JP2019087543A - Object treating method, cleaning agent, semiconductor device, and manufacturing method thereof - Google Patents

Abstract

To provide an object treatment method with less residual temporary fixing material on an object in a method of processing and moving an object while temporarily fixing the object to be processed on a support by using a temporary fixing material and subsequently separating the support and the object.SOLUTION: An object treatment method includes (1) a step of forming a laminate having a support, a temporary fixing material, and an object to be processed and holding the object on a temporary fixing material, (2) a step of processing the object and/or moving the laminate, (3) a step of separating the object from the support, and (4) a step of washing the object with a cleaning agent containing a base (B1) and a surfactant (B2) having a group containing an aromatic hydrocarbon structure as a lipophilic group.SELECTED DRAWING: None

Description

  The present invention relates to a method for treating an object such as a method for processing an object while a target such as a semiconductor wafer is bonded to a support such as a glass substrate via a temporary fixing material. The present invention relates to a semiconductor device and a method of manufacturing the same.

  A method has been proposed in which processing such as backside grinding and photofabrication is performed on an object such as a semiconductor wafer while the object such as a semiconductor wafer is bonded to a support such as a glass substrate via a temporary fixing material. . The temporary fixing material is required to be able to temporarily fix an object on a support during processing, and to be able to easily separate the support and the object after processing.

  In the separation treatment, the adhesion of the temporary fixing material is reduced by irradiating light energy such as ultraviolet light and infrared light to the temporary fixing material in the laminate having the support, the temporary fixing material, and the object, Then, the method of separating a support body and a subject is proposed (refer patent documents 1-2).

International Publication No. 2017/056662 U.S. Published Patent Application No. 2014/0106473

  When the object is separated from the support, since the residue of the temporary fixing material is usually present on the object, the object is washed with a detergent to remove the residue. However, even if this cleaning is performed, the residue of the temporary fixing material may not be removed well.

  The present invention is a method for processing and moving an object while temporarily fixing the object to be treated on a support using a temporary fixing material, and subsequently separating the support and the object from each other on the object. It is an object of the present invention to provide a method of treating an object having a small amount of residual temporary fixing material, and to provide a cleaning agent preferably used in the method of treating the object, a semiconductor device and a method of manufacturing the same.

  The present inventors diligently studied to solve the above problems. As a result, it has been found that the problem can be solved by the method for processing an object having the following constitution, and the present invention has been completed. That is, the present invention relates to, for example, the following [1] to [14].

[1] (1) a step of forming a laminate having a support, a temporary fixing material and an object to be treated, wherein the object is held on the temporary fixing material; (2) the object (3) separating the object from the support; and (4) moving the laminate from the base (B1) to an aromatic hydrocarbon structure. Washing the object with a detergent containing a surfactant containing the group as a lipophilic group (B2);
[2] The method for treating an object according to [1], wherein the hydrophilic group of the surfactant (B2) is a polyoxyalkylene group.
[3] The method for treating an object according to [1] or [2], wherein the base (B1) is an inorganic base.
[4] The method of treating an object according to [3], wherein the inorganic base is a hydroxide of an alkali metal.
[5] The method for treating an object according to any one of the above [1] to [4], wherein the detergent is an aqueous solution.
[6] In the step (3), the temporary fixing material is irradiated with light to decompose or deteriorate the temporary fixing material, and the object is separated from the support. A method of processing an object according to item 1.
[7] The method of treating an object according to [6], wherein the light irradiation is performed by a laser having a wavelength of 300 to 400 nm.
[8] The above-mentioned [1] to [7] having a layer (I) formed of the temporary fixing composition containing 70% by mass or more of the polymer having an aromatic hydrocarbon structure in the solid content. ] The processing method of the target of any one of Claim 1.
[9] The method for processing an object according to [8], wherein the layer (I) is a layer in contact with the object to be treated.
[10] The method for treating an object according to any one of the above [1] to [9], wherein in the step (1), a treatment object having at least a wiring layer is formed on a temporary fixing material.
[11] The method of treating an object according to the above [10], wherein the processing in the step (2) includes disposing at least one selected from a semiconductor wafer and a semiconductor chip on the wiring layer.
[12] A detergent containing a base (B1) and a surfactant (B2) having a group containing an aromatic hydrocarbon structure as a lipophilic group.
[13] A method of manufacturing a semiconductor device, wherein a semiconductor device is manufactured by processing an object by the processing method according to any one of [1] to [11].
[14] A semiconductor device obtained by the manufacturing method according to [13].

  According to the present invention, in the method of processing and moving the object while temporarily fixing the object to be treated on the support using the temporary fixing material, and subsequently separating the support and the object, It is possible to provide a method of treating an object with a small amount of residual temporary fixing material on the object, and also provide a cleaning agent preferably used in the method of treating the object, a semiconductor device and a method of manufacturing the same. .

  Hereinafter, after describing the laminate formed by the method of processing an object of the present invention, a method of processing an object, a semiconductor device, and a method of manufacturing the same will be described. The cleaning agent of the present invention will be described in the section on the method of treating an object.

Each component exemplified in the present specification, for example, each component in the composition may be used alone or in combination of two or more unless otherwise stated.
In the present invention, the temporary fixing material is a material used to temporarily fix an object on a support so that the object does not shift from the support when processing and / or moving the object to be treated. It is. The object to be treated means an object to be subjected to the processing treatment or the movement treatment in the step (2) described later (for example, the step in the step (1) or (2) described later) It may mean a later object (eg, a step in steps (3) and (4) described later). Hereinafter, the processing object is also referred to simply as the "object".

