KR101221853B1 - Manufacturing methode of membrane for chemical mechanical polishing and membrane for chemical mechanical polishing using the same - Google Patents

Abstract

PURPOSE: A method for manufacturing a membrane for Chemical Mechanical Polishing and the membrane manufactured by the same method are provided to improve reproducibility by using an injection molding method. CONSTITUTION: Reactive polymer raw material is supplied to an injector(211). The reactive polymer raw material includes base polymer, cross-linking agent, and catalyst. The reactive polymer raw material is put into the internal space of a mold(221) through a nozzle of the injector. In the internal space of the mold, the reactive polymer raw material is molded to form a membrane.

Description

Manufacturing method of membrane for chemical mechanical polishing apparatus and thereby manufactured membrane for chemical mechanical polishing apparatus {Manufacturing methode of membrane for Chemical Mechanical Polishing and membrane for Chemical Mechanical Polishing using the same}

The present invention relates to a method for manufacturing a membrane for a chemical mechanical polishing apparatus and a membrane for a chemical mechanical polishing apparatus manufactured by the same, and more particularly, to a polishing head of a chemical mechanical polishing apparatus, which is applied to a polishing head of a chemical mechanical polishing apparatus to be identical or to each other in a plurality of regions of a semiconductor substrate. The present invention relates to a method for manufacturing a membrane for a chemical mechanical polishing apparatus, and a membrane for a chemical mechanical polishing apparatus manufactured thereby, by applying different pressure to improve the uniformity of the chemical mechanical polishing process.

A semiconductor device is an electronic device formed by integrating a device having a fine size on a substrate, and a thin film deposition process, a photolithography process, an etching process, an ion implantation process, and the like are applied to manufacture such a semiconductor device. In order to form devices such as transistors and capacitors with high integration in semiconductor devices, semiconductor layers, metal layers, and insulating layers are formed by a complicated structure. For this purpose, the steps of the surface gradually increase as the thin film deposition and etching processes are repeatedly performed. Will be increased. If the step height of the surface is increased, the photoresist will be limited in forming a narrow line width in the subsequent photolithography process, so the planarization process should be added in the middle of the process.

Recently, chemical mechanical polishing (hereinafter referred to as 'CMP') has been widely used as a technology for planarizing a semiconductor surface. CMP is a process in which a surface containing a slurry containing abrasive particles and an etchant is rotated while contacting a surface of a pad with a surface of a substrate to simultaneously perform chemical mechanical polishing on an upper layer of the substrate. In such a CMP process, it is important to uniformly polish on a wafer-type substrate. If the polishing is not uniformly performed at the center and the outer portion of the wafer, the thickness of the interlayer insulating layer may be changed for each part of the wafer. This can cause open defects in the interior.

The membrane for CMP is a part that pressurizes the back side of the wafer so as to maintain a uniform pressure between the wafer and the CMP pad. The membrane for CMP is made of a polymer resin having elasticity, and after being bonded to a polishing head, is divided into a plurality of regions so that a gas can be injected from the outside. When the gas is injected from the outside at a constant pressure, each region of the membrane divided into a plurality of regions may swell, and may independently transmit pressure to different regions of the wafer. The structure and function of the membrane for CMP are disclosed in detail in Korean Patent Laid-Open Publication No. 2004-74269. The prior art relates to a CMP apparatus, comprising a platen, a polishing pad provided on the platen, and a polishing head for pressing the semiconductor substrate onto the polishing pad to polish the semiconductor substrate, wherein the polishing head includes the polishing head. A support plate having a plurality of holes formed on a bottom surface of the support plate, a pressing part positioned below the support plate and having a plurality of holes formed therein, a first fixing part extending upward from an edge of the pressing part, and an upper portion from the plurality of holes And a clamp having a second fixing part extended to the support plate, and a clamp positioned on the support plate to fix the membrane, thereby improving polishing uniformity of the wafer.

The conventional CMP membrane was manufactured by molding a gum-like solid-state silicone polymer compound by a press molding method. At this time, the solid-state silicone polymer compound is a raw material of a silicone polymer compound called heat cured elastomer (hereinafter referred to as 'HCE'), HCE is ViMe ₂ SiO (Me ₂ SiO) _n (MeViSiO) _m SiMe _It is a siloxane polymer compound represented by the structural formula of ₂ Vi (Vi: vinyl group, an integer of n + m = 3000 to 10000), a solid state in a gum state at room temperature and can be cured by the following reaction formula 1.

Scheme 1

The manufacturing method of the membrane for CMP by the press molding method is advanced by the method of roll-milling HCE with a hardening | curing agent, and shape | molding by a press method. The manufacturing method of the membrane for CMP by the press molding method is a complicated process in terms of productivity, the operation safety may be a problem at a high process temperature, there is a lot of flash, there is a problem that low productivity due to the slow crosslinking speed. In addition, the quality of the finished product is poor in reproducibility, low elasticity, it is difficult to restore after deformation or discoloration by the by-products of the peroxide series. Therefore, there is a great need to develop a new method for producing a new membrane for CMP while maintaining excellent properties such as elasticity and chemical resistance.

