KR100727851B1 - Chemical mixing apparatus and method - Google Patents

Abstract

A DSP chemical mixing apparatus for preparing DSP chemical and a method thereof are provided to allow efficient preparation of DSP chemical for removing remaining polymer from a semi-conductive board, to minimized heat generation during preparation of DSP chemical, and to save manufacturing cost. The DSP chemical mixing apparatus for preparing DSP chemical comprises: a mixing container(110) providing a space for preparing DSP chemical by mixing sulfuric acid, hydrogen superoxide, fluoric acid, and ultra-pure water; a circulation member(120); a treatment solution supplying member(130) supplying the chemical substances to the mixing container(110); and a control part(140) controlling the supplying amount of the sulfuric acid and fluoric acid.

Description

CHEMICAL MIXING APPARATUS AND METHOD

1 is a view showing a semiconductor manufacturing equipment equipped with a chemical liquid mixing apparatus according to the present invention.

2 is a flow chart showing a method of mixing the chemical liquid according to the present invention.

3A to 3D are views for explaining a process of the chemical liquid mixing apparatus according to the present invention.

* Description of the symbols for the main parts in the drawings *

1: semiconductor manufacturing equipment

10: chemical supply unit

20: substrate processing unit

100: chemical liquid mixing device

110: mixing vessel

120: circulation member

130: treatment liquid supply member

The present invention relates to an apparatus and a method for mixing a chemical liquid, and more particularly, to a device and a method for mixing a DSP chemical liquid (DSP: Diluted Sulfate Peroxide chemical, which is used in a semiconductor and flat panel display manufacturing process). It is about.

A general semiconductor device uses aluminum, copper, or the like as the material of the metal wiring. Accordingly, in the semiconductor manufacturing process, a process of forming a metal thin film on a wafer and a dry etching process of removing an unnecessary portion of the formed metal thin film are performed to manufacture a metal wiring. In this case, a polymer remains on the wafer after the dry etching process as a reaction by-product generated when the metal wiring is formed.

These polymers are usually removed by solvent-based chemicals or by etching solutions such as DSP. Among these, DS is an etchant in which sulfuric acid (H 3 SO 4), hydrogen peroxide (H 2 O 2), and hydrofluoric acid (HF) are mixed in an appropriate ratio.

DS is manufactured by a chemical mixing apparatus. The chemical liquid mixing apparatus for manufacturing a general DS includes a mixing vessel, a circulation member, and a treatment liquid supply member. The mixing vessel receives sulfuric acid, hydrogen peroxide, hydrofluoric acid, and ultrapure water from the treatment liquid supply member. The circulation member circulates the treatment liquids in the mixing vessel to produce a die that satisfies the predetermined concentration and temperature conditions.

However, the above-described chemical liquid mixing apparatus supplies sulfuric acid, hydrogen peroxide, hydrofluoric acid, and ultrapure water to the mixing vessel at the same time, and then the circulation member circulates and mixes the treatment liquids. Is generated. This is because sulfuric acid, hydrogen peroxide, and hydrofluoric acid, which are used to make DSP, generate an explosive heat when reacted with water. In general, since the dies at room temperature (25 ° C.) are used to remove the polymer, a general treatment liquid mixing device adds time for cooling the high temperature dies, and thus the manufacturing time of the dies is long.

In order to improve this, a cooling member such as a cooling trap for cooling the hot dies generated at present is added to the chemical liquid mixing apparatus. However, since the cooling member has a limitation in cooling the high temperature dies in a short time, the time for cooling the dies is increased, and a lot of time is consumed in producing the dies satisfying the process temperature.

In addition, the cooling member added to the chemical liquid mixing apparatus is usually a cooling trap and a cooling-water line for supplying cooling water to the cooling trap and a large-capacity storage tank. Since expensive accessories such as the back are required, the manufacturing cost of the chemical liquid mixing apparatus increases.

In order to solve the above-mentioned problems, an object of the present invention is to provide a chemical liquid mixing apparatus and method for producing a chemical liquid efficiently. In particular, it is an object of the present invention to provide a chemical liquid mixing apparatus and method for efficiently producing a DS chemical liquid for removing a polymer remaining on a semiconductor substrate.