[Laminate]
The laminate formed in the present invention has a support, a temporary fixing material, and an object to be treated, wherein the object to be treated is held on the temporary fixing material. For example, the processing object to be processed or moved is temporarily fixed on the support via the temporary fixing material. Specifically, the laminate preferably has a support, a temporary fixing material, and an object to be treated in this order in the stacking direction.

  The temporary fixing material is a layer (I) formed from a temporary fixing composition containing a polymer having an aromatic hydrocarbon structure (hereinafter, also referred to as “polymer (A)”) (hereinafter, “separation layer (I) It is preferable to have "."

  The temporary fixing material may have, in addition to the separation layer (I), an adhesive layer (II) formed directly in contact with the layer (I) or sandwiching the other layer. The adhesive layer (II) is formed of a known adhesive for temporarily fixing an object, such as an adhesive of a thermoplastic resin type, an elastomer type or a thermosetting resin type, and two or more types selected from these. A mixed adhesive may be used.

  The temporary fixing material may have any other layer in addition to the layer (I) and the layer (II). In the case of a laminate having the above components in the order of the support, the adhesive layer (II), the separation layer (I) and the object, for example, an intermediate layer is provided between the layer (I) and the layer (II) Other layers may be provided between the layer (II) and the support or between the layer (I) and the object.

  In the laminate, the separation layer (I) is preferably a layer in contact with an object. In this case, when the object is separated from the support, the residue derived from the separation layer (I) tends to remain on the object, but the residue can be favorably removed by using the cleaning agent of the present invention.

  The total thickness of the temporary fixing material is usually 0.01 to 1000 μm, preferably 0.1 to 500 μm, more preferably 0.2 to 300 μm. In addition, the thickness of each layer of layer (I) and layer (II) is each independently usually 0.01 μm or more, preferably 0.1 μm or more, and more preferably 0.2 μm or more. In such an embodiment, the temporary fixing material has sufficient holding power for temporarily fixing the object, and the object does not fall off from the temporary fixing surface during processing or movement processing.

[Separation layer (I)]
The separation layer (I) preferably contains a polymer (A) having an aromatic hydrocarbon structure. The separation layer (I) is formed from a temporary fixing composition containing a polymer (A). The composition for temporary fixation may contain a solvent.

  In one embodiment, when the separation layer (I) is irradiated with a light described later, the polymer (A) absorbs the light and decomposes or degrades the light. Due to this decomposition or deterioration, the strength or adhesion of the separation layer (I) decreases before and after light irradiation. By applying an external force to the laminate, cohesive failure occurs in the separation layer (I) or interfacial failure occurs between the separation layer (I) and the layer in contact with the layer. Therefore, the support and the object can be easily separated by applying an external force to the laminate after the light irradiation treatment. Generally, workpieces such as semiconductor wafers and semiconductor chips are weak to light and may deteriorate when exposed to light. After the temporary fixing material is irradiated with light to reduce its adhesive force or light irradiation is performed, the light used in the light irradiation separation method for separating the support and the object does not reach the object, It is preferable that the temporary fixing material can block the light.

  It is preferable that the separation layer (I) has a low light transmittance to light used in the light irradiation treatment from the viewpoint of decomposition or deterioration of the separation layer (I) and light blocking properties. In the separation layer (I), the light transmittance at the wavelength of light used in the light irradiation treatment is, for example, preferably 10% T or less, more preferably 5% T or less, more preferably 10% T or less. It is less than 1% T.

<Polymer (A)>
The aromatic hydrocarbon structure in the polymer (A) has, for example, a benzene ring, naphthalene ring, azulene ring, anthracene ring, phenanthrene ring, pyrene ring, chrysene ring, triphenylene ring, perylene ring, etc. And aromatic hydrocarbon rings. The aromatic hydrocarbon structure in the polymer (A) may be the same as or different from the aromatic hydrocarbon structure in the surfactant (B2) described later.

  As the polymer (A), for example, novolak resin, polybenzoxazole resin, polybenzothiazole resin, polybenzimidazole resin, cyclization reaction (ring closure reaction) in the molecule upon receiving heat, benzoxazole ring, benzothiazole Resins (polybenzoxazole resin, polybenzothiazole resin, precursor resin of polybenzimidazole resin), dihydrobenzoxazine resin, phenoxy resin, aromatic polyimide resin, and the like, among which novolak resins can be mentioned. Resins are preferred.

  Novolak resins include, for example, dihydroxynaphthalene / formaldehyde condensates, phenol / formaldehyde condensates, cresol / formaldehyde condensates, phenol-naphthol / formaldehyde condensates. Specifically, polymers having a structural unit represented by the following (A1) (hereinafter also referred to as “structural unit (A1)”) can be mentioned.

式（Ａ１）中、各記号の詳細は以下のとおりである。

The details of each symbol in the formula (A1) are as follows.

