JP2011171688A - Method for manufacturing electronic component provided with adhesive film and method for manufacturing mounting body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent cutting dusts and the like from adhering to an adhesive layer at the time of dividing a wafer in a state wherein the adhesive layer is adhered on the surface of a wafer. <P>SOLUTION: A method for manufacturing an electronic component provided with an adhesive film includes: an adhering step wherein the adhesive film, which is formed by laminating a base material and the adhesive layer, is adhered on the surface of the wafer having electronic components formed thereon; an image pickup step wherein an image of the surface of the wafer is picked up by receiving light that has been reflected on the surface of the wafer and passed through the base material and the adhesive layer; a dividing position determining step wherein the positions where the wafer is to be divided are determined on the basis of the image; and a dividing step wherein the electronic components are individualized by dividing the wafer. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for manufacturing an electronic component with an adhesive film and a method for manufacturing a mounting body.

In recent years, a wafer on which a plurality of semiconductor devices are formed is divided into individual semiconductor devices, and the separated semiconductor devices are mounted on a wiring board (see, for example, Patent Document 1). . It is also known to mount a semiconductor chip on a circuit board using an adhesive sheet material having a plastic film and an adhesive composition (see, for example, Patent Document 2).
Patent Document 1 JP 2000-021915 JP Patent Document 2 JP 2007-2111246 A

  When the wafer is divided while the adhesive composition is adhered to the wafer, cutting waste generated when the wafer is divided into individual semiconductor chips easily adheres to the adhesive composition. Further, when the wafer is divided while the plastic film and the adhesive composition are attached to the wafer, the plastic film is easily peeled from the adhesive composition.

  In order to solve the above-mentioned problems, in the first aspect of the present invention, a sticking step of sticking an adhesive film formed by laminating a base material and an adhesive layer on the surface of a wafer on which an electronic component is formed, and the wafer An imaging stage for capturing an image of the surface of the wafer by receiving light reflected by the surface of the substrate and transmitted through the base material and the adhesive layer, and a division position determination stage for determining a position to divide the wafer based on the image And a method of manufacturing an electronic component with an adhesive film, comprising: a dividing step of dividing the wafer into individual pieces.

  In the above method, the attaching step may include a step of pressing the adhesive film against the surface of the wafer with an elastic body held by the head. In the above method, the peeling force between the base material and the adhesive layer may be 0.17 N / 5 cm or more. In the above method, the thickness of the base material may be 75 μm or more. In the above method, the transmittance of light having a wavelength of 440 nm to 700 nm in the adhesive film may be 74% or more.

  In the above method, a back grinding step of grinding the back surface of the wafer having an adhesive film attached to the surface may be further included before the imaging step. In the above method, the back surface grinding step may include a step of grinding the back surface of the wafer on which the protective layer protecting the base material is not attached on the base material. In the above method, the adhesive layer may include NCF or ACF.

  In the second aspect of the present invention, from the adhesive layer of the electronic component with an adhesive film produced by the above method, the peeling step of peeling the substrate and the electronic component with the adhesive layer from which the substrate has been peeled are bonded. There is provided a manufacturing method of a mounting body including an adhesion step of adhering to a surface of a substrate using a layer.

  In the above method, the bonding step may include a pressing step of pressing the electronic component with an adhesive layer against the surface of the substrate with an elastic body held by the head. In the above method, the pressing step may include a step of simultaneously pressing a plurality of electronic components with an adhesive layer against the surface of the substrate with an elastic body.

  In the above method, the dividing step may include a step of dividing the wafer in a state where the dicing tape is attached to the back surface of the wafer, and the separating step includes attaching a plurality of electronic components with adhesive films to the dicing tape. You may have the step which peels a base material from each contact bonding layer of a some electronic component with an adhesive film with the state attached. In the above method, after the peeling step, the method may further include a sorting step of checking whether the base material is peeled off from the adhesive layer of the electronic component with the adhesive film. An electronic component with an adhesive layer that has been confirmed to be peeled may be adhered to the surface of the substrate using the adhesive layer.

  It should be noted that the above summary of the invention does not enumerate all the necessary features of the present invention. In addition, a sub-combination of these feature groups can also be an invention.

An example of a section of mounting object 100 is shown roughly. An example of wafer 200 is shown roughly. An example of the stage which adheres wafer 200 to jig 300 is shown roughly. An example of the stage which affixes the adhesive film 400 on the wafer 200 is shown schematically. An example of the stage which places wafer 200 on chuck table 520 of dicing machine 510 is shown roughly. An example of the stage which picturizes the image of the surface of wafer 200 is shown roughly. An example of the stage which divides wafer 200 is shown roughly. An example of the step which peels substrate 402 from adhesion layer 404 is shown roughly. An example of the step which confirms that substrate 402 is exfoliated is shown roughly. An example of the step of bonding the chip 900 with an adhesive layer to the circuit board 110 is schematically shown. The other example of the method of mounting the chip | tip 120 on the circuit board 110 is shown roughly. The other example of the method of mounting the chip | tip 120 on the circuit board 110 is shown roughly.

  Hereinafter, the present invention will be described through embodiments of the invention, but the following embodiments do not limit the invention according to the claims. In addition, not all the combinations of features described in the embodiments are essential for the solving means of the invention.

  Hereinafter, embodiments will be described with reference to the drawings. In the description of the drawings, the same or similar parts may be denoted by the same reference numerals, and redundant description may be omitted. The drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio, and the like may differ from the actual ones. In addition, for convenience of explanation, there may be a case where the drawings have different dimensional relationships or ratios.

  FIG. 1 schematically shows an example of a cross section of the mounting body 100. The mounting body 100 includes a circuit board 110, a chip 120, and an adhesive layer 130. The mounting body 100 is obtained by mounting the chip 120 on the circuit board 110. The mounting body 100 may include a plurality of chips 120. The plurality of chips 120 may be mounted on the circuit board 110 in the same process.

  The circuit board 110 has electrodes 114 on the surface on which the chip 120 is mounted. Examples of the circuit board 110 include a printed wiring board, a multilayer wiring board, and a flexible board. The circuit board 110 may be an example of a board.

  The chip 120 has a device 122 and bumps 124. The chip 120 may be an example of an electronic component. The bump 124 is electrically connected to the electrode 114 of the circuit board 110, and electrically connects the device 122 and the circuit board 110.