Accordingly, the first problem to be solved by the present invention is to provide a method for producing a membrane for a chemical mechanical polishing apparatus having high production speed, high reproducibility, and excellent physical properties such as elasticity and chemical resistance.

The second problem to be solved by the present invention is to provide a membrane for a chemical mechanical polishing apparatus manufactured by the above manufacturing method.

In order to achieve the first object, the present invention is applied to a polishing head of a chemical mechanical polishing apparatus, and a pressure adjusting portion for applying the same or different pressure to different regions of the substrate contact portion and the substrate contact portion which contacts the rear surface of the substrate. A method of manufacturing a membrane for a chemical mechanical polishing apparatus comprising: supplying a reactive polymer raw material to an injector, introducing a reactive polymer raw material supplied to the injector into an internal space of a mold through a nozzle of the injector, and Reacting a reactive polymer raw material in the inner space of the molding to provide a membrane, and the method for producing a membrane for a chemical mechanical polishing device comprising the step of separating the membrane formed in the mold from the mold.

According to one embodiment of the present invention, the reactive polymer raw material may include a base polymer, a crosslinking agent and a catalyst.

According to another embodiment of the present invention, in the step of supplying the reactive polymer raw material to the injector, the reactive polymer raw material may be separately inputted into a first part including a base polymer and a catalyst and a second part including a base polymer and a crosslinking agent. Can be.

According to another embodiment of the present invention, the method may further include mixing the reactive polymer raw material after supplying the reactive polymer raw material to the injector.

According to another embodiment of the present invention, the temperature inside the mold is preferably controlled to 60 to 160 ℃ in the step of forming a membrane by reacting the reactive polymer raw material in the inner space of the mold.

According to another embodiment of the present invention, the mold, the core mold and the ejection mold and spaced apart from each other in the inner space of the molding case to have a first molding path corresponding to the shape of the pressure adjusting portion, and the core A closing block for closing one side of the molds so as to have a second molding furnace corresponding to the thickness of the substrate contact portion and in communication with the first molding furnace when one surface of the mold and the ejection mold is located on the same plane; And closing the one surface of the core mold and the ejecting mold in a state in which the closing block is approached to the core mold and the ejecting mold, and the core mold and the ejecting member in a state in which the closing block is spaced apart from the core mold and the ejecting mold. It comprises a moving means for relatively moving the core mold, the ejection mold and the closed block on the same axis so that one side of the mold is exposed to the outside The membrane formed of the substrate contacting portion and the pressure regulating portion may be formed by injecting a reactive polymer raw material into at least one of the first molding furnace and the second molding furnace while one surface of the core mold and the ejection mold is closed by the closing block. It is possible to mold, it is possible to be configured to enable the removal of the molded membrane by releasing the closed state by the closed block on one surface of the core mold and the ejection mold.

In order to achieve the second object, the present invention is applied to a polishing head of a chemical mechanical polishing apparatus, and includes a substrate contact portion contacting the rear surface of the substrate and a pressure regulator for applying the same or different pressures to different regions of the substrate contact portion. Provided as a membrane for a chemical mechanical polishing apparatus, a membrane for chemical mechanical polishing apparatus is prepared by an injection molding method in which a liquid reactive polymer raw material is introduced into a mold and a crosslinking reaction is performed.

According to an embodiment of the present invention, the mold may include a closing block for molding one surface of the substrate contact portion, a molding case installed to enable distance adjustment in one direction of the closing block, and fixedly coupled to the molding case. A core mold for forming a central portion of the other surface of the substrate contact portion spaced apart from the closed block by a predetermined distance, and a second mold for forming an outer portion of the other surface of the substrate contact portion spaced apart from the closed block at predetermined intervals; And a first blowout mold and a second blowout mold for forming a pressure control unit installed at a predetermined interval from the first takeout mold and coupled to the other surface of the substrate contacting part in a space spaced from the first takeout mold. can do.

Since the manufacturing method of the membrane for CMP of the present invention is carried out by the injection molding method, productivity and reproducibility are very high as compared with the conventional manufacturing method using the press molding method. The production method of the press molding method requires a relatively large working space, slow polymer crosslinking speed, flash generation, and post-crosslinking process. It is very advantageous in terms of productivity, such as a small installation space of the device, fast crosslinking speed, almost no flash, and no post-crosslinking process. In addition, since the raw polymer is a liquid phase, it is advantageous to mold the complex structure of the membrane, and the process can be performed in an automated process, so the process reproducibility is very high, and thus the quality of the prepared CMP membrane is excellent.