Ar is an aromatic hydrocarbon ring, preferably a fused polycyclic aromatic hydrocarbon ring. The number of rings constituting the fused polycyclic aromatic ring (eg, the number of benzene nuclei) is preferably 2 to 5, more preferably 2 to 3, and still more preferably 2. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, a triphenylene ring, and a perylene ring. Preferably, it is a naphthalene ring in that the light transmittance of (1) is hardly increased. The aromatic hydrocarbon ring may have a substituent other than —OR ¹ below, such as a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

-OR ¹ is a group bonded to the aromatic hydrocarbon ring. R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. When there are a plurality of -OR ^{1 's} , they may be identical to or different from each other.

As a halogen atom, a fluorine, chlorine, a bromine is mentioned, for example.
As a C1-C20 hydrocarbon group, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C18 aryl group, a C2-C20 alkynyl group is mentioned, for example Can be mentioned.

a is an integer of 1 or more. For example, when a is an integer of 2 or more, the Ar-OR ¹ portion in the structural unit (A1) is considered to be subjected to high-temperature heat treatment to form a quinone structure having high light shielding properties. a is preferably an integer of 2 or more, more preferably an integer of 2 to 4, further preferably 2 from the viewpoint of formation of a quinone structure.

R ² is a hydrogen atom or an organic group. R ² may be identical to or different from one another.
Examples of the organic group in R ² include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl and propyl; cycloalkyl groups having 3 to 20 carbons such as cyclopentyl and cyclohexyl; phenyl and naphthyl Aryl group having 6 to 18 carbon atoms such as group, anthracenyl group, fluorenyl group, pyrenyl group and the like; furyl group and thienyl group. In the organic group, at least one hydrogen atom contained in the alkyl group, the cycloalkyl group and the aryl group is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl having 6 to 18 carbon atoms It may be substituted by at least one group selected from a group, an alkoxy group having 1 to 20 carbon atoms, a hydroxy group, a nitro group and a halogen atom.

The content of the structural unit (A1) is usually 80% by mass or more, preferably 90% by mass or more, and more preferably 99% by mass or more in 100% by mass of the polymer (A). When the content is in the above range, the separation layer (I) having high sensitivity to light irradiation and excellent in light shielding property tends to be obtained. The content can be measured by ¹³ C NMR.

  The novolac resin can be obtained, for example, by addition condensation of a phenol compound and an aldehyde compound in the presence of an acidic catalyst such as oxalic acid. As reaction conditions, in a solvent, a phenol compound and an aldehyde compound are usually reacted at 40 to 200 ° C. for about 0.5 to 10 hours.

  The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography (GPC) method is usually 500 to 30,000, preferably 1,000 to 15,000, and further Preferably, it is 1,000 to 10,000. When Mw is in the above range, a layer (I) excellent in film thickness uniformity can be formed. Details of the method of measuring Mw are described in the examples.

  The content of the polymer (A) is usually 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more, in 100% by mass of the solid content contained in the temporary fixing composition. The solid content refers to all components other than the solvent. When the content of the polymer (A) is in the above-mentioned range, it is preferable in terms of the adhesion, separation, light shielding property and heat resistance of the separation layer (I).

<Other ingredients>
The temporary fixing composition is, if necessary, at least one selected from a tackifying resin, an antioxidant, a polymerization inhibitor, an adhesion aiding agent, a surfactant, a polystyrene crosslinked particle, a crosslinking agent and a metal oxide particle. You may contain.

<Production of composition for temporary fixation>
The composition for temporary fixation is a known device used for processing of the resin composition as required, for example, using a twin-screw extruder, a single-screw extruder, a continuous kneader, a roll kneader, a pressure kneader, and a Banbury mixer. , Can be produced by mixing the components. In addition, for the purpose of removing foreign matter, filtration can be appropriately performed.

  A solvent may be used in the preparation of the temporary fixing composition in order to set the viscosity in a range suitable for coating. Examples of the solvent include hydrocarbon solvents, alcohol solvents, ether solvents, ester solvents, lactone solvents, ketone solvents, amide solvents and lactam solvents. Specific examples thereof include those listed as solvents in the cleaning agent of the present invention described later.

  When the composition for temporary fixing contains a solvent, it becomes easy to adjust the viscosity of these, and therefore, it becomes easy to form a temporary fixing material on an object or a support. For example, the solvent can be used in the range in which the solid content concentration of the temporary fixing composition is usually 5 to 70% by mass, more preferably 5 to 50% by mass. Here, the "solid content concentration" is the total concentration of all components other than the solvent.

[Method of processing object]
The method for treating an object according to the present invention comprises the step (1) of forming the laminate, wherein the object is held on the temporary fixing material, the object is processed, and / or the object is processed. Step (2) of moving the laminate, step (3) of separating the object from the support, base (B1), the group containing the aromatic hydrocarbon structure, and lipophilic group And (4) washing with a detergent containing the surfactant (B2) having

<Step (1)>
In the step (1), for example, the temporary fixing material is formed on the surface of the support and / or the target, and the target is supported by bonding the target and the support via the temporary fixing material. Temporarily fix on the body. Alternatively, the temporary fixing material may be formed on the surface of the support, and the target may be temporarily fixed on the support by forming an object such as a resin coating film or a wiring layer on the temporary fixing material. Good. The object may be surface-treated as needed.

  As a method of forming the above-mentioned temporary fixing material, for example, a method of directly forming each layer of the temporary fixing material on a support and / or an object, a composition for temporary fixing on a film subjected to release treatment After forming a film with a constant film thickness using an object or an adhesive, there is a method of transferring each layer to a support and / or an object by a lamination method. From the viewpoint of film thickness uniformity, the method of direct formation is preferable.

