CN115094424A - Cu etching liquid crystallization suppression device - Google Patents

Cu etching liquid crystallization suppression device Download PDF

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Publication number
CN115094424A
CN115094424A CN202210711514.2A CN202210711514A CN115094424A CN 115094424 A CN115094424 A CN 115094424A CN 202210711514 A CN202210711514 A CN 202210711514A CN 115094424 A CN115094424 A CN 115094424A
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China
Prior art keywords
etching liquid
etching
liquid
ion
pipeline
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CN202210711514.2A
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Chinese (zh)
Inventor
刘丹
方亮
黄中浩
刘毅
吴芳
张淑芳
吴旭
陈国良
管飞
林鸿涛
刘高斌
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Chongqing University
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Chongqing University
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Priority to CN202210711514.2A priority Critical patent/CN115094424A/en
Publication of CN115094424A publication Critical patent/CN115094424A/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/46—Regeneration of etching compositions

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)

Abstract

The invention discloses a Cu etching liquid crystallization inhibiting device; the Cu etching liquid crystallization inhibiting device comprises an ion removal circulating pipeline, a cooling device, a centrifugal filter and an ion adsorption device, wherein the ion removal circulating pipeline is connected with an etching liquid tank and used for leading etching liquid out of the etching liquid tank for treatment and then sending the etching liquid back to the etching liquid tank, the cooling device is used for cooling the etching liquid, the centrifugal filter is used for centrifugally separating crystal substances in the etching liquid, the ion adsorption device is used for adsorbing metal ions in the etching liquid, and the cooling device, the centrifugal filter and the ion adsorption device are sequentially arranged on the ion removal circulating pipeline along the flow direction of the etching liquid. The method can effectively keep the concentration of metal ions in the Cu etching liquid at a low level, and efficiently remove crystals in the Cu etching liquid.