It is also an object of the present invention to provide a chemical liquid mixing apparatus and method for shortening the manufacturing time of DS.

In addition, an object of the present invention is to provide a chemical liquid mixing apparatus and method for minimizing the exothermic phenomenon generated during the manufacturing of the DS.

In addition, an object of the present invention is to provide a chemical liquid mixing apparatus and method that can reduce the production cost.

The chemical liquid mixing apparatus according to the present invention for achieving the above object is a mixing vessel for providing a space for producing a chemical liquid by mixing the treatment liquid containing sulfuric acid, hydrogen peroxide, hydrofluoric acid, and ultrapure water therein, the treatment with the mixing vessel A processing liquid supply member for supplying liquids, a circulation line for circulating and mixing the processing liquids in the mixing vessel, and a controller for controlling supply of sulfuric acid, hydrogen peroxide, hydrofluoric acid, and ultrapure water of the processing liquid supply member, wherein The apparatus produces the chemical liquid without a cooling member for cooling the heat generated due to the mixing of the treatment liquids.

According to an embodiment of the present invention, the control unit supplies the treatment liquid such that the treatment liquid supply member simultaneously supplies the ultrapure water and the hydrogen peroxide to the mixing vessel, and simultaneously supplies the sulfuric acid and the hydrofluoric acid when the chemical liquid is manufactured. To control the member.

According to an embodiment of the present invention, the temperature of the mixed chemical liquid is 40 ° C or less.

The chemical liquid mixing method according to the present invention for achieving the above object is supplied with ultrapure water and hydrogen peroxide to the mixing vessel at the same time, and then supplying sulfuric acid and hydrofluoric acid to the mixing vessel at the same time, the ultrapure water supplied into the mixing vessel, A chemical solution is prepared by mixing hydrogen peroxide, sulfuric acid, and hydrofluoric acid.

According to an embodiment of the present invention, the chemical liquid mixing method is performed while circulating the ultrapure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid in the mixing vessel along the circulation line when the chemical liquid is mixed.

According to an embodiment of the present invention, the temperature of the mixed chemical liquid is 40 ° C or less.

In order to achieve the above object, a chemical liquid mixing method according to the present invention is a mixing vessel which provides a space for generating a chemical liquid by mixing treatment liquids including ultrapure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid, and circulating the treatment liquids in the mixing vessel. A circulating line for mixing the mixture, an ultrapure water supply line for supplying the ultrapure water to the mixing vessel and controlling a supply amount of the ultrapure water, a second for supplying the hydrogen peroxide to the mixing vessel and controlling the supply amount of hydrogen peroxide Hydrogen peroxide supply line is provided with a valve, sulfuric acid supply line is provided with a third valve for supplying the sulfuric acid to the mixing vessel and controls the amount of sulfuric acid, supplying the hydrofluoric acid to the mixing vessel and controlling the amount of hydrofluoric acid supply A hydrofluoric acid supply line in which a fourth valve is installed, and a control unit for controlling the valves In the chemical liquid mixing method of the chemical liquid mixing device, (a) the control unit by opening the first valve and the second valve, supplying the ultrapure water and the hydrogen peroxide by the predetermined amount of supply to the mixing vessel at the same time (b) the control unit closes the first valve and the second valve, opens the third valve and the fourth valve, and simultaneously supplies the sulfuric acid and the hydrofluoric acid in a predetermined amount by the predetermined amount to the mixing vessel. And (c) the control unit closing the third valve and the fourth valve and mixing the processing liquids in the mixing vessel while circulating along the circulation line to generate the chemical liquid.

According to an embodiment of the present invention, the step (c) is such that the heat generated by the mixing of the treatment liquids is 40 ° C or less, thereby completing the generation of the chemical liquid without cooling the generated chemical liquid.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided to ensure that the disclosed subject matter is thorough and complete, and that the spirit of the present invention to those skilled in the art will fully convey. Portions denoted by like reference numerals denote like elements throughout the specification.