  When the temporary fixing material is formed on the object, the object surface (for example, a circuit surface) may be subjected to surface treatment in advance in order to make the temporary fixing material uniformly spread in the plane. As a method of surface treatment, for example, a method of applying a surface treatment agent to an object surface in advance may be mentioned. As a surface treatment agent, coupling agents, such as a silane coupling agent, are mentioned, for example.

  Hereinafter, the method of forming the separation layer (I) will be described. Examples of the method for applying the temporary fixing composition include a spin coating method and an inkjet method. After applying the composition for temporary fixing and forming a coating film, it heats as needed and evaporates a solvent, and forms isolation layer (I). The heating conditions are appropriately determined according to the boiling point of the solvent, and for example, the heating temperature is usually 100 to 350 ° C., and the heating time is usually 1 to 60 minutes.

  The pressure bonding condition between the object and the support via the temporary fixing material is, for example, preferably 5 to 400 ° C., more preferably 150 to 400 ° C. for 1 to 20 minutes, and laminating each layer with a pressure of 0.01 to 100 MPa. It may be performed by adding in the direction. After pressure bonding, heat treatment may be further performed at 150 to 300 ° C. for 10 minutes to 3 hours. In this way, the object is firmly held on the support via the temporary fixing material.

  Examples of the processing object to be processed (moved) include a semiconductor wafer, a semiconductor chip, a glass substrate, a resin substrate, a metal substrate, a metal foil, a polishing pad, a resin coating film, and a wiring layer. The semiconductor wafer and the semiconductor chip may be formed with at least one selected from bumps, wires, through holes, through hole vias, insulating films, and various elements. Various elements may be formed or mounted on the substrate. Examples of the resin coating film include a layer containing an organic component as a main component; specifically, a photosensitive resin layer formed of a photosensitive material, an insulating resin layer formed of an insulating material, The photosensitive insulating resin layer formed from a photosensitive insulating resin material is mentioned.

  As the support, it is preferable that the separation layer (I) be altered by light irradiation from the support side in the step (3), so a substrate transparent to light used for light irradiation is preferable, for example, a glass substrate And quartz substrates and transparent resin substrates.

  Below, the process target object which has a wiring layer at least is demonstrated. In this process, a temporary fixing material is formed on a support, and an object to be treated having at least a wiring layer is first formed on the temporary fixing material, for example, as a layer independent of a semiconductor wafer or chip, and subsequently described later. In the step (2), a semiconductor wafer or a semiconductor chip in which a plurality of semiconductor elements are formed on a wafer substrate is disposed on the wiring layer. The wiring layer functions as a rewiring layer of the semiconductor wafer or chip by being electrically connected to the semiconductor wafer or chip. The present invention is also applicable to the Redistribution Layer (RDL) -First structure in such a Fan-Out Wafer Level Package (FO-WLP) technology.

  The wiring layer has, for example, an insulating portion, a wiring portion, and a connection conductor portion that can be connected to an electrode of a semiconductor wafer or a chip. A semiconductor wafer or chip is disposed on the wiring layer, and the connecting conductor of the wiring layer and the electrode of the semiconductor wafer or chip are electrically connected by a bonding member such as solder, anisotropic conductive paste, or anisotropic conductive film. Connect to Underfill material may be filled if a gap occurs between the semiconductor wafer or chip and the wiring layer.

  The internal structure in the wiring layer is not particularly limited. As materials for the wiring portion and the connecting conductor portion, for example, metals such as copper, gold, silver, platinum, lead, tin, nickel, cobalt, indium, rhodium, chromium, tungsten, ruthenium and the like, and two or more of them are listed. Alloys are listed. Examples of the material of the insulating portion include known synthetic resins such as polyimide resin, acrylic resin, polyether nitrile resin, polyether sulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin, etc. . The thickness of the wiring layer is usually 1 to 1,000 μm.

  Subsequently, for example, the semiconductor wafer or the chip is resin-sealed in the step (2), and the temporary fixing material and the wiring layer are separated in the step (3). Can be obtained.

<Step (2)>
Step (2) is a step of processing the object temporarily fixed on the support and / or moving the obtained laminate. The moving step is a step of moving an object such as a semiconductor wafer from one apparatus to another together with a support. Examples of processing of the object temporarily fixed on the support include dicing of the object, thinning of the object (back grinding, etc.), photofabrication, lamination of semiconductor wafers or chips, mounting of various elements, Resin sealing is mentioned. Photofabrication includes, for example, one or more processes selected from formation of a resist pattern, etching, formation of a sputtered film, plating, and plating reflow. The etching process and the formation of the sputtered film are performed, for example, in a temperature range of about 25 to 300 ° C., and the plating process and the plating reflow process are performed, for example, in a temperature range of about 225 to 300 ° C. The processing of the object is not particularly limited as long as the holding power of the temporary fixing material is not lost.

  For example, in the above-described RDL-First, a processing target object having at least a wiring layer is formed on the temporary fixing material in the step (1), and is selected from the semiconductor wafer and the semiconductor chip on the wiring layer in the step (2). At least one type is disposed, and then the wiring layer and the semiconductor wafer or chip are electrically connected. Subsequently, resin sealing of the semiconductor wafer or chip is performed as necessary.

