Indium cerium oxide target and method for manufacturing the same

Abstract

The application belongs to the field of target material preparation, and specifically discloses a preparation method of a multilayer laminated indium oxide cerium oxide target material, which comprises the following steps: (1) preparing mixed powder A from indium oxide powder and cerium oxide powder through pulping and first granulation; (2) preparing mixed powder B from the mixed powder A through pre-sintering and second granulation; (3) performing green body forming on the mixed powder B: first, forming a plurality of small-size target blanks, stacking the plurality of small-size target blanks to form a target blank whole, and laminating the target blank whole to obtain a formed target blank; and (4) sintering the formed target blank to obtain the indium oxide cerium oxide target material. Under the premise of not affecting the size of the target material and changing the composition thereof, the small-size target blanks are first pressed, and then laminated to make the target material have a multilayer structure, so that the longitudinal thermal conductivity of the target material is reduced, heat is preferentially conducted in the transverse direction, and the utilization rate of the target material during evaporation film coating is improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of target material preparation, and particularly relates to an indium cerium oxide target material and a preparation method thereof. BACKGROUND

[0002] Indium Tin Oxide (ITO) thin film has high carrier concentration, high visible light transmittance, ultraviolet absorption rate and other excellent semiconductor properties, and is widely used in screen displays, photovoltaic cells, functional glass and other fields, but its light transmittance in the near-infrared region is poor, resulting in large photoelectric conversion loss.

[0003] Existing research shows that the indium cerium oxide (ICO) target material prepared by using cerium oxide to replace tin oxide and indium oxide for doping can effectively improve the electron mobility and infrared band light transmittance. However, when using the traditional ICO target material for evaporation coating, the target material is prone to incomplete evaporation due to too fast longitudinal heat conduction, resulting in low utilization rate, and too much residual waste after evaporation, which pollutes the instrument and reduces the coating efficiency. SUMMARY

[0004] The present application aims to provide an indium cerium oxide target material and a preparation method thereof to solve at least one technical problem in the background art.

[0005] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows:

[0006] A preparation method of an indium cerium oxide target material, comprising the following steps:

[0007] (1) preparing a mixed powder A by slurry preparation and first granulation of indium oxide powder and cerium oxide powder;

[0008] (2) preparing a mixed powder B by pre-sintering and second granulation of the mixed powder A;

[0009] (3) performing green body forming on the mixed powder B: first forming a plurality of small-size target blanks, stacking the plurality of small-size target blanks to form a target blank whole, and performing laminating on the target blank whole to obtain a formed target blank;

[0010] (4) sintering the formed target blank to obtain an indium cerium oxide target material.

[0011] Further, the mass ratio of the indium oxide powder and the cerium oxide powder is 96-98:2-4.

[0012] Further, the purity of the indium oxide powder is greater than or equal to 4N, and the particle size is 120-270 nm.

[0013] Further, the purity of the cerium oxide powder is greater than or equal to 4N, and the particle size is 120-270 nm.

[0014] Further, the pulping in step (1) is:

[0015] (11) The cerium oxide powder, dispersant I and water are mixed for pre-dispersion, and after uniform dispersion, ball milling is performed to obtain slurry one;

[0016] (12) The indium oxide powder, dispersant II and water are added to the slurry one for secondary pre-dispersion to obtain slurry two.

[0017] Further preferably, the dispersant I is at least one of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate, sodium hexadecyl benzene sulfonate or polycarboxylic acid compound.

[0018] Further preferably, the dispersant II is at least one of polyvinylpyrrolidone, sodium dodecyl benzene sulfonate or sodium hexadecyl benzene sulfonate.

[0019] Further preferably, the mass of the dispersant I accounts for 2-5% of the total mass of the added cerium oxide powder, dispersant I and water.

[0020] Further preferably, the mass of the dispersant II accounts for 2-5% of the total mass of the added indium oxide powder, dispersant II and water.

[0021] Further, the mixed powder A after pre-sintering is mixed with a binder for secondary granulation.

[0022] Further preferably, the binder is one of polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose or polypropionic acid compound.

[0023] Further preferably, the added amount of the binder is 1-3% of the mass of the mixed powder A.

[0024] Further, in step (2), the mixed powder A passing through an 80-mesh screen is pre-sintered.

