JP4307271B2 - Semiconductor device dust removal board - Google Patents

Description

The present invention relates to a dust removal substrate for a semiconductor device. In particular, the present invention relates to a semiconductor dust removal substrate obtained by using a predetermined polyamideimide resin or polyesterimide resin.

Low-elasticity polyimide is used as a low-stress and heat-resistant material for semiconductor protective films, insulating films for multilayer circuit boards, semiconductor adhesive films, coverlays for flexible circuit boards, and the like. (See Patent Documents 1, 2, 3, 4, and 5).
However, since these low elastic modulus polyimides are obtained by copolymerizing diamine containing silicone or tetracarboxylic anhydride, serious obstacles occur due to silicone contamination, such as HDD applications and some semiconductor applications. It could not be used in applications.
In particular, it cannot be effectively used for cleaning semiconductor devices that require both high transportability and high dust removal.

JP-A-5-170901 JP-A-6-73178 JP-A-6-207024 JP-A-6-73178 JP 2002-50854 A

  The present invention is a heat-resistant dust removal resin that can be used while satisfying both high transportability and high dust removal performance even in situations where serious troubles may occur due to silicone contamination, such as HDD applications and some semiconductor applications. It is an object of the present invention to provide a dust removal substrate using the above.

  According to the present invention, a dust removing substrate for a semiconductor device, wherein a cleaning layer made of polyamideimide having a structural unit represented by the following general formula (1) or (2) or a precursor thereof is provided on at least one surface of the substrate. (Cleaning sheet) is provided.

In the above formula, R ₁ is H or an aliphatic hydrocarbon group, and R ₂ and R ₃ are an aliphatic hydrocarbon group or aliphatic ether group having 2 or more carbon atoms.

  For removing dust from a semiconductor device by applying a heat resistant resin composition comprising a polyamideimide having a structural unit represented by the above general formula (1) or (2) or a precursor thereof and a thermosetting resin on a substrate. A substrate can also be obtained.

  After applying the above-mentioned polyamideimide or a precursor thereof, or the above-mentioned heat-resistant resin composition on the substrate, the tensile modulus of elasticity at the room temperature or the surface temperature of the semiconductor device to be removed is 1.5 GPa or less. A substrate for dust removal of a semiconductor device can also be obtained by heat treatment at a temperature not lower than ° C.

  Furthermore, according to the present invention, there is provided a dust removing substrate for a semiconductor device, wherein a cleaning layer made of a polyamideimide resin precursor having a structural unit represented by the following general formula (3) is provided on at least one surface of the substrate.

In the above formula, R ₁ is an aliphatic hydrocarbon group having 1 or more carbon atoms, and R ₂ and R ₃ are an aliphatic hydrocarbon group or aliphatic ether group having 2 or more carbon atoms.

  Furthermore, according to the present invention, a semiconductor device in which a cleaning layer comprising an aliphatic polyesterimide or a precursor thereof containing a structural unit represented by the following general formula (4) in the main chain is provided on at least one surface of a substrate. A substrate for dust removal is provided.

In the above formula, R ₁ and R ₂ are an aliphatic hydrocarbon group or an aliphatic ether group having 2 or more carbon atoms.

  It is also possible to apply a heat-resistant resin composition comprising a polyesterimide having a structural unit represented by the general formula (4) or a precursor thereof and a thermosetting resin on a substrate to obtain a dust removal substrate for a semiconductor device. it can.

  Apply the above-mentioned polyesterimide or its precursor, or a heat-resistant resin composition, which has a tensile modulus of elasticity of 1.5 GPa or less at room temperature or the surface temperature of a semiconductor device to be dusted, on a substrate and heat-treat at 150 ° C. or higher. Thus, a dust removal substrate for the semiconductor device can be obtained.

By bringing the resin surface of the substrate for dust removal of the semiconductor device into contact with each other, the surface of the semiconductor device can be removed.

  The dust removal substrate of the semiconductor device of the present invention is effective for cleaning the semiconductor device and can satisfy both high transportability and high dust removal performance at the same time.