<Step (3)>
After processing of the object or transfer of the laminate, in step (3) the object is separated from the support. As a method of separating an object and a support, for example, a method of applying a force to an object or a support in a direction parallel to the support surface or the object surface to separate them; one of the object and the support Is fixed, and the other is separated at an angle from the parallel direction with respect to the support surface or the object surface to separate them from each other.

  In the former method, by sliding the object horizontally relative to the surface of the support, at the same time fixing the support or applying a force to the support that counteracts the force applied to the object. And methods of separating the support and the object.

  In the latter method, it is preferable to separate the support and the object by applying a force in a direction substantially perpendicular to the surface of the support or the object. The phrase "applying a force in a direction substantially perpendicular to the support surface or the object surface" means generally 0 ° to 60 ° with respect to the z-axis which is an axis perpendicular to the support surface or the object surface. Range, preferably in the range of 0 ° to 45 °, more preferably in the range of 0 ° to 30 °, still more preferably in the range of 0 ° to 5 °, particularly preferably 0 °, ie relative to the support surface or the object surface It means applying force in the vertical direction. As a separation method, for example, a method of lifting the periphery of an object or a support and peeling off sequentially from the periphery toward the center while applying a force in a direction substantially perpendicular to the support surface or the object surface (hook pull method) Can be done with

  The separation may be performed usually at 5 to 100 ° C, preferably 10 to 45 ° C, and more preferably 15 to 30 ° C. In addition, when separation is performed, a reinforcing tape, for example, a commercially available dicing tape may be attached to the surface of the target opposite to the temporary fixing surface with the support in order to prevent breakage of the target.

  In the step (3), the temporary fixing material is irradiated with light to decompose or deteriorate the temporary fixing material, thereby reducing the strength and adhesion of the temporary fixing material, and then separating the object from the support. It is preferable to do. In one embodiment, the separation layer (I) of the temporary fixing material is irradiated with light from the support side. By light irradiation, the polymer (A) which is a component of the separation layer (I) absorbs light, and the strength and adhesion of the separation layer (I) decrease. Therefore, after the light irradiation to the separation layer (I), the support can be easily separated from the object without particularly requiring the heat treatment of the temporary fixing material.

  It is preferable to use an ultraviolet ray for light irradiation, for example, an ultraviolet ray having a wavelength of 10 to 400 nm is employed, and an ultraviolet ray having a wavelength of 300 to 400 nm is particularly preferable. As a light source of irradiation light, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a laser are mentioned, for example. Among these, a laser is preferable. It is preferable to irradiate the entire surface of the separation layer (I) while scanning the laser from the support side, and it is more preferable to focus the laser on the separation layer (I) for irradiation.

  Examples of the laser include solid-state lasers (eg, all solid-state lasers using light-excited semiconductor lasers, YAG lasers), liquid lasers (eg, dye lasers), and gas lasers (eg, excimer lasers). Among these, an all-solid-state laser (wavelength: 355 nm), a YAG laser (wavelength: 355 nm), and an excimer laser using a photoexcited semiconductor laser are preferable.

The conditions for light irradiation vary depending on the type of light source etc., but in the case of an all-solid-state laser using a photoexcited semiconductor laser and a YAG laser, usually 1 mW to 100 W, and the integrated light amount is usually 1.4 × 10 ^-7 to 1. It is 4 × 10 ⁷ mJ / cm ² .

  Subsequently, by applying a force to the object or the support, the object is separated from the support or the like to separate them. In addition, although it is preferable to separate after finishing light irradiation, you may separate, performing light irradiation.

<Step (4)>
After separating the support and the object, the temporary fixing material tends to remain on the object. The temporary fixing material remaining on the object after the separation step, that is, the residue of the temporary fixing material includes a base (B1) and a surfactant (B2) having a group containing an aromatic hydrocarbon structure as a lipophilic group. It can be removed well using the cleaning agent of the present invention contained.

  In particular, in the present invention, when the light irradiation separation method is used, the temporary fixing material remaining on the object can be removed well. For example, a separation layer (composition for temporary fixing) containing a high carbon content material (eg, a polymer (A) having an aromatic hydrocarbon structure) in order to increase the light shielding rate against light irradiation for separation When I) is used, the separation layer (I) is irradiated with light to become a carbonized film. This tendency is enhanced when using a laser for light irradiation. Thus, the membrane of the temporary fixing material is present as a residue on the object separated from the support. When the separation layer (I) is a layer in contact with the object to be treated, the membrane is more likely to remain on the object. It is considered that the residue consisting of organic matter can be removed by corroding or decomposing the organic matter using, for example, a detergent containing a base, but since the residue of the temporary fixing material described above has a similar structure to the carbonized film, Even if this cleaning agent is used, the liquid is repelled and it can not be removed well.

  In the present invention, a detergent comprising the base (B1) and the surfactant (B2) having a group containing an aromatic hydrocarbon structure as a lipophilic group is the target substance to which the residue of the temporary fixing material is attached. Use and wash. Thereby, the residue of such a temporary fixing material can be removed favorably. This is because the use of the surfactant (B2) having, as a lipophilic group, a group containing an aromatic hydrocarbon structure having high affinity to the carbonized film described above suppresses the liquid repellency of the cleaning agent due to the residue of the temporary fixing material. Therefore, it is considered that the decomposition and removal of the residue of the temporary fixing material by the base (B1) can be performed well.

