Powder, snO 2 Powder, ceO 2 The particle size ratio of the powder is (1.0-2.0): (2.0-5.0): 1, ceO 2 The particle size of the powder is 50nm-100nm;
the In is 2 O 3 、SnO 2 、CeO 2 The purity of the powder is above 99.99%;
in the mixed powder, the atomic percentage of In to Sn to Ce is 90 (10-x) to x, and the value range of x is 0.1-9.9.
3. The method for preparing the indium tin cerium oxide target material according to claim 1 or 2, wherein the method comprises the following steps: the ball milling is wet ball milling, zirconium oxide balls with the diameter of 1-3 mm are used as grinding balls, water is used as a ball milling medium, a dispersing agent is added, and the mass ratio of the mixed powder to the grinding balls is controlled to be 1:1 to 5; the mass ratio of the ball milling medium to the mixed powder is 1:0.5 to 4 percent of dispersing agent, wherein the adding amount of the dispersing agent is 0.1 to 1.0 weight percent of the mass of the mixed powder;
the dispersing agent is polyacrylic dispersing agent;
the rotation speed of the ball milling is 200-1000 r/min, and the ball milling time is 10-180 min.
4. The method for preparing the indium tin cerium oxide target material according to claim 1 or 2, wherein the method comprises the following steps: the granulating mode is spray drying, and the particle size of the granules is 30-150 mu m.
5. The method for preparing the indium tin cerium oxide target material according to claim 1 or 2, wherein the method comprises the following steps: the near net forming mode is cold isostatic pressing, wherein the cold isostatic pressing process is that the pressure is firstly increased to 280-400 MPa, the pressure is firstly maintained, then reduced to 200-300 MPa, the pressure is secondly maintained, then reduced to 150-250 MPa, the pressure is thirdly maintained, and finally reduced to 50-120 MPa, and the pressure is maintained for the fourth time;
the time of the first pressure maintaining, the second pressure maintaining, the third pressure maintaining and the third pressure maintaining is 1-10 min.
6. The method for preparing an indium tin cerium oxide target according to claim 5, wherein the method comprises the following steps: during the near-net forming, firstly, the granules are put into a cold pressing mold, and after vibration and vacuumizing operation, the granules are directly formed by cold isostatic pressing.
7. The method for preparing the indium tin cerium oxide target material according to claim 1, wherein the method comprises the following steps: the sintering is carried out in a sintering furnace, and before sintering, the sintering furnace is vacuumized until the vacuum degree is less than or equal to 10 -1 Pa, then pure oxygen is injected to the standard atmospheric pressure, and the sintering is carried out by repeatedly introducing oxidizing atmosphere for 3 to 5 times; the oxidizing atmosphere is oxygen or air.
8. The method for preparing an indium tin cerium oxide target according to claim 1 or 7, wherein the method comprises the following steps: the sintering process comprises the following steps: heating to 600-1150 ℃, performing step 1 sintering, controlling the time of step 1 sintering to be 4-12 h, introducing the flow of the oxidizing atmosphere during step 1 sintering to be 5-20L/min, then heating to 1200-1500 ℃, performing step 2 sintering, controlling the time of step 2 sintering to be 1-10 h, introducing the flow of the oxidizing atmosphere during step 2 sintering to be 20-30L/min, then heating to 1500-1700 ℃, performing step 3 sintering, controlling the time of step 3 sintering to be 0.5-10 h, introducing the flow of the oxidizing atmosphere during step 3 sintering to be 30-50L/min, then cooling to 1350-1520 ℃, performing step 4 sintering, controlling the time of step 4 sintering to be 1-8 h, introducing the flow of the oxidizing atmosphere during step 4 sintering to be 20-30L/min, and finally cooling to room temperature.
9. An indium tin cerium oxide target prepared by the method of any one of claims 1 to 8; the method is characterized in that: the main phase of the ITCO target material is indium oxide phase, the relative density is 98-99.5%, the flexural strength is 100-250 MPa, and the resistivity is 1.0 multiplied by 10 -4 ~1.0×10 -3 Ω·cm。
10. The use of the indium tin cerium oxide target material prepared by the preparation method according to any one of claims 1 to 8, characterized in that: and applying the ITCO target material as a preparation raw material of the transparent conductive layer in the HIT battery.
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