  The device 122 may be an active element or a passive element. Active elements include semiconductor devices such as MISFET, HBT, and HEMT, integrated circuit elements such as IC and LSI, light emitting devices such as semiconductor lasers, light emitting diodes, and light emitting thyristors, light receiving devices such as light sensors and light receiving diodes, or the sun A battery can be illustrated. Examples of passive elements include resistors, capacitors, and inductors. The device 122 may be an example of an electronic component.

  The adhesive layer 130 adheres the circuit board 110 and the chip 120. The adhesive layer 130 is obtained, for example, by thermosetting a composition containing a thermosetting resin. An example of a method for mounting the chip 120 on the circuit board 110 will be described with reference to FIGS.

  FIG. 2 schematically shows an example of the wafer 200. In the present embodiment, first, the wafer 200 is prepared. An example of the wafer 200 is a semiconductor wafer such as a silicon wafer. A plurality of devices 122 may be formed on the surface of the wafer 200. A lattice-like scribe line 202 may be formed on the surface of the wafer 200. Each of the plurality of devices 122 may be formed in each of a plurality of regions partitioned by the scribe line 202. Bumps 124 may be formed on the surface of the wafer 200 on which the device 122 is formed (sometimes referred to as a functional surface). The wafer 200 may be ground on the surface opposite to the functional surface (sometimes referred to as a back surface) by a back grinding apparatus or the like. Thereby, the thickness of the wafer 200 can be reduced.

  FIG. 3 schematically shows an example of a cross-sectional view at the stage where the wafer 200 is bonded to the jig 300. In the present embodiment, the prepared wafer 200 is fixed to the jig 300. The jig 300 may include a ring-shaped or frame-shaped frame 302 having a diameter larger than the diameter of the wafer 200, and a dicing tape 304 having one surface having adhesiveness. The dicing tape 304 may be attached to one side of the frame 302 and spread on the inside of the frame 302. The wafer 200 may be attached to the center portion of the jig 300. The wafer 200 may be attached to the dicing tape 304 on the surface opposite to the functional surface.

  The dicing tape 304 may be an adhesive film whose peeling force is reduced by irradiating ultraviolet rays. Thus, after the wafer 200 is divided into a plurality of chips, the dicing tape 304 is irradiated with ultraviolet rays, so that it becomes easy to separate the chips from the dicing tape 304 when picking up individual chips.

  FIG. 4 schematically shows an example of a cross-sectional view at the stage of attaching the adhesive film 400 to the wafer 200. In the present embodiment, first, an adhesive film 400 in which a base material 402 and an adhesive layer 404 are laminated is disposed on the functional surface of the wafer 200.

  The base material 402 prevents the adhesive layers 404 from adhering to each other when the adhesive film 400 is wound in a reel shape. The base material 402 prevents the cutting dust and the like from adhering to the adhesive layer 404 when the wafer 200 is divided using a dicing apparatus or the like. Examples of the substrate 402 include plastic materials such as a polyester film and a polyethylene terephthalate film, or papers such as fine paper and glassine paper. The substrate 402 may be subjected to a release treatment such as silicone treatment on the surface.

  The substrate 402 may transmit visible light. Accordingly, even when an inexpensive optical system is used, an image of the surface of the wafer 200 can be taken with the base material 402 and the adhesive layer 404 attached to the wafer 200. That is, an image of the device 122, the scribe line 202, the bump 124, the alignment mark, and the like formed on the functional surface of the wafer 200 can be taken without using an expensive optical system such as an IR camera.

  The base material 402 may absorb light having a specific wavelength among visible light. The substrate 402 may absorb light having a specific wavelength among light having a wavelength of 440 nm to 700 nm. In this case, when a visible light image of the surface of the wafer 200 is captured, a region where the base material 402 exists in the visible light image appears to be colored.

  Thereby, the presence or absence of the base material 402 can be determined based on the visible light image obtained by imaging the surface of the wafer 200. Even if the base material 402 absorbs light of a specific wavelength, if the base material 402 sufficiently transmits light other than light of the specific wavelength among visible light, the base material 402 In the existing area, the surface pattern of the wafer 200 can be determined.

  For example, when the base material 402 is peeled off from the adhesive layer 404 during the process of dividing the wafer 200 into a plurality of chips 120, cutting scraps may adhere to the adhesive layer 404. In such a case, it is preferable to determine that the chip 120 from which the substrate 402 has been peeled is a defective product. Therefore, after performing the process of dividing the wafer 200, a visible light image of the surface of the wafer 200 may be taken to determine the presence or absence of the substrate 402. Thereby, it can suppress that the chip | tip 120 contaminated with the cutting waste is mounted.

  Further, the substrate 402 is peeled off from the adhesive layer 404 before the mounting process. However, if the mounting process is performed without the base material 402 being peeled off, there is a possibility that a problem occurs in the mounting body 100. Therefore, after performing the step of peeling the base material 402, a visible light image of the surface of the wafer 200 may be taken to determine the presence or absence of the base material 402. Thereby, it can suppress that a mounting process is implemented, without the base material 402 peeling.

  The thickness of the substrate 402 may be 75 μm or more. When the thickness of the base material 402 is less than 75 μm, the base material 402 may be peeled off from the adhesive layer 404 during the process of dividing the wafer 200 using a dicing apparatus or the like. It is inferior in workability compared with the case of 75 micrometers or more. The thickness of the substrate 402 may be 125 μm or less. When the thickness of the base material 402 exceeds 125 μm, it is difficult to apply the adhesive layer 404 on the base material 402 when the adhesive layer 404 is applied on the base material 402 to manufacture the adhesive film 400.

  The adhesive layer 404 may include a film forming resin, a liquid curable component, and a curing agent. The adhesive layer 404 may include additives such as various rubber components, softeners, various fillers, and may further include conductive particles. The adhesive layer 404 may be an NCF (Non Particle Conductive Film), an ACF (Anisotropic Conductive Film), or a laminate of them.

  Examples of the film forming resin include phenoxy resin, polyester resin, polyamide resin, and polyimide resin. It is preferable to include a phenoxy resin from the viewpoint of easy availability of materials and connection reliability. Examples of the liquid curing component include liquid epoxy resins and acrylates. It is preferable to have two or more functional groups from the viewpoints of connection reliability and cured product stability. Examples of the curing agent include imidazole, amines, sulfonium salts, onium salts, and phenols when the liquid curing component is a liquid epoxy resin. When the liquid curing component is an acrylate, an organic peroxide can be exemplified as the curing agent.