Hereinafter, the cleaning agent of the present invention used in the step (4) will be described.
The cleaning agent of the present invention contains a base (B1) and a surfactant (B2) having a group containing an aromatic hydrocarbon structure as a lipophilic group.

  Examples of the base (B1) include, for example, inorganic bases, specifically hydroxides, carbonates or hydrogencarbonates of alkali metals or alkaline earth metals, and more specifically sodium hydroxide, Potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate can be mentioned, and organic bases can be mentioned. Specifically, ethylamine, n-propylamine, diethylamine, ethanolamine, diethanolamine And amines such as triethanolamine and triethylamine; ammonia; and ammonium salts such as tetramethyl ammonium hydroxide and tetraethyl ammonium hydroxide. Among these, inorganic bases are preferable in terms of strong alkalinity, and hydroxides of alkali metals are more preferable.

The base (B1) may be used alone or in combination of two or more.
The content of the base (B1) in the detergent of the present invention is usually more than 0% by mass and 20% by mass or less, preferably 1 to 15% by mass, more preferably 2 to 10% by mass. It can wash | clean, suppressing the damage to a target object as it is such an aspect.

The surfactant is a general term for compounds having a lipophilic group and a hydrophilic group, and the surfactant (B2) used in the present invention has a group containing an aromatic hydrocarbon structure as the lipophilic group. .
As an aromatic hydrocarbon structure in the said lipophilic group of surfactant (B2), C6-C20 aromatic hydrocarbon rings, such as a benzene ring and a naphthalene ring, are mentioned, for example, The said ring is a carbon number It may have a substituent such as 1 to 20 hydrocarbon groups. As a C1-C20 hydrocarbon group as a substituent, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C18 aryl group, an aryl group substituted alkyl is mentioned, for example And aryl substituted alkenyl groups. As a group containing the aromatic hydrocarbon structure as a lipophilic group, the said aromatic hydrocarbon ring itself and the aromatic hydrocarbon ring which has the said substituent are mentioned, for example.

  The hydrophilic group in the surfactant (B2) may be a nonionic or ionic hydrophilic group, preferably a nonionic hydrophilic group, and among the nonionic hydrophilic groups, a polyoxyalkylene group is preferred. Is preferred. As a polyoxyalkylene group as a hydrophilic group, a polyoxyethylene group and a polyoxypropylene group are mentioned, for example. The number of repetition of the oxyalkylene group in the polyoxyalkylene group is usually 2 to 20, preferably 2 to 15.

As surfactant (B2), for example,
Polyoxyalkylene phenyl ether; Polyoxyalkylene methyl phenyl ether, Polyoxyalkylene octyl phenyl ether, Polyoxyalkylene nonyl phenyl ether, Polyoxyalkylene alkyl phenyl ether such as polyoxyalkylene dodecyl phenyl ether; Polyoxyalkylene naphthyl ether, Polyoxy Alkylene alkyl naphthyl ether; polyoxyalkylene (poly) styrenated phenyl ether such as polyoxyalkylene styryl phenyl ether, polyoxy alkylene di styryl phenyl ether (distyryl phenol ethoxylate etc), polyoxy alkylene tris styryl phenyl ether etc; polyoxy Nonionic surfactants such as alkylene cumyl phenyl ether;
Alkyl aryl sulfonates such as sodium dodecyl benzene sulfonate, alkyl diaryl ether disulfonates; polyoxyalkylene alkyl phenyl ether sulfates, polyoxyalkylene (poly) styrenated phenyl ether sulfates, etc. Anionic surfactants such as sulfates of active agents;
(The above-mentioned alkylene is, for example, ethylene group or propylene group)
Can be mentioned.

  Among these, the temporary fixing material has a separation layer (I) formed of a temporary fixing composition containing a polymer (A) having an aromatic hydrocarbon structure, particularly a condensed polycyclic aromatic hydrocarbon structure. When having a layer formed from the composition for temporary fixation which contains a polymer, polyoxyalkylene (poly) styrenated phenyl ether is preferable.

Surfactant (B2) may be used individually by 1 type, and may use 2 or more types together.
When the temporary fixing material has a separation layer (I) formed of a temporary fixing composition containing a polymer (A) having an aromatic hydrocarbon structure, the temporary fixing material contains an aromatic hydrocarbon structure. The cleaning effect is enhanced by using the surfactant (B2) having a group containing an aromatic hydrocarbon structure as a lipophilic group.

  Although the cleaning agent and the object to be treated come into contact with each other by the cleaning, the object to be treated may be deteriorated by the influence of dissolved oxygen or the like at the time of the contact. For example, when copper wiring, a copper pad, and an insulating film are formed on an object to be treated, it is preferable to suppress oxidation of copper and corrosion of the insulating film, but in the present invention, the surfactant (B2) is an object to be treated An object (eg, a copper wiring, a copper pad, an insulating film, or the like included in the object to be treated) can be protected.

  The content ratio of the surfactant (B2) in the cleaning agent of the present invention is usually more than 0% by mass and 30% by mass or less, preferably 1 to 25% by mass, more preferably 5 to 20% by mass. It is compatible in peeling performance and cleaning removal performance as it is such an aspect.

  Further, in the detergent of the present invention, the surfactant (B2) is preferably 1 to 10 times, more preferably 1.5 to 8 times, still more preferably 2 to 5 times the base (B1). It can be used in the range of the content (mass basis).

