Filtering system of semiconductor developing solution

Abstract

The utility model discloses a filtering system of a semiconductor developing solution. The filtering system comprises a raw material mixing tank, the liquid inlet end of the filtering part is connected with the raw material mixing tank; an inlet of the semi-finished product transfer tank is connected with the liquid outlet end of the filter part, an outlet of the semi-finished product transfer tank is connected with the liquid inlet end of the filter part, and the semi-finished product transfer tank is further provided with a first detection outlet; an inlet of the finished product tank is connected with an outlet of the semi-finished product transfer tank; and an inlet of the replacement liquid tank is connected with the liquid outlet end of the filtering part and is connected with the semi-finished product transfer tank in parallel, and an outlet of the replacement liquid tank is connected with the liquid inlet end of the filtering part. Therefore, when the filtering system is subjected to a system cleaning procedure, the replacement liquid tank collects the solution flowing out of the filtering piece and enables the solution to circularly pass through the filtering piece, so that the filtering system can achieve adsorption saturation and filter wetting through less solution consumption, and the replacement liquid utilization rate of the filtering system can be improved.

Description

TECHNICAL FIELD

[0001] The utility model relates to a semiconductor technical field especially is related to a kind of semiconductor developing solution's filtration system. BACKGROUND

[0002] In the manufacturing process of semiconductor integrated circuit, photoetching process is to transfer the circuit pattern designed to wafer by exposure, development, etching, to ensure product yield, the developing solution needs to be filtered and purified. The developing solution is a solution with specific configuration. When the solution is filtered by the device, the solute concentration of the filtered solution and the solution before filtering should be kept the same.

[0003] In the prior art, the solute molecules in the developing solution have certain aggregation and adsorption, and the device for filtering impurities is usually made of porous material, which leads to the consumption of a large amount of solution to be filtered during the displacement flushing stage until the porous material absorbs the solute molecules to saturation. However, this will cause a large amount of displacement liquid to be wasted. SUMMARY

[0004] The utility model aims at at least one of the technical problems existing in the prior art. To this end, the utility model provides a semiconductor developing solution filtration system, which can improve the utilization rate of displacement liquid.

[0005] The semiconductor developing solution filtration system according to the utility model embodiment comprises a raw material mixing tank, a filter, a semi-finished product transfer tank, a finished product tank and a displacement liquid tank. The inlet end of the filter is connected with the raw material mixing tank. The inlet of the semi-finished product transfer tank is connected with the outlet end of the filter. The outlet of the semi-finished product transfer tank is connected with the inlet end of the filter. The semi-finished product transfer tank is also provided with a first detection outlet. The inlet of the finished product tank is connected with the outlet of the semi-finished product transfer tank. The inlet of the displacement liquid tank is connected with the outlet end of the filter and is connected in parallel with the semi-finished product transfer tank. The outlet of the displacement liquid tank is connected with the inlet end of the filter.

[0006] Therefore, by connecting a displacement liquid tank with the filter between the outlet end and the inlet end of the filter, the displacement liquid tank collects the solution flowing out of the filter and circulates the liquid through the filter when the filtration system performs the system cleaning process. This can make the filtration system reach adsorption saturation and filter wetting with less solution consumption, thereby improving the utilization rate of displacement liquid of the filtration system.

[0007] According to some embodiments of the utility model, a second detection outlet is arranged between the inlet of the displacement liquid tank and the outlet end of the filter.

[0008] According to some embodiments of the present application, the displacement liquid tank is further provided with a third detection outlet.

[0009] According to some embodiments of the present application, the filter element is integrated with a particulate filter membrane and a resin type purification column.

[0010] According to some embodiments of the present application, the filter element comprises a resin type purification column unit and a microporous filter unit, the resin type purification column unit and the microporous filter unit are arranged in series, the displacement liquid tank comprises a first displacement liquid tank and a second displacement liquid tank, the inlet of the first displacement liquid tank is connected with the liquid outlet end of the resin type purification column unit, the outlet of the first displacement liquid tank is connected with the liquid inlet end of the resin type purification column unit, the inlet of the second displacement liquid tank is connected with the liquid outlet end of the microporous filter unit, and the outlet of the second displacement liquid tank is connected with the liquid inlet end of the microporous filter unit.

[0011] According to some embodiments of the present application, the resin type purification column unit is multiple, the multiple resin type purification column units are arranged in series, and one first displacement liquid tank is connected with the multiple resin type purification column units.

[0012] According to some embodiments of the present application, the resin type purification column unit is multiple, the multiple resin type purification column units are arranged in series, the first displacement liquid tank is multiple, and the multiple first displacement liquid tanks are connected with the multiple resin type purification column units one by one.

[0013] According to some embodiments of the present application, the microporous filter unit is multiple, the multiple microporous filter units are arranged in series, and one second displacement liquid tank is connected with the multiple microporous filter units.

[0014] According to some embodiments of the present application, the microporous filter unit is multiple, the multiple microporous filter units are arranged in series, the second displacement liquid tank is multiple, and the multiple second displacement liquid tanks are connected with the multiple microporous filter units one by one.

[0015] According to some embodiments of the present application, the raw material mixing tank is provided with a fourth detection outlet.

[0016] Additional aspects and advantages of the present application will be in part apparent and in part pointed out hereinafter. BRIEF DESCRIPTION OF DRAWINGS

[0017] The above and / or additional aspects and advantages of the present application will become apparent and be readily appreciated from the following description, including the appended drawings.

[0018] Figure 1is a formula type developing solution production flowchart according to an embodiment of the present utility model;

[0019] Figure 2 is a whole route diagram of prior art filtering system;

[0020] Figure 3 is a schematic diagram of filtering system according to an embodiment of the present utility model;

[0021] Figure 4 is a partial schematic diagram of filtering system according to an embodiment of the present utility model;

[0022] Figure 5 is a partial schematic diagram of filtering system according to an embodiment of the present utility model;

[0023] Figure 6 is a partial schematic diagram of filtering system according to some embodiments of the present utility model;

[0024] Figure 7 is a partial schematic diagram of filtering system according to some other embodiments of the present utility model;

[0025] Figure 8 is a partial schematic diagram of filtering system according to some other embodiments of the present utility model;

[0026] Figure 9 is a partial schematic diagram of filtering system according to some other embodiments of the present utility model;

[0027] Figure 10 is a dynamic surface tension monitoring result diagram of filtering element replacement liquid circulation process according to embodiment 1 in an embodiment of the present utility model;

[0028] Figure 11 is a dynamic surface tension monitoring result diagram of filtering element replacement liquid circulation process according to embodiment 2 in an embodiment of the present utility model;

[0029] Figure 12 is a dynamic surface tension monitoring result diagram of filtering element replacement liquid circulation process according to embodiment 3 in an embodiment of the present utility model;

[0030] Figure 13 is a dynamic surface tension diagram measured by segment sampling of filtering element in replacement liquid discharge process according to contrast experiment 3 in an embodiment of the present utility model;

[0031] Figure 14 is a dynamic surface tension monitoring result diagram of filtering element replacement liquid circulation process according to embodiment 4 in an embodiment of the present utility model;

[0032] Figure 15 is a dynamic surface tension monitoring result diagram of filtering element replacement liquid circulation process according to embodiment 5 in an embodiment of the present utility model;

[0033] Figure 16 is a dynamic surface tension monitoring result chart of the first group of filter units according to the embodiment 6 in the embodiment of the present application in the displacement liquid circulation process;

[0034] Figure 17 is a dynamic surface tension monitoring result chart of the second group and the third group of filter units according to the embodiment 6 in the embodiment of the present application in the displacement liquid circulation process;

[0035] Figure 18 is a dynamic surface tension monitoring result chart of the filter element in the displacement liquid circulation process according to the control experiment 1 in the embodiment of the present application;

[0036] Figure 19 is a dynamic surface tension monitoring result chart of the filter element in the displacement liquid circulation process according to the control experiment 2 in the embodiment of the present application.

[0037] Reference signs:

[0038] 100, filter system;

[0039] 1, raw material mixing tank;

[0040] 2, filter element; 201, resin type purification column unit; 2011, cation exchange resin purification column; 2012, chelating resin purification column; 202, microporous filter unit; 2021, first microporous filter; 2022, second microporous filter;

[0041] 3, semi-finished product transfer tank; 4, finished product tank;

[0042] 5, displacement liquid tank; 501, first displacement liquid tank; 502, second displacement liquid tank;

[0043] 6, first detection outlet; 7, second detection outlet; 8, third detection outlet; 9, fourth detection outlet; 10, raw material transfer tank;

[0044] 11, on-off valve; 1101, first on-off valve; 1102, second on-off valve; 1103, third on-off valve; 1104, fourth on-off valve; 1105, fifth on-off valve; 1106, sixth on-off valve; 1107, seventh on-off valve; 1108, eighth on-off valve; 1109, ninth on-off valve; 1110, tenth on-off valve;

[0045] 12, three-way valve; 1201, first three-way valve; 1202, second three-way valve;

[0046] 13, ultrapure water machine; 14, stirring paddle. DETAILED DESCRIPTION

[0047] The embodiments of the present application are described in detail below, and the embodiments described with reference to the drawings are exemplary, and the embodiments of the present application are described in detail below.

[0048] The embodiments of the present application are described in detail below, and the embodiments described with reference to the drawings are exemplary, and the embodiments of the present application are described in detail below. Figures 3-9 The filtering system 100 of the semiconductor developing solution according to the embodiments of the present application is described.