  The peeling force between the substrate 402 and the adhesive layer 404 may be 0.17 N / 5 cm or more. Here, the peeling force between the base material 402 and the adhesive layer 404 indicates a peeling force when T-type peeling is performed in the direction of 180 degrees based on JIS Z0237. When the peeling force between the base material 402 and the adhesive layer 404 is less than 0.17 N / 5 cm, the base material 402 peels from the adhesive layer 404 during the process of dividing the wafer 200 using a dicing apparatus or the like. In some cases, the workability is inferior compared to the case where the peel force between the substrate 402 and the adhesive layer 404 is 0.17 N / 5 cm or more.

  The peeling force between the substrate 402 and the adhesive layer 404 may be smaller than the peeling force between the wafer 200 and the dicing tape 304 at the stage of bonding the wafer 200 to the jig 300 described with reference to FIG. The peeling force between the substrate 402 and the adhesive layer 404 may be smaller than the peeling force between the wafer 200 and the dicing tape 304 before the peeling force is reduced by ultraviolet irradiation or the like.

  The base material 402 may have a thickness of 75 μm or more and a peeling force between the base material 402 and the adhesive layer 404 of 0.17 N / 5 cm or more. Thereby, the adhesive film 400 excellent in workability in the process of dividing the wafer 200 using a dicing apparatus or the like is obtained.

  The adhesive film 400 may have a light transmittance of 74% or more at a wavelength of 440 nm to 700 nm. The light transmittance can be adjusted by the material, thickness, surface treatment, and the like of the substrate 402 or the adhesive layer 404. The light transmittance can be adjusted by the type or amount of additive added to the substrate 402 or the adhesive layer 404. For example, the light transmittance of the adhesive layer 404 can be reduced by adding an inorganic filler to the adhesive layer 404.

  Here, the transmittance of light having a wavelength of 440 nm to 700 nm is 74% or more indicates that the maximum transmittance of light having a wavelength of 440 nm to 700 nm is 74% or more. The light transmittance varies depending on the thickness of the adhesive film 400. Therefore, the light transmittance indicates the light transmittance in the thickness of the adhesive film 400 in a state of being attached to the wafer 200. The adhesive film 400 may have a light transmittance of 74% or more over the entire range of wavelengths from 440 nm to 700 nm.

  Next, the adhesive film 400 is attached to the wafer 200 using the pressing device 410. The pressing device 410 may include a stage 420 and a head 430. The stage 420 may place the wafer 200 thereon. The wafer 200 may be placed on the stage 420 while being held by the jig 300. The stage 420 may have a heating device 422. It should be noted that the heating device 422 need not be used at the stage of attaching the adhesive film 400 to the wafer 200.

  The head 430 may include a pressing member 432 and a holding portion 434 that holds the pressing member 432. The head 430 presses the pressing member 432 toward the stage 420 side. The pressing member 432 may be an elastic body. The elastic body may be an elastomer such as silicone rubber. Thereby, compared with a metal pressing member, the adhesive film 400 can be evenly attached to the wafer 200.

  The pressing device 410 presses the wafer 200 having the adhesive film 400 disposed on the surface thereof between the stage 420 and the head 430. In the present embodiment, first, the wafer 200 held by the jig 300 is placed on the stage 420. Next, the adhesive film 400 is pressed against the functional surface of the wafer 200 with the pressing member 432 held by the head 430. Thereby, the adhesive film 400 can be stuck on the wafer 200.

  In the present embodiment, the case where the adhesive film 400 is attached to the wafer 200 using the pressing device 410 has been described. However, the method for attaching the adhesive film 400 to the wafer 200 is not limited to this. For example, the adhesive film 400 may be attached to the wafer 200 using a roll laminator.

  FIG. 5 schematically shows an example of the stage of placing the wafer 200 on the chuck table 520 of the dicing apparatus 510. In the present embodiment, first, the wafer 200 to which the adhesive film 400 is attached is placed on the chuck table 520 of the dicing apparatus 510. The wafer 200 may be placed on the chuck table 520 while being held by the jig 300.

  FIG. 5 schematically shows an example of a cross section of the dicing apparatus 510. For example, the dicing apparatus 510 divides the wafer 200 along the scribe line 202. Thereby, the wafer 200 can be divided into a plurality of chips 120. The dicing apparatus 510 may be an example of a dividing apparatus that divides a wafer. The wafer 200 may be divided while being held by the jig 300. The wafer 200 may be divided with the adhesive film 400 attached to the surface.

  The dicing apparatus 510 may include a chuck table 520, an alignment stage 530, an imaging unit 540, a cutting unit 550, and a control unit 560. The chuck table 520 can place the jig 300 holding the wafer 200. The chuck table 520 may be fixed on the chuck table 520 by sucking the jig 300 with a decompression device (not shown).

  The alignment stage 530 may move the chuck table 520 in the x direction and the y direction based on instructions from the control unit 560. The alignment stage 530 may be an xy stage.

  The imaging unit 540 may capture an image of the surface of the wafer 200 by receiving the light reflected by the surface of the wafer 200 and transmitted through the adhesive film 400. The imaging unit 540 includes, for example, an illumination member that illuminates the wafer 200, an optical system that receives light reflected from the surface of the wafer 200, and an imaging element that captures an image captured by the optical system. The imaging unit 540 may transmit information of the captured image to the control unit 560. The imaging unit 540 is not particularly limited, but the imaging unit 540 preferably captures a visible light image. Thereby, an inexpensive optical system can be used.

  The cutting unit 550 may cut the wafer 200 based on an instruction from the control unit 560. The cutting unit 550 may include a blade 552 that cuts the wafer 200. The cutting unit 550 may cut the wafer 200 by pressing the rotating blade 552 against the wafer 200.

  The control unit 560 may include an image processing unit 562 and a driving unit 564. The image processing unit 562 may receive image information on the surface of the wafer 200 from the imaging unit 540. The image processing unit 562 may determine the position of the scribe line 202 based on the received image information. The image processing unit 562 may determine to divide the wafer 200 at the position of the scribe line 202. The image processing unit 562 may transmit information regarding the position where the wafer 200 is divided to the driving unit 564.