Description

Cu etching liquid crystallization suppression device
Technical Field
The invention relates to the technical field of microelectronic processing, in particular to a Cu etching liquid crystallization inhibiting device.
Background
The grid, source and drain of the Thin Film Transistor (TFT) for the liquid crystal display are made of Cu and Al thin films through wet etching. The Cu has lower resistance than Al, can avoid the risk of signal delay and has more advantages in the field of large-size liquid crystal displays. In TFT industry, Cu is wet etched and H is used 2 O 2 As an etching liquid. The wet etching equipment consists of a dry interval, an etching interval, a water washing interval and an air drying interval, wherein each interval is provided with a transmission shaft, the glass substrate is transmitted on the transmission shaft, and the wet etching can be completed after sequentially passing through the intervals.
As shown in fig. 1, in an etching chamber 1, an etching liquid tank 2 is communicated with a spray pipe 4 through a spray pump 3, the spray pipe 4 sprays etching liquid to a substrate 5, and the etching liquid reacts with metal and then flows back to the etching liquid tank 2. The etching liquid management system 6 monitors Cu ions and H in the etching liquid 2 O 2 And (4) concentration. The gas generated in the etching reaction is exhausted through an exhaust pipe 7, and an exhaust pump 8 provides power for the exhaust. In order to promote the Cu etching, a thermocouple 9 in the etching liquid tank 2 heats the Cu etching liquid. In order to ensure that the temperature of the etching solution is uniformly distributed, an etching solution circulating pipeline is arranged and comprises a circulating pump 10 and a circulating pipeline 11.
In wet etching, H 2 O 2 Acting as an oxidant to oxidize Cu; then, H 2 O 2 It is acidic and dissolves Cu oxide. Cu dissolved in the etching solution exists in the form of Cu ions, and the Cu ions promote H 2 O 2 Decomposition of H 2 O 2 The decomposition is exothermic. When in the etching liquidWhen the concentration of Cu ions (Cu ppm) reaches a certain threshold value, the etching solution is discharged, and then the etching solution is replaced by new etching solution. In order to save the production cost, the service life of the Cu etching solution needs to be prolonged, and the concentration threshold of Cu ions for replacing the etching solution is increased, so that the Cu ppm in the etching solution is higher. However, the Cu ppm in the etching liquid is increased, the etching liquid can gradually separate out crystals, the crystals can be attached to a pipeline filter to cause the flow to be reduced until the flow is alarmed, and the etching equipment is stopped to lose the capacity; meanwhile, part of crystals are mixed with the etching liquid in a particle form and sprayed to the substrate, and the crystal particles can scratch the photoresist and form metal broken lines after etching, so that the yield loss of products is caused; in addition, the etching solution can be sputtered to the outlet, the inlet and the inner wall of the etching chamber, and after the etching solution is volatilized, crystals are attached to the positions, and the crystals at the positions can scratch the film layer on the substrate, so that the yield loss of products can be caused. In addition, the Cu ion concentration in the etching solution increases, H 2 O 2 The decomposition rate increases and the exotherm increases, which can lead to explosion risks; cu ions in the etching solution also affect the etching rate and the robustness of the electrode dimensions.
In the prior art, there is a report that the etching solution is drawn out and then adsorbed to reduce metal ions in the etching solution. For example, patent document CN113046563A discloses an etching solution regeneration device, an etching system device, and an etching method, where the etching system device includes the etching solution regeneration device and the etching device which are connected in a circulating manner, the regeneration device includes a casing into which etching solution is injected, the casing is externally connected with a circulating pipeline, the circulating pipeline is divided into an independent recovery branch and a circulating branch, and the circulating branch is connected into the casing, and a recovery device is arranged on the recovery branch and used for recovering metal ions in the etching solution. And when the concentration of the metal ions in the etching liquid is higher, starting a recoverer on the recovery branch to recover the metal ions in the etching liquid.
However, the inventors of the present invention have found that the treatment effect is very poor only by ion adsorption of the Cu etching liquid. The reason is that the Cu etching solution contains crystals which hinder the etching solution and adsorbed substancesContact, resulting in a decrease in the metal ion adsorption efficiency. In addition, the main component in the Cu etching solution is H 2 O 2 ，H 2 O 2 The decomposition rate is increased under the heating condition, so that the risk of explosion is generated, the heating temperature of the Cu etching liquid needs to be strictly controlled, and heating adsorption and other means are avoided as much as possible. Therefore, how to effectively keep the concentration of metal ions in the Cu etching solution low and efficiently remove the crystals in the Cu etching solution is a big problem in the industry.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a crystallization inhibiting device for a Cu etching solution, which can effectively maintain a low level of metal ion concentration in the Cu etching solution and efficiently remove crystals in the Cu etching solution.
In order to achieve the purpose, the invention provides the following technical scheme:
the Cu etching liquid crystallization inhibiting device comprises an ion removing circulating pipeline, a cooling device, a centrifugal filter and an ion adsorption device, wherein the ion removing circulating pipeline is connected with an etching liquid tank and is used for leading etching liquid out of the etching liquid tank for treatment and then sending the etching liquid back to the etching liquid tank, the cooling device is used for cooling the etching liquid, the centrifugal filter is used for centrifugally separating crystals in the etching liquid, the ion adsorption device is used for adsorbing metal ions in the etching liquid, and the cooling device, the centrifugal filter and the ion adsorption device are sequentially arranged on the ion removing circulating pipeline along the flowing direction of the etching liquid.
As a preferred technical solution, the cooling device comprises a conical cylinder; a material baffle is arranged in the conical barrel to separate the conical barrel into a U-shaped flow channel, a liquid supply pipe is arranged at the upper part of one side of the U-shaped flow channel, a liquid outlet pipe is arranged at the lower part of the other side of the U-shaped flow channel, and the pipe diameter of the liquid outlet pipe is 0.5-0.8 times that of the liquid supply pipe; the bottom of the conical cylinder body is provided with a cold air nozzle, and the top of the conical cylinder body is provided with an exhaust pipeline and a spraying device.
As a preferred technical scheme, two liquid level sensors with different heights are installed in the conical cylinder.
As a preferred technical scheme, the inner wall of an inlet pipeline of the centrifugal filter is provided with shape memory alloy, and a hot air nozzle is arranged opposite to the shape memory alloy.