[0025] Further, the mixed powder A after pre-sintering passing through an 80-mesh screen is subjected to secondary granulation.

[0026] Further, in step (1), the particle size range of the mixed powder A is D50<0.5 μm and D90<0.8 μm.

[0027] Considering the high production efficiency, uniform particle size, good flowability and simple operation of the spray granulation, the present application further preferably the first granulation is spray granulation.

[0028] The pre-sintering can remove the organic matter in the spray granulation process, and can also make the powder shrink partially, so that the target material is not broken due to the large volume shrinkage of the powder during the subsequent sintering of the target material, thereby avoiding the cracking of the target material during the preparation process.

[0029] Further preferably, the pre-sintering is carried out in an oxygen atmosphere at normal pressure.

[0030] Considering that the dry granulation process is easy to scale up, simple to operate, low in cost, uniform in particle size, and high in bulk density, the second granulation is preferably dry granulation.

[0031] Further, the pressure of the dry granulation is 30-50 kg, and the pressing time is 3-5 s.

[0032] Further, in step (3):

[0033] The shape and size of the cross section of the small-size target blank are the same as those of the shaped target blank.

[0034] The thickness of each small-size target blank differs by no more than ±0.1 mm.

[0035] The height of the target blank as a whole is higher than that of the shaped target blank.

[0036] The forming pressure of the small-size target blank is 30-40 kg, and the pressing time is 3-5 s.

[0037] The pressure used in the lamination forming is 30-50 kg, and the pressing time of the lamination forming is 3-5 s.

[0038] Further, in step (4), the sintering temperature of the shaped target blank is 1200-1600℃, and the sintering time is 10-14 h.

[0039] The application also discloses an indium cerium oxide target material prepared by the preparation method.

[0040] Compared with the prior art, the application has the following beneficial effects:

[0041] Without affecting the size of the target material and changing its composition, the application first presses a small-size target blank, and then laminates to make the target material have a multi-layer structure, so that the longitudinal thermal conductivity of the target material is reduced, heat is preferentially conducted horizontally, thereby improving the utilization rate of the target material during evaporation film deposition, reducing the residue after evaporation, and maintaining the cleanliness of the evaporation equipment.

[0042] The present application adopts the lamination mode to make the density of the prepared target material more uniform, thereby improving the uniformity of the evaporation film. BRIEF DESCRIPTION OF DRAWINGS

[0043] The accompanying drawings are included to provide a further understanding of the present application, and are incorporated in and constitute a part of the specification, illustrate embodiments of the present application and explain the principles of the present application, and are not intended to limit the present application.

[0044] In the drawings:

[0045] Fig. 1 It is a schematic diagram of the overall structure of the shaped target blank of the present application.

[0046] Fig. 2 It is a schematic diagram of the structure of the small-size target blank of the present application.

[0047] Fig. 3 It is a schematic diagram of the lamination forming structure of the present application. DETAILED DESCRIPTION

[0048] In order to facilitate the understanding of the present application, the present application will be described in more detail below in combination with the preferred embodiments, but the protection scope of the present application is not limited to the following specific embodiments.

[0049] Unless otherwise defined, all the professional terms used in the following are the same as the meanings commonly understood by the skilled in the art. The professional terms used in the present application are only for the purpose of describing the specific embodiments and are not intended to limit the protection scope of the present application.

[0050] Unless otherwise specified, the various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by the existing method.

[0051] Example 1

[0052] (1) 19.4 kg of indium oxide powder with a purity of 4N and a particle size of 120-270 nm, and 0.6 kg of cerium oxide powder with a purity of 4N and a particle size of 120-270 nm were weighed.

[0053] The 0.6 kg of cerium oxide powder, sodium dodecylbenzenesulfonate and 6 kg of pure water were poured into a slurry barrel for a first pre-dispersion, the dispersion time was 1 h, the mass of the sodium dodecylbenzenesulfonate accounted for 3% of the total mass of the cerium oxide powder, the sodium dodecylbenzenesulfonate and the 6 kg of pure water, and after uniform dispersion, the solution was transferred to a ball mill tank, the ball mill rotation speed was 300 r / min, the ball milling time was 20 h, and slurry one was obtained.