  The driving unit 564 may receive information regarding the position where the wafer 200 is divided from the image processing unit 562. The drive unit 564 may drive the alignment stage 530 and the cutting unit 550 based on the information regarding the position where the wafer 200 is divided. Accordingly, the drive unit 564 can divide the wafer 200 and divide the device 122 into pieces.

  For example, when the image processing unit 562 determines to divide the wafer 200 in the x direction along the scribe line 202, the drive unit 564 drives the alignment stage 530 so that one end of the scribe line 202 has the blade 552. The chuck table 520 is moved so as to be positioned below.

  Next, the drive unit 564 drives the cutting unit 550 to move the cutting unit 550 downward in a state where the blade 552 is rotated, so that the blade 552 is pressed against the wafer 200. Thereafter, the drive unit 564 drives the alignment stage 530 to move the wafer 200 in the x direction. Thus, the wafer 200 can be divided in the x direction along the scribe line 202.

  FIG. 6 schematically shows an example of a cross-sectional view at the stage of capturing an image of the surface of the wafer 200. In the present embodiment, first, the imaging unit 540 of the dicing apparatus 510 receives the light reflected by the surface of the wafer 200 and transmitted through the base material 402 and the adhesive layer 404, thereby capturing an image of the surface of the wafer 200. To do.

  In the case where the transmittance of light from 440 nm to 700 nm of the adhesive film 400 is 74% or more, an inexpensive device that captures an image in the visible light region can be used as the imaging unit 540. Further, images of the scribe line 202, the bump 124, the circuit pattern, the alignment mark, and the like can be taken with the base material 402 and the adhesive layer 404 attached to the surface of the wafer 200. As a result, the wafer 200 can be divided with the base material 402 and the adhesive layer 404 attached to the surface of the wafer 200.

  Next, the image processing unit 562 of the dicing device 510 receives information on the image captured by the imaging unit 540. The image processing unit 562 determines a position to divide the wafer 200 based on the image information. The image processing unit 562 may recognize the position of the scribe line 202 from the functional surface image of the wafer 200 and determine to divide the wafer 200 along the scribe line 202. The image processing unit 562 may recognize the position of the scribe line 202 by recognizing the position of the bump 124 or the alignment mark from the functional surface image of the wafer 200.

  FIG. 7 schematically shows an example of a cross-sectional view at the stage of dividing the wafer 200. In this embodiment, when the image processing unit 562 determines the position at which the wafer 200 is divided, the driving unit 564 drives the alignment stage 530 and the cutting unit 550 based on the above determination, and divides the wafer 200 to obtain chips. 120 is divided into pieces. The dicing apparatus 510 may divide the wafer 200 with the dicing tape 304 attached to the back surface of the wafer 200. This facilitates handling after the wafer 200 is divided.

  The chip 700 with an adhesive film can be manufactured through the above steps. According to the present embodiment, since the chip 700 with an adhesive film can be manufactured in a state where the surface of the adhesive layer 404 is covered with the base material 402, it is possible to suppress the attachment of cutting waste to the surface of the adhesive layer 404. it can. The chip 700 with an adhesive film may be an example of an electronic component with an adhesive film.

  FIG. 8 schematically shows an example of a cross-sectional view at the stage of peeling the substrate 402 from the adhesive layer 404. In this embodiment, first, the adhesive film 800 is affixed on the base material 402 of the plurality of chips 700 with adhesive film while the plurality of chips 700 with adhesive film are affixed to the dicing tape 304. The material of the adhesive film 800 may be selected so that the peeling force between the adhesive film 800 and the substrate 402 is greater than the peeling force between the substrate 402 and the adhesive layer 404.

  Next, the base material 402 is peeled from the adhesive layer 404 of the chip 700 with an adhesive film by pulling the adhesive film 800 in the direction of the arrow in the drawing. Thereby, the base material 402 can be peeled from each adhesive layer 404 of the plurality of chips 700 with adhesive film while the plurality of chips 700 with adhesive film are attached to the dicing tape 304.

  FIG. 9 schematically shows an example of a cross-sectional view at the stage of confirming whether the substrate 402 is peeled off. As shown in FIG. 9, the chip | tip 900 with an adhesive layer can be manufactured by peeling the base material 402 from the adhesive layer 404 of the chip | tip 700 with an adhesive film. In this embodiment, after peeling the base material 402 from the adhesive layer 404 of the chip 700 with an adhesive film, the imaging unit 540 of the dicing apparatus 510 captures an image of the surface of the wafer 200. The image processing unit 562 processes the image of the surface of the wafer 200 and confirms whether or not the base material 402 is peeled from the adhesive layer 404 of the chip 700 with an adhesive film.

  For example, when a material that absorbs light having a specific wavelength out of light having a wavelength of 440 nm to 700 nm is used as the base material 402, a region where the base material 402 exists in the visible light image on the surface of the wafer 200 is colored. Looks. Thereby, it can be confirmed whether the base material 402 is peeled from the adhesive layer 404 of the chip 700 with an adhesive film. The image processing unit 562 may select the chip 900 with the adhesive layer from which the base material 402 is peeled off.

  In the present embodiment, the case where the dicing apparatus 510 confirms whether or not the base material 402 is peeled from the adhesive layer 404 of the chip 700 with the adhesive film has been described. However, the above confirmation method is not limited to this. For example, a pickup device that separates each chip 900 with an adhesive layer from the dicing tape 304 may check whether the base material 402 is peeled from the adhesive layer 404 of the chip 700 with an adhesive film.

  Further, in the present embodiment, a case has been described in which it is confirmed whether or not the base material 402 has been peeled off from the adhesive layer 404 of the chip with adhesive film 700 by performing image processing on a visible light image on the surface of the wafer 200. . However, the above confirmation method is not limited to this. For example, when the pickup device that separates the individual chips 900 with the adhesive layer from the dicing tape 304 picks up the chips 900 with the adhesive layer, when the base material 402 is not peeled from the adhesive layer 404, the base material 402 is removed from the adhesive layer 404. The pick-up device and the chip 900 with the adhesive layer come into contact with each other at a point where the distance between the tip of the pick-up device and the dicing tape 304 is longer than when the film is peeled off. Then, based on the pressure change which a pickup apparatus detects, you may confirm whether the base material 402 has peeled from the contact bonding layer 404 of the chip | tip 700 with an adhesive film.