[0049] The filtering system 100 of the semiconductor developing solution according to the embodiments of the present application is described. Figure 3 As shown in the drawings, the filtering system 100 of the semiconductor developing solution according to the embodiments of the present application can mainly include: a raw material mixing tank 1, a filter 2, a semi-finished product transfer tank 3, a finished product tank 4 and a displacement liquid tank 5, the materials of the raw material mixing tank 1, the semi-finished product transfer tank 3, the finished product tank 4 and the displacement liquid tank 5 include but are not limited to stainless steel 316 or stainless steel 316L, preferably stainless steel 316L, the tank contains a container with a chemical corrosion resistant lining, the lining material includes but is not limited to clean material polytetrafluoroethylene or soluble polytetrafluoroethylene, more preferably soluble polytetrafluoroethylene. In addition, the raw material mixing tank 1 is provided with a stirring paddle 14, and the stirring paddle 14 is preferably a polytetrafluoroethylene stirring paddle 14.

[0050] Specifically, the raw material mixing tank 1 is used to contain the solution to be filtered in the filtering system 100, the filter 2 can filter the pollutants mixed in the solution to be filtered during the configuration process, thereby improving the cleanliness of the solution to be filtered, which can prevent the pollution of the machine and the mechanical arm in the subsequent process of the semiconductor on the one hand, and can improve the yield of the product on the other hand.

[0051] Further, the liquid inlet end of the filter 2 is connected with the raw material mixing tank 1, so that the solution to be filtered in the raw material mixing tank 1 can flow into the filter 2, so that the filter 2 can filter the solution to be filtered in the raw material mixing tank 1.

[0052] Further, the inlet of the semi-finished product transfer tank 3 is connected with the liquid outlet end of the filter 2, the outlet of the semi-finished product transfer tank 3 is connected with the liquid inlet of the filter 2, and the semi-finished product transfer tank 3 is also provided with a first detection outlet 6. Specifically, the semi-finished product transfer tank 3 is used to contain the solution flowing out of the filter 2, and the filtrate can be sampled and detected through the first detection outlet 6 to determine whether the filtrate has reached the required cleanliness for the configuration of the semiconductor developing solution. If the filtrate does not reach the required cleanliness, the filtrate in the semi-finished product transfer tank 3 needs to flow from the outlet of the semi-finished product transfer tank 3 to the liquid inlet of the filter 2, so that the filtrate can be filtered circularly to improve the cleanliness of the filtrate.

[0053] Further, the inlet of the finished product tank 4 is connected with the outlet of the semi-finished product transfer tank 3, if the filtrate has reached the required cleanliness, the filtrate in the semi-finished product transfer tank 3 can flow from the outlet of the semi-finished product transfer tank 3 to the inlet of the finished product tank 4, so that the filtrate can enter the finished product tank 4, and the finished product tank 4 can store or fill the filtrate.

[0054] The filter system 100 needs to use the solution to be filtered to flush the filter element 2 during replacement, so that the solute molecules in the porous material are saturated, and thus the solute concentration of the filtrate can be maintained during the subsequent filtration.

[0055] Further, the inlet of the replacement liquid tank 5 is connected to the liquid outlet end of the filter element 2, and is arranged in parallel with the semi-finished product transfer tank 3, and the outlet of the replacement liquid tank 5 is connected to the liquid inlet end of the filter element 2. Specifically, during replacement of the filter system 100, the replacement liquid does not flow into the semi-finished product transfer tank 3. At this time, the replacement liquid tank 5 is adapted to contain the replacement liquid, and the solution in the replacement liquid tank 5 can flow back to the filter element 2, so that the filtrate repeatedly flows through the filter element 2, so that the porous material in the filter element 2 continuously adsorbs the solute molecules in the replacement liquid, and finally reaches a saturated state. Thus, when the subsequent solution flows through the filter element 2, only the pollutants will be removed by the filter element 2, and the solute molecules in the solution to be filtered will not be reduced, and the solution concentration will not be reduced, so that the subsequent filtrate can meet the requirements of the semiconductor process, and will not affect the subsequent process and product yield.

[0056] In this way, the replacement liquid can be repeatedly used until the solute adsorption capacity in the filter element 2 reaches saturation. Unlike the prior art, which uses the solution to be filtered to continuously flush during the replacement stage of the filter system 100, the embodiment of the utility model can recycle the replacement liquid to avoid wasting a large amount of solution.

[0057] Therefore, the utility model increases a replacement liquid tank 5 connected to the filter element 2 between the liquid outlet end and the liquid inlet end of the filter element 2, so that when the filter system 100 performs the system cleaning process, the replacement liquid tank 5 collects the solution flowing out of the filter element 2 and circulates the liquid through the filter element 2, so that the filter system 100 can reach adsorption saturation with less amount of solution, thereby improving the utilization rate of the replacement liquid of the filter system 100.

[0058] As shown in Figure 3 The inlet of the replacement liquid tank 5 is connected to the liquid outlet end of the filter element 2, and is arranged in parallel with the semi-finished product transfer tank 3, and the outlet of the replacement liquid tank 5 is connected to the liquid inlet end of the filter element 2. Specifically, during replacement of the filter system 100, the replacement liquid does not flow into the semi-finished product transfer tank 3. At this time, the replacement liquid tank 5 is adapted to contain the replacement liquid, and the solution in the replacement liquid tank 5 can flow back to the filter element 2, so that the filtrate repeatedly flows through the filter element 2, so that the porous material in the filter element 2 continuously adsorbs the solute molecules in the replacement liquid, and finally reaches a saturated state. Thus, when the subsequent solution flows through the filter element 2, only the pollutants will be removed by the filter element 2, and the solute molecules in the solution to be filtered will not be reduced, and the solution concentration will not be reduced, so that the subsequent filtrate can meet the requirements of the semiconductor process, and will not affect the subsequent process and product yield.

[0059] As shown in Figure 3As shown, the displacement liquid tank 5 is also provided with a third detection outlet 8. Specifically, in the case that the filter element 2 adsorbs the solute and does not reach the saturation amount, the solute molecules in the displacement liquid will continue to be accumulated and adsorbed by the filter element 2, so that the solute concentration in the displacement liquid gradually decreases, until the solute concentration in the displacement liquid no longer changes, and the displacement liquid reaches equilibrium with the filter element 2. The third detection outlet 8 of the embodiment of the present application can be used for sampling and detecting the displacement liquid in the displacement liquid tank 5, so that the solute concentration change of the displacement liquid can be monitored in the displacement stage of the filtration system 100.

[0060] According to the embodiment of the present application, the filter element 2 is integrated with a particulate filter membrane and a resin type purification column. Specifically, the pollution in the to-be-filtered solution mainly includes metal pollution and particulate pollution, the metal pollution can cause the leakage current in the PN junction, and further cause the breakdown voltage of the oxide to decrease, and the particulate pollution can cause the blocking or shielding effect in the etching process, and if the particulate has conductivity, it can cause the short circuit of the semiconductor circuit.

[0061] In the embodiment of the present application, the resin type purification column is used for removing the free metal ions in the to-be-filtered solution, and the particulate filter membrane is used for removing the particulate impurities.

[0062] In combination with Figures 4-9 As shown, the filter element 2 includes a resin type purification column unit 201 and a microporous filter unit 202, and the resin type purification column unit 201 and the microporous filter unit 202 are arranged in series.

[0063] Specifically, in the embodiment of the present application, the resin type purification column unit 201 is used for removing the free metal ions in the to-be-filtered solution, and the microporous filter unit 202 is used for removing the particulate impurities. The resin type purification column unit 201 and the microporous filter unit 202 are sequentially connected in series, so that the solution entering the filter element 2 can pass through the resin type purification unit and the microporous filter unit 202, and the reliability of the filter element 2 for filtering the metal pollutants and the particulate pollutants in the to-be-filtered solution can be ensured.

[0064] Further, the resin type purification column unit 201 and the microporous filter unit 202 are different in material, and the adsorption capacity of the two for the surfactant molecules in the developing solution is also different, and the required displacement liquid amount is also different.

[0065] In combination with Figure 5 , Figure 7 and Figure 8As shown, the displacement liquid tank 5 includes a first displacement liquid tank 501 and a second displacement liquid tank 502, the inlet of the first displacement liquid tank 501 is connected with the liquid outlet end of the resin type purification column unit 201, the outlet of the first displacement liquid tank 501 is connected with the liquid inlet end of the resin type purification column unit 201, the inlet of the second displacement liquid tank 502 is connected with the liquid outlet end of the microporous filter unit 202, and the outlet of the second displacement liquid tank 502 is connected with the liquid inlet end of the microporous filter unit 202.

[0066] In this way, the first displacement liquid tank 501 can perform single displacement liquid circulation on the resin type purification column unit 201, and the second displacement liquid tank 502 can perform single displacement liquid circulation on the microporous filter unit 202. In this way, when the adsorption capacity of the solute in the displacement liquid of any one of the resin type purification column unit 201 and the microporous filter unit 202 is higher than that of the other unit, single displacement liquid circulation can be performed on the unit with high adsorption capacity, thereby improving the utilization rate of the displacement liquid, and the total amount of the displacement liquid can be reduced.

[0067] According to some embodiments of the present application, in combination with Figure 7 As shown, the resin type purification column unit 201 is multiple, the multiple resin type purification column units 201 are connected in series, and one first displacement liquid tank 501 is connected with the multiple resin type purification column units 201. Specifically, in the embodiments of the present application, the filter member 2 includes multiple resin type purification column units 201, and the resin type purification column unit 201 is used to remove free metal ions in the solution to be filtered. The free metal ions in the solution to be filtered include but are not limited to at least one of sodium ions, potassium ions, calcium ions and iron ions introduced from raw materials, containers and experimental operations. The multiple resin type purification column units 201 include but are not limited to at least one of cation exchange resin and chelating resin, and the base material is polystyrene. The resin-loaded shell and other components that can contact the solution should be made of materials with good chemical compatibility and cleanliness, including but not limited to polyethylene, polypropylene, high-density polyethylene, polytetrafluoroethylene or soluble polytetrafluoroethylene, preferably high-density polyethylene, polytetrafluoroethylene or soluble polytetrafluoroethylene.