In addition, in the embodiment of the present invention will be described taking a chemical mixing device for producing a DS etching solution as an example. However, the present invention can be applied to any apparatus for mixing various kinds of treatment liquids.

(Example)

1 is a view showing a semiconductor manufacturing equipment equipped with a chemical liquid mixing apparatus according to the present invention. Referring to FIG. 1, the semiconductor manufacturing equipment 1 according to the present invention has a substrate processing unit 10 and a processing liquid supply unit 20. The substrate processing unit 10 receives a DSP chemical liquid (DSP) from the processing liquid supply unit 20 to remove the polymer remaining on the semiconductor substrate W. . DSP is an etchant mixed with sulfuric acid (H3SO4), hydrogen peroxide (H2O2), and hydrofluoric acid (HF) in an appropriate ratio. It is usually used to remove the polymer remaining on the substrate (W) subjected to the dry etching process. . The processing liquid supply unit 20 generates a DS and supplies it to the substrate processing unit 10.

The substrate processing unit 10 includes at least one process chamber 12. The process chamber 12 includes a housing 13, a support 14, a driver 15, a nozzle 16, and a drain 17. The housing 13 provides a space for performing a process of removing reaction by-products such as polymer remaining on the substrate W therein. The support part 14 supports and rotates the substrate W in the housing 13 during the process. The driver 15 rotates and lifts the support 14. The nozzle unit 16 receives the DS from the processing liquid supply unit 20 and supplies the DS to the processing surface of the substrate W seated on the support unit 14 during the process. In addition, the drain unit 17 drains the DS used in the process to the outside of the housing 13.

The treatment liquid supply unit 20 has a chemical mixing apparatus. The chemical liquid mixing apparatus mixes a plurality of treatment liquids to produce a DS. The chemical liquid mixing apparatus 100 includes a mixing vessel 110, a circulation member 120, a treatment liquid supply member 130, and a controller 140.

The mixing vessel 110 provides a space for mixing the plurality of processing liquids therein. That is, the mixing vessel 110 receives and stores treatment liquids for producing DSP during the process, that is, sulfuric acid (H 2 SO 4), hydrogen peroxide (H 2 O 2), hydrofluoric acid (HF), and ultrapure water (DIW: Deionized Water). A plurality of level sensors are installed on the outside of the mixing vessel 110 to detect the level of the processing liquids stored therein. Each level sensor detects the level of the processing liquid in the mixing vessel 110 at a predetermined height. In the present exemplary embodiment, the level of the processing liquid in the mixing container 110 is detected by using a plurality of level sensors as an example. However, various techniques may be applied to the method of detecting the level of the processing liquid in the mixing container 110. have.

The circulation member 120 circulates the treatment liquids in the mixing vessel 110. The circulation member 120 has a recycle line, a pressure member 123, a densitometer 125, a filter member 127, and a temperature control member 128. The circulation line includes a supply line 121 and a recovery line 122. The supply line 121 supplies the DS to the substrate processing unit 10 from the mixing vessel 110. The recovery line 122 branches from the supply line 121, and recovers the DS supplied to the supply line 121 to the mixing vessel 110.

The pressing member 123 is installed on the supply line 121 to provide a flow pressure to the supply line 121. A pump may be used as the pressure member 123. Densitometer 125 is installed on the supply line 121 to measure the concentration of the DS moving along the supply line 121. The filter member 127 is installed on the supply line 121 to filter foreign matter in the DS moving along the supply line 121. At least one filter is used as the filter member 127.

The temperature regulating member 128 adjusts the temperature of the DS etching liquid moved along the supply line 121. The temperature control member 128 includes a body (not shown) installed to surround the supply line 121 and a constant temperature line (not shown) provided to allow constant temperature water to flow inside the body. The temperature regulating member 128 allows the DS moving along the supply line 121 to be maintained at room temperature by the constant temperature water flowing along the constant temperature water line.