  FIG. 10 schematically shows an example of a cross-sectional view at the stage where the chip 900 with an adhesive layer is bonded to the circuit board 110. In the present embodiment, first, the chip 900 with an adhesive layer in which the base material 402 is confirmed to be peeled is picked up and placed at a predetermined position on the surface of the circuit board 110. The chip 900 with the adhesive layer and the circuit board 110 are aligned so that the bumps 124 of the chip 900 with the adhesive layer and the electrode 114 of the circuit board 110 are electrically connected when both are pressed.

  Next, the circuit board 110 on which the chip 900 with the adhesive layer is arranged is placed on the stage 420 of the pressing device 410. Then, the chip 900 with the adhesive layer is pressed against the surface of the circuit board 110 with the pressing member 432 held by the head 430. At this time, the heating device 422 may heat the adhesive layer 404 via the stage 420. Thereby, the chip | tip 900 with the contact bonding layer from which the base material 402 was peeled can be adhere | attached on the surface of the circuit board 110 using the contact bonding layer 404. FIG.

  The pressing member 432 may be an elastic body. Thereby, even if it is a case where the several chip | tip 900 with an adhesive layer is simultaneously pressed on the surface of the circuit board 110, the chip | tip 900 with an adhesive layer and the circuit board 110 can be connected favorably.

  The mounting body 100 can be manufactured through the above steps. In the present embodiment, the wafer 200 is divided into individual chips 120 with the adhesive film 400 attached to the functional surface side of the wafer 200. Thereby, it can suppress that cutting waste etc. adhere to adhesive layer 404 of adhesive film 400. In the present embodiment, the adhesive film 400 may have a light transmittance of 74% or more at a wavelength of 440 nm to 700 nm. Thereby, the position which divides | segments the wafer 200 can be determined in the state which the adhesive film 400 affixed on the functional surface side of the wafer 200. FIG.

  In the present embodiment, the thickness of the base material 402 of the adhesive film 400 may be 75 μm or more, and the peeling force between the base material 402 and the adhesive layer 404 may be 0.17 N / 5 cm or more. . Accordingly, even when the wafer 200 is divided with the adhesive film 400 attached to the functional surface side of the wafer 200, it is possible to prevent the substrate 402 from being peeled from the adhesive layer 404 in the dividing step. it can.

  In the present embodiment, it has been described that the wafer 200 may be diced by grinding the back surface of the wafer 200 and then attaching the adhesive film 400 to the functional surface of the wafer 200. However, the manufacturing method of the mounting body 100 is not limited to this. For example, after the adhesive film 400 is attached to the functional surface of the wafer 200, the back surface grinding of the wafer 200 and the dicing of the wafer 200 may be performed. When grinding the back surface of the wafer 200, the adhesive film 400 may be used as a protective layer for protecting the functional surface of the wafer 200, and a protective layer may be further provided on the adhesive film 400.

  FIG. 11 schematically shows another example of a method for mounting the chip 120 on the circuit board 110. In FIG. 11, the same or similar parts as those in FIGS. 1 to 10 are denoted by the same reference numerals as in FIGS. 1 to 10, and redundant description may be omitted.

  In this embodiment, the wafer 200 is prepared in S1102. In step S <b> 1104, the adhesive film 400 is attached to the functional surface of the wafer 200. Adhesion of the adhesive film 400 can be performed in the same manner as described with reference to FIG.

  In S1106, the back surface of the wafer 200 with the adhesive film 400 attached to the functional surface is ground. The backside grinding of the wafer 200 can be performed, for example, by the following procedure. First, on the chuck table 1162 of the back grinding apparatus, the wafer 200 with the adhesive film 400 attached to the functional surface is placed.

  At this time, the wafer 200 is placed so that the surface on the adhesive film 400 side and the chuck table 1162 face each other. In this embodiment, since the adhesive film 400 is affixed to the functional surface of the wafer 200, a protective layer (back grind tape) that protects the substrate 402 is affixed on the substrate 402 of the adhesive film 400. It does not have to be. Thereby, the manufacturing cost of the mounting body 100, the chip | tip 700 with an adhesive film, and the chip | tip 900 with an adhesive layer can be suppressed.

  Next, the grinding wheel 1164 of the back grinding apparatus is rotated, and the rotating grinding wheel 1164 is pressed against the back surface of the wafer 200. Thereby, the back surface of the wafer 200 can be ground.

  In step S <b> 1108, the wafer 200 is transferred to the dicing tape 304. Thereby, the wafer 200 can be bonded to the jig 300. At this time, the back surface of the wafer 200 and the dicing tape 304 may be attached. In step S1110, the wafer 200 is diced. Thereby, the chip | tip 700 with an adhesive film can be manufactured. The dicing of the wafer 200 can be performed in the same manner as described with reference to FIGS.

  In step S1112, the substrate 402 is peeled from the adhesive layer 404. Thereby, the adhesive layer 404 is exposed. Moreover, the chip | tip 900 with an adhesive layer is obtained. The substrate 402 can be peeled in the same manner as described with reference to FIG. In S1114, the chip 900 with the adhesive layer that has been separated is picked up. The pickup tool 1172 of the pickup device may pick up the chip 900 with the adhesive layer by sucking the chip 900 with the adhesive layer.

  At this time, the chip 900 with the adhesive layer in which the base material 402 is confirmed to be peeled may be selected and picked up. Selection of the chip 900 with an adhesive layer is performed by confirming that the base material 402 is peeled from the adhesive layer 404 of the chip 700 with an adhesive film, in the same manner as the method described with reference to FIG. be able to.

  In step S <b> 1116, the chip 900 with an adhesive layer is disposed at a predetermined position on the circuit board 110. In step S <b> 1118, the chip 900 with an adhesive layer is pressure bonded to the circuit board 110. The placement and pressure bonding of the chip 900 with the adhesive layer can be performed in the same manner as the method described with reference to FIG. The mounting body 100 can be manufactured through the above steps.

  In the above-described embodiment, the case where a plurality of chips 900 with an adhesive layer are collectively mounted on the circuit board 110 using an elastic body such as an elastomer for the pressing member 432 has been described. However, the method of mounting the chip 120 on the circuit board 110 is not limited to this. For example, the chip 900 with an adhesive layer may be mounted on the circuit board 110 without using an elastic body such as an elastomer. A plurality of chips with adhesive layers 900 may be mounted on the circuit board 110 one by one.

