Polyimide Precursor Composition, Polyimide Film Formed Therefrom, and Method of Manufacturing Semiconductor Device Using the Same

Abstract

The present invention relates to a polyimide precursor composition, a polyimide film formed therefrom, and a method of manufacturing a semiconductor device using the same. The present invention provides a polyimide precursor composition comprising an imide precursor represented by Chemical Formula 1 or Chemical Formula 2, wherein, in Chemical Formulas 1 and 2, X is a divalent aliphatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, Y is a tetravalent aliphatic hydrocarbon group having 4 to 30 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms, Z is a moiety derived from a compound containing a cyclic ether group having 4 to 30 carbon atoms, and n and m are each an integer of 5 to 100. The polyimide film formed using the polyimide precursor composition has improved heat resistance and mechanical properties and has high absorbance in a wavelength range in the ultraviolet region. [Chemical Formula 1][Chemical Formula 2]

Description

[0001] Cross-reference to related applications

[0002] This application claims priority to Korean Patent Application No. 10-2022-0008379, filed with the Korean Intellectual Property Office (KIPO) on January 20, 2022, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] The present invention relates to a polyimide precursor composition, a polyimide film formed therefrom, and a method of manufacturing a semiconductor device using the same. More particularly, the present invention relates to a polyimide precursor composition capable of forming a polyimide structure, a polyimide film formed therefrom, and a method of manufacturing a semiconductor device using the same. Background Art

[0004] A polyimide (PI) copolymer is a polymer having an isimide ring in the main chain and can be prepared by polycondensation of an aromatic dianhydride and an aromatic diamine, followed by imidization. Polyimide copolymers have high heat resistance, flame retardancy, mechanical properties, low dielectric constant, etc., and can be applied to a wide range of fields such as electronic materials, coating materials, molding materials, composite materials, etc.

[0005] Recently, in the field of electronic devices such as semiconductor devices and display devices, the critical dimension of patterns is being reduced to achieve a high-resolution structure. For example, as electronic devices such as smartphones are reduced in weight, thickness, and size, the demand for thin-sized compact devices such as semiconductor devices, PCBs, flip chips, etc. with highly integrated electronic components is also increasing.

[0006] In the manufacture of a semiconductor device, a grinding process such as back grinding may be performed on a semiconductor substrate to reduce the size and thickness of the semiconductor device. In this case, the semiconductor device may be attached to a support substrate using an adhesive.

[0007] However, due to the adhesive attached to the semiconductor substrate, the substrate may warp during or after the manufacturing process, and the semiconductor device may be damaged during the peeling or releasing process. Therefore, it is necessary to develop a release layer having improved peeling characteristics and heat resistance and capable of suppressing damage during the manufacturing process.

[0008] Korean Patent Publication No. 10-2007-0114280 discloses an example of a polyimide film. Summary of the Invention

[0009] According to an aspect of the present invention, there is provided a polyimide composition having improved reliability and stability.

[0010] According to one aspect of the present invention, there is provided a polyimide film formed from a polyimide composition and having heat resistance and debonding properties.

[0011] According to one aspect of the present invention, there is provided a method for manufacturing a semiconductor device using a polyimide precursor composition.

[0012] (1) A polyimide precursor composition comprising an imide precursor represented by Chemical Formula 1 or Chemical Formula 2.

[0013] [Chemical Formula 1]

[0014]

[0015] [Chemical Formula 2]

[0016]

[0017] In Chemical Formulas 1 and 2, X is a divalent aliphatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, Y is a tetravalent aliphatic hydrocarbon group having 4 to 30 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms, Z is a moiety derived from a compound containing a cyclic ether group having 4 to 30 carbon atoms, and n and m are each an integer from 5 to 100.

[0018] (2) The polyimide precursor composition according to (1) above, wherein the compound containing a cyclic ether group further contains a linear ether group or an ester group (-COO-) in addition to the cyclic ether group.

[0019] (3) The polyimide precursor composition according to (2) above, wherein the compound containing a cyclic ether group includes at least one selected from the group consisting of: tert-butyl glycidyl ether, neopentyl glycol diglycidyl ether, glycidyl propargyl ether, glycidyl phenyl ether, glycidyl methyl ether, glycidyl methacrylate, glycidyl lauryl ether, glycidyl isopropyl ether, glycidyl acrylate, glycidyl 4-tert-butylbenzoate, glycidyl 2-methoxyphenyl ether, ethylene glycol diglycidyl ether, ethyl glycidyl ether, 4-cyclohexene-1,2-dicarboxylic acid diglycidyl ester, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, butyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, 2,2-bis(4-glycidyloxyphenyl)propane, and 1,4-butanediol diglycidyl ether.