[0068] The multiple resin type purification column units 201 are connected in series, so that the solution to be displaced can pass through the multiple resin type purification column units 201 in turn, and the multiple resin type purification column units 201 can be subjected to displacement liquid circulation through one first displacement liquid tank 501. In this way, the displacement efficiency of the multiple resin type purification column units 201 can be improved, and the displacement time can be saved.

[0069] According to some embodiments of the present application, in combination with Figure 8As shown, the resin type purification column units 201 are multiple, the multiple resin type purification column units 201 are connected in series, and the first displacement liquid tanks 501 are multiple, and the multiple first displacement liquid tanks 501 are connected with the multiple resin type purification column units 201 one by one. Specifically, in the embodiment of the utility model, the filter piece 2 includes multiple resin type purification column units 201, and the resin type purification column units 201 are used for removing free metal ions in the solution to be filtered. The free metal ions in the solution to be filtered include but are not limited to sodium ions, potassium ions, calcium ions and iron ions introduced from raw materials, containers and experimental operations. The multiple resin type purification column units 201 include but are not limited to at least one of cation exchange resin and chelating resin.

[0070] The multiple resin type purification column units 201 are connected in series, so that the solution to be displaced can pass through the multiple resin type purification column units 201 in turn, and the multiple resin type purification column units 201 are connected with a corresponding first displacement liquid tank 501, so that each resin type purification column unit 201 can be individually displaced, so that the units with strong adsorption capacity in the multiple resin type purification column units 201 can be individually displaced, thereby improving the utilization rate of the displacement liquid, so that the total amount of the displacement liquid can be reduced.

[0071] According to some embodiments of the utility model, in combination with Figure 7 and Figure 8 As shown, the multiple micro-pore filter units 202 are connected in series, and a second displacement liquid tank 502 is connected with the multiple micro-pore filter units 202. Specifically, in the embodiment of the utility model, the filter piece 2 includes multiple micro-pore filter units 202, and the micro-pore filter units 202 are used for removing particulate impurities in the solution to be filtered.

[0072] The particulate impurities are easily brought out after the solution is contacted with the cation exchange resin and the chelating resin, and therefore the microporous filter units 202 in the embodiments of the utility model are all arranged behind the last one of the plurality of resin type purification column units 201. The filter membrane average pore size of the plurality of microporous filter units 202 is 0.01-5 μm, preferably 0.01-0.5 μm, more preferably 0.01-0.1 μm, and the filter membrane pore size of the plurality of series-connected microporous filter units 202 gradually decreases. The same kind of filter membrane material should be selected in the microporous filter units 202 in the same stage, and the filter membrane needs to have good chemical compatibility with the strong alkali aqueous solution, and the filter membrane material includes but is not limited to at least one of nylon, polyether sulfone, polypropylene, ultra-high molecular weight polyethylene and polytetrafluoroethylene, and the ultra-high molecular weight polyethylene material and the polytetrafluoroethylene material are preferred. The filter shell and other components that can contact the solution should be made of materials with good chemical compatibility and cleanliness, including but not limited to polyethylene, polypropylene, high-density polyethylene, polytetrafluoroethylene or soluble polytetrafluoroethylene, and the high-density polyethylene, polytetrafluoroethylene or soluble polytetrafluoroethylene is preferred.

[0073] The plurality of microporous filter units 202 are connected in series, so that the displacement solution can sequentially pass through the plurality of microporous filter units 202, and the plurality of microporous filter units 202 can circulate the displacement solution through one second displacement liquid tank 502. In this way, the displacement efficiency of the plurality of microporous filter units 202 can be improved, and the displacement time can be saved.

[0074] According to some other embodiments of the utility model, the plurality of microporous filter units 202 are connected in series, and the plurality of second displacement liquid tanks 502 are connected to the plurality of microporous filter units 202 one by one. Specifically, in the embodiments of the utility model, the filter 2 includes a plurality of microporous filter units 202, and the microporous filter units 202 are used to remove particulate impurities in the solution to be filtered. The plurality of microporous filter units 202 are connected in series, so that the displacement solution can sequentially pass through the plurality of microporous filter units 202, and the plurality of microporous filter units 202 are each connected to a corresponding second displacement liquid tank 502. In this way, each microporous filter unit 202 can be individually displaced, so that the displacement liquid circulation of the microporous filter unit 202 with strong adsorption capacity in the plurality of microporous filter units 202 can be performed individually, and the utilization rate of the displacement liquid can be improved, thereby reducing the total amount of the displacement liquid.

[0075] In combination Figure 3As shown, the raw material mixing tank 1 is provided with a fourth detection outlet 9. Specifically, the fourth detection outlet 9 is used to sample and test the solution to be filtered in the raw material mixing tank 1. By testing the solution to be filtered in the raw material mixing tank 1, it can serve as a reference for the solution test results in the subsequent filtration and replacement processes.

[0076] In the embodiment of the present invention, the solution to be filtered includes but is not limited to a developer and a surfactant raw material. The filtration system 100 of the present invention can be used for filtering and purifying the developer, and can also be used for pre-purification of the surfactant raw material.

[0077] In the embodiment of the present invention, the developer includes but is not limited to a strongly alkaline tetramethylammonium hydroxide (TMAH) aqueous solution with a mass concentration of 2.0wt%-3.0wt%, preferably 2.30wt%-2.40wt%, and a 25% aqueous solution of tetramethylammonium hydroxide is used as a raw material. The raw material quality standard is SEMI C46-03061, which requires that the content of a single metal element is less than 10ppb.

[0078] To ensure sufficient contact between the developer and the photoresist, a nonionic surfactant is typically added to reduce surface tension and improve wetting for optimal development. The concentration of nonionic surfactant in the developer ranges from 0.01wt% to 0.5wt%. Using commercially available industrial-grade secondary alcohol polyoxyethylene ether as a raw material, at a concentration of 1.00wt%, the static surface tension of the nonionic surfactant is 43.0±1.0mN / m (25°C), and the aqueous solution is neutral.

[0079] Developer is a formulated wet electronic chemical that requires full control and assessment of the quality of raw materials and contamination introduced by compounding operations. Appropriate filtration and purification processes are also required to produce high-purity products that meet semiconductor standards. The specific process is as follows: Figure 1 As shown, Figure 1 This is the production process of formulated developer.

[0080] Reference below Figure 3 The replacement method of the filter system 100 according to an embodiment of the present invention is described, wherein the filter system 100 for semiconductor developer further includes: a switch valve 11, a three-way valve 12 and a raw material transfer tank 10, wherein the switch valve 11 and the three-way valve 12 are both multiple.

[0081] In the embodiment of the utility model, the outlet of raw material mixing tank 1 is communicated with the inlet of raw material transfer tank 10, the outlet of raw material transfer tank 10 is communicated with the liquid inlet of filter piece 2, the outlet of semi-finished product transfer tank 3 is communicated with the main flow path between the outlet of raw material transfer tank 10 and the liquid inlet of filter piece 2, and the outlet of displacement liquid tank 5 is also communicated with the main flow path between the outlet of raw material transfer tank 10 and the liquid inlet of filter piece 2.

[0082] Further, the main flow path is the flow path of the solution after entering the filter system 100 along the outlet of raw material mixing tank 1-inlet of raw material transfer tank 10-outlet of raw material transfer tank 10-liquid inlet of filter piece 2-liquid outlet of filter piece 2-inlet of semi-finished product transfer tank 3-outlet of semi-finished product transfer tank 3-inlet of finished product tank 4. The filter system 100 of the semiconductor developing solution further includes a circulating filter branch flow path, and the circulating filter branch flow path is the flow path of the solution from the outlet of semi-finished product transfer tank 3 to the liquid inlet of filter piece 2. The filter system 100 of the semiconductor developing solution further includes a displacement circulating branch flow path, and the displacement circulating branch flow path is the flow path of the solution along the liquid outlet of filter piece 2-inlet of displacement liquid tank 5-outlet of displacement liquid tank 5-liquid inlet of filter piece 2. It should be noted that the pipelines of the solution flowing in the main flow path, the circulating filter branch flow path and the displacement circulating branch flow path can all be clean polytetrafluoroethylene pipes.

[0083] In the embodiment of the utility model, the switch valve 11 includes a first switch valve 1101, a second switch valve 1102, a third switch valve 1103, a fourth switch valve 1104, a fifth switch valve 1105, a sixth switch valve 1106, a seventh switch valve 1107, an eighth switch valve 1108 and a ninth switch valve 1109, and the material of the switch valve 11 includes but is not limited to stainless steel 304, stainless steel 316 or polytetrafluoroethylene, preferably stainless steel 316 and polytetrafluoroethylene, and more preferably polytetrafluoroethylene.