  The polyamideimide resin used in the present invention has a structural unit represented by the general formula (1) or (2) in the main chain. Polyamideimide resin can be obtained by the following method, for example.

  That is, the first method is to mix trimellitic anhydride and a primary diamine of an aliphatic or aliphatic ether in a suitable organic solvent at a substantially equimolar ratio (equivalent) and azeotropically. This is a method of dehydration and condensation.

  In the second method, trimellitic anhydride and 1/2 equivalent of an aliphatic or aliphatic ether primary diamine are mixed in an appropriate organic solvent, azeotropically dehydrated and imidized to obtain a dicarboxylic acid compound. In this method, 1/2 equivalent of aliphatic or aliphatic ether diamine is added, followed by azeotropic dehydration and condensation.

  In the third method, trimellitic anhydride and 1/2 equivalent of aliphatic secondary diamine or aliphatic ether secondary diamine are mixed in an appropriate organic solvent, subjected to azeotropic dehydration condensation, and amide bonds are interposed. This is a method in which a tetracarboxylic acid anhydride formed is further reacted with a half equivalent of a primary diamine of an aliphatic or aliphatic ether.

  The fourth method is a method in which trimellitic anhydride and one-end primary and one-end secondary aliphatic diamine or aliphatic ether diamine are mixed together in an appropriate organic solvent, followed by azeotropic dehydration and condensation. Can be mentioned.

  In the second and third methods, the polyamideimide resin having the structural unit represented by (1) is used. In the first method, the polyamideimide resin having both the structural units (1) and (2) is used. In the fourth method, a polyamideimide resin having the structural unit represented by (2) can be obtained. Further, in the third method, when the remaining 1/2 equivalent of diamine is reacted and then azeotropic dehydration and imidization are not performed, the precursor of polyamideimide resin having the structural unit (3) is used. The polyamic acid resin can be obtained. Furthermore, this polyamic acid resin is converted into a polyamide-imide resin having the structural unit (1) by azeotropic dehydration as it is for imidization, or by applying it to a substrate and heat-treating it.

  Examples of the diamine used above include ethylenediamine, hexamethylenediamine, 1,8-diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, 1,4-butanediol, and bis (3-aminopropyl). ) Primary amines such as ether (= 3,9-dioxadodecanediamine), secondary diamines that become N-alkylated compounds such as N, N′-dimethylethylenediamine, N, N′-dimethylhexa A typical example is methylenediamine. These may be used alone or in combination with a plurality of diamines.

  Examples of the solvent used in the first to fourth methods include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, etc. In any of the above cases, In order to perform azeotropic dehydration, for example, it is necessary to add an azeotropic solvent of water represented by xylene. The addition amount of these azeotropic solvents varies depending on the desired reaction temperature, but is usually about 1/2 to 1/100 of the entire reaction product. If the amount of the azeotropic solvent is large, the boiling point is lowered and the reaction temperature cannot be increased, and if the amount of the azeotropic solvent is small, water cannot be effectively removed. In the first to fourth methods, a polyamideimide resin can be obtained by azeotropic dehydration in the range of 130 ° C to 210 ° C.

  In addition, if necessary, the present polyamideimide resin can be copolymerized by adding an aromatic diamine or aromatic tetracarboxylic dianhydride in the polymerization process of each of the above methods, and if necessary, It can also be modified by adding a thermosetting resin such as an epoxy resin, a phenol resin, or a bismaleimide resin.

  Next, the polyesterimide resin used in the present invention has the structural unit represented by (4) in the main chain. The polyesterimide resin can be obtained, for example, by the following method.

  In the first method, bistrimellitate and tetracarboxylic dianhydride are synthesized and isolated from trimellitic anhydride and a diol of aliphatic or aliphatic ether, and this is combined with aliphatic or aliphatic ether diamine. Can be reacted in a substantially equal molar amount (equivalent) in an appropriate solvent to obtain a polyamic acid resin that becomes a precursor of the polyesterimide resin. Furthermore, this is azeotropically dehydrated as it is, or imidized, or applied onto a substrate and heat-treated to obtain a polyesterimide resin having the structural unit represented by (4). Examples of such tetracarboxylic acid anhydrides include ethylene-1,2-bistrimellitate, tetracarboxylic dianhydride, n-decylene-1,10-bistrimellitate, tetracarboxylic dianhydride, n -Dodecylene-11,12-bistrimellitate, tetracarboxylic dianhydride and the like.