[0020] (4) The polyimide precursor composition according to (1) above, wherein the imide precursor is a product of a monomer blend comprising a diamine compound, a dianhydride compound, and a compound containing a cyclic ether group.

[0021] (5) The polyimide precursor composition according to the above (4), wherein the diamine compound includes a compound represented by Chemical Formula 3.

[0022] [Chemical Formula 3]

[0023] H2N-X-NH2

[0024] In Chemical Formula 3, X is a divalent aliphatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0025] (6) The polyimide precursor composition according to the above (5), wherein the diamine compound includes at least one of the compounds represented by Chemical Formulas 5 to 9.

[0026] [Chemical Formula 5]

[0027]

[0028] [Chemical Formula 6]

[0029]

[0030] [Chemical Formula 7]

[0031]

[0032] [Chemical Formula 8]

[0033]

[0034] [Chemical Formula 9]

[0035]

[0036] (7) The polyimide precursor composition according to the above (4), wherein the dianhydride compound includes a compound represented by Chemical Formula 4,

[0037] [Chemical Formula 4]

[0038]

[0039] In Chemical Formula 4, Y is a tetravalent aliphatic hydrocarbon group having 4 to 30 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0040] (8) The polyimide precursor composition according to the above (7), wherein the dianhydride compound includes at least one of the compounds represented by Chemical Formulas 10 to 14:

[0041] [Chemical Formula 10]

[0042]

[0043] [Chemical Formula 11]

[0044]

[0045] [Chemical Formula 12]

[0046]

[0047] [Chemical Formula 13]

[0048]

[0049] [Chemical Formula 14]

[0050]

[0051] (9) The polyimide precursor composition according to the above (4), wherein the content of the compound containing a cyclic ether group in the monomer blend is in the range of 10 moles to 150 moles based on 100 moles of the dianhydride compound.

[0052] (10) The polyimide precursor composition according to the above (4), wherein the content of the diamine compound in the monomer blend is in the range of 80 moles to 120 moles based on 100 moles of the dianhydride compound.

[0053] (11) A polyimide film comprising a cured product of the polyimide precursor composition of the above embodiment.

[0054] (12) The polyimide film according to the above (11), wherein the polyimide film is used as a release layer for laser lift-off (LLO).

[0055] (13) The polyimide film according to the above (11), wherein the light transmittance at a wavelength of 308 nm measured at a thickness of is 25% or less.

[0056] (14) A method of manufacturing a semiconductor device, comprising: forming a carrier laminate including a carrier substrate and a release layer formed of the polyimide precursor composition of the above embodiment on the top surface of a semiconductor substrate; polishing the bottom surface of the semiconductor substrate; and removing the carrier laminate from the semiconductor substrate.

[0057] (15) The method according to the above (14), wherein removing the carrier laminate from the semiconductor substrate includes irradiating the release layer with a laser; and detaching the release layer from the semiconductor substrate.

[0058] (16)According to the method of (14) above, it further includes forming a circuit device on the top surface of the semiconductor substrate before forming the carrier laminate on the top surface of the semiconductor substrate, wherein polishing the bottom surface of the semiconductor substrate includes flipping the semiconductor substrate so that the carrier laminate surface faces downwards.

[0059] (17)According to the method of (14) above, it further includes forming a pressure-sensitive adhesive layer on the top surface of the semiconductor substrate before forming the carrier laminate on the top surface of the semiconductor substrate; and removing the pressure-sensitive adhesive layer from the semiconductor substrate after removing the carrier laminate from the semiconductor substrate.

[0060] The polyimide precursor composition according to an exemplary embodiment may include an imide precursor formed from a diamine compound and a dianhydride compound. Accordingly, a polyimide having high heat resistance and mechanical properties can be formed from the polyimide precursor composition.

[0061] The imide precursor may have an organic group derived from a compound containing a cyclic ether group at a molecular end. Due to the structure of the compound containing a cyclic ether group, the time-dependent stability of the polyimide precursor composition can be improved. Accordingly, even when stored for a long time under severe conditions of high temperature / high humidity, the polyimide precursor composition may have a low viscosity, and the thickness change ratio of the film formed from the polyimide precursor composition may become small.