  As the solvent in the cleaning agent of the present invention, for example, water; pentane, hexane, decane, limonene, mesitylene, dipentene, pinene, bicyclohexyl, cyclododecene, 1-tert-butyl-3,5-dimethylbenzene, butylcyclohexane, Hydrocarbon solvents such as cyclooctane, cycloheptane, cyclohexane, methylcyclohexane and the like; anisole, propylene glycol monomethyl ether, dipropylene glycol methyl ether, diethylene glycol monoethyl ether, alcohol and ether solvents such as diglyme; ethylene carbonate, ethyl acetate, acetic acid N -Butyl, ethyl lactate, ethyl 3-ethoxypropionate, methoxypropyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, propylene carbonate, γ-butyrolac Ester or lactone solvent emissions, and the like; cyclopentanone, cyclohexanone, methyl isobutyl ketone, ketone solvents such as 2-heptanone; amide or lactam solvents such as N- methyl-2-pyrrolidinone. Among these, water is preferable, that is, an aqueous solution is preferable as the cleaning agent.

  As the cleaning method, for example, a method of immersing an object in the cleaning agent of the present invention, a method of spraying the cleaning agent of the present invention on the object, and the like may be mentioned. The temperature of the cleaning agent at the time of washing the object is not particularly limited, but is usually 10 to 80 ° C., preferably 15 to 55 ° C., more preferably 20 to 40 ° C., still more preferably 25 to 40 ° C. The washing time, for example, the immersion time is usually 2 to 20 minutes, preferably 5 to 15 minutes.

  Moreover, in one embodiment, it is preferable that the dissolved oxygen amount of the cleaning agent of this invention is small from a viewpoint of preventing deterioration of the process target object mentioned above. For this reason, it is preferable to perform the said washing | cleaning using the cleaning agent of this invention which carried out the bubbling process by inert gas, such as nitrogen. For example, in the method of immersing the object in the cleaning agent of the present invention, it is preferable to carry out the cleaning while the cleaning agent is subjected to the bubbling treatment.

  In the step (4), after washing with the detergent of the present invention, washing with an acid-containing detergent (hereinafter also referred to as "acid detergent") may be carried out. By using an acid cleaner, the metal surface can be removed if it is oxidized. In addition, after the cleaning with the cleaning agent of the present invention, or before and / or after the cleaning with the acid cleaning agent, another cleaning agent may be used to clean the object to be treated. In one embodiment, washing with the detergent of the present invention, washing with water, washing with an acid detergent and washing with water are sequentially performed.

  Examples of the acid in the acid cleaner include inorganic acids such as sulfuric acid; and organic acids such as acetic acid, oxalic acid, benzenesulfonic acid and dodecylbenzenesulfonic acid. The content ratio of the acid in the acid cleaner is usually more than 0% by mass and 10% by mass or less, preferably 0.01 to 8% by mass, more preferably 0.1 to 5% by mass. Such an embodiment is preferable because it can be cleaned while suppressing metal corrosion.

  Examples of the solvent in the acid cleaner include the solvents exemplified in the cleaner of the present invention, and water is preferable, that is, an acid aqueous solution is preferable as the acid cleaner. Examples of the cleaning method using an acid cleaner include a method of immersing the object in the acid cleaner, and a method of spraying the acid cleaner on the object, and ultrasonic waves may be applied during the immersion. Although the temperature of the acid cleaner is not particularly limited, it is usually 10 to 80 ° C, preferably 15 to 55 ° C. The washing time, for example, the immersion time is usually 0.02 to 15 minutes, preferably 0.5 to 10 minutes.

  Other cleaning agents include the solvents exemplified in the cleaning agent of the present invention, and pure water is preferable. The washing method and conditions using other detergents are the same as the washing method and conditions using an acid detergent.

After the above washing, drying treatment can be performed to obtain the object to be treated.
As described above, the support and the object can be separated without residue. Further processing may be performed on the separated object. For example, in the above-described RDL-First, bump formation on the wiring layer, cutting into individual packages by dicing, and the like may be performed.

[Semiconductor Device and Method of Manufacturing the Same]
The semiconductor device of the present invention can be manufactured by processing the object according to the method of processing an object of the present invention. The temporary fixing material can be removed by the cleaning treatment in the step (4) after separating the semiconductor device (example: semiconductor element) obtained by processing the object from the support. Therefore, in the semiconductor device of the present invention, deterioration due to light irradiation at the time of separation is small, and contamination such as stains and charring by the temporary fixing material is reduced.

  Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In the description of the following examples etc., unless otherwise stated, "part" shows a "mass part".

  The weight-average molecular weight (Mw) of the polymer is measured using a GPC column (two G2000HXL, one G3000HXL, one G4000HXL) manufactured by Tosoh Corp., in terms of polystyrene, as a measuring device "HLC-8220-GPC" ( It measured using Tosoh Co., Ltd. product).

<1. Manufacture of cleaning agent>
[Example 1A, Comparative Examples 1A to 4A]
Detergents 1 to 5 containing the components shown in Table 1 were produced.

<2. Production of temporary fixing composition>
Production Example 1 Production of Composition (I-1) for Temporary Fixation 100 parts of 2,6-dihydroxynaphthalene, 100 parts of propylene glycol monomethyl ether acetate, and para were added to a reaction apparatus equipped with a condenser, a thermometer and a stirrer. Fifty parts of formaldehyde (formaldehyde equivalent) were charged, 2 parts of oxalic acid were added, and the mixture was heated at 120 ° C. for 5 hours while being dehydrated.