1 is a photograph of a membrane for CMP prepared according to one embodiment of the present invention.
Figure 2 shows a cross section of the membrane for CMP prepared according to one embodiment of the present invention.
Figure 3 schematically shows an injection molding apparatus used in the method for producing a membrane for CMP of the present invention.
Figure 4 shows a mold apparatus applied to the method for producing a membrane for CMP of the present invention.
5 to 8 sequentially show the operation of the mold apparatus applied to the manufacturing method of the membrane for CMP of the present invention.
9 is a result of measuring the hardness change after aging the membrane for CMP and the conventional CMP membrane prepared in accordance with an embodiment of the present invention at 250 ℃ for 75 hours.
10 is a result of measuring the change in tensile strength after aging the CMP membrane prepared according to an embodiment of the present invention and the conventional CMP membrane for 250 hours at 250 ℃.
11 is a result of measuring the change in elongation rate after aging the CMP membrane prepared according to an embodiment of the present invention and the conventional CMP membrane for 250 hours at 250 ℃.
12 shows the results of thermal mass spectrometry performed on the CMP membrane and the conventional CMP membrane prepared according to one embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention is applied to a polishing head of a chemical mechanical polishing apparatus, and includes a substrate contact in contact with a rear surface of a substrate and a pressure adjusting portion for applying the same or different pressure to different regions of the substrate contact. A manufacturing method, comprising: supplying a reactive polymer raw material to an injector, introducing a reactive polymer raw material supplied to the injector into an inner space of a mold through a nozzle of the injector, and reacting the reactive polymer raw material in the inner space of the mold; And forming a membrane into the membrane, and separating the membrane formed from the mold from the mold.

With reference to Figures 1 to 3 will be described for the CMP membrane of the present invention and the injection molding apparatus used for its manufacture.

1 is a picture of the membrane for CMP prepared according to an embodiment of the present invention, Figure 2 shows a cross section of the membrane for CMP prepared according to an embodiment of the present invention. 1 and 2, the membrane 100 for CMP is made of a polymer resin having elasticity, and a plurality of pressures extending from the substrate contacting portion 110 and the substrate contacting portion 110 contacting the rear surface of the substrate. It consists of the adjusting unit (111 ~ 115). The membrane 100 for CMP may independently apply pressure to different areas of the substrate contact while gas is injected into the empty space between the different pressure regulators and the substrate contact. The structure of the membrane for CMP shown in the drawings is only an example, and the number and shape of the pressure regulator may be variously modified.

Figure 3 schematically shows an injection molding apparatus used in the method for producing a membrane for CMP of the present invention. Referring to FIG. 3, the injection molding apparatus may be broadly divided into a portion into which a reactive polymer raw material is mixed and introduced, a portion to supply the injected raw material to a mold at a predetermined pressure, and a portion to mold the supplied raw material into a mold. The portion into which the reactive polymer raw material is introduced includes a first raw material tank 201, a second raw material tank 202, a mixing tank 203, and a mixer 204. The first raw material tank 201 and the second raw material tank 202 are portions in which raw materials for forming the CMP membrane are stored. In the CMP membrane manufacturing method of the present invention, the reactive polymer raw materials are crosslinked and solidified in the mold. Since the molding is performed in the process, components of the reactive polymer raw material are separated and stored in the first raw material tank and the second raw material tank in order to suppress the crosslinking reaction from occurring in the raw materials stored in the respective tanks. For example, when the base polymer and the catalyst are stored in the first raw material tank and the base polymer and the crosslinking agent are stored in the second raw material tank, the crosslinking reaction can be suppressed from occurring in the raw materials stored in the respective tanks. The first raw material tank 201 and the second raw material tank 202 are connected to the mixing tank 203, respectively, and a valve may be installed on the connection path, and although not shown in the drawings, a transfer pump and a flow rate for transferring raw materials The adjusting unit may be installed. In the mixing tank 203, the supplied reactive polymer raw material is primarily mixed, and the mixing tank 203 is connected to the mixer 204. The mixer 204 is a device for uniformly mixing the raw materials supplied from the first raw material tank 201 and the second raw material tank 202, and may be various kinds of mixers, such as a static mixer and an ultrasonic mixer. A portion for supplying the injected raw material into the mold at a predetermined pressure is an injection unit 210 including an injector 211 and an injector temperature controller 212. The injector 211 may be an extruder made of a screw, and serves to supply the mixed reactive polymer raw material into the mold at a constant pressure. Temperature control unit 212 is a part for controlling the temperature inside the extruder, although not shown in the figure may include a heating means and / or cooling means, wherein the cooling means may be composed of a cooling water line for circulating water to cool. have. The part for molding the supplied raw material is a mold unit 220, and includes a mold 221, a non-return valve 222, a mold temperature controller 223, and a clamping controller 224. The mold 221 has a structure corresponding to the shape of the CMP membrane as the CMP membrane is molded, and the detailed structure and operation method will be described later in other parts of the present specification. The non-return valve 222 functions to prevent the raw material supplied into the mold from flowing back toward the extruder. The mold temperature controller 223 is a part for controlling the temperature inside the mold. In this specification, the term mold temperature controller is used as a concept including a heating means installed inside or outside the mold. In the CMP membrane manufacturing method of the present invention, since the molding is performed in a manner in which the liquid reactive polymer raw material crosslinks and solidifies inside the mold, it is important to maintain the temperature inside the mold at a temperature at which the reaction is actively occurring. The clamping control unit 224 controls the opening or closing of the mold by changing the position of the closing block, the ejection mold, etc. as a part for controlling the opening and closing of the mold. The operation of the clamping control unit may be performed using a driving method such as a cylinder or motor by gas pressure or hydraulic pressure.