[0084] Specifically, the first switch valve 1101 is arranged between the outlet of the raw material mixing tank 1 and the inlet of the raw material transfer tank 10, and the opening and closing of the first switch valve 1101 can control the solution in the raw material mixing tank 1 to selectively flow to the raw material transfer tank 10. The second switch valve 1102 is arranged between the outlet of the raw material transfer tank 10 and the liquid inlet of the filter 2, and the opening and closing of the second switch valve 1102 can control the solution in the raw material transfer tank 10 to selectively flow to the filter 2. The third switch valve 1103 is arranged between the outlet of the raw material transfer tank 10 and the outlet of the displacement liquid tank 5 in the main flow path, and the opening and closing of the third switch valve 1103 can control the solution in the main flow path to selectively flow into the filter 2. When the filter system 100 is in the filtering mode, the third switch valve 1103 is opened, so that the solution in the raw material transfer tank 10 can flow into the filter 2. When the filter system 100 is in the displacement mode, the third switch valve 1103 is closed, so that the solution in the displacement liquid tank 5 cannot flow back to the raw material transfer tank 10, and the circulation of the displacement liquid can be ensured. The fourth switch valve 1104 is connected between the liquid outlet of the filter 2 and the inlet of the semi-finished product transfer tank 3, and the opening and closing of the fourth switch valve 1104 can control the solution in the filter 2 to selectively flow to the semi-finished product transfer tank 3. The fifth switch valve 1105 is connected between the outlet of the semi-finished product transfer tank 3 and the inlet of the third switch valve 1103, and the opening and closing of the fifth switch valve 1105 can control the solution in the semi-finished product transfer tank 3 to selectively flow to the third switch valve 1103. When the third switch valve 1103 is opened, the solution in the semi-finished product transfer tank 3 can continue to flow to the filter 2, so that the circulation filtering of the filter system 100 can be realized. The outlet of the displacement liquid tank 5 is connected to the outlet of the third switch valve 1103 and the liquid inlet of the filter 2, and the sixth switch valve 1106 and the seventh switch valve 1107 are arranged between the outlet of the displacement liquid tank 5 and the outlet of the third switch valve 1103 in sequence. The opening and closing of the sixth switch valve 1106 and the seventh switch valve 1107 can control the solution in the displacement liquid tank 5 to selectively flow to the filter 2. Only when the sixth switch valve 1106 and the seventh switch valve 1107 are opened at the same time, the solution in the displacement liquid tank 5 can flow into the filter 2, so that the displacement circulation of the filter system 100 can be realized. The eighth switch valve 1108 is connected between the outlet of the raw material mixing tank 1 and the fourth detection outlet 9, and the opening and closing of the eighth switch valve 1108 can control the solution in the raw material mixing tank 1 to selectively flow out of the fourth detection outlet 9, so that the solution to be filtered in the raw material mixing tank 1 can be sampled and detected. The ninth switch valve 1109 is arranged between the displacement liquid outlet and the third detection outlet 8, so that the displacement liquid in the displacement liquid tank 5 can be sampled and detected.

[0085] The three-way valve 12 includes a first three-way valve 1201 and a second three-way valve 1202, and the material of the three-way valve 12 includes but is not limited to stainless steel 304, stainless steel 316 or polytetrafluoroethylene, preferably stainless steel 316 and polytetrafluoroethylene, and more preferably polytetrafluoroethylene.

[0086] Specifically, the first port of the first three-way valve 1201 is connected to the outlet of the semi-finished product transfer tank 3, the second port of the first three-way valve 1201 is connected to the inlet of the finished product tank 4, and the third port of the first three-way valve 1201 is connected to the first detection outlet 6. The first port of the second three-way valve 1202 is connected to the liquid outlet of the filter element 2, the second port of the second three-way valve 1202 is connected to the inlet of the displacement liquid tank 5, and the third port of the second three-way valve 1202 is connected to the second detection outlet 7.

[0087] Before the filter system 100 is started or after the filter element is replaced, the filter system 100 needs to be cleaned. The cleaning liquid is ultrapure water, which can be prepared by an ultrapure water machine 13 and provided to the semiconductor developer filtering system 100. The water quality needs to meet the EW-I electronic grade water standard specified in the national standard GB / T 11446.1-2013. After cleaning with ultrapure water, the pipeline and filter element 2 in the filter system 100 are flushed with the solution to be filtered.

[0088] Further, in the prior art, after the filter system 100 is cleaned with ultrapure water, the pipeline and filter element 2 in the filter system 100 are flushed with the solution to be filtered by injecting the solution to be filtered into the raw material mixing tank 1. The solution flows along the main flow path to the first detection outlet 6 and is discharged from the first detection outlet 6 to the waste liquid tank. The solution is sampled quantitatively or at a fixed time from the liquid outlet until the pH and surface tension of the effluent liquid are restored to be consistent with the original solution, and the solution in the device is replaced. It is found in actual use that when the amount of the effluent liquid is 1.5-3.0 times the total volume of the filter element 2, the pH of the solution flowing out of the first detection outlet 6 has been restored to be consistent with the original solution, i.e., the ultrapure water remaining in the filter system 100 after the cleaning process has been completely discharged, but the surface tension value is higher than that of the original solution, i.e., the concentration of the surfactant in the solution has been reduced. Since the surfactant has the characteristics of gathering and adsorbing on the interface, at any solid-liquid interface in the filter system 100, especially the filter membrane or the base of the purification column in the filter element 2, which is usually a polymer-based porous material, the area of the solid-liquid interface is larger, and the amount of the surfactant adsorbed by the porous material is also larger until saturation, which leads to the need for a large amount of solution to restore the surface tension value of the effluent liquid to the surface tension value consistent with the original solution, which easily causes waste of raw materials.

[0089] In the embodiment of the utility model, the specific steps that filter system 100 carries out replacement liquid circulation are: closing valve fourth switch valve 1104, fifth switch valve 1105 and first three -way valve 1201, after solution flows along main stream path and filters 2, second three -way valve 1202 adjusts the solution in filters 2 to flow into replacement circulation branch stream path, enters replacement liquid tank 5, after collecting 1.0-3.0 volume of solution relative to the total capacity of filters 2, closing valve third switch valve 1103, to stop raw material mixing tank 1 to supply liquid to replacement circulation branch stream path, open valve sixth switch valve 1106 and seventh switch valve 1107, make solution continue along replacement circulation branch stream path and flow back to the liquid inlet of filter, start replacement circulation.

[0090] During the replacement liquid circulation process, the ninth switch valve 1109 is opened at regular intervals, and a solution sample is taken from the third detection outlet 8 to monitor the change of the surface tension of the replacement liquid. Because the replacement liquid containing surfactant will repeatedly contact the porous material in the filter during the circulation process, the surfactant molecules will continue to be accumulated and adsorbed by the porous material if the amount of adsorbed surfactant molecules on the porous material does not reach the saturation amount. Therefore, the concentration of surfactant molecules in the replacement liquid will gradually decrease, and the surface tension of the replacement liquid will gradually increase until the surface tension of the replacement liquid reaches a certain balance and basically does not change. At this time, the second three-way valve 1202, the sixth switch valve 1106 and the seventh switch valve 1107 are closed.

[0091] Further, when the surface tension of the replacement liquid reaches equilibrium, there are two states, the first equilibrium state is that the adsorption of the porous material in the filter 2 to the surfactant molecules has reached saturation, and the second equilibrium state is that the adsorption of the porous material in the filter 2 to the surfactant molecules has not reached saturation. However, due to the low concentration of the surfactant in the aqueous solution, the surfactant molecules on the liquid-solid interface exist in a dynamic balance of adsorption-desorption due to the influence of the interaction force between the solute, the solvent and the adsorbed material, and therefore the surfactant concentration remains unchanged.

[0092] According to the embodiment of the utility model, the verification method of the surface tension equilibrium state of the replacement liquid is as follows: opening the third switch valve 1103, the solution in the raw material mixing tank 1 is supplemented into the filter 2, adjusting the second three-way valve 1202 to make the supplemented solution flow out from the second detection outlet 7, that is, a new raw liquid is introduced into the filter 2, and then a sample is taken from the second detection outlet 7 for testing the surface tension. After sampling, the second three-way valve 1202 is adjusted to be closed.

[0093] The detected surface tension of the sample solution is compared with the surface tension of the original solution. If the surface tension of the sample solution is consistent with that of the original solution, the surface tension equilibrium state of the displacement solution is the first equilibrium state, that is, the adsorption of the porous material in the filter 2 to the surfactant molecules has reached saturation, and the solution in the filtration system 100 has been completely replaced by the to-be-filtered solution, and at this time, the to-be-filtered solution can be formally filtered.

[0094] If the surface tension of the sample solution has not yet recovered to be consistent with that of the original solution, the surface tension equilibrium state of the displacement solution is the second equilibrium state, that is, there is a dynamic balance of adsorption-desorption of the surfactant molecules on the liquid-solid interface. At this time, the displacement solution in the displacement solution tank 5 needs to be discharged through the third detection outlet 8, and the displacement solution needs to be circulated for two or more times until the first equilibrium state is reached. In the repeated displacement circulation, the displacement solution tank 5 needs to collect 0.5-3.0 volumes of solution relative to the total capacity of the filter 2, and the amount of solution to be collected needs to be reduced gradually with the increase of the number of repetitions.

[0095] Compared with the prior art, the filtration system 100 in the embodiment of the utility model can quantitatively replace the solution during the solution replacement process when the displacement solution is circulated, so that the surfactant molecules in the displacement solution can be fully adsorbed in the porous material of the filter 2, and then the adsorption of the filter 2 to the solute molecules can reach the saturation amount by using less amount of solution, so that the solution replacement efficiency and the component utilization rate can be improved.

[0096] Further, the solution in the filtration system 100 in the embodiment of the utility model continuously flows in the displacement circulation branch path when the displacement solution is circulated, and the surfactant molecules on the liquid-solid interface are promoted to diffuse by external force, so that the adsorption efficiency of the porous material to the surfactant molecules is improved, and the time required to reach the equilibrium state in a single displacement solution circulation is shortened.

[0097] Further, in the process of the filtration system 100 in the embodiment of the utility model circulating the displacement solution, the surface of the porous material can be changed to a state of affinity to the to-be-filtered solution, so that the filtration efficiency can be improved, and a high-purity developing solution with lower amounts of metal ions and particulate impurities can be obtained.

[0098] The following will be described in combination with Figure 7 The staged displacement of the filter 2 is described.