[0054] 19.4 kg of indium oxide powder, polyvinyl pyrrolidone and 5 kg of pure water were added to the obtained slurry 1 for secondary pre-dispersion. The dispersion time was 1 hour, and the polyvinyl pyrrolidone accounted for 3% of the total mass of the indium oxide powder, polyvinyl pyrrolidone and 5 kg of pure water to obtain slurry 2.

[0055] The slurry 2 is injected into a spray drying tower in the form of a fluid for spray granulation, and then mixed and sieved to obtain an indium cerium oxide precursor, which is a mixed powder A. The indium cerium oxide precursor has a D50 of less than 0.5 μm and a D90 of less than 0.8 μm.

[0056] (2) Pre-sinter the indium cerium oxide precursor by placing it in a normal pressure sintering furnace in an oxygen atmosphere at 1300°C for 5 hours, and then taking it out after it naturally cools to room temperature.

[0057] The pre-sintered indium cerium oxide precursor was sieved through an 80-mesh sieve, and the sieve residue was taken as qualified powder. A polyvinyl alcohol binder was added at a concentration of 2% by weight of the total powder. The powder after the binder addition was dry granulated at a pressure of 40 kg and a pressing time of 3 seconds to obtain a mixed powder B.

[0058] (3) If Figs. 1-3 As shown, the obtained mixed powder B is molded to obtain a molded target blank 1. In the molding process, 8 small-sized target blanks 2 with a size of D26*5.5mm are first pressed in a mold 3, and then the 8 small-sized target blanks 2 are stacked and laminated to obtain a molded target blank 1 with a size of D26*40mm.

[0059] During the hydraulic forming, the forming pressure of the small-sized target blank 2 is 35 kg, and the pressing time of the hydraulic forming is 3 s; during the stacking forming, the forming pressure is 30 kg, and the pressing time of the stacking forming is 3 s.

[0060] (4) Place the prepared target blank on an alumina gasket and put it into a sintering furnace. Then, sinter it to 1200°C with oxygen and keep it warm for 14 hours. After it cools down to room temperature naturally, take it out to obtain the target material.

[0061] The target material produced in this embodiment was subjected to surface dust removal, and the density was measured by the Archimedean drainage method to be 4.596 g / cm 3 When using this target for coating, the target can be effectively evaporated to the target substrate due to the faster lateral heat conduction than the longitudinal heat conduction. By weighing the mass of the target before and after evaporation and calculating the ratio of the two, the target utilization rate can be obtained to be 63%.

[0062] Example 2

[0063] (1) Weigh 19.4 kg of indium oxide powder with a purity of 4N and a particle size of 120-270 nm and 0.6 kg of cerium oxide powder with a purity of 4N and a particle size of 120-270 nm.

[0064] 0.6 kg of cerium oxide powder, sodium dodecyl benzene sulfonate and 6 kg of pure water were poured into a slurry tank for primary dispersion, the dispersion time was 1 h, the mass of sodium dodecyl benzene sulfonate accounted for 3% of the total mass of cerium oxide powder, sodium dodecyl benzene sulfonate and 6 kg of pure water, after uniform dispersion, the solution was transferred to a ball mill tank, the ball mill rotation speed was 300 r / min, the ball mill time was 20 h, and slurry one was obtained.

[0065] 19.4 kg of indium oxide powder, polyvinylpyrrolidone and 5 kg of pure water were added to the obtained slurry one for secondary dispersion, the dispersion time was 1 h, and the polyvinylpyrrolidone accounted for 3% of the total mass of indium oxide powder, polyvinylpyrrolidone and 5 kg of pure water, to obtain slurry two.

[0066] The slurry two was sprayed into a spray drying tower in a fluid form for spray granulation, and then mixed and sieved to obtain an indium cerium oxide precursor, which was a mixed powder A, the indium cerium oxide precursor D50 < 0.5 μm, D90 < 0.8 μm.

[0067] (2) The indium cerium oxide precursor was pre-sintered by being placed in an atmospheric pressure sintering furnace in an oxygen atmosphere at 1300°C for 5 h, and then taken out after natural cooling to room temperature.

[0068] The pre-sintered indium cerium oxide precursor was sieved using an 80 mesh sieve, and the undersize was a qualified powder, and 2% of the total mass of the powder was added as a polyvinyl alcohol binder; the powder after adding the binder was dry granulated, and the dry granulation used a pressure of 40 kg and a pressing time of 3 s to obtain a mixed powder B.