  In the second method, trimellitic anhydride and 1/2 equivalent of aliphatic or aliphatic ether diol are azeotropically dehydrated and condensed in an appropriate organic solvent, and the resulting tetracarboxylic acid anhydride and fat are then condensed. The polyamic acid resin used as the precursor of a polyesterimide resin can be obtained by making it react with diamine of a group. Furthermore, this is azeotropically dehydrated as it is, or imidized, or is applied onto a substrate and heat treated to obtain a polyesterimide resin having the structural unit represented by (4). Examples of the diol used here include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, and polyethylene glycol. Etc. These may be used alone or in combination with a plurality of diols.

  Suitable solvents used in the first and second methods include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like. However, when performing azeotropic dehydration, for example, it is necessary to add an azeotropic solvent of water represented by xylene and toluene. The addition amount of the azeotropic solvent used here varies depending on the desired reaction temperature, but is usually about 1/2 to 1/100 of the entire reaction system. If the amount of the azeotropic solvent is large, the boiling point is lowered and the reaction temperature cannot be increased, and if the amount of the azeotropic solvent is small, water cannot be effectively removed. In the second method, trimellitic anhydride and diol can be condensed by azeotropic dehydration in the range of 130 ° C to 210 ° C.

  The ester imide resin can be copolymerized by adding an aromatic diamine or aromatic tetracarboxylic dianhydride in the polymerization process of each of the above methods, if necessary. Further, it can be modified by adding a curable resin such as epoxy resin, phenol resin, or bismaleimide resin.

  Next, the substrate for dust removal of the semiconductor device of the present invention is obtained by applying the above polyesterimide resin or polyamideimide resin or polyamic acid resin as a precursor thereof onto the substrate, drying and removing the solvent, and further heat-treating at a high temperature. Obtainable.

  The polyesterimide resin or polyamideimide resin preferably has a tensile modulus of 1.5 GPa or less from the viewpoint of dust removal.

  As a method for providing the cleaning layer, a spin coat method, a spray method, or the like is used, and it is applied directly on an appropriate substrate such as a silicon wafer, or a comma coat method, a fountain method, a gravure on a PET film or a polyimide film. It may be formed by coating using a method or the like, and transferred and laminated on an appropriate substrate such as a silicon wafer. The temperature at which the heat treatment is performed after drying the solvent is preferably 150 ° C. or higher. In order to prevent oxidative degradation of the resin, it is desirable to perform the treatment under an inert atmosphere such as a nitrogen atmosphere or a vacuum. Thereby, the volatile component remaining in the resin can be completely removed. The surface on which the cleaning layer is provided may be provided on at least one side, or may be provided on both sides. Moreover, you may provide only in an end surface (edge part). The type of substrate is not limited. Examples thereof include semiconductor wafers, flat panel display substrates such as LCDs and PDPs, compact disks, and MR head substrates.

  The tensile elastic modulus was measured by a method according to the test method JIS K7127. That is, a sample made of a heat resistant resin was subjected to a tensile test using Tensilon, and an initial elastic modulus was measured. However, the size of the sample was 10 mm wide × 50 mm long, the distance between chucks was 10 mm, and the pulling speed was 50 mm / min. The tensile elastic modulus is preferably 1.5 GPa or less, particularly preferably 1 MPa to 1.5 GPa. By setting the tensile elastic modulus to 1 MPa or more, there is no possibility of causing a conveyance trouble during conveyance into the substrate processing apparatus. On the other hand, if the tensile modulus of elasticity of the layer becomes too large, the performance of collecting adhering foreign matter on the transport system in the substrate processing apparatus tends to be lowered, so it is desirable that the upper limit is 1.5 GPa.