[0099] According to some embodiments of the present application, the filter 2 can mainly include a resin type purification column unit 201 and a microporous filter unit 202, the displacement liquid tank 5 includes a first displacement liquid tank 501 and a second displacement liquid tank 502, the first displacement liquid tank 501 is connected with the resin type purification column unit 201 correspondingly, and the second displacement liquid tank 502 is connected with the microporous filter unit 202 correspondingly. The tenth switch valve 1110 is arranged between the outlet of the resin type purification column unit 201 and the inlet of the microporous filter unit 202, and the opening and closing of the tenth switch valve 1110 can control the solution in the resin type purification column unit 201 to flow to the microporous filter unit 202 selectively. The material of the tenth switch valve 1110 includes but is not limited to stainless steel 304, stainless steel 316 or polytetrafluoroethylene, preferably the material is stainless steel 316 and polytetrafluoroethylene, and more preferably the material is polytetrafluoroethylene.

[0100] Further, in the embodiments of the present application, the resin type purification column unit 201 is first subjected to displacement circulation through the first displacement liquid tank 501, the amount of displacement liquid collected by the first displacement liquid tank 501 is 0.5-3.0 volumes relative to the total capacity of the purification column in the resin type purification column unit 201, and with the increase of the number of displacement circulation repetitions, the amount of solution collected by the first displacement liquid tank 501 is reduced gradually. After the solution displacement of the resin type purification column unit 201 is completed, the tenth switch valve 1110 is opened, so that the displacement liquid enters the microporous filter unit 202, and the microporous filter unit 202 is subjected to displacement circulation in the same step, the amount of displacement liquid collected by the second displacement liquid tank 502 is 0.5-3.0 volumes relative to the total capacity of the filter in the microporous filter unit 202, and with the increase of the number of displacement circulation repetitions, the amount of solution collected by the second displacement liquid tank 502 is reduced gradually.

[0101] According to the embodiments of the present application, combined with Figure 8 The more preferred scheme of the hierarchical displacement of the filter 2 is to further divide the resin type purification column unit 201 and the microporous filter unit 202 respectively, and each unit is connected with the displacement liquid tank 5 corresponding thereto, so that the resin type purification column unit 201 of different materials is subjected to hierarchical displacement, and the microporous filter unit 202 of different pore sizes is subjected to hierarchical displacement.

[0102] Because the developing solution is strong alkaline, the condition for removing metal impurities is more demanding. In the embodiment of the present application, the cation exchange resin and the chelating resin have better adsorption to free metal ions in a weakly acidic-weakly alkaline (pH = 5-9) environment, but when the acidity or alkalinity is too strong, the adsorption performance of the cation exchange resin and the chelating resin will decrease, which will lead to the decrease of the removal efficiency of the filter 2 to metal ions, and then the cycle number of filtration needs to be increased to sufficiently remove the metal ion impurities. Therefore, when preparing the developing solution, the amount of metal impurities in the solution needs to be controlled to the maximum extent at the raw material stage, so as to be beneficial to reducing the amount of impurities accumulated in the developing solution after compounding, to reduce the processing pressure of the subsequent filtration system 100, and then the production efficiency can be improved.

[0103] In the synthesis route of the surfactant, LiOH, NaOH, KOH and other alkali catalysts are usually used, and even after desalting treatment, there are still many metal ions remaining in the finished product. On the other hand, most of the existing surfactants are industrial products, which contain a large amount of dust particle impurities. Therefore, the surfactant needs to be pre-purified before the developing solution is configured. In order to ensure the simplicity of operation and the monitorability of the change of the composition of the filtrate or the replacement liquid, the surfactant to be purified is diluted to a mass concentration of 1.00wt% aqueous solution by using ultrapure water, and then a filter 2 with a suitable material is used to form a filtration system 100 for pre-purification. In addition, the aqueous solution of the surfactant is usually neutral, and a small number of functional products with special groups are weakly acidic or weakly alkaline, so the ability of the cation exchange resin or the chelating resin to adsorb free metal ions is less affected.

[0104] The filtration system 100 of the present application is suitable for filtering solutions including but not limited to surfactant solutions, developing solutions and other formula type wet electronic chemicals such as cutting fluid, etching liquid and circuit board cleaning liquid which will add surfactants and other auxiliary agents. The filter 2 of the present application can be composed of units with suitable materials according to the properties of the chemical to be purified.

[0105] The method for monitoring the surface tension of the solution in the embodiment of the present application is to take samples from the corresponding detection outlet for testing. The test index of the surface tension can be static surface tension or dynamic surface tension, and in the present application, the dynamic surface tension is taken as the index, which can better reflect the changes of the molecular migration and diffusion characteristics in the solution when the concentration of the surfactant changes.

[0106] In actual production, under the condition that the pilot line or the mass production line uses semi-automatic or automatic devices, after appropriate equipment and circuit system are assembled, the change of the surface tension at the corresponding position in the filtration system 100 can be monitored online.

[0107] In the process of filtering the solution to be filtered by the filtering system 100 or the displacement circulation of the filtering system 100, nitrogen gas is filled into the filtering system 100 through the inlet of the raw material mixing tank 1, and the solution to be filtered can be pressed out and delivered to the downstream by the gas pressure. The nitrogen gas used is high-purity nitrogen gas (99.999%), and the output gas pressure is 0.05-0.1 MPa. The solution flow rate can be adjusted by adjusting the gas pressure. In the process of preparing the developer, the nitrogen gas introduced can also protect the developer from being polluted by carbon dioxide.

[0108] The solution preparation, filtration and testing are all carried out in a clean laboratory or clean workshop. The clean laboratory or clean workshop environment should meet the air cleanliness level Class 6, Class 5 or Class 4 in the international standard ISO14644-1 according to the particle concentration, that is, the environment commonly referred to as thousand level, hundred level or ten level.

[0109] In the embodiment of the utility model, combined with Figure 3 As shown in the figure, in the preparation process of the developer, all the valves are closed, the surfactant and the tetramethylammonium hydroxide solution raw materials are added into the raw material mixing tank 1 through the inlet of the raw material mixing tank 1, the ultrapure water is introduced by the ultrapure water machine 13, the mass concentration of the surfactant aqueous solution is 1.00wt%, or the developer of the set formula is prepared, and the stirring paddle 14 is started to stir the solution, so that the surfactant is fully dissolved and uniformly dispersed.

[0110] According to the embodiment of the utility model, in the process of pre-purifying the surfactant, after the solution is fully mixed, the eighth switch valve 1108 is opened, the solution is sampled from the fourth detection outlet 9 for testing the pH, dynamic surface tension, metal ions and particulate impurities, which is used as a reference for the subsequent process. The eighth switch valve 1108 is closed, the first switch valve 1101, the second switch valve 1102 and the third switch valve 1103 are opened, the second three-way valve 1202 is adjusted to make the solution flow out from the second detection outlet 7, that is, the solution flows out from the raw material mixing tank 1, is transported to the filter element 2 through the raw material transfer tank 10, and then flows into the displacement circulation branch path, and then flows out from the second detection outlet 7. At this time, the solution flowing out is introduced into the waste liquid tank.

[0111] Since the surfactant used is a mass concentration of 1.00wt% aqueous solution and neutral, it is difficult to judge whether the residual ultrapure water in the filter element 2 is discharged by only the pH value of the solution flowing out from the second detection outlet 7, and in the process of discharging water, the adsorption of the resin type purification column or the particulate filter membrane to the surfactant molecules is also carried out at the same time. Therefore, the embodiment of the utility model takes out the solution of 1.5 times the total volume of the filter element 2, tests the dynamic surface tension of the solution once, and confirms whether it is consistent with the original solution.

[0112] The standard for judging the consistency of dynamic surface tension is that the difference between the surface tension values measured at the same bubble lifetime is within the range of ±1.0 mN / m. If consistent, the filtration process can be directly performed.

[0113] When it is judged that the dynamic surface tension of the liquid flowing out of the second detection outlet 7 is inconsistent with the original liquid, the displacement liquid circulation process needs to be performed on the filtration system 100. At this time, the second three-way valve 1202 is adjusted to close the second detection outlet 7, and the liquid is switched to flow to the displacement liquid tank 5. After the displacement liquid tank 5 collects a solution with a volume of 1.0-2.0 times the total capacity of the filter element 2, the third on-off valve 1103 is closed to stop the solution in the raw material mixing tank 1 from continuing to flow into the displacement liquid tank 5. At this time, the sixth on-off valve 1106 and the seventh on-off valve 1107 are opened, so that the solution continues to flow back to the liquid inlet of the filter element 2 along the displacement circulation branch, and the circulation is started.

[0114] Further, during the displacement liquid circulation process, the ninth on-off valve 1109 is opened at regular time intervals to take a sample of the solution from the third detection outlet 8 to monitor the change in the surface tension of the displacement liquid. During the circulation process, the displacement liquid containing the surfactant will repeatedly contact the resin type purification column or the particulate filter membrane in the filter element 2 multiple times. When the resin type purification column or the particulate filter membrane does not reach the saturation amount of the adsorbed surfactant molecules, the surfactant molecules will continue to be accumulated and adsorbed by the resin type purification column or the particulate filter membrane. Therefore, the concentration of the surfactant molecules in the displacement liquid will gradually decrease, and the surface tension of the displacement liquid will gradually increase until it reaches a certain balance and basically no longer changes. At this time, the second three-way valve 1202, the sixth on-off valve 1106, and the seventh on-off valve 1107 are closed.