[0069] (3) The obtained mixed powder B was formed to obtain a formed target blank. In the forming process, first, 5 small size target blanks with a size of D26*8.5 mm were pressed in a mold, and then the 5 small size target blanks were stacked and formed by stacking to obtain a formed target blank with a size of D26*40 mm.

[0070] The forming pressure of the small size target blank was 35 kg during hydraulic forming, and the pressing time of the hydraulic forming was 3 s; the pressure of the stacking forming was 30 kg, and the pressing time of the stacking forming was 3 s.

[0071] (4) The prepared formed target blank was placed on an aluminum oxide gasket and placed in a sintering furnace, and then sintered to 1200°C by oxygen, and kept for 14 h, and then taken out after natural cooling to room temperature, to obtain a target material.

[0072] The target material discharged from the furnace in this embodiment was surface dusted, and the density was 4.595 g / cm 3The target material is used for coating, and the target material can be effectively evaporated to the target substrate due to the faster transverse heat conduction compared with the longitudinal heat conduction. The utilization rate of the target material is 56% by weighing the target material before and after evaporation and calculating the ratio of the two.

[0073] Example 3

[0074] (1) 19.4 kg of indium oxide powder with a purity of 4N and a particle size of 120-270 nm and 0.6 kg of cerium oxide powder with a purity of 4N and a particle size of 120-270 nm were weighed.

[0075] The 0.6 kg of cerium oxide powder, sodium dodecyl benzene sulfonate and 6 kg of pure water were poured into a slurry barrel for primary dispersion, the dispersion time was 1 h, the mass of sodium dodecyl benzene sulfonate accounted for 3% of the total mass of the cerium oxide powder, sodium dodecyl benzene sulfonate and 6 kg of pure water, and after uniform dispersion, the solution was transferred to a ball mill tank, the ball mill rotation speed was 300 r / min, the ball mill time was 20 h, and slurry one was obtained.

[0076] 19.4 kg of indium oxide powder, polyvinylpyrrolidone and 5 kg of pure water were added to the obtained slurry one for secondary dispersion, the dispersion time was 1 h, and the polyvinylpyrrolidone accounted for 3% of the total mass of the indium oxide powder, polyvinylpyrrolidone and 5 kg of pure water, and slurry two was obtained.

[0077] The slurry two was sprayed into a spray drying tower in a fluid form for spray granulation, and then mixed and sieved to obtain an indium cerium oxide precursor, which was a mixed powder A, the indium cerium oxide precursor D50 was less than 0.5 μm, and D90 was less than 0.8 μm.

[0078] (2) The indium cerium oxide precursor was pre-sintered, and was placed in a normal pressure sintering furnace in an oxygen atmosphere at 1200°C for 5 h, and was taken out after natural cooling to room temperature.

[0079] The pre-sintered indium cerium oxide precursor was sieved using an 80 mesh sieve, and the undersize was a qualified powder, and 2% of the total mass of the powder was added as a polyvinyl alcohol binder; the powder after adding the binder was dry granulated, the dry granulation used a pressure of 40 kg, and the pressing time was 3 s, and a mixed powder B was obtained.

[0080] (3) The obtained mixed powder B was subjected to hydraulic forming to obtain a formed target blank. In the forming process, 10 small size target blanks with a size of D26*4.5 mm were first pressed, and then the 10 small size target blanks were stacked for final stacking and forming to obtain a formed target blank with a size of D26*40 mm.

[0081] The forming pressure of the small size target blank was 35 kg during hydraulic forming, the pressing time of the hydraulic forming was 3 s; the pressure of the stacking and forming was 30 kg, and the pressing time of the stacking and forming was 3 s.

[0082] (4) Put the prepared shaped target blank on an alumina gasket, put into a sintering furnace, then sinter to 1200℃ with oxygen, keep for 14h, take out after natural cooling to room temperature, and get the target material.

[0083] The target material taken out of the furnace in this example is surface-dusted, and the density is 4.595 g / cm 3 When using the target material for film plating, the target material can be effectively evaporated to the target substrate due to the faster transverse heat conduction compared with the longitudinal heat conduction, and the utilization rate of the target material is 68% by weighing the mass of the target material before and after evaporation and calculating the ratio of the two.

[0084] Comparative Example 1

[0085] This comparative example is basically the same as Example 1, and the difference is in step (3), which is that this comparative example does not have the process of making a small-size target blank, and directly forms a shaped target blank with a size of D26*40mm.