The dust removal performance was evaluated by the following method. That is, dust removal evaluation was performed using a liner film peeling apparatus (manufactured by Nitto Seiki, HR-300CW) for manufacturing a dust removing substrate (apparatus A). First, 20 pieces of aluminum cut to 1 mm × 1 mm were placed on the chuck table of the apparatus. Next, the cleaning layer side of the cleaning transport member was dummy transported to the apparatus A, vacuum-adsorbed (0.5 kg / cm ² ) to the chuck table, and the cleaning layer and the chuck table contact portion were strongly bonded. Thereafter, the vacuum suction was released, and the dust removal rate was measured from the number of aluminum pieces on the chuck table when the cleaning conveyance member was removed from the chuck table. The measurement was performed three times and the average was obtained.

  Further, regarding the transportability, it was evaluated whether or not the cleaning member could be peeled off from the chuck table with the lift pins after being transported onto the chuck table in the same manner as described above, performing vacuum suction, and releasing the vacuum.

Example 1
28.2 g of 1,4-butanediol, bis (3-aminopropyl) ether (hereinafter abbreviated as DOD) and 30.0 g of trimellitic anhydride represented by the formula (5) are mixed with N-methyl-2- Azeotropic dehydration was performed in a mixed solvent consisting of 58 g of pyrrolidone (hereinafter abbreviated as NMP) and 29 g of xylene under a nitrogen stream at 130 ° C. to 200 ° C. until no distilled water was consumed. After cooling, the obtained resin solution was applied onto the mirror surface of an 8-inch silicon wafer and the rolled copper foil shine surface with a spin coater, and dried at 90 ° C. for 20 minutes. This was heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to form a resin film having a thickness of 30 μm. The 8-inch silicon wafer on which the resin film was formed was evaluated for dust removal and transportability by the above method using the resin film as the dust removal surface. Moreover, about the resin film formed on the copper foil, after removing the copper foil by etching with a ferric chloride solution, the tensile modulus was measured according to the above method.

Example 2
14.1 g of DOD and 30.0 g of trimellitic anhydride were azeotropically dehydrated in a mixed solvent composed of 59 g of NMP and 30 g of xylene under a nitrogen stream at 130 ° C. to 200 ° C. until no distilled water was consumed. After cooling, 15.6 g of 1,12-diaminododecane and 25 g of xylene removed by azeotropic distillation were added again, and azeotropic dehydration was performed again at 130 ° C. to 200 ° C. until there was no distilled water. After cooling, the test was performed in the same manner as in Example 1 using the obtained resin solution.

Example 3
DOD (14.1 g) and trimellitic anhydride (30.0 g) were azeotropically dehydrated in a mixed solvent consisting of NMP (56 g) and xylene (28 g) at 130 ° C. to 200 ° C. until there was no distilled water. After cooling, 11.3 g of N, N′-dimethylhexamethylenediamine and 23 g of xylene removed by azeotropy were added again, and azeotropic dehydration was performed again at 130 ° C. to 200 ° C. until no distilled water disappeared. After cooling, the test was performed in the same manner as in Example 1 using the obtained resin solution.

Example 4
Example 1 except that 2.9 g of bis (4-maleimidophenyl) methane (hereinafter abbreviated as BMPM) represented by the formula (6) was added to the resin solution obtained in Example 1 and dissolved. The test was conducted in the same manner as above.

Example 5
After 2.9 g of BMPM was added to the resin solution obtained in Example 1 and dissolved, heat treatment was performed again at 150 ° C. for 1 hour under a nitrogen stream. Using the resin solution obtained by cooling, the test was conducted in the same manner as in Example 1.

Example 6
1,12-dodecanediol 14.9 g and trimellitic anhydride 30.0 g in a mixed solvent consisting of 59 g of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) and 30 g of xylene in a nitrogen stream at 130 ° C. Azeotropic dehydration was performed at 200 ° C. until there was no distilled water. After cooling, 14.1 g of DOD was further added and reacted to obtain a resin solution of a polyesterimide precursor. To this, 11.8 g of bisphenol A type epoxy resin was added, and the resulting solution was tested in the same manner as in Example 1.