[0115] Further, when the surface tension of the displacement liquid reaches the balance state, there are two states. The first balance state is that the porous material in the filter element 2 has reached the saturation of the adsorption of the surfactant molecules. The second balance state is that the resin type purification column or the particulate filter membrane has not reached the saturation of the adsorption of the surfactant molecules, but due to the low concentration of the surfactant in the aqueous solution, the surfactant molecules exist in a dynamic balance of adsorption-desorption on the liquid-solid interface due to the influence of the interaction force between the solute, the solvent, and the adsorption material. Therefore, the surfactant concentration also remains unchanged.

[0116] According to the embodiments of the present application, the verification method of the surface tension balance state of the displacement liquid is as follows: the third on-off valve 1103 is opened to supplement the solution in the raw material mixing tank 1 into the filter element 2, and the second three-way valve 1202 is adjusted to make the supplemented solution flow out of the second detection outlet 7, that is, a new section of the original liquid is introduced into the filter element 2, and then a sample is taken from the second detection outlet 7 to test the surface tension. After the sample is taken, the second three-way valve 1202 is adjusted to be closed.

[0117] The surface tension of the replacement fluid flowing out of the second detection outlet 7 is compared with the surface tension of the solution to be filtered flowing out of the fourth detection outlet 9. If the surface tensions of the two are consistent, the surface tension equilibrium state of the replacement fluid is the first equilibrium state, that is, the adsorption of surfactant molecules by the resin-type purification column or particulate filter membrane has reached saturation, and the solution in the filtration system 100 has been completely replaced by the solution to be filtered. At this time, the solution to be filtered can be formally filtered.

[0118] If the surface tension of the replacement fluid flowing out of the second detection outlet 7 has not yet recovered to the same level as the surface tension of the solution to be filtered flowing out of the fourth detection outlet 9, the surface tension equilibrium state of the replacement fluid is the second equilibrium state, that is, the surfactant molecules are in a dynamic equilibrium of adsorption and desorption at the liquid-solid interface. At this time, the replacement fluid in the replacement fluid tank 5 must be drained through the third detection outlet 8, and then the replacement fluid circulation is performed twice or more until the first equilibrium state is reached. In repeated replacement cycles, the replacement fluid tank 5 needs to collect 0.5-2.0 volumes of solution relative to the total capacity of the filter element 2. As the number of repetitions increases, the amount of solution to be collected decreases.

[0119] According to an embodiment of the present invention, during the filtration and purification of the developer solution, after the solution is thoroughly mixed in the raw material mixing tank 1, the eighth on-off valve 1108 is opened, and a sample is taken from the fourth detection outlet 9 for testing the solution's pH, dynamic surface tension, metal ions, and particulate impurities, which serves as a reference for subsequent steps. The eighth on-off valve 1108 is closed, and the first on-off valve 1101, the second on-off valve 1102, and the third on-off valve 1103 are opened. The second three-way valve 1202 is adjusted so that the solution flows out of the second detection outlet 7. Specifically, the solution flows from the raw material mixing tank 1, passes through the raw material transfer tank 10, and is transferred to the filter element 2. After that, it enters the replacement circulation branch and flows out of the second detection outlet 7. The discharged solution is then directed to the waste liquid tank. When the volume of the discharged solution reaches 1.0 times the total filter capacity of the filter element 2, a sample is taken for testing. If the pH is confirmed to be consistent with the original solution (within a range of ±0.02), the solution proceeds directly to filtration and purification. If it is confirmed that the pH has not yet returned to the original solution, the solution proceeds directly to filtration and purification. Subsequently, the liquid is discharged in batches at a volume of 1 / 5-2 / 5 relative to the filter capacity, and the pH of the effluent is tested each time until it is restored to the same level as the original solution (the difference in values ​​is within the range of ±0.02), and then the replacement fluid cycle is performed.

[0120] Further, during the circulation of the displacement liquid, the ninth switch valve 1109 is opened at regular intervals to take a solution sample from the third detection outlet 8 to monitor the change of the surface tension of the displacement liquid. During the circulation, the displacement liquid containing surfactant molecules repeatedly contacts the resin type purification column or the particulate filter membrane in the filter element 2. When the surfactant molecules adsorbed by the resin type purification column or the particulate filter membrane do not reach the saturation amount, the surfactant molecules continue to be accumulated and adsorbed by the resin type purification column or the particulate filter membrane, so the concentration of the surfactant molecules in the displacement liquid gradually decreases, and the surface tension of the displacement liquid gradually increases, until it reaches a certain balance and basically no longer changes. At this time, the second three-way valve 1202, the sixth switch valve 1106 and the seventh switch valve 1107 are closed.

[0121] Further, when the surface tension of the displacement liquid reaches the balance state, there are two states, the first balance state is that the adsorption of the porous material in the filter element 2 to the surfactant molecules reaches saturation, and the second balance state is that the adsorption of the resin type purification column or the particulate filter membrane to the surfactant molecules does not reach saturation, but due to the low concentration of the surfactant in the aqueous solution, the surfactant molecules on the liquid-solid interface exist in the dynamic balance of adsorption-desorption due to the influence of the interaction force between the solute, the solvent and the adsorption material, so the surfactant concentration remains unchanged.

[0122] According to the embodiments of the present application, the verification method of the surface tension balance state of the displacement liquid is as follows: the third switch valve 1103 is opened, the solution in the raw material mixing tank 1 is supplemented into the filter element 2, the second three-way valve 1202 is adjusted to make the supplemented solution flow out from the second detection outlet 7, that is, a new raw solution is introduced into the filter element 2, and then a sample is taken from the second detection outlet 7 to test the surface tension. After sampling, the second three-way valve 1202 is adjusted to be closed.

[0123] The surface tension of the displacement liquid flowing out from the second detection outlet 7 is compared with the surface tension of the to-be-filtered solution flowing out from the fourth detection outlet 9. If the surface tensions of the two are consistent, the surface tension balance state of the displacement liquid is the first balance state, that is, the adsorption of the resin type purification column or the particulate filter membrane to the surfactant molecules reaches saturation, and the solution in the filter system 100 is completely replaced by the to-be-filtered solution. At this time, the to-be-filtered solution can be formally filtered.

[0124] If the surface tension of the displacement liquid flowing out from the second detection outlet 7 has not yet recovered to be consistent with the surface tension of the to-be-filtered solution flowing out from the fourth detection outlet 9, the surface tension equilibrium state of the displacement liquid is the second equilibrium state, that is, there is a dynamic balance of adsorption-desorption of the surfactant molecules on the liquid-solid interface. At this time, the displacement liquid in the displacement liquid tank 5 needs to be discharged through the third detection outlet 8 first, and then the displacement liquid circulation is repeated for two or more times until the first equilibrium state is reached. In the repeated displacement circulation, the displacement liquid tank 5 needs to collect 0.5-2.0 volumes of solution relative to the total capacity of the filter 2, and the amount of solution to be collected needs to be reduced gradually with the increase of the number of repetitions.

[0125] According to the embodiment of the utility model, after the displacement liquid circulation is completed, the solution can be filtered. In this process, the first switch valve 1101, the second switch valve 1102, the third switch valve 1103 and the fourth switch valve 1104 are all opened, the fifth switch valve 1105 is closed, and the second three-way valve 1202 is adjusted to be closed. The solution is transported to the filter 2 after passing through the raw material transfer tank 10 along the pipeline of the main flow path, and at least one resin type purification column unit 201 and at least one microporous filter unit 202 are assembled in the filter 2 to remove the pollutants in the solution. The solution filtered through the filter 2 flows into the semi-finished product transfer tank 3 along the main flow path, and at this time, the first three-way valve 1201 is adjusted so that the solution flows out from the first detection outlet 6, and after the filtrate sample is taken at the first detection outlet 6, the first three-way valve 1201 is closed. If the filtrate has reached the required cleanliness, the first three-way valve 1201 is adjusted so that the solution in the semi-finished product transfer tank 3 continues to flow into the finished product tank 4 along the main flow path. If the filtrate has not reached the required cleanliness, the first three-way valve 1201 is adjusted to be closed, and the fifth switch valve 1105 is opened, so that the solution in the semi-finished product transfer tank 3 flows back to the liquid inlet of the filter 2 along the circulating filtration branch flow path, and the circulation filtration is continued. In this process, after each single filtration is completed, the second three-way valve 1202 is adjusted to be opened at the second detection outlet 7, and the sample is taken and tested at the second detection outlet 7 until the filtrate reaches the required cleanliness, then the fifth switch valve 1105 is closed, the filtration circulation is stopped, and the first three-way valve 1201 is adjusted so that the solution in the semi-finished product transfer tank 3 continues to flow into the finished product tank 4 along the main flow path.

[0126] The following will be described by taking experiments as examples, and in combination with Figures 3-9 The embodiments of the utility model are further described. Among them, examples 1-3 are the pre-purification of surfactants; examples 4-6 are the preparation of the developed solution using the pre-purified surfactants, and the fine purification of the developed solution.

[0127] In combination with Figure 3 And Figure 6As shown in Embodiment 1, the route consisting of the resin-type purification column unit 201 and the microfiltration filter unit 202 in series is the entire filter 2, which is connected in parallel with the displacement liquid tank 5. The output gas pressure of the nitrogen gas at the front end of the raw material mixing tank 1 is adjusted so that the flow rate of the solution in the pipeline is 500 mL / min.

[0128] The material, precision, and capacity of each resin-type purification column unit 201 and microfiltration filter unit 202 are shown in Table 1.