The treatment liquid supply member 130 supplies a plurality of treatment liquids to the mixing vessel 110. The treatment liquid supply member 130 has an ultrapure water supply 132, a hydrogen peroxide supply 134, a hydrofluoric acid supply 136, and a sulfuric acid supply 138. The ultrapure water supply 132 has an ultrapure water supply 132a and an ultrapure water supply line 132b. The ultrapure water source 132a receives the ultrapure water, and the ultrapure water supply line 132b supplies ultrapure water from the ultrapure water source 132a to the mixing vessel 110. Hydrogen peroxide supply 134 has a peroxide supply source 134a and a hydrogen peroxide supply line 134b. The hydrogen peroxide source 134a receives hydrogen peroxide, and the hydrogen peroxide supply line 134b supplies hydrogen peroxide from the hydrogen peroxide source 134a to the mixing vessel 110. The hydrofluoric acid feeder 136 has a hydrofluoric acid source 136a and a hydrofluoric acid supply line 136b. The hydrofluoric acid source 136a receives the hydrofluoric acid, and the hydrofluoric acid supply line 136b supplies the hydrofluoric acid from the hydrofluoric acid source 136a to the mixing vessel 110. The sulfuric acid supply 138 has a sulfuric acid source 138a and a sulfuric acid supply line 138b. The sulfuric acid source 138a contains sulfuric acid, and the sulfuric acid supply line 138b supplies sulfuric acid from the sulfuric acid source 138a to the mixing vessel 110.

Here, each of the ultrapure water supply 132, the hydrogen peroxide supply 134, the sulfuric acid supply 136, and the hydrofluoric acid supply 138 are each a mixture of ultrapure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid for the production of DSP having a predetermined concentration during the process. Ultrapure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid are supplied to the mixing vessel 110 in proportion. For example, a typical DSP etchant is prepared by mixing 12% sulfuric acid, 5.4% hydrogen peroxide, and 0.01 ppm hydrofluoric acid in a weight percent unit. Accordingly, each of the ultrapure water supply 132, the hydrogen peroxide supply 134, the sulfuric acid supply 136, and the hydrofluoric acid supply 138 may convert the ultrapure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid into the mixing vessel 110 by the mixing ratio during the process. Supply.

The control unit 140 controls the semiconductor manufacturing equipment 1 described above. That is, the controller 140 opens and closes the valves V1, V2, V3, V4, V5, V6, and V7 provided in the processing liquid mixing device, and drives the pressing member 123. In addition, the controller 140 controls the substrate W processing process of the substrate processor 10.

Hereinafter, the process of the semiconductor manufacturing equipment 1 described above will be described in detail. Here, the same reference numerals of the same components as the above-described components, and the detailed description of the components will be omitted.

2 is a flow chart showing a treatment liquid mixing method according to the present invention. 3A to 3D are views for explaining a process of the treatment liquid mixing apparatus according to the present invention.

Referring to FIG. 2, when the process of the semiconductor manufacturing equipment 1 is started, the treatment liquid supply member 130 simultaneously supplies ultrapure water and hydrogen peroxide to the mixing vessel 110 (S110). That is, referring to FIG. 3A, the controller 140 opens the valves V4 and V5. Accordingly, the ultrapure water supply line 132b supplies ultrapure water from the ultrapure water source 132a to the mixing vessel 110, and at the same time the hydrogen peroxide supply line 134b supplies hydrogen peroxide from the hydrogen peroxide source 134a to the mixing vessel 110. Supply. At this time, the controller 140 opens the valves V4 and V5 for a predetermined time, such that the ultrapure water supply 132 and the hydrogen peroxide supply 134 supply the ultrapure water and the hydrogen peroxide by the predetermined supply amount.

When the supply of ultrapure water and hydrogen peroxide is completed, the treatment liquid supply member 130 simultaneously supplies sulfuric acid and hydrofluoric acid to the mixing vessel 110 (S120). That is, referring to FIG. 3B, the control unit 140 closes the valves V4 and V5 and opens the valves V6 and V7. Thus, sulfuric acid supply line 136b supplies sulfuric acid from sulfuric acid source 136a to mixing vessel 110, and hydrofluoric acid supply line 138b supplies hydrofluoric acid from hydrofluoric acid source 138a to mixing vessel 110. At this time, the controller 140 controls the opening and closing times of the valves V6 and V7 so that the sulfuric acid supplier 136 and the hydrofluoric acid supplier 138 supply sulfuric acid and hydrofluoric acid by a predetermined supply amount.