  FIG. 12 schematically shows another example of a method for mounting the chip 120 on the circuit board 110. FIG. 12 schematically shows an example of a cross-sectional view at the stage where the chip 900 with an adhesive layer is bonded to the circuit board 110. In FIG. 12, the same or similar parts as in FIGS. 1 to 11 are denoted by the same reference numerals as in FIGS. 1 to 11, and redundant description may be omitted.

  The pressing device 1210 electrically connects the circuit board 110 and the chip 120 by flip chip bonding. The pressing device 1210 includes a stage 1220 and a ceramic tool 1230. The pressing device 1210 and the stage 1220 may have the same configuration as the pressing device 410 and the stage 420, respectively.

  The ceramic tool 1230 presses the chip 900 with an adhesive layer against the circuit board 110. The ceramic tool 1230 may press the plurality of chips 900 with an adhesive layer against the circuit board 110 one by one. Ceramic tool 1230 may include a ceramic such as silicon carbide, silicon nitride, aluminum nitride. The ceramic tool 1230 may be an example of a head. The ceramic tool 1230 may include a heating device 1232 that heats the ceramic tool 1230. The heating device 1232 may be a ceramic heater.

(Examples 1-9)
As shown in Example 1 to Example 8 in Table 1, eight types of adhesive films having different “peeling force between adhesive layer and substrate”, “thickness of substrate” and “transmittance of visible light” are different. Prepared. In Examples 1 to 8, NCF was used as an example of the adhesive layer of the adhesive film. As Example 9, an adhesive film using ACF was prepared as an example of the adhesive layer. As the base material of each adhesive film, a PET film having a thickness different from that of the mold release treatment method was used.

  The adhesive films from Example 1 to Example 8 were produced by the following procedure. First, 10 parts by mass of phenoxy resin (YP-50, manufactured by Toto Kasei Co., Ltd.), 10 parts by mass of liquid epoxy resin (EP 828, manufactured by Japan Epoxy Resin Co., Ltd.), imidazole-based latent curing agent (Novacure 3941HP, manufactured by Asahi Kasei Co., Ltd.) ) 100 parts by mass of toluene is added to 15 parts by mass, 5 parts by mass of a rubber component (RKB, manufactured by Resinas Kasei Co., Ltd.) and 1 part by mass of a silane coupling agent (A-187, manufactured by Momentive Performance Materials) and stirred. Thus, a uniform resin solution was prepared.

  Next, the above resin solution was applied onto each of the substrates used in Examples 1 to 8 using a bar coater. The base material coated with the resin solution was placed in an oven at 80 ° C., the solvent was evaporated, and the resin solution was dried to produce an adhesive film having a PET film and NCF. All the NCF thicknesses of the produced adhesive films were 30 μm.

  The adhesive film of Example 9 was produced by the following procedure. First, 10 parts by mass of phenoxy resin (YP-50, manufactured by Toto Kasei Co., Ltd.), 10 parts by mass of liquid epoxy resin (EP 828, manufactured by Japan Epoxy Resin Co., Ltd.), imidazole-based latent curing agent (Novacure 3941HP, manufactured by Asahi Kasei Co., Ltd.) ) 15 parts by mass, rubber component (RKB, manufactured by Resinas Kasei Co., Ltd.) 5 parts by mass, silane coupling agent (A-187, manufactured by Momentive Performance Materials) and conductive particles (AUE, Sekisui Chemical) Industry) 100 parts by mass of toluene was added to 5 parts by mass and stirred to prepare a uniform resin solution.

  Next, the above resin solution was applied onto the base material used in Example 9 using a bar coater. The base material coated with the resin solution was placed in an oven at 80 ° C., the solvent was evaporated, and the resin solution was dried, thereby producing an adhesive film having a PET film and ACF. The ACF thickness of the produced adhesive film was 30 μm.

  In the adhesive films of Example 1 to Example 9, the peeling force between the adhesive layer and the base material is adjusted by performing a release treatment on the surface of the base material before applying the resin solution on the base material. did. The mold release treatment was performed by applying a silicone-based release agent to the surface of the substrate, and then heating the substrate to dry the substrate. By adjusting the composition of the silicone release agent, adhesive films having different peeling forces between the adhesive layer and the substrate were produced.

  The peeling force between the substrate and the adhesive layer was measured using Tensilon (manufactured by Orientec Co., Ltd.). The measurement was carried out using an adhesive film having a width of 50 mm and a length of 100 mm. The tensile direction was 180 ° and the tensile method was T-type peeling. The tensile speed was set to 300 mm / min. The measurement was performed under conditions of a temperature of 23 ± 2 ° C. and a humidity of 55 ± 10% RH.

  The transmittance of the adhesive film was measured for parallel light transmittance using MCPD-2000 (manufactured by Otsuka Electronics Co., Ltd.). The transmittance of the adhesive film was calculated according to the following procedure. First, each adhesive film was affixed on the glass substrate so that the adhesive layer of the adhesive film and the glass substrate faced to prepare a measurement sample. The thickness of the glass substrate was 1.1 mm. Next, the parallel light transmittance of the glass substrate alone was measured. The measurement was performed by continuously changing the wavelength of transmitted light from 300 nm to 1100 nm. Next, the parallel light transmittance was similarly measured for each of the prepared measurement samples. The transmittance of each adhesive film was calculated with the parallel light transmittance of the glass substrate alone being 100%.

  The thickness of the base material was measured using a micrometer (manufactured by Mitutoyo Corporation).

  Next, each of the adhesive films of Example 1 to Example 9 was attached to the entire surface of one surface of the silicon wafer to prepare a sample used for a dicing test. The diameter of the silicon wafer was 6 inches, and the thickness of the silicon wafer was 400 μm.

  Next, each of the above samples was divided into 6.3 mm × 6.3 mm chips by dicing, and the visibility and workability of the pattern were evaluated. As the dicing apparatus, DFD-651 (manufactured by DISCO Corporation) was used. As the blade, NBC-ZB2030-0.04t (manufactured by DISCO Corporation) was used. The thickness of the blade was 40 μm. The rotation speed of the blade was set to 30000 rpm. The blade feed speed was set to 10 mm / sec.

  Regarding the visibility of the pattern, the pattern formed on the surface of the silicon wafer was observed with a CCD camera mounted on the DFD-651. The line width of the pattern was 30 μm. The workability was evaluated by measuring the number of chips from which the base material was peeled off from the adhesive layer when the silicon wafer was divided by a dicing apparatus and separated into 6.3 mm × 6.3 mm chips.