[0129]

[0130] Table 1

[0131] In combination Figure 3 and Figure 7 As shown in Embodiment 2, the displacement liquid tank 5 includes a first displacement liquid tank 501 and a second displacement liquid tank 502. A plurality of resin-type purification column units 201 arranged in series form a group, and a displacement cycle device is formed with the first displacement liquid tank 501. A plurality of microfiltration filter units 202 arranged in series form a group, and a displacement cycle device is formed with the second displacement liquid tank 502. The displacement liquid is displaced in the plurality of resin-type purification column units 201 arranged in series, and then is displaced in the plurality of microfiltration filter units 202 arranged in series. After all displacement processes are completed, the surfactant or the developer is filtered. The output gas pressure of the nitrogen gas at the front end of the raw material mixing tank 1 is adjusted so that the flow rate of the solution in the pipeline is 500 mL / min.

[0132] The material, precision, and capacity of each resin-type purification column unit 201 and microfiltration filter unit 202 are shown in Table 2.

[0133]

[0134] Table 2

[0135] In combination Figure 3 and Figure 8As shown in the embodiment 3, the surface treatment of the cation exchange resin and the chelating resin is different, and the adsorption capacity of the surfactant is different, so a displacement solution tank 5 is connected in parallel with each of the different resin type purification column units 201, the filter membrane materials of the microfiltration filter units 202 are the same, so the plurality of microfiltration filter units 202 are regarded as a whole unit, and are connected in parallel with a displacement solution tank 5, and the displacement is sequentially performed from the first resin type purification unit to the last resin type purification unit, and after the displacement of all the resin type purification units is completed, the tenth switch valve 1110 is opened, and the plurality of microfiltration filter units 202 are displaced. After the solution displacement process is completed, the surfactant solution or the developer is filtered. The output gas pressure of the nitrogen gas at the front end of the raw material mixing tank 1 is adjusted, so that the solution flow rate in the pipeline is 500 mL / min.

[0136] As shown in the embodiment 3, the surface treatment of the cation exchange resin and the chelating resin is different, and the adsorption capacity of the surfactant is different, so a displacement solution tank 5 is connected in parallel with each of the different resin type purification column units 201, the filter membrane materials of the microfiltration filter units 202 are the same, so the plurality of microfiltration filter units 202 are regarded as a whole unit, and are connected in parallel with a displacement solution tank 5, and the displacement is sequentially performed from the first resin type purification unit to the last resin type purification unit, and after the displacement of all the resin type purification units is completed, the tenth switch valve 1110 is opened, and the plurality of microfiltration filter units 202 are displaced. After the solution displacement process is completed, the surfactant solution or the developer is filtered. The output gas pressure of the nitrogen gas at the front end of the raw material mixing tank 1 is adjusted, so that the solution flow rate in the pipeline is 500 mL / min.

[0137]

[0138] Table 3

[0139] In combination Figure 3 and Figure 6 As shown in the embodiment 4, the prepared developer is composed of 2.38wt% of TMAH, 0.20wt% of surfactant secondary alcohol polyoxyethylene ether, and the balance of ultrapure water. The surfactant used for preparing the developer is the 1.00wt% surfactant aqueous solution purified in the embodiment 1. The output gas pressure of the nitrogen gas at the front end of the raw material mixing tank 1 is adjusted, so that the solution flow rate in the pipeline is 500 mL / min.

[0140] As shown in the embodiment 3, the surface treatment of the cation exchange resin and the chelating resin is different, and the adsorption capacity of the surfactant is different, so a displacement solution tank 5 is connected in parallel with each of the different resin type purification column units 201, the filter membrane materials of the microfiltration filter units 202 are the same, so the plurality of microfiltration filter units 202 are regarded as a whole unit, and are connected in parallel with a displacement solution tank 5, and the displacement is sequentially performed from the first resin type purification unit to the last resin type purification unit, and after the displacement of all the resin type purification units is completed, the tenth switch valve 1110 is opened, and the plurality of microfiltration filter units 202 are displaced. After the solution displacement process is completed, the surfactant solution or the developer is filtered. The output gas pressure of the nitrogen gas at the front end of the raw material mixing tank 1 is adjusted, so that the solution flow rate in the pipeline is 500 mL / min.

[0141]

[0142] Table 4

[0143] In combination Figure 3 and Figure 7 As shown in the embodiment 5, the prepared developer is composed of 2.38wt% of TMAH, 0.20wt% of surfactant secondary alcohol polyoxyethylene ether, and the balance of ultrapure water. The surfactant used for preparing the developer is the 1.00wt% surfactant aqueous solution purified in the embodiment 2. The output gas pressure of the nitrogen gas at the front end of the raw material mixing tank 1 is adjusted, so that the solution flow rate in the pipeline is 500 mL / min.

[0144] The material, precision, and capacity of each resin purification column unit 201 and microporous filter unit 202 are shown in Table 5.

[0145]

[0146] Table 5

[0147] In combination Figure 3 And Figure 8 As shown in Table 1, the prepared developer in Example 1 has a mass concentration of 2.38wt% of TMAH, a mass concentration of 0.20wt% of surfactant secondary alcohol polyoxyethylene ether, and the balance is ultrapure water. The surfactant used for preparing the developer is a 1.00wt% surfactant aqueous solution purified in Example 3. The output gas pressure of nitrogen at the front end of the raw material mixing tank 1 is adjusted so that the solution flow rate in the pipeline is 500mL / min.

[0148] The material, precision, and capacity of each resin purification column unit 201 and microporous filter unit 202 are shown in Table 6.

[0149]

[0150] Table 6

[0151] In the embodiment of the utility model, the prior art process route directly filters the formula developer as a control experiment 1, Figure 2 It is the whole route diagram of prior art filter system 100, the prior art process route is not provided with displacement liquid tank 5, and the surfactant is not pre-purified. Figure 9 It is the filter unit composition used for developer filtration and purification in the prior art. The output gas pressure of nitrogen at the front end of the raw material mixing tank 1 is adjusted so that the solution flow rate in the pipeline is 500mL / min. The material, precision, and capacity of each resin purification column unit 201 and microporous filter unit 202 are shown in Table 4.

[0152] Before formally receiving the filtrate, the filter element 2 is directly replaced by the solution by continuously flushing with the solution to be filtered. The specific steps are as follows: after preparing the developer, the first switch valve 1101, the second switch valve 1102, the third switch valve 1103 and the fourth switch valve 1104 are opened, and the first three-way valve 1201 is adjusted to flow out from the first detection outlet 6. The early displacement liquid passes through the filter element 2, then passes through the semi-finished product transfer tank 3, and flows out from the first detection outlet 6 to the waste liquid tank. In this process, the sample is quantitatively taken from the first detection outlet 6 to test the pH value and dynamic surface tension, until it is confirmed that the pH value and dynamic surface tension have both returned to the same as the original solution, then the first three-way valve 1201 is closed, and the filtration process of the developer is formally carried out.

[0153] The present embodiment also includes a control experiment 2, in which the displacement circulation loop of the filtration system 100 is the same as that of Example 4. In control experiment 2, the surfactant is not pre-purified and is directly prepared into a developer solution before filtration and purification. A displacement liquid tank 5 is used to displace the filter solution to be tested on multiple resin-type purification column units 201 and multiple microporous filter units 202. After the solution displacement process is completed, the surfactant solution or developer solution is filtered, and the output pressure of the nitrogen gas at the front end of the raw material mixing tank 1 is adjusted to ensure that the solution flow rate in the pipeline is 500 mL / min. The material selection, precision, and capacity of each resin-type purification column unit 201 and microporous filter unit 202 are shown in Table 4.

[0154] The present invention also includes a control experiment 3. Figure 2 The existing filtration system 100 in the present invention is used for pre-purification of surfactant. Figure 2 The overall process route is composed of a pre-purification treatment of a surfactant aqueous solution with a mass concentration of 1.00wt%. Figure 9 This is the composition of the filtration unit used for developer filtration and purification in this example. The nitrogen output pressure at the front end of the raw material mixing tank 1 was adjusted to maintain a solution flow rate of 500 mL / min. The materials, precision, and capacity of each resin-type purification column unit 201 and microporous filter unit 202 are shown in Table 1.

[0155] According to the embodiments of the present invention, when filtering the developer in Examples 4-6 and Control Experiments 1-2, it is necessary to monitor the pH value of the effluent in the preceding solution replacement step. The monitoring results are shown in Table 7.

[0156]

[0157] Table 7

[0158] When the pH value of the effluent is within the range of ±0.02 based on the pH value of the original solution, it is judged that the alkalinity of the solution has been restored and the ultrapure water remaining in the filter has been completely discharged.

[0159] With reference to Table 7, in Example 4, Control Experiment 1, and Control Experiment 2, multiple resin-type purification column units 201 and multiple microporous filter units 202 were connected in series as a whole, and the amount of solution required for pH recovery was 2.5-2.6 times the volume of the total capacity of the multiple resin-type purification column units 201 and the multiple microporous filter units 202.

[0160] In combination with Table 7, in Example 5, the resin-type purification column units 201 are taken as the first group, the microporous filter units 202 are taken as the second group, and the solution replacement of each group is sequentially performed from the first group to the second group. The solution amount required for pH value recovery is 2.7 times the volume of the capacity of the first group and 1.9 times the volume of the capacity of the second group, respectively. As can be seen from Comparative Example 1, the replacement solution is mainly consumed in the resin-type purification column units 201, because the cation exchange resin or the chelating resin in the purification column is a porous particulate material, and the water in the inter-particle gap and the microporous cavity is difficult to be replaced, so more solution needs to be introduced for replacement. In addition, by grouping the filter 2, the total solution amount for pH value recovery is also reduced.

[0161] In combination with Table 7, in Example 6, the cation exchange resin purification column 2011 is taken as the first group of resin-type purification column units 201, the chelating resin purification column 2012 is taken as the second group of resin-type purification column units 201, and the microporous filter units 202 of the same material are taken as the third group, and the solution replacement of each group is sequentially performed along the order of the first group, the second group and the third group. The solution amount required for pH value recovery is 3.0 times the volume of the capacity of the first group, 2.0 times the volume of the capacity of the second group, and 1.9 times the volume of the capacity of the third group.