According to a preferable technical scheme, the Cu etching liquid crystallization inhibiting device further comprises a vortex tube, a cold air tube of the vortex tube is connected with the cold air nozzle, and a hot air tube of the vortex tube is connected with the hot air nozzle.
As a preferred technical scheme, a removal pipeline pump and a removal pipeline valve are arranged on the ion removal circulating pipeline.
The invention has the beneficial effects that:
the invention designs a set of Cu etching liquid circulating system to lead out Cu etching liquid for treatment, firstly, the etching liquid is cooled, Cu ions are promoted to rapidly separate out crystal substances at low temperature, the mixed solution of the crystal substances and the etching liquid is separated by a centrifugal filter, the separated etching liquid flows through an ion adsorption device, and as a large amount of Cu ions are removed in the form of crystal substances, the etching liquid can be fully contacted with adsorption substances after entering the ion adsorption device, and the Cu ions in the etching liquid are further adsorbed and removed.
Compared with the mode of only carrying out ion adsorption on the Cu etching liquid, the method greatly improves the removal efficiency of the Cu ions, can promote the precipitation and removal of crystal substances under the condition of low Cu ion concentration, and enables the etching liquid to be in a low-temperature state in the whole circulating treatment system, namely H 2 O 2 Is relatively stable and not easy to decompose, and avoids explosion risks.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a schematic structural diagram of a conventional wet etching apparatus;
FIG. 2 is a schematic structural diagram of a Cu etchant crystallization inhibiting device according to the present invention;
FIG. 3 is a schematic view of the cooling apparatus;
FIG. 4 is a schematic structural view of a centrifugal filter.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
As shown in figure 2, a Cu etching liquid crystallization inhibiting device comprises an ion removal circulating pipeline 12, a cooling device 13, a centrifugal filter 14 and an ion adsorption device 15, wherein the ion removal circulating pipeline 12 is connected with an etching liquid tank 2 and used for leading etching liquid out of the etching liquid tank 2 for treatment and then returning the etching liquid to the etching liquid tank 2, the cooling device 13 is used for cooling the etching liquid, the centrifugal filter 14 is used for centrifugally separating crystal substances in the etching liquid, the ion adsorption device 15 is used for adsorbing metal ions in the etching liquid, and the cooling device 13, the centrifugal filter 14 and the ion adsorption device 15 are sequentially arranged on the ion removal circulating pipeline 12 along the flow direction of the etching liquid. The ion removal circulation pipeline 12 is provided with a removal pipeline pump 16 and a removal pipeline valve 17. The cooling device 13 cools the etching liquid (the Cu etching liquid needs to be cooled to 1-20 ℃), Cu ions in the etching liquid do not reach the saturated concentration, but the low temperature promotes the Cu ions to rapidly separate out crystals, the mixture of the etching liquid and the crystals in the cooling device 13 is conveyed to the centrifugal filter 14, the mixture realizes the separation of the crystals and the etching liquid under the action of the centrifugal filter 14, the separated etching liquid can be conveyed to the ion adsorption device 15, and the Cu ions in the etching liquid are adsorbed and then flow back to the etching liquid tank 2.
As shown in fig. 3, the cooling device 13 comprises a conical cylinder; a material baffle 131 is arranged in the conical barrel to divide the conical barrel into U-shaped flow channels, a liquid supply pipe 132 is arranged at the upper part of one side of each U-shaped flow channel, a liquid outlet pipe 133 is arranged at the lower part of the other side of each U-shaped flow channel, and the pipe diameter of each liquid outlet pipe is 0.5-0.8 times that of each liquid supply pipe; the bottom of the conical cylinder is provided with a cold air nozzle 134, and the top is provided with an exhaust pipeline 135 and a spraying device 136. The cold air is continuously sprayed from the cold air nozzle 134, the etching liquid and the cold air exchange heat, the temperature is reduced, and the crystal is separated out. The gas that participates in cooling is discharged from the exhaust duct 135 after heat exchange. The drain pipe diameter is 0.5 ~ 0.8 times of feed pipe diameter, and under the balanced condition of flow, the liquid velocity of flow in the drain pipe is higher than the feed pipe, and the drain pipe velocity of flow increases, promotes the centrifugal filtration efficiency to the crystallization thing, and in addition, such pipe diameter difference can also make and carry out cooling device and maintain the liquid level of take the altitude, and the liquid level can slow down the velocity of flow of etching liquid in cooling device, prolongs the cool time, is favorable to the etching liquid cooling. Two liquid level sensors 137 with different heights are arranged in the conical barrel; the lower liquid level sensor detects the liquid level, which indicates that the liquid level is lower at the moment, and the supply of the etching liquid is increased under the condition; when the upper liquid level sensor detects the liquid level, the liquid level is higher, and the supply of the etching liquid is reduced under the condition.
In addition, the cold air sprayed from the cold air nozzle 134 promotes the volatilization of water in the etching solution, thereby adjusting H 2 O 2 The effect of concentration. Etching liquid management system monitors H in etching liquid 2 O 2 In the case of H 2 O 2 The concentration is low, the gas flow of the cold air nozzle 134 can be increased, the water volatilization of the etching liquid in the cooling device is increased, and further the H is improved 2 O 2 And (4) concentration.
As shown in FIG. 4, the inner wall of the inlet pipe of the centrifugal filter 14 is provided with a shape memory alloy 18, the shape memory alloy 18 is covered with a rubber layer, and a hot air nozzle 19 is arranged opposite to the shape memory alloy 18. When the hot air nozzle 19 sprays hot gas to the shape memory alloy 18, the shape memory alloy 18 deforms, the pipe diameter is reduced (as shown in figure 4 b), and when the pipe diameter of the pipeline at the inlet of the centrifugal filter is reduced, the flow velocity of a mixture of etching liquid and crystal in the pipeline is increased, and the centrifugal filtering effect is improved.
The Cu etching liquid crystallization inhibiting device further comprises a vortex tube 20, a cold air tube of the vortex tube 20 is connected with the cold air nozzle 134, and a hot air tube of the vortex tube 20 is connected with the hot air nozzle 19. The cold air separated by the vortex tube 20 is passed into the cold air nozzle 134 as a cooling medium, and the hot air separated is passed into the hot air nozzle 19 as a heating medium. The cold air flow of the vortex tube 20 can be adjusted, so that the cooling degree of the cooling device can be adjusted. The cold gas pipe of the vortex tube 20 is combined with another compressed gas pipeline, and the flow of the other compressed gas and the cold air act together to adjust the cooling degree and the gas flow.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (6)