Step by step method for producing a membrane for CMP using the injection molding apparatus described above are as follows. First, the reactive polymer raw material is supplied to the injector. In this step, the reactive polymer raw materials are separated from the first raw material tank and the second raw material tank and supplied to the mixing tank, the supplied raw materials are primarily mixed in the mixing tank, and the mixed raw materials are uniformly mixed again in the mixer to inject the The process proceeds to the supply. Detailed components and compositions for the reactive polymer raw materials stored in the first raw material tank and the second raw material tank are described again in other parts of this specification. Subsequently, the reactive polymer raw material supplied to the injector is introduced into the inner space of the mold through the nozzle of the injector. This step is a process in which the raw material is supplied from the extruder constituting the injector and discharged through a nozzle of the extruder at a predetermined pressure through a rotating screw. The injector unit is formed by supplying a temperature control unit including a heating means or a cooling means. The temperature can be adjusted. When supplying a low viscosity liquid base polymer and a crosslinking agent as the reactive polymer raw material, the temperature of the extruder may be maintained at room temperature. However, when the viscosity of the reactive polymer raw material is increased, the temperature of the extruder may be increased within a certain range. Subsequently, the reactive polymer raw material is reacted in the inner space of the mold to form a CMP membrane. This step is a process of filling the inside of the mold with a reactive polymer raw material and performing a crosslinking reaction at a high temperature. The temperature inside the mold for the crosslinking reaction is preferably 60 to 160 ° C, and a more preferable temperature range may be selected in consideration of the time required for the crosslinking reaction and the possibility of deformation of the molding in the above temperature range. Finally, the membrane formed in the mold is separated from the mold. This step is to separate the CMP membrane formed in the mold from the mold. This process can be carried out by relatively changing the position of the closing block, the ejection mold and the like constituting the mold.

4 to 8 will be described the structure and operation of the mold apparatus applied to the CMP membrane manufacturing method of the present invention. 4 is a cross-sectional view of a mold apparatus of a membrane for a CMP according to an embodiment of the present invention, and FIGS. 5 to 8 are views sequentially showing operation states after the operation state of the embodiment shown in FIG. 4.

The mold of the mold apparatus used in the CMP membrane manufacturing method of the present invention is a closed block for molding one surface of the substrate contact portion of the CMP membrane, a molding case installed to enable distance adjustment in one direction of the closed block, and The core mold is fixedly coupled to a molding case and spaced apart from the closed block at a predetermined interval to form a central portion of the other surface of the substrate contact portion, and spaced apart from the closed block at a predetermined interval so that A first takeout mold for forming an outer portion, and a second takeout mold for forming a pressure regulating part of the membrane for CMP in a space spaced from the first takeout mold and spaced apart from the first takeout mold; It is characterized by including. The second ejection mold is a part for forming a pressure regulating portion of the membrane for CMP, and when the structure or number of pressure regulating portions of the membrane for CMP is changed, a third extraction mold may be added. Hereinafter, a mold apparatus of a CMP membrane including a first ejection mold, a second ejection mold, and a third ejection mold will be described with reference to the drawings.

As shown in the figure, a mold apparatus of a membrane for CMP according to the present invention (hereinafter referred to as a 'molding apparatus') is used to contact a substrate (not shown) and pressurize the substrate to pressurize the substrate (not shown). Disc-shaped substrate contacts (110 in FIG. 1) and pressure regulators extending from the substrate contacts and forming a plurality of pressurized regions on the substrate (111, 112, 113, 114, 115 in FIG. 1). It is for forming a membrane for CMP comprising a plurality of ejection molds (311, 312, 313), including a core mold 314, a closed block 315 and a moving means.

The ejection molds 311, 312, and 313 and the core mold 314 are disposed to be spaced apart from each other in an inner space of the molding case M, and are installed in the molding case M so as to be relatively movable. The first molding furnace S1 formed by the ejection molds 311, 312, and 313 and the core mold 314 spaced apart from each other has a shape of the pressure adjusting units 111, 112, 113, 114, and 115. It is made in the shape corresponding to. The pressure regulating parts are molded by hardening the liquid raw material into the first molding furnace S1 and then curing the liquid.

In the present embodiment, the core mold 314 is fixed to the molding case M and moved together with the molding case M, and is disposed on the central axis L of the membrane for CMP. . Meanwhile, since the center axis L is also an axis that is a reference of the relative movement direction of the ejection molds 311, 312, and 313, the core mold 314, and the closed block 315, the axis is referred to as an 'axis'. It will be called. The ejection molds 311, 312, and 313 are provided at positions eccentric with respect to the axis L, and are installed in the molding case M so as to be relatively movable. Here, the extraction means that the molded CMP membrane can be easily removed from the mold.

As shown in FIG. 6, the ejection molds may be arranged in a first ejection mold according to a degree of protruding to the furthest position along the axis L direction of the ejection molds 311, 312, and 313. 311), the second ejection mold 312, and the third ejection mold (313).