Example 7
A polyesterimide precursor obtained by reacting 15.0 g of 1,12-diaminododecane represented by the formula (7) with 41.2 g of n-dodecylene-1,12-bistrimellitate and 41.2 g of tetracarboxylic dianhydride in 131 g of NMP A body resin solution was obtained. To this was added 11.2 g of bisphenol A type epoxy resin, 6.4 g of bisphenol A, and 0.17 g of tetraphenylphosphonium tetraphenylborate, and the resulting solution was tested in the same manner as in Example 1.

Comparative Example 1
The resin removal was not applied on the 8-inch silicon wafer, and the dust removal property, the time to reach the vacuum, and the conveyance property were evaluated using the mirror surface as the adhesive surface.

  As mentioned above, although various embodiment of this invention was described, this invention is not limited to the matter shown in the said embodiment, Based on description of a claim and detailed description of invention, and a well-known technique, Modifications and applications by those skilled in the art are also intended by the present invention, and are included in the scope of protection.

Claims (12)

A substrate,
A cleaning layer provided on at least one surface of the substrate;
The cleaning layer is made of polyamideimide having a structural unit represented by the following general formula (1) or (2), or a precursor thereof, R ₁ is H or an aliphatic hydrocarbon group, and R ₂ , R ₃ is a substrate for dust removal of a semiconductor device, which is an aliphatic hydrocarbon group or aliphatic ether group having 2 or more carbon atoms.

  The substrate for dust removal of a semiconductor device according to claim 1, wherein the cleaning layer is made of a heat resistant resin composition further containing a thermosetting resin.   Obtained by heat-treating at 150 ° C. or higher after coating the polyamideimide or its precursor, which has a tensile modulus of 1.5 GPa or less at room temperature or at the surface temperature of the semiconductor device to be dusted, on the substrate, A dust removing substrate for a semiconductor device according to claim 1.   The heat-resistant resin composition having a tensile elastic modulus of 1.5 GPa or less at room temperature or the surface temperature of a semiconductor device to be dusted is formed on the substrate and then heat-treated at 150 ° C. or higher. Item 3. A substrate for dust removal of a semiconductor device according to Item 2.   A dust removal method for removing dust from a surface of the semiconductor device according to claim 1 by bringing the resin surface of the substrate for dust removal into contact with the surface of the semiconductor device. A substrate,
A cleaning layer provided on at least one surface of the substrate;
The cleaning layer is made of a polyamideimide resin precursor having a structural unit represented by the following general formula (3), R ₁ is an aliphatic hydrocarbon group having 1 or more carbon atoms, and R ₂ and R ₃ are 2 or more carbon atoms. A substrate for dust removal of a semiconductor device, which is an aliphatic hydrocarbon group or an aliphatic ether group.

  A dust removal method for removing dust from a surface of the semiconductor device according to claim 6 by bringing the resin surface of the substrate for dust removal into contact with the surface of the semiconductor device. A substrate,
A cleaning layer provided on at least one surface of the substrate;
The cleaning layer is composed of an aliphatic polyesterimide or a precursor thereof containing a structural unit represented by the following general formula (4) in the main chain, and R ₁ and R ₂ are aliphatic hydrocarbons having 2 or more carbon atoms. A substrate for dust removal of a semiconductor device, which is a group or an aliphatic ether group.

  9. The dust removal substrate for a semiconductor device according to claim 8, wherein the cleaning layer is made of a heat resistant resin composition further containing a thermosetting resin.   Obtained by forming the polyesterimide or a precursor thereof having a tensile modulus of elasticity of 1.5 GPa or less at room temperature or the surface temperature of the semiconductor device to be dusted, on the substrate, and then heat-treating at 150 ° C. or higher. A dust removing substrate for a semiconductor device according to claim 8.   The heat-resistant resin composition having a tensile modulus of elasticity of 1.5 GPa or less at room temperature or the surface temperature of a semiconductor device to be dusted is applied on the substrate, and then heat-treated at 150 ° C. or higher. Item 10. A substrate for dust removal of a semiconductor device according to Item 9.   A dust removal method for removing dust from a surface of a semiconductor device according to claim 8 by bringing the resin surface of the substrate for dust removal into contact with the surface of the semiconductor device.