[0062] In addition, the polyimide film formed from the polyimide precursor composition may have a high absorbance in the wavelength range of the ultraviolet region, and thus the laser debonding characteristics can be improved. Accordingly, even when the polyimide film is irradiated with, for example, a low-energy peeling laser, the debonding characteristics with respect to, for example, a semiconductor substrate can be improved.

[0063] The polyimide film can be applied to the manufacture of semiconductor devices and can be used, for example, as a release layer between a semiconductor device and a carrier substrate. In this case, the semiconductor device can be easily separated from the carrier substrate without physical damage such as cracks or fractures and chemical damage such as corrosion. Description of the Drawings

[0064] Figures 1 to 4 is a schematic cross-sectional view showing a method of manufacturing a semiconductor device according to an exemplary embodiment. Detailed Description

[0065] The polyimide precursor composition according to an embodiment of the present invention (hereinafter, it may be abbreviated as a precursor composition) may include a structure derived from a diamine compound, a dianhydride compound, and a compound containing a cyclic ether group.

[0066] In addition, a polyimide film formed from the polyimide precursor composition and a method of manufacturing a semiconductor device using the polyimide precursor composition are provided.

[0067] Hereinafter, embodiments of the present invention will be described in detail.

[0068] <Polyimide precursor composition>

[0069] The polyimide precursor composition according to an exemplary embodiment may include an imide precursor represented by the following Chemical Formula 1 or Chemical Formula 2.

[0070] [Chemical Formula 1]

[0071]

[0072] [Chemical Formula 2]

[0073]

[0074] In Chemical Formulas 1 and 2, X may be a divalent organic group having 6 to 30 carbon atoms. For example, X may be a divalent aliphatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0075] As used herein, the term "aliphatic hydrocarbon group" may refer to an organic group including a straight-chain, branched-chain, or cycloaliphatic hydrocarbon group and containing no aromatic ring. As used herein, the term "aromatic hydrocarbon group" may refer to an organic group containing at least one aromatic ring.

[0076] For example, the divalent aliphatic hydrocarbon group may be an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkenylene group, or a cycloalkynylene group. For example, the divalent aromatic hydrocarbon group may be an arylene group, an alkylarylene group, or an arylalkylene group.

[0077] The divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may contain at least one heteroatom selected from oxygen, nitrogen, sulfur, and fluorine. The heteroatom may be present in the main chain or a side chain. For example, the divalent organic group may include a trifluoromethyl group (-CF3), an ether group (-O-), a thioether group (-S-), a carbonyl group (-C(=O)-), a sulfinyl group (-(S=O)-), or a sulfonyl group (-SO2-).

[0078] Preferably, X may be a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0079] Y may be a tetravalent organic group having 4 to 30 carbon atoms. For example, Y may be a tetravalent aliphatic hydrocarbon group having 4 to 30 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0080] The tetravalent organic group may contain at least one heteroatom selected from oxygen, nitrogen, sulfur, and fluorine. The heteroatom may be present in the main chain or side chain. For example, the tetravalent organic group may include a trifluoromethyl group (-CF3), an ether group (-O-), a thioether group (-S-), or a carbonyl group (-C(=O)-), a sulfinyl group (-(S=O)-), or a sulfonyl group (-SO2-), etc.

[0081] Preferably, Y may be a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0082] Z may be an organic group derived from a compound having a cyclic ether group with 4 to 30 carbon atoms. For example, Z may include a moiety derived from a compound having a cyclic ether group. As used herein, the term "cyclic ether group" may refer to a ring structure having, for example, a monocyclic structure, a polycyclic structure, or a heterocyclic structure and containing an ether group in the ring structure.

[0083] The imide precursor may have a Z unit derived from a compound having a cyclic ether group, such that the laser peeling characteristics of the polyimide film can be improved, and the time-dependent stability and storage stability of the composition can be improved.

[0084] In some embodiments, the compound having a cyclic ether group may further include a linear ether group (-O-) or an ester group (-C(=O)O-) in addition to the cyclic ether group. As used herein, the term "linear ether group" may refer to a functional group containing an ether group in a chain of a linear structure.

[0085] For example, Z may be an aliphatic hydrocarbon group having 4 to 30 carbon atoms and including a linear ether group or an ester group, or an aromatic hydrocarbon group having 6 to 30 carbon atoms and including a linear ether group or an ester group.