In the present exemplary embodiment, the controller 140 adjusts the supply amount of the processing liquids by adjusting the opening / closing time of the valve. However, various techniques may be applied to the method of controlling the supply amount of the processing liquids. For example, according to another embodiment of the present invention, the load cell (load-cell) for sensing the load of the processing liquids supplied into the mixing vessel 110, the treatment according to the load of the processing liquids in the mixing vessel 110 The amount of liquid supplied can be adjusted. Alternatively, the supply amount of the processing liquids may be adjusted according to the level of the processing liquid supplied into the mixing container 110 sensed by the level sensors using the level sensors provided in the mixing container 110. Since the technology for adjusting the supply amount of the treatment liquid is a technique generally understood by those skilled in the semiconductor industry, a detailed description thereof will be omitted.

When the supply of sulfuric acid and hydrofluoric acid is completed, the circulation member 120 mixes the processing liquids in the mixing vessel 110 (S130). Referring to FIG. 3C, the control unit 140 closes the valves V6 and V7, opens the valves V1 and V2, and operates the pressing member 123. Thus, the processing liquids in the mixing vessel 110 are mixed into the DS with a predetermined concentration while being circulated along the supply line 121 and the recovery line 122. In addition, the treatment liquids circulated along the supply line 121 and the recovery line 122 are adjusted to room temperature by the temperature adjusting member 128, and contaminants in the treatment liquids are removed by the filter member 127.

When the treatment liquids in the mixing vessel 110 are mixed for a predetermined time, the densitometer 125 measures the concentration of the circulating dies circulated. In addition, the controller 140 determines whether the density of the DS measured by the densitometer 125 satisfies a predetermined concentration condition (S140). If the concentration of the DS etching solution measured by the densitometer 125 is out of a predetermined concentration condition, the controller 140 selectively opens and closes the valves V4, V5, V6, and V7 to mix the processing liquids required for the concentration control. It is further supplied to the container (110).

If the concentration of the DS measured by the densitometer 125 satisfies a predetermined concentration condition, the controller controls the processing liquid supply unit 20 to be in a standby state for supplying the DS (S140). That is, the control unit continuously or periodically operates the pressure member 123 while the valves V1 and V2 are opened to circulate the DSP in the mixing vessel 110. At this time, when the substrate processing process is performed in the substrate processing unit 10, when seated and rotated on the support 13 of the process chamber 11, the controller opens the valve V3, and the supply line 121 is a mixing vessel ( The DS is supplied from the 110 to the nozzle unit 16. The nozzle unit 16 injects the supplied DS to the processing surface of the substrate W, and the injected DS removes the polymer remaining on the substrate W surface. The used DS is drained out of the process chamber 12 through the drain 17. Alternatively, the used DS is recovered and reused into the mixing vessel 110 through a separate recovery pipe (not shown).

The above-mentioned chemical liquid mixing apparatus and method minimize the heat generated when mixing ultrapure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid for manufacturing DS. That is, according to the experiment, the manufacturing method of the DS in accordance with the present invention, the temperature of the mixed DS is less than 40 ℃, the method of simultaneously supplying each of the conventional treatment liquids under the same conditions, the temperature of the mixed DS is 60 More than Therefore, the chemical liquid mixing apparatus and method according to the present invention can control the DS to the process temperature only by controlling the temperature by constant temperature water without the process of cooling the conventional DS more than 60 ℃.

In addition, the chemical liquid mixing apparatus and method according to the present invention can produce a mixture of the DS to be mixed at a temperature of 40 ℃ or less, such as a means for cooling a high temperature DS, such as a cooling trap (cooling trap) and the cooling trap No cooling water line for supplying cooling water, and a large cooling water tank are added. Therefore, the present invention can reduce the manufacturing cost of the device.