[0162] This example can further confirm that the main solution consumption in the purification column unit is in the first group of resin-type purification column units 201 with the cation exchange resin purification column 2011. The possible reason is that the cation exchange resin is a strong acid resin, and in this stage, in addition to removing residual water, part of the tetramethylammonium ion (TMA+) is replaced with the acidic groups on the surface of the resin. This phenomenon can also make the resin exhibit a state of affinity to TMAH.

[0163] In the embodiments of the present application, the dynamic surface tension measurement method of the chemical includes but is not limited to the rapid bubble method. The experimental temperature is 25.0±1.0℃, and the bubble lifetime ranges from 0.015s to 25.0s.

[0164] According to the embodiments of the present application, in Example 1, Example 2, Example 3 and Comparative Experiment 3, the surfactant needs to be pre-purified. In the replacement solution circulation stage of Examples 1-3 and the direct flushing replacement stage of Comparative Experiment 3, the process steps, replacement solution circulation time and replacement solution amount are shown in Table 8.

[0165]

[0166]

[0167] Table 8

[0168] Figure 10The dynamic surface tension monitoring result chart of the replacement liquid circulation process of filter piece 2 in Example 1. Figure 11 The dynamic surface tension monitoring result chart of the replacement liquid circulation process of filter piece 2 in Example 2. Figure 12 The dynamic surface tension monitoring result chart of the replacement liquid circulation process of filter piece 2 in Example 3. Figure 13 The dynamic surface tension chart measured by segment sampling of filter piece 2 in the replacement liquid discharge process of Comparative Experiment 3.

[0169] Compared with the direct flushing replacement of Comparative Experiment 3, the total solution amount used in the replacement liquid circulation in Example 1, Example 2 and Example 3 is less than that used in the replacement liquid circulation of Comparative Experiment 3.

[0170] It is known from Example 2 that the adsorption of the surfactant in the solution in filter piece 2 mainly comes from the resin type purification column unit 201. Example 3 further confirms that the cation exchange resin used in this experiment has a large saturated adsorption amount of the surfactant.

[0171] According to the embodiments of the present application, the formula developing solution is filtered and purified in Example 4, Example 5, Example 6, Comparative Experiment 1 and Comparative Experiment 2. In the replacement liquid circulation stage of Example 4, Example 5, Example 6 and Comparative Experiment 2, and the direct flushing replacement stage of Comparative Experiment 1, the process steps, the replacement liquid circulation time and the replacement liquid amount are shown in Table 9.

[0172]

[0173]

[0174] Table 9

[0175] Figure 14 The dynamic surface tension monitoring result chart of the replacement liquid circulation process of filter piece 2 in Example 4. Figure 15 The dynamic surface tension monitoring result chart of the replacement liquid circulation process of filter piece 2 in Example 5. Figure 16 The dynamic surface tension monitoring result chart of the replacement liquid circulation process of the first group of filter units in Example 6. Figure 17 The dynamic surface tension monitoring result chart of the replacement liquid circulation process of the second group and the third group of filter units in Example 6. Figure 18 The dynamic surface tension monitoring result chart of the replacement liquid circulation process of filter piece 2 in Comparative Experiment 1. Figure 19 The dynamic surface tension monitoring result chart of the replacement liquid circulation process of filter piece 2 in Comparative Experiment 2.

[0176] Compared with the direct flushing replacement (Comparative Experiment 1), the total solution amount used in the replacement liquid circulation in Example 4, Example 5 and Comparative Experiment 2 is less than that used in the replacement liquid circulation of Comparative Experiment 1.

[0177] As can be seen from Example 5, the adsorption of the surfactant in the solution by the filter 2 is mainly from the resin type purification column unit 201. Example 6 further confirms that the cation exchange resin used in this experiment has a large saturated adsorption capacity for the surfactant. This phenomenon is consistent with the law in the pre-purification of the surfactant in Examples 1, 2 and 3.

[0178] In the embodiments of the present application, the test items of the cleanliness of the filtered solution include metal ion content test and particulate matter content test, wherein the method of the metal ion content test includes but is not limited to the method of testing the metal ion content in the positive glue developing solution for integrated circuits in the SJ / T 11508-2015 standard, for example, inductively coupled plasma-mass spectrometry (ICP-MS), and the standard addition method is used as the analysis method to monitor the cation content, and the detected elements include but are not limited to sodium ion, magnesium ion, aluminum ion, potassium ion, calcium ion, manganese ion, iron ion, copper ion and silver ion.

[0179] Further, the particulate matter content test method includes but is not limited to the test method for particles in electronic chemicals in the SJ / T 11638-2016 standard, and the particle size of the detected particulate matter is above 0.5 μm.

[0180] The impurity contents of the metal ions and the particulate matters in the surfactant solution after the pre-purification of Examples 1, 2, 3 and Comparative Experiment 3 are shown in Table 10.

[0181]

[0182] Table 10

[0183] According to the composition of the developing solution and considering the influence on the subsequent purification process, the impurity content in the surfactant aqueous solution with a mass concentration of 1.00 wt% after purification should meet the requirements that the concentration of a single metal ion impurity is less than 50 ppb, and the number of particulate matters (>0.5 μm) per milliliter of solution is less than 100 pcs. Among them, the surfactant solutions prepared in Examples 1, 2 and 3 all meet the use standard. However, after the same number of cycles, the surfactant solution in Comparative Experiment 3 still does not reach the required cleanliness. The possible reason is that in the displacement liquid circulation process of Examples 1, 2 and 3, the filter solution repeatedly wets the resin of the purification column and the filter membrane of the microporous filter, so that the surface is changed into a state of affinity to the aqueous solution, thereby helping to improve the filtration efficiency.

[0184] The impurity contents of the metal ions and the particulate matters in the developing solutions prepared in Examples 4, 5 and 6 are shown in Table 11.

[0185]

[0186] Table 11

[0187] According to the cleanliness requirement of the semiconductor developing solution, the impurity content in the filtered solution should meet the requirement that the concentration of single metal ion impurity should be lower than 1 ppb, and the number of particles (>0.5 μm) in each milliliter of the solution should be lower than 5 pcs. According to the test results, the developing solutions prepared in Example 4, Example 5 and Example 6 all meet the cleanliness requirement.

[0188] The metal and particle impurity contents in the developing solutions prepared in Control Experiment 1 and Control Experiment 2 are shown in Table 12.

[0189]

[0190] Table 12

[0191] The impurity content of the developing solution stock prepared without pre-purification of the surfactant is far beyond the limited range, and the effect is not ideal after the same cycle filtration.

[0192] In the description of the present specification, the description referring to the terms "one embodiment", "some embodiments", "exemplary embodiment", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the exemplary description of the above terms does not necessarily mean the same embodiment or example.

[0193] Although the embodiments of the present application have been shown and described, it should be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the claims and their equivalents.

Claims

1. A semiconductor developer filtering system, characterized in that: include: Raw material mixing tank; A filter element, wherein the liquid inlet end of the filter element is connected to the raw material mixing tank; a semi-finished product transfer tank, wherein the inlet of the semi-finished product transfer tank is connected to the liquid outlet end of the filter element, the outlet of the semi-finished product transfer tank is connected to the liquid inlet end of the filter element, and the semi-finished product transfer tank is further provided with a first detection outlet; a finished product tank, the inlet of which is connected to the outlet of the semi-finished product transfer tank; A replacement fluid tank, the inlet of which is connected to the liquid outlet of the filter element and is arranged in parallel with the semi-finished product transfer tank, and the outlet of which is connected to the liquid inlet of the filter element.

2. The semiconductor developer filtering system according to claim 1, wherein: A second detection outlet is provided between the inlet of the replacement fluid tank and the liquid outlet end of the filter element.

3. The semiconductor developer filtering system according to claim 1, characterized in that: The replacement fluid tank is further provided with a third detection outlet.

4. The semiconductor developer filtering system according to any one of claims 1 to 3, characterized in that: The filter element is integrated with a particle filter membrane and a resin-type purification column.

5. The semiconductor developer filtering system according to any one of claims 1 to 3, characterized in that: The filter element includes a resin-type purification column unit and a microporous filter unit, and the resin-type purification column unit and the microporous filter unit are arranged in series. The replacement fluid tank includes a first replacement fluid tank and a second replacement fluid tank. The inlet of the first replacement fluid tank is connected to the liquid outlet end of the resin-type purification column unit, the outlet of the first replacement fluid tank is connected to the liquid inlet end of the resin-type purification column unit, the inlet of the second replacement fluid tank is connected to the liquid outlet end of the microporous filter unit, and the outlet of the second replacement fluid tank is connected to the liquid inlet end of the microporous filter unit.

6. The semiconductor developer filtering system according to claim 5, characterized in that: There are a plurality of resin-type purification column units, which are arranged in series, and one first replacement fluid tank is connected to the plurality of resin-type purification column units.

7. The semiconductor developer filtering system according to claim 5, characterized in that: There are multiple resin-type purification column units, which are arranged in series. There are multiple first replacement fluid tanks, which are connected to the multiple resin-type purification column units in a one-to-one correspondence.

8. The semiconductor developer filtering system according to claim 5, characterized in that: There are multiple microporous filter units, which are arranged in series, and one second replacement fluid tank is connected to the multiple microporous filter units.

9. The semiconductor developer filtering system according to claim 5, characterized in that: There are a plurality of microporous filter units, which are arranged in series. There are a plurality of second replacement fluid tanks, which are connected to the microporous filter units in a one-to-one correspondence.

10. The semiconductor developer filtering system according to claim 1, wherein: The raw material mixing tank is provided with a fourth detection outlet.

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