According to the present exemplary embodiment having the ejection molds protruding to different positions as described above, as shown in FIG. 6, in a state in which a part 115 of the pressure regulating portions is removed from the third ejection mold 313. As detachment by manual operation is possible and the substrate contact portion 110 has elastic force due to the expansion of the substrate contact portion 110, the elastic force is applied even if a detachment force by an operator is applied to the membrane 100 for CMP. The advantage is that the membrane for CMP is easily removed from the molds.

As shown in FIG. 4, the closing block 315 may be disposed on one surface of the ejection molds 311, 312, and 313 and one surface of the core mold 314 located on the same plane. By closing it serves to enable the formation of the substrate contact and the pressure regulator. The second molding furnace S2 formed by closing the ejection molds 311, 312, and 313 and one surface of the core mold 314 may have a thickness corresponding to the thickness of the substrate contact portion. It is in communication with the first molding furnace (S1).

As such, the first molding furnace S1 and the second molding furnace S2 communicating with each other by the ejection molds 311, 312, and 313 and the core mold 314 and the closed block 315 may be formed. As a result, the CMP membrane can be integrally formed by injecting a liquid raw material into any one of the first molding furnace S1 and the second molding furnace S2. Such integral injection molding of the CMP membrane enables mass production of the product.

The means for moving the ejection molds 311, 312, and 313 and the core mold 314 and the closing block 315 relative to the same axis L, and fixes the position of the closing block 315. The ejection molds 311, 312, and 313 and the core mold 314 may be configured to be moved relative to the closed block 315. That is, in the present embodiment, the moving means includes an ejector 304 for moving the ejection molds 311, 312, and 313 and the core mold 314, and the molding case M with the molds. And a cylinder device (not shown) for moving together.

 In the present invention having such a configuration, the ejector 304 may be formed while the ejection molds 311, 312, and 313 and the core mold 314 are moved with respect to the closed block 315. The movement of the molds by) leads to the advantage of allowing the CMP membrane to be removed from the molds smoothly. This advantage, in turn, can increase the molding efficiency of the product to improve the mass productivity of the product.

In this embodiment, there is provided a thin film expansion means for removing the CMP membrane from the molds more smoothly. The thin film expansion means protrudes at least one of the plurality of regions of the substrate contacting portion 110 defined by the pressure regulating portions 111, 112, 113, 114, and 115 in the direction of the axis L. As shown in FIG. By inflation by the method, it is possible to remove the portion 115 of the pressure regulators from the molds before the removal of the membrane for the CMP by the operator, as well as the substrate control unit 110 Has a large elastic force.

As a specific configuration of the above-mentioned thin film expansion means for exerting such a function, a differential projecting unit is employed in this embodiment. As shown in FIG. 6, the differential protruding unit makes the ejection molds 311, 312, and 313 and the core mold 314 protrude differently on the axis L to different positions. The plurality of regions of the substrate contact portion defined by the pressure regulating portions are expanded differently along the axis L direction. The differential projecting unit includes a plurality of moving plates 321, 322, and 323 and a plurality of rods 331, 332, and 333. As shown in FIG. 4, the movable plates 321, 322, and 323 have one surface of the ejection molds 311, 312, and 313 and the core mold 314 by the closing block 315. In the closed state, spaced apart from each other in the molding case (M), as shown in Figure 6, the ejection molds 311, 312, 313 and the core mold 314 When the closed state of one surface of the) is released, it is disposed in contact with each other.

The rods 331, 332, and 333 have one end coupled to each of the ejection molds 311, 312, and 313 and the other end coupled to each of the moving plates 321, 322, and 323, thereby allowing the ejector 304 to be disposed. It acts to deliver the pressing force by the side to the ejection molds. Hereinafter, for convenience, a rod connected to the first ejection mold 311 is called a first rod 331, and a movable plate connected to the first rod 331 is called a first movable plate 321. The rod connected to the second ejection mold 312 is called a second rod 332, and the movable plate connected to the second rod 332 is called a second movable plate 322. The rod connected to 313 is called a third rod 333, and the movable plate connected to the third rod 333 is called a third movable plate 323.

In this embodiment having such a configuration, when the operation process is sequentially shown in FIGS. 5 and 6, when the ejector 304 presses the first moving plate 321, the first moving plate ( 321 may move by at least the distance of the distance between the first moving plate 321 and the second moving plate 322 and the distance between the second moving plate 322 and the third moving plate 323. The second moving plate 322 is moved by at least the distance between the second moving plate 322 and the third moving plate 323. In the present exemplary embodiment, the third moving plate 323 is also configured to move at its original position, so that the first moving plate 321 may adjust the summing distance and the moving distance of the third moving plate 323. The distance will be increased.

As such, according to the present embodiment, the first ejection mold 311, the second ejection mold 312, and the third ejection mold 313 are protruded to different positions, as shown in FIG. 6. Before the removal of the membrane 100 for the CMP by an operator is performed, at least a part of the pressure regulating portions 115 is separated from the third ejection mold 313, and the substrate contact portion has a greater elastic force. As it has, as shown in Figure 7 when the removal of the membrane for the CMP by the operator to increase the work efficiency of the product can be improved as well as to reduce the production cost of the product by preventing waste of unnecessary labor costs Derive the benefits.