Table 1 shows the pattern visibility and workability when the silicon wafer was divided using the adhesive films of Examples 1 to 8. In Table 1, “◎” indicates that the condition was very good. ○ indicates that it was good.

  As shown in Table 1, the pattern on the silicon wafer could be well distinguished with the adhesive films of Examples 1 to 8 attached. As shown in Table 1, even when the silicon wafer was diced with the adhesive films of Examples 1 to 8 attached, it was possible to suppress the peeling of the base material from the adhesive layer.

  As for the adhesive film of Example 9, the pattern on the silicon wafer could be well distinguished with the adhesive film of Example 9 attached to the silicon wafer. Further, even when the silicon wafer was diced in a state where the adhesive film of Example 9 was attached to the silicon wafer, peeling of the base material from the adhesive layer could be suppressed.

  In the same manner as in Example 9, an adhesive film having a thickness of 5 to 30 μm ACF as an adhesive layer was produced. About each of the manufactured adhesive film, it carried out similarly to Example 1- Example 9, and evaluated the visibility and workability of a pattern. For these adhesive films, the pattern on the silicon wafer could be well distinguished. Moreover, even when the silicon wafer was diced in a state where these adhesive films were attached to the silicon wafer, peeling of the base material from the adhesive layer could be suppressed. Moreover, the same effect was able to be acquired also when the adhesive film which has the contact bonding layer obtained by laminating | stacking NCF and ACF was manufactured.

(Comparative Examples 1-10)
As shown in Comparative Example 1 to Comparative Example 10 in Table 2, 10 types of adhesive films having different “peeling force between adhesive layer and substrate”, “thickness of substrate” and “transmittance of visible light” are different. Prepared. “Peeling force between adhesive layer and substrate”, “thickness of substrate” and “transmittance of visible light” were measured in the same manner as in Examples 1 to 9.

  The adhesive film of Comparative Example 1 was produced by the same method as the adhesive films of Examples 1 to 8. By adjusting the composition of the silicone release agent, an adhesive film having a weaker peeling force between the adhesive layer and the substrate was prepared as compared with the adhesive films of Examples 1 to 8.

  The adhesive films of Comparative Example 2 and Comparative Example 3 were produced by the following procedure. First, 10 parts by mass of phenoxy resin (YP-50, manufactured by Toto Kasei Co., Ltd.), 10 parts by mass of liquid epoxy resin (EP 828, manufactured by Japan Epoxy Resin Co., Ltd.), imidazole-based latent curing agent (Novacure 3941HP, manufactured by Asahi Kasei Co., Ltd.) ) 15 parts by mass, rubber component (RKB, manufactured by Resinas Kasei Co., Ltd.), 5 parts by mass, inorganic filler (SOE2, manufactured by Admatex Co., Ltd.), 50 parts by mass, silane coupling agent (A-187, Momentive Performance Materials) 100 parts by mass of toluene was added to 1 part by mass and stirred to prepare a uniform resin solution.

  Next, on each base material used in Comparative Example 2 and Comparative Example 3, the above resin solution was applied using a bar coater. The base material coated with the resin solution was placed in an oven at 80 ° C., the solvent was evaporated, and the resin solution was dried to produce an adhesive film having a PET film and NCF. All the NCF thicknesses of the produced adhesive films were 30 μm.

  Also in the comparative example 2 and the comparative example 3, before apply | coating a resin solution on a base material, the peeling force of an adhesive layer and a base material was adjusted by performing the mold release process on the surface of a base material. The mold release treatment was performed by applying a silicone-based release agent to the surface of the substrate, heating the substrate, and drying the substrate. By adjusting the composition of the silicone release agent, adhesive films having different peeling forces between the adhesive layer and the substrate were produced.

  The adhesive films from Comparative Example 4 to Comparative Example 10 were produced in the same manner as the adhesive films from Example 1 to Example 8, except that a PET film having a thickness of 25 μm or 50 μm was used as the substrate.

  Also in Comparative Example 4 to Comparative Example 10, the release force between the adhesive layer and the substrate was adjusted by performing a release treatment on the surface of the substrate before applying the resin solution on the substrate. The mold release treatment was performed by applying a silicone-based release agent to the surface of the substrate, heating the substrate, and drying the substrate. By adjusting the composition of the silicone release agent, adhesive films having different peeling forces between the adhesive layer and the substrate were produced.

  Each of the adhesive films from Comparative Example 1 to Comparative Example 10 was attached to the entire surface of one surface of the silicon wafer to prepare a sample used for a dicing test. The diameter of the silicon wafer was 6 inches, and the thickness of the silicon wafer was 400 μm. In the same manner as in Example 1 to Example 9, each of the above samples was divided into 6.3 mm × 6.3 mm chips by dicing, and the pattern visibility and workability were evaluated.

Table 2 shows the visibility and workability of the pattern when the silicon wafer is divided using the adhesive films of Comparative Examples 1 to 10. In Table 2, “◎” indicates that it was very good. ○ indicates that it was good. Δ indicates that it was partially defective. X represents that it was defective.

  As shown in Table 2, Comparative Example 1 is inferior in workability as compared with Examples 1 to 9. In the adhesive film of Comparative Example 1, the peeling force between the adhesive layer and the substrate was smaller than 0.17 N / 5 cm, and thus the substrate sometimes peeled from the adhesive layer when the dicing process was completed.

  In Comparative Example 2 and Comparative Example 3, the transmittance of light having a wavelength of 440 nm or more and 700 nm or less is smaller than 74%, so that the pattern visibility is inferior as compared with Examples 1 to 9. Moreover, in the comparative example 2 and the comparative example 3, workability is a little inferior compared with Example 1-9. In the adhesive films of Comparative Example 2 and Comparative Example 3, since the inorganic filler was added to the base material, the surface of the base material sometimes became rough when the dicing process was completed.

  In Comparative Examples 4 to 10, the processability is inferior compared to Examples 1 to 9. Since the thickness of the base material of the adhesive films of Comparative Example 4 to Comparative Example 10 was less than 75 μm, the base material sometimes peeled from the adhesive layer when the dicing process was completed.