[0086] In this case, the decomposition and gelation of the imide precursor due to the long-term storage of the composition can be prevented while maintaining a high absorbance of the imide precursor to light in the ultraviolet region. Therefore, the time-dependent stability of the resin composition can be improved, and the physical properties and laser debonding characteristics of the polyimide film formed therefrom can be improved.

[0087] In Chemical Formulas 1 and 2, n and m may each be an integer from 5 to 100.

[0088] For example, when n and m are less than 5, the heat resistance and mechanical properties of the polyimide formed from the imide precursor may deteriorate. For example, when n and m are greater than 100, the storage stability of the composition may deteriorate, and the viscosity of the composition may increase during long-term storage. Therefore, the physical properties and film-forming properties of the polyimide film may deteriorate.

[0089] In an exemplary embodiment, the imide precursor can be a product of a monomer blend comprising a diamine compound, a dianhydride compound, and a compound containing a cyclic ether group. For example, the imide precursor can include a copolymer of a diamine compound, a dianhydride compound, and a compound containing a cyclic ether group.

[0090] In an embodiment, X in Chemical Formulas 1 and 2 can have a structure derived from a diamine compound and can be, for example, a moiety from the diamine compound. In an embodiment, Y in Chemical Formulas 1 and 2 can have a structure derived from a dianhydride compound and can be, for example, a moiety from the dianhydride compound.

[0091] In some embodiments, the diamine compound can include a compound represented by the following Chemical Formula 3.

[0092] [Chemical Formula 3]

[0093] H2N-X-NH2

[0094] In Chemical Formula 3, X can be a divalent organic group having 6 to 30 carbon atoms, such as a divalent aliphatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0095] Preferably, X can be a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0096] For example, the diamine compound can include 3,4-oxydiphenylether, 4,4'-oxydiphenylether (ODA), 4,4'-methylenedianiline, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, bis[4-(3-aminophenoxy)phenyl]-sulfone, bis[4-(4-aminophenoxy)phenyl]-sulfone, 2,2-bis(trifluoromethyl)benzidine, 2,2-bis[4-(4-aminophenoxy)-phenyl]hexafluoropropane), 2,2-bis(trifluoromethyl)benzidine (TFMB), 3,3'-sulfonyldianiline, 4,4'-diaminodiphenylsulfone, 4,4'-(1,3-phenylenedioxy)dianiline, 9,9-bis(4-amino-3-fluorophenyl)fluorene, 4-aminobenzoic acid 4-aminophenyl ester, 4,4'-diaminobenzanilide, 9,9-bis(4-aminophenyl)fluorene, etc. These can be used alone or in combination thereof.

[0097] For example, the diamine compound can include at least one of the compounds represented by the following Chemical Formulas 5 to 9.

[0098] [Chemical Formula 5]

[0099]

[0100] [Chemical Formula 6]

[0101]

[0102] [Chemical Formula 7]

[0103]

[0104] [Chemical Formula 8]

[0105]

[0106] [Chemical Formula 9]

[0107]

[0108] In some embodiments, the dianhydride compound may include a compound represented by the following Chemical Formula 4.

[0109] [Chemical Formula 4]

[0110]

[0111] In Chemical Formula 4, Y may be a tetravalent organic group having 4 to 30 carbon atoms, such as an aliphatic hydrocarbon group having 4 to 30 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0112] Preferably, Y may be a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0113] For example, the dianhydride compound may include 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,3,3',4-biphenyltetracarboxylic dianhydride (a-BPDA), 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4'-oxydiphthalic anhydride (ODPA), 3,3',4,4'-diphenylsulfone-tetracarboxylic dianhydride (DSDA), 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA), hydroquinone diphthalic anhydride (HQDA), 1,2,4,5-cyclohexane-tetracarboxylic dianhydride (CHDA), etc. These may be used alone or in combination thereof.

[0114] For example, the dianhydride compound may include at least one of the compounds represented by the following Chemical Formulas 10 to 14.

[0115] [Chemical Formula 10]

[0116]

[0117] [Chemical Formula 11]

[0118]

[0119] [Chemical Formula 12]

[0120]

[0121] [Chemical Formula 13]

[0122]

[0123] [Chemical Formula 14]

[0124]

[0125] In an exemplary embodiment, the compound containing a cyclic ether group may include a compound containing an epoxy group. In this case, the reactivity between the compound containing a cyclic ether group and the amine group may be improved due to the epoxy group. Therefore, the unreacted ratio of the compound containing a cyclic ether group may be reduced during the polymerization reaction, and the self-crosslinking reaction between the compounds containing a cyclic ether may be suppressed, thereby improving the structural stability and time-dependent stability of the imide precursor.