On the other hand, after the removal of the membrane for the CMP by the operator in the state shown in FIG. 7 after the closing block (reference numeral 315 of FIG. 5) is moved in the molding case (M) direction the first ejection mold 311 ), The second ejection mold 312 and the third ejection mold 313 are pulled back in order, so that the entire mold is matched. By this process, as shown in Figure 4 it is possible to repeat the molding of the membrane for CMP.

That is, in the mold apparatus having the configuration as described above, the liquid raw material for molding the CMP membrane in the state as shown in FIG. 4 is injected after the first molding furnace (S1) and the second molding furnace (S2) and cured. The CMP membrane (see FIG. 1) is formed, and after the molding case M is retracted together with the molds in the direction A of FIG. 5 for forming the CMP membrane repeatedly, the ejector 304 is formed. By pressing the first moving plate 321 in the direction B of FIG. 6 so that the first ejection mold 311, the second ejection mold 312 and the third ejection mold 313 protrude to different positions, As shown in FIG. 7, the operator can easily remove the membrane for CMP, and as shown in FIG. 8, the closed block (refer to 315 of FIG. 5) moves in the molding case M direction and retracts the first ejection mold 311. The second ejection mold 312 and the third ejection mold 313 are pulled back in order, so that the entire mold is removed. The value allows for repetitive forming of the membrane for CMP.

The method for producing a membrane for CMP of the present invention proceeds to a process of forming a crosslinked reactive polymer material in an injection mold. Accordingly, the crosslinking reaction of the polymer occurs in the mold, and the reactants, products, and chemical reactions related thereto will be described below.

In the present invention, the membrane for CMP is molded by thermal curing by mixing the polymer chain and the crosslinking agent represented by the formula (1) having a liquid viscosity at room temperature. In Formula 1, as the number of n increases, the molecular weight of the polymer chain increases. In the range of n to 40 to 2000, the material constituting the polymer chain is liquid at room temperature, and thus it is possible to mold by liquid injection molding. Do. If n is less than 40, the length of the polymer chain is too short to satisfy the properties of the CMP membrane, and if it is more than 2000, the viscosity is high, making it difficult to form an accurate shape in injection molding.

Formula 1

In this case, a material represented by the following Chemical Formula 2 or Chemical Formula 3 may be used as the crosslinking agent. In Formulas 2 and 3, m, l, and k are related to the physical properties of the crosslinked silicone polymer compound, in Formula 2, m is an integer from 10 to 30, l is an integer from 10 to 150, and m: l is 1: It is preferable that it is 1 to 1: 5, and it is preferable that k is an integer of 10-100 in general formula (3). This range of values is related to the number of vinyl groups included in the material constituting the polymer chain of Formula 1, and also to physical properties such as elasticity of the crosslinked silicone polymer compound.

(2)

(m is an integer from 10 to 30, l is an integer from 10 to 150, m: l is 1: 1 to 1: 5)

(3)

(k is an integer of 10 to 100)

The chemical reaction in which the polymer chain is crosslinked by the crosslinking agent is performed according to Scheme 2 below. According to Scheme 2 below, the vinyl group in the polymer chain reacts with the hydrogen group of the crosslinking agent under heat and catalytic conditions to proceed with crosslinking. In the present invention, the vinyl group of the polymer chain and the hydrogen group ratio of the crosslinking agent are preferably 1: 1 to 1: 8, and the crosslinking agent is preferably added at 0.5 to 5% based on the mass of the material constituting the polymer chain. The catalyst is a Pt (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex) Can be used. The amount of catalyst can be added in an amount of 5 to 50 ppm relative to the total composition. The reactant may include an inhibitor to prevent further reaction. Polymerization inhibitors include 1-ethynyl-1-cyclohexanol, 3,5-dimethyl-1-hexyn-3-ol (3,5-dimethyl-1-hexyn-3- ol), 2-methyl-3-butyn-2-ol, vinylmethyl cyclosiloxane or divinyltetramethyldisiloxane may be used. have.

Scheme 2

In the present invention, the membrane for CMP may be filled with silica particles in a silicone polymer compound, and the silica particles may be complexed with the silicone polymer compound to improve physical properties related to the tensile strength of the membrane. Silica may be a silica prepared in a dry manner (Fumed silica) or a wet prepared silica (precipitated silica) can be used. The reactant may include hexamethyldisilazane in order for the silica to be uniformly dispersed in the polymer and firmly bonded to the polymer material.