(Example 10)
A silicon wafer having a plurality of bumps formed on the surface was prepared. The silicon wafer had a diameter of 6 inches and a thickness of 0.6 mm. The bump was formed by pre-coating solder on the surface of the Cu electrode. The solder thickness was 25 μm. The Cu electrode had a diameter of 33 mm and a thickness of 25 μm. The bump pitch was 85 μm. The number of bumps was 272.

  Next, an adhesive film was produced in the same manner as in Examples 1 to 8. As a base material for the adhesive film of Example 10, a transparent PET film having a thickness of 100 μm was used. As the adhesive layer of the adhesive film of Example 10, the same NCF as in Examples 1 to 8 was used. The NCF thickness of the adhesive layer of Example 10 was 30 μm. In the adhesive film of Example 10, the peel force between the adhesive layer and the substrate was 0.72 N / 5 cm. In the adhesive film of Example 10, the transmittances of light having wavelengths of 440 nm, 550 nm, and 700 nm were all 74% or more.

  Next, the produced adhesive film was affixed on the entire surface of the silicon wafer on which the bumps were formed. Next, using a back grinder (DFG8540, manufactured by DISCO Corporation), the surface of the silicon wafer where the adhesive film was not attached was ground to a thickness of 200 μm. The conditions for back grinding were 0.4 μm / sec for roughing and 0.3 μm / sec for finishing.

  After carrying out back grinding, the adhesive film was peeled off, and the presence or absence of damage and deformation of the bumps was examined. Whether the bumps were damaged or deformed was observed by observing an image taken with a CCD camera mounted on the DFG8540. As a result, no damage or deformation of the bumps was observed in all the bumps. Further, the silicon wafer was not chipped or cracked in the back grind. A part of the ground surface was found to have uneven processing called transfer. However, the degree of processing unevenness was the same as when a general back grind tape was attached to the functional surface of the silicon wafer to back grind the silicon wafer.

  As mentioned above, although this invention was demonstrated using embodiment, the technical scope of this invention is not limited to the range as described in the said embodiment. It will be apparent to those skilled in the art that various modifications or improvements can be added to the above-described embodiment. It is apparent from the scope of the claims that the embodiments added with such changes or improvements can be included in the technical scope of the present invention.

  The order of execution of each process such as operations, procedures, steps, and stages in the apparatus, system, program, and method shown in the claims, the description, and the drawings is particularly “before” or “prior to”. It should be noted that the output can be realized in any order unless the output of the previous process is used in the subsequent process. Regarding the operation flow in the claims, the description, and the drawings, even if it is described using “first”, “next”, etc. for convenience, it means that it is essential to carry out in this order. It is not a thing.

DESCRIPTION OF SYMBOLS 100 Mounting body 110 Circuit board 114 Electrode 120 Chip 122 Device 124 Bump 130 Adhesive layer 200 Wafer 202 Scribe line 300 Jig 302 Frame 304 Dicing tape 400 Adhesive film 402 Base material 404 Adhesive layer 410 Pressing device 420 Stage 422 Heating device 430 Head 432 Press member 434 Holding unit 510 Dicing device 520 Chuck table 530 Alignment stage 540 Imaging unit 550 Cutting unit 552 Blade 560 Control unit 562 Image processing unit 564 Drive unit 700 Chip with adhesive film 800 Adhesive film 900 Chip with adhesive layer 1162 Chuck table 1164 Grinding Wheel 1172 Pickup tool 1210 Pressing device 1220 Stage 1230 Sera Kkutsuru 1232 heating device

Claims (13)

Affixing step of affixing an adhesive film formed by laminating a base material and an adhesive layer on the surface of a wafer on which electronic components are formed;
An imaging step of capturing an image of the surface of the wafer by receiving light reflected by the surface of the wafer and transmitted through the substrate and the adhesive layer;
A division position determining step for determining a position to divide the wafer based on the image;
A dividing step of dividing the wafer into pieces of the electronic components;
A method for manufacturing an electronic component with an adhesive film comprising: The sticking step includes a step of pressing the adhesive film against the surface of the wafer with an elastic body held by a head.
The manufacturing method of the electronic component with an adhesive film of Claim 1. The peeling force between the substrate and the adhesive layer is 0.17 N / 5 cm or more.
The manufacturing method of the electronic component with an adhesive film of Claim 1 or 2. The substrate has a thickness of 75 μm or more.
The manufacturing method of the electronic component with an adhesive film in any one of Claim 1 to 3. In the adhesive film, the transmittance of light having a wavelength of 440 nm to 700 nm is 74% or more.
The manufacturing method of the electronic component with an adhesive film in any one of Claim 1 to 4. The adhesive layer includes NCF or ACF;
The manufacturing method of the electronic component with an adhesive film in any one of Claim 1 to 5. Before the imaging step, further comprising a back grinding step of grinding the back surface of the wafer having the adhesive film affixed to the front surface,
The manufacturing method of the electronic component with an adhesive film in any one of Claim 1 to 6. The back surface grinding step includes a step of grinding the back surface of the wafer in which a protective layer for protecting the base material is not attached on the base material.
The manufacturing method of the electronic component with an adhesive film of Claim 7. A peeling step of peeling the base material from the adhesive layer of the electronic component with an adhesive film manufactured by the method for manufacturing an electronic component with an adhesive film according to any one of claims 1 to 8,
Adhering step of adhering the electronic component with an adhesive layer from which the base material has been peeled, to the surface of the substrate using the adhesive layer;
A method of manufacturing a mounting body comprising: The bonding step includes a pressing step of pressing the electronic component with an adhesive layer against the surface of the substrate with an elastic body held by a head.
The manufacturing method of the mounting body of Claim 9. The pressing step includes a step of simultaneously pressing a plurality of the electronic components with an adhesive layer against the surface of the substrate with the elastic body.
The manufacturing method of the mounting body of Claim 10. The dividing step includes a step of dividing the wafer in a state where a dicing tape is attached to the back surface of the wafer,
The peeling step includes a step of peeling the base material from each of the adhesive layers of the plurality of electronic parts with adhesive films while the plurality of electronic parts with adhesive films are attached to the dicing tape. Have
The manufacturing method of the mounting body in any one of Claim 9 to 11. After the peeling step, from the adhesive layer of the electronic component with the adhesive film, further comprising a selection step of checking whether the substrate is peeled off,
The adhering step includes the step of adhering the electronic component with an adhesive layer, on which the base material has been peeled, to the surface of the substrate using the adhesive layer.
The manufacturing method of the mounting body in any one of Claim 9 to 12.