[0126] In some embodiments, the compound containing an epoxy group may include at least one of the following: tert-butyl glycidyl ether, neopentyl glycol diglycidyl ether, glycidyl propargyl ether, glycidyl phenyl ether, glycidyl methyl ether, glycidyl methacrylate, glycidyl lauryl ether, glycidyl isopropyl ether, glycidyl acrylate, glycidyl 4-tert-butylbenzoate, glycidyl 2-methoxyphenyl ether, ethylene glycol diglycidyl ether, ethyl glycidyl ether, diglycidyl 4-cyclohexene-1,2-dicarboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, butyl glycidyl ether, benzyl glycidyl ether, allyl glycidyl ether, 2,2-bis(4-glycidyloxyphenyl)propane, 1,4-butanediol diglycidyl ether.

[0127] In an exemplary embodiment, the content of the diamine compound in the monomer blend is in the range of 80 to 120 moles, preferably 90 to 110 moles, more preferably 95 to 110 moles, based on 100 moles of the dianhydride compound.

[0128] Within the above range, the reactivity and efficiency of the diamine compound and the dianhydride compound can be improved, and an imide precursor with an appropriate molecular weight and a high degree of polymerization can be formed. In addition, the mechanical properties and thermal stability of the polyimide film formed therefrom can be improved.

[0129] In an exemplary embodiment, the content of the compound containing a cyclic ether group in the monomer blend is in the range of 10 to 150 moles, preferably 50 to 100 moles, based on 100 moles of the dianhydride compound.

[0130] For example, when the content of the compound containing a cyclic ether group is less than 10 moles, the reactivity between the compound containing a cyclic ether group and the terminal amine group of the polyamic acid may deteriorate. As a result, unreacted polyamic acid may be produced, for example, a unit derived from the compound containing a cyclic ether group is not bonded to the terminal imide precursor. Therefore, the yield of the imide precursor represented by Chemical Formula 1 or Chemical Formula 2 may decrease, and the time-dependent stability and storage characteristics of the resin composition may deteriorate.

[0131] For example, when the content of the compound containing a cyclic ether group is greater than 150 moles, the compounds containing a cyclic ether group may react with each other. In this case, the reactivity between the terminal amine group of the polyamic acid compound and the compound containing a cyclic ether group may decrease, and the yield of the imide precursor may also decrease. Therefore, the time-dependent stability of the polyimide precursor composition may deteriorate, and the heat resistance and mechanical properties of the polyimide film may deteriorate due to the self-reacting compound containing a cyclic ether group.

[0132] In an embodiment, the imide precursor may be formed by reacting a polyamic acid compound (formed by reacting a diamine compound and a dianhydride compound) with a compound containing a cyclic ether group.

[0133] For example, the polyamic acid compound may be prepared by mixing and reacting a diamine compound and a dianhydride compound at a temperature in the range of 0 °C to 20 °C for 24 hours to 48 hours. In this case, the polyamic acid having an amide structure may be formed by ring-opening the acid anhydride group of the dianhydride monomer to condense with the amine group (-NH2) of the diamine monomer.

[0134] In an embodiment, a polyamic acid compound having carboxyl groups and amine groups at both ends may be prepared by mixing and reacting polyamic acid and water at a temperature in the range of 20 °C to 70 °C for 12 hours to 48 hours.

[0135] Water can induce the decomposition reaction of the polyamic acid compound and can control the molecular weight and viscosity of the imide precursor. For example, an imide precursor having a desired viscosity level can be prepared by adjusting the content of water reacting with the polyamic acid compound.

[0136] For example, the amount of water added ranges from 0.1 mole to 10 moles based on 100 moles of the dianhydride compound. If the water content is 0.1 mol or less, the viscosity of the imide precursor may increase, and the coating characteristics and film-forming characteristics may deteriorate. If the water content is greater than 10 moles, the molecular weight of the imide precursor may decrease, and the physical properties of the polyimide may deteriorate.