[0086] Specifically:

[0087] (3) The obtained mixed powder B is subjected to hydraulic forming to obtain a shaped target blank with a size of D26*40mm. The pressure is 30kg and the pressing time is 3s during hydraulic forming.

[0088] The target material taken out of the furnace in this example is surface-dusted, and the density is 4.295 g / cm 3 When using the target material for film plating, the utilization rate of the target material is 51% by weighing the mass of the target material before and after evaporation and calculating the ratio of the two.

[0089] Comparative Example 2

[0090] This comparative example is basically the same as Example 1, and the difference is in step (2), which is that this comparative example does not have a pre-sintering step.

[0091] (2) Add 2% of the total mass of the indium cerium oxide precursor of polyvinyl alcohol binder; the powder after adding the binder is subjected to dry granulation, and the pressure is 40kg and the pressing time is 3s during dry granulation, to obtain mixed powder B.

[0092] Cracking occurs during the sintering process in step (4) of this comparative example.

[0093] The above is only a preferred embodiment of the present application and is not used to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application shall be included in the scope of the present application.

Claims

1. A method for preparing an indium cerium oxide target, characterized in that: The following steps are involved: (1) Indium oxide powder and cerium oxide powder are slurried and granulated for the first time to prepare mixed powder A; (2) Mixed powder A is pre-sintered and granulated for the second time to prepare mixed powder B; (3) green compacting the mixed powder B: first, forming a plurality of small-sized target blanks, wherein the cross-sectional shape and size of the small-sized target blanks are identical to the cross-sectional shape and size of the formed target blanks, the plurality of small-sized target blanks are stacked to form a target blank as a whole, and the target blank as a whole is laminated to obtain a formed target blank; (4) Sintering the formed target blank to obtain the indium cerium oxide target material.

2. The preparation method according to claim 1, wherein The mass ratio of the indium oxide powder to the cerium oxide powder is 96-98:2-4; The indium oxide powder has a purity of ≥4N and a particle size of 120-270 nm; The purity of the cerium oxide powder is ≥4N and the particle size is 120-270 nm.

3. The preparation method according to claim 1 or 2, wherein The pulping in step (1) is as follows: (11) Pre-dispersing the cerium oxide powder, dispersant I, and water, and then ball milling the mixture to obtain slurry I after uniform dispersion. (12) Indium oxide powder, dispersant II, and water are added to slurry 1 for secondary pre-dispersion to obtain slurry 2.

4. The preparation method according to claim 3, wherein The dispersant I is at least one of polyvinyl pyrrolidone, sodium dodecylbenzenesulfonate, sodium hexadecylbenzenesulfonate or a polycarboxylic acid compound; The dispersant II is at least one of polyvinyl pyrrolidone, sodium dodecylbenzenesulfonate or sodium hexadecylbenzenesulfonate; The mass of the dispersant I accounts for 2-5% of the total mass of the added cerium oxide powder, dispersant I and water; The mass of the dispersant II accounts for 2-5% of the total mass of the added indium oxide powder, dispersant II and water.

5. The preparation method according to claim 1, wherein In step (2), the pre-sintered mixed powder A is mixed with a binder and then granulated for the second time; The binder is at least one of polyvinyl alcohol, polyethylene glycol, carboxymethyl cellulose or polypropionic acid compounds; The mass of the binder is 1-3% of the mass of the mixed powder A.

6. The preparation method according to claim 1, wherein In step (1): The particle size range of the mixed powder A is D50<0.5μm, D90<0.8μm; The first granulation is spray granulation.

7. The preparation method according to claim 1, wherein Step (2): The pre-sintering temperature is 1200-1400° C. and the pre-sintering time is 2-6 hours. The second granulation is dry granulation; The pressing time of the dry granulation is 3 to 5 seconds.

8. The preparation method according to claim 1, wherein In step (3): The thickness of each small-sized target blank should be within ±0.1mm; The forming and pressing time of the small-sized target blank is 3 to 5 seconds; The pressing time of stacking molding is 3~5s.

9. The preparation method according to claim 1, wherein In step (4), the sintering temperature of the molded target blank is 1200~1600℃; and the sintering time is 10~14h.

10. An indium cerium oxide target prepared by the preparation method according to any one of claims 1 to 9.

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