1. A Cu etching liquid crystallization suppression device is characterized in that: the Cu etching liquid crystallization inhibiting device comprises an ion removal circulating pipeline, a cooling device, a centrifugal filter and an ion adsorption device, wherein the ion removal circulating pipeline is connected with an etching liquid tank and used for leading etching liquid out of the etching liquid tank for treatment and then sending the etching liquid back to the etching liquid tank, the cooling device is used for cooling the etching liquid, the centrifugal filter is used for centrifugally separating crystal substances in the etching liquid, the ion adsorption device is used for adsorbing metal ions in the etching liquid, and the cooling device, the centrifugal filter and the ion adsorption device are sequentially arranged on the ion removal circulating pipeline along the flow direction of the etching liquid.
2. The crystallization inhibiting device for the Cu etching liquid according to claim 1, wherein: the cooling device comprises a conical cylinder; a material baffle is arranged in the conical barrel to divide the conical barrel into U-shaped flow channels, a liquid supply pipe is arranged at the upper part of one side of each U-shaped flow channel, a liquid outlet pipe is arranged at the lower part of the other side of each U-shaped flow channel, and the pipe diameter of each liquid outlet pipe is 0.5-0.8 times that of each liquid supply pipe; the bottom of the conical cylinder body is provided with a cold air nozzle, and the top of the conical cylinder body is provided with an exhaust pipeline and a spraying device.
3. The crystallization inhibiting device for the Cu etching liquid according to claim 2, wherein: two liquid level sensors with different heights are installed in the conical barrel.
4. The crystallization inhibiting device for the Cu etching liquid according to claim 2, wherein: the inner wall of the inlet pipeline of the centrifugal filter is provided with shape memory alloy, and a hot air nozzle is arranged right opposite to the shape memory alloy.
5. The crystallization inhibiting device for the Cu etching liquid according to claim 4, wherein: the Cu etching liquid crystallization inhibiting device further comprises a vortex tube, a cold air tube of the vortex tube is connected with the cold air nozzle, and a hot air tube of the vortex tube is connected with the hot air nozzle.
6. The crystallization inhibiting device for the Cu etching liquid according to claim 1, wherein: and the ion removal circulating pipeline is provided with a removal pipeline pump and a removal pipeline valve.
CN202210711514.2A 2022-06-22 2022-06-22 Cu etching liquid crystallization suppression device Pending CN115094424A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210711514.2A CN115094424A (en) 2022-06-22 2022-06-22 Cu etching liquid crystallization suppression device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210711514.2A CN115094424A (en) 2022-06-22 2022-06-22 Cu etching liquid crystallization suppression device

Publications (1)

Publication Number Publication Date
CN115094424A true CN115094424A (en) 2022-09-23

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110197802A (en) * 2019-05-16 2019-09-03 武汉华星光电半导体显示技术有限公司 Wet-method etching equipment
CN114249477A (en) * 2021-11-15 2022-03-29 中国科学院上海微系统与信息技术研究所 Regeneration method of nitride film etching liquid and etching method of nitride film
CN114432832A (en) * 2021-12-31 2022-05-06 西安交通大学 Air capture CO driven by waste heat of iron and steel plant2And CO2Using method of

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110197802A (en) * 2019-05-16 2019-09-03 武汉华星光电半导体显示技术有限公司 Wet-method etching equipment
CN114249477A (en) * 2021-11-15 2022-03-29 中国科学院上海微系统与信息技术研究所 Regeneration method of nitride film etching liquid and etching method of nitride film
CN114432832A (en) * 2021-12-31 2022-05-06 西安交通大学 Air capture CO driven by waste heat of iron and steel plant2And CO2Using method of

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