The foregoing detailed description illustrates the present invention. In addition, the foregoing description merely shows and describes preferred embodiments of the present invention, and the present invention can be used in various other combinations, modifications, and environments. That is, changes or modifications may be made within the scope of the concept of the invention disclosed in this specification, the scope equivalent to the disclosed contents, and / or the skill or knowledge in the art. The above-described embodiments are for explaining the best state in carrying out the present invention, the use of other inventions such as the present invention in other state known in the art, and the specific fields of application and uses of the present invention. Various changes are also possible. Accordingly, the detailed description of the invention is not intended to limit the invention to the disclosed embodiments. Also, the appended claims should be construed to include other embodiments.

For example, the present embodiment has been described by supplying ultrapure water and hydrogen peroxide at the same time and then supplying sulfuric acid and hydrofluoric acid at the same time, the supply of ultrapure water and hydrogen peroxide and the supply of sulfuric acid and hydrofluoric acid may be sequentially or periodically, such ultra pure water and Simple changes in the order of feeding hydrogen peroxide and the order of feeding sulfuric acid and hydrofluoric acid are included within the scope of the present invention.

As described above, the chemical liquid mixing apparatus and method according to the present invention does not require a process of cooling the heat generated during the manufacture of the DS chemical liquid to the process temperature. Therefore, the manufacturing time of the DS chemical liquid which satisfy | fills process conditions, such as temperature and a concentration, is shortened. That is, the chemical liquid mixing apparatus and method according to the present invention reduces the temperature of the DS to be mixed below 40 ° C. Therefore, in contrast to the conventional DSP produced at a high temperature of 60 ℃ or more, the process of cooling the mixed DSP is not added to shorten the manufacturing time of the DSP.

In addition, the chemical liquid mixing apparatus and method according to the present invention can reduce the temperature of the mixed DS to less than 40 ℃, there is no added device for cooling the mixed DS to the process temperature, reducing the manufacturing cost of the device do.

Claims (5)

In the method of mixing the chemical liquid, Ultrapure water and hydrogen peroxide are simultaneously supplied to the mixing vessel, and then sulfuric acid and hydrofluoric acid are simultaneously supplied to the mixing vessel, and then ultrapure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid are mixed into the mixing vessel to prepare a chemical liquid. Chemical liquid mixing method. The method of claim 1, The chemical liquid mixing method, The method of mixing the chemical liquid, characterized in that the ultra-pure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid in the mixing vessel is circulated along the circulation line. The method according to claim 1 or 2, The temperature of the mixed chemical liquid, A chemical liquid mixing method, characterized in that 40 ℃ or less. A mixing vessel providing a space for producing a chemical liquid by mixing treatment liquids including ultrapure water, hydrogen peroxide, sulfuric acid, and hydrofluoric acid, a circulation line for circulating and mixing the treatment liquids in the mixing vessel, and supplying the ultrapure water to the mixing vessel And an ultrapure water supply line having a first valve for controlling the supply amount of ultrapure water, a hydrogen peroxide supply line for supplying the hydrogen peroxide to the mixing vessel and a second valve for controlling the supply amount of hydrogen peroxide, the sulfuric acid as the mixing vessel. Sulfuric acid supply line is provided with a third valve for supplying and supplying the sulfuric acid, the hydrofluoric acid supply line is provided with a fourth valve for supplying the hydrofluoric acid to the mixing vessel and controls the amount of hydrofluoric acid, and the valves In the chemical liquid mixing method of the chemical liquid mixing device having a control unit for controlling, (a) the control unit opening the first valve and the second valve to simultaneously supply the ultrapure water and the hydrogen peroxide to the mixing vessel by a predetermined amount of supply; (b) the control unit closes the first valve and the second valve, opens the third valve and the fourth valve, and simultaneously supplies the sulfuric acid and the hydrofluoric acid by a predetermined supply amount to the mixing vessel. Steps, (c) the controller closing the third valve and the fourth valve and mixing the processing liquids in the mixing vessel while circulating along the circulation line to generate the chemical liquid. Way. The method of claim 4, wherein In step (c), The chemical liquid mixing method characterized in that the heat generated by the mixing of the treatment liquid to be 40 ℃ or less, thereby completing the generation of the chemical liquid without cooling the generated chemical liquid.

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