Water was added to the reaction solution and stirred. The precipitate was collected, washed with water and dried at 50 ° C. for 17 hours to obtain 2,6-dihydroxynaphthalene / formaldehyde condensate (Mw = 1,550).
100 parts of the condensate was uniformly dissolved in 550 parts of a mixed solvent of cyclohexanone / methoxypropyl acetate = 60/40 (% by mass) to prepare a temporary fixing composition (I-1).

<3. Production of laminate>
Production Example 2
The composition for temporary fixing (I-1) is spin-coated on a 4-inch silicon wafer having a copper film on the surface, heated at 180 ° C. for 1 minute using a hot plate, and further heated at 300 ° C. for 2 minutes A substrate 1 having a uniform layer (I-1) of 10 μm was obtained.
The substrate 1 is cut into a square of 1 cm long and 1 cm wide and then bonded to a glass substrate (1 cm long and 1 cm wide; support) through the layer (I-1) using a die bonder apparatus. A pressure of 0.2 MPa was applied at 250 ° C. for 2 minutes to produce a laminate.

<4. Separation of target (implementation of step (3))>
[Production Example 3]
The laminate obtained in Production Example 2 was subjected to an all-solid high-power laser device (trade name: “Genesis CX 355 STM Compact”, manufactured by Coherent Japan Ltd.) with an output of 100 mW and an integrated light amount of 2.08 × 10 ^−4. A UV laser (wavelength 355 nm) was irradiated from the glass substrate side at mJ / cm ² . Using a universal bond tester (trade name "Dage 4000", manufactured by Dage Corporation) for the test laminate after light irradiation, in the hook-pull method, in the direction of the axis (z-axis) perpendicular to the surface of the glass substrate Force (500 μm / sec, 23 ° C.) was applied to separate the glass substrate from the silicon wafer. A residue substrate having a residue of layer (I-1) on a silicon wafer was obtained.

<5. Cleaning treatment with detergent (conduct of step (4))>
[Examples 1B to 3B, Comparative Examples 1B to 4B]
The residual substrate obtained in Production Example 3 was immersed in various cleaning agents under the conditions shown in Table 2 below, and then the surface of the silicon wafer was sprayed with pure water for 2 minutes to rinse it out, and then dried (drying processing 1). The presence or absence of the residue after the drying treatment 1 and the state of the copper film on the surface of the silicon wafer were observed with an optical microscope. The evaluation results are shown in Table 2.

  Then, acid rinse was performed. The acid rinse was performed by immersing the cleaned silicon wafer in a sulfuric acid aqueous solution (1% by mass) at 23 ° C. for 2 minutes, then spraying the surface of the silicon wafer with pure water for 2 minutes to rinse it out, and then drying it (drying process 2) ). The presence or absence of the residue after the drying treatment 2 and the state of the copper film on the surface of the silicon wafer were observed with an optical microscope. The evaluation results are shown in Table 2.

In addition, the observation result by an optical microscope was evaluated by the following references | standards.
A: No residue of layer (I-1). No discoloration of copper film.
B: No residue of layer (I-1). There is discoloration of copper film.
C: There is a little residue of the layer (I-1). There is discoloration of copper film.
D: There is a residue of layer (I-1). There is discoloration of copper film.

Claims (14)

(1) forming a laminate having a support, a temporary fixing material, and an object to be treated, wherein the object is held on the temporary fixing material;
(2) processing the object and / or moving the laminate;
(3) separating the target from the support; and (4) a surfactant (B2) having a base (B1) and a group containing an aromatic hydrocarbon structure as a lipophilic group. Washing with a detergent containing
A method of processing an object, comprising:   The method for treating an object according to claim 1, wherein the hydrophilic group of the surfactant (B2) is a polyoxyalkylene group.   The method for treating an object according to claim 1, wherein the base (B1) is an inorganic base.   The method for treating an object according to claim 3, wherein the inorganic base is a hydroxide of an alkali metal.   The method for treating an object according to any one of claims 1 to 4, wherein the detergent is an aqueous solution.   The object according to any one of claims 1 to 5, wherein in the step (3), the temporary fixing material is irradiated with light to decompose or deteriorate the temporary fixing material, and the object is separated from the support. How to handle objects.   The method of processing an object according to claim 6, wherein the light irradiation is performed by a laser having a wavelength of 300 to 400 nm.   The said temporary fixing material has a layer (I) formed from the composition for temporary fixing containing 70 mass% or more in solid content of the polymer which has an aromatic hydrocarbon structure. The method of processing an object described in.   The method for treating an object according to claim 8, wherein the layer (I) is a layer in contact with the object to be treated.   The method for treating an object according to any one of claims 1 to 9, wherein in the step (1), an object to be treated having at least a wiring layer is formed on the temporary fixing material.   11. The method of processing an object according to claim 10, wherein the processing in the step (2) includes disposing at least one selected from a semiconductor wafer and a semiconductor chip on the wiring layer.   A cleaning agent comprising a base (B1) and a surfactant (B2) having a group containing an aromatic hydrocarbon structure as a lipophilic group.   The manufacturing method of the semiconductor device which processes an object by the processing method of any one of Claims 1-11, and manufactures a semiconductor device.   A semiconductor device obtained by the manufacturing method according to claim 13.