Referring to the process for producing a membrane for CMP in the present invention. First, the reactant to be a raw material is prepared by dividing it into A and B parts. Part A includes silica, base polymer, hexamethyldisilazane and platinum catalyst, and the mixing ratio is 200 to 400 parts by weight of the base polymer, 10 to 40 parts by weight of hexamethyldisilazane, 0.1 to about 100 parts by weight of silica. 2.5 parts by weight of platinum catalyst. Part B includes silica, a base polymer, hexamethyldisilazane, a polymerization inhibitor and a crosslinking agent, and a mixing ratio is 200 to 400 parts by weight of the base polymer, 10 to 40 parts by weight of hexamethyldisilazane, based on 100 parts by weight of silica, 2 to 30 parts by weight of a crosslinking agent and 0.1 to 1.5 parts by weight of a polymerization inhibitor, and a more preferable mixing ratio is 200 to 400 parts by weight of the base polymer, 10 to 40 parts by weight of hexamethyldisilazane, 5 to 5 parts by weight of silica. 30 parts by weight of crosslinking agent and 0.1 to 1.5 parts by weight of polymerization inhibitor.

Hereinafter, the CMP membrane manufacturing method of the present invention will be described in detail using specific examples, and the physical properties of the CMP membrane of the present invention will be described using evaluation examples. However, this embodiment is not limited to the scope of the present invention by the embodiment as an embodiment presented to facilitate the present invention.

Example 1-1 (Preparation of Raw Material)

VTP4M (Polymer represented by Formula 4 below), 69.5 g, Aerosil 300 (silica, purchased from Evonik) 24 g, hexamethyldisilazane (purchased from Evonik) 6 g, Pt (0) -1,3-di 0.5 g of vinyl-1,1,3,3-tetramethyldisiloxane complex (platinum catalyst) was mixed to prepare Part A of the raw material.

64.5 g of VTP4M (polymer represented by the following formula (4), purchased from Siyoung Tech), 24 g of Aerosil 300 (silica, purchased from Evonik), 6 g of hexamethyldisilazane, 1-ethynyl-1-cyclohexanol (polymerization inhibitor) 0.5 g, YC483 (crosslinking agent represented by Chemical Formula 5 below, purchased from Siyoung Tech) was mixed to prepare B portion of the raw material.

Formula 4

(n is an integer from 1000 to 1300)

Formula 5

(m is an integer of 10 to 30, l is an integer of 10 to 30)

Example 1-2 (injection molding)

Part A and part B of the raw material prepared according to 1-1 were loaded into the first raw material tank and the second raw material tank, respectively. The loaded raw material A part and B part were supplied to the mixing tank at the same flow rate, and the mixing tank was supplied with the static mixer to mix the raw materials. Subsequently, in the static mixer, the raw material mixed with the extruder, which is an injector, was supplied, and the supplied raw material was introduced into the mold through the nozzle of the extruder front end through the extruder. At this time, the temperature of the extruder was 25 degreeC and the temperature of the metal mold | die was 120 degreeC. The raw material introduced into the mold was cured for 5 minutes, and the molded CMP membrane was separated from the mold as the mold was separated. The membrane for CMP separated from the mold was then left in an oven at 200 ° C. for 240 minutes to remove residual volatiles.

Experimental Example (Aging Test)

CMP membrane manufactured according to the above embodiment and CMP membrane commercially sold by Company A (molded by press method with HCE as a raw material, hereinafter referred to as 'A company membrane') for hardness, tensile strength and An aging test was conducted to evaluate the elongation rate. The aging test proceeded by leaving each membrane in an oven at 250 ° C. for 72 hours before taking it out of room temperature.

Evaluation Example 1 (Measurement of Hardness Before and After Aging)

The CMP membrane prepared according to the embodiment of the present invention and the A company membrane were compared by measuring the hardness after the aging test according to the initial hardness and the experimental example. The hardness measurement method followed ASTM D2240.

9 is a result of measuring the hardness change after aging the membrane for CMP and A company membrane at 250 ℃ 75 hours according to an embodiment of the present invention. 9, the membrane for CMP of the present invention exhibited an initial hardness of 45 Shore A, and 47 Shore A after the aging test. In contrast, membrane A exhibited an initial hardness of 44 Shore A, and 42 Shore A after the aging test.

Evaluation Example 2 (Measurement of Tensile Strength Before and After Aging)

The CMP membrane prepared according to the embodiment of the present invention and the A company membrane were compared by measuring the tensile strength after the aging test according to the initial hardness and the experimental example. Tensile strength measurement method was according to ASTM D412.

10 is a result of measuring the change in tensile strength after aging the membrane for CMP and A company membrane at 250 ℃ 75 hours according to an embodiment of the present invention. Referring to FIG. 10, the membrane for CMP of the present invention exhibited an initial tensile strength of 8.6 MPa and 8.1 MPa after an aging test. In contrast, company A's membrane exhibited an initial tensile strength of 6.7 MPa and 3.1 MPa after the aging test. The membrane for CMP of the present invention was found to have a relatively low tensile strength decrease with aging compared to the A company membrane.

Evaluation example 3 (measurement of elongation rate before and after aging)

The CMP membrane prepared according to the embodiment of the present invention and the A company membrane were compared by measuring the elongation rate after the aging test according to the initial elongation rate and the experimental example. The elongation measurement method was according to ASTM D412.

11 is a result of measuring the change in elongation after aging the membrane for CMP and A company membrane at 250 ℃ 75 hours according to an embodiment of the present invention. Referring to FIG. 11, the membrane for CMP of the present invention exhibited an initial elongation of 630% and 439% after the aging test. In contrast, membrane A exhibited an initial elongation of 697% and 209% after the aging test. Membrane for CMP of the present invention was relatively low in elongation decrease with aging, company A membrane elongation was lowered to 30% or less than the initial level with aging.

Evaluation example  4( Thermal mass spectrometry )

CMP membrane manufactured according to an embodiment of the present invention, a membrane commercially sold by the company A and B company (molded by the press method from HCE as a raw material, hereinafter referred to as 'B company membrane') thermal mass Thermo gravimetry analysis (TGA) was performed. The temperature increase rate of the thermal mass spectrometry conditions was 20 ℃ / min, the analysis was carried out in a nitrogen atmosphere.

12 is a thermal mass spectrometry of the CMP membrane, the A company membrane and the B company membrane according to an embodiment of the present invention. Referring to FIG. 12, the A company membrane and the B company membrane started to decompose at about 330 ° C. and then rapidly decomposed at 400 ° C. or more, and the A company membrane decomposed to about 590 ° C. and the B company membrane to about 630 ° C. You can see that it stops. In contrast, the membrane for CMP according to the embodiment of the present invention can be seen that decomposition occurs slowly in the 350 ℃ to 650 ℃ section. Therefore, it can be seen that the membrane for CMP according to the embodiment of the present invention is thermally very stable as compared with the A company membrane and the B company membrane, which is consistent with the results of Evaluation Example 2 and Evaluation Example 3. In addition, the membrane for CMP of the present invention was found to have excellent results in comparison with the conventional CMP membrane manufactured by the press method using HCE also in the chemical resistance of the slurry for CMP.

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, . Therefore, the embodiments described in the present invention are not intended to limit the scope of the present invention but to limit the scope of the present invention. The scope of protection of the present invention should be construed according to the claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.

100: membrane for CMP 110: substrate contact portion
111 to 115: pressure regulator 201: first raw material tank
202: second raw material tank 203: mixing tank
204 mixer 210 injection unit
211: injector 212: injector temperature control
220: mold unit 221: mold
222: non-return valve 223: mold temperature control unit
224: clamping adjustment unit 304: ejector
311: first ejection mold 312: second ejection mold
313: third ejection mold 314: core mold
315: closed block 321: first moving plate
322: second moving plate 323: third moving plate
331: first rod 332: second rod
333: 3rd rod L: axis
M: Molding Case S1: First Molding Furnace
S2: second molding furnace

Claims (8)

A method for manufacturing a membrane for a chemical mechanical polishing apparatus, which is applied to a polishing head of a chemical mechanical polishing apparatus, and includes a substrate contact portion contacting a rear surface of a substrate and a pressure adjusting portion for applying the same or different pressure to different regions of the substrate contact portion. In
Supplying a reactive polymer raw material to the injector;
Injecting the reactive polymer raw material supplied to the injector into the internal space of the mold through the nozzle of the injector;
Reacting the reactive polymer raw material in the inner space of the mold to form a membrane; And
Separating the membrane formed in the mold from the mold; Method of manufacturing a membrane for a chemical mechanical polishing apparatus comprising a. The method according to claim 1,
The reactive polymer raw material manufacturing method of a membrane for a chemical mechanical polishing device, characterized in that it comprises a base polymer, a crosslinking agent and a catalyst. The method according to claim 1,
In the supplying of the reactive polymer raw material to the injector, the reactive polymer raw material is input into the first part containing the base polymer and the catalyst and separated into the second part containing the base polymer and the crosslinking agent. Method for preparing a membrane. The method according to claim 1,
And mixing the reactive polymer raw material after supplying the reactive polymer raw material to the injector. The method according to claim 1,
In the step of forming a membrane by reacting the reactive polymer raw material in the inner space of the mold temperature of the inside of the mold is a manufacturing method of the membrane for chemical mechanical polishing apparatus, characterized in that it is controlled. The method according to claim 1,
The mold is
A core mold and a blowout mold disposed to be spaced apart from each other in an inner space of the molding case so as to have a first molding path corresponding to the shape of the pressure adjusting units;
When the one surface of the core mold and the ejection mold is located on the same plane, the closing to close one surface of the molds to have a second molding furnace corresponding to the thickness of the substrate contact portion and in communication with the first molding furnace block; And
It is possible to close the one surface of the core mold and the ejection mold in the state that the closing block is approaching the core mold and the ejection mold, the core mold and the ejection in the state that the closing block is spaced apart from the core mold and the ejection mold And moving means for relatively moving the core mold, the ejection mold, and the closed block on the same axis so that one surface of the mold is exposed to the outside.
Injecting a reactive polymer raw material into at least one of the first molding furnace and the second molding furnace in a state in which one surface of the core mold and the blowout mold is closed by the closing block to form a membrane composed of the substrate contact portion and the pressure regulating portion. And a state in which the closed state of the core mold and the ejection mold by the closed block is released to enable the removal of the molded membrane. delete delete

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