[0137] The prepared polyamic acid compound and the compound containing a cyclic ether group can be mixed and reacted at a temperature in the range of 20°C to 70°C for 24 hours to 72 hours to prepare an imide precursor represented by Chemical Formula 1 or 2.

[0138] In this case, the cyclic ether group of the compound containing a cyclic ether group can be ring-opened to condense with the amino group (-NH2) located at the end of the polyamic acid compound. Accordingly, the Z unit derived from the compound containing a cyclic ether group can be located at the end of the imide precursor.

[0139] In an exemplary embodiment, the resin composition may further comprise a surfactant and / or a solvent.

[0140] For example, the solvent may include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 1-methyl-2-pyrrolidone, N,N-dimethylpropanamide, diethylacetamide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 1-ethyl-2-pyrrolidone, N,N-dimethylisobutylamide, N,N-diethylformamide, N,N-dimethylformamide, N-methylformamide, N-ethylformamide, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, α-ethyl lactone, β-propiolactone, δ-valerolactone, etc. These may be used alone or in combination thereof.

[0141] For example, the surfactant may include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid-modified polyester, tertiary amine-modified polyurethane, polyethyleneimine, etc. Commercially available surfactants may include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Megafac (MEGAFAC) (manufactured by Dainippon Ink Chemical Co., Ltd.), Flourad (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA Chemicals), PB 821 (manufactured by by Ajinomoto Co., Ltd.). These may be used alone or in combination thereof.

[0142] In an embodiment, the content of the surfactant is in the range of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the imide precursor.

[0143] Within the above range, the applicability and coatability of the resin composition can be improved, and the thickness uniformity and film-forming property of the coating layer can be enhanced. In addition, a thin coating layer can be formed so that microfabrication can be achieved during the manufacturing process of semiconductor devices.

[0144] For example, the coating method of the resin composition may include spin coating, slit coating, dip coating, spray coating, drop coating, screen printing, inkjet printing, offset printing, knife coating, roll coating, curtain coating, etc.

[0145] <Polyimide film>

[0146] The polyimide film according to an exemplary embodiment may include a cured product of the polyimide precursor composition as described above. For example, the polyimide film may include polyimide formed by imidization of the imide precursor. The imide precursor can be converted into a polyimide structure through a baking or thermal curing process.

[0147] The polyimide precursor composition can be coated on a substrate and then thermally cured to form a polyimide film. In an exemplary embodiment, the thermal curing process may include a low-temperature curing process performed at a temperature of about 350 °C or less. In some embodiments, the thermal curing process may be performed at a temperature in the range of 100 °C to 300 °C.

[0148] In an exemplary embodiment, the light transmittance of the polyimide film measured at a thickness and a wavelength of 308 nm may be 25% or less. For example, the polyimide film may have a high absorbance and low sensitivity to a wavelength of 308 nm. Therefore, the polyimide film can absorb most of the laser energy in the 308 nm wavelength range emitted by a laser source, and the polyimide can be easily decomposed even under a short irradiation time and a small amount of light.

[0149] In some embodiments, the polyimide film may have a glass transition temperature (Tg) of 320 °C or higher, for example, at a temperature in the range of 320 °C to 350 °C. For example, the glass transition temperature can be measured by raising the temperature from 25 °C to 400 °C at a heating rate of 10 °C / min.

[0150] In some embodiments, the thermal decomposition temperature (Td1%) of the polyimide film may be 350 °C or higher, preferably 370 °C or higher, and more preferably 380 °C or higher. For example, the thermal decomposition temperature may be the temperature at which the weight decreases by 1% from the initial weight when heated from room temperature at a heating rate of 10 °C / min in a nitrogen atmosphere.

[0151] Within the above range, the thermal stability of the polyimide film can be improved. Therefore, shrinkage, breakage, and lifting of the polyimide film due to heat applied during semiconductor device manufacturing or polishing processes, such as the CMP process, can be prevented.

[0152] In addition, the imide precursor according to the exemplary embodiment may have a Z unit derived from an epoxide at the end of the molecular structure to have a high laser energy margin and improved heat resistance. Therefore, the polyimide film formed from the above resin composition may have improved debonding characteristics and enhanced thermal stability.

[0153] For example, the polyimide film can be used as a release layer for laser lift-off (LLO) in a method of manufacturing a semiconductor device.

[0154] <Method of manufacturing a semiconductor device>

[0155] Figures 1 to 4 is a schematic cross-sectional view showing a method of manufacturing a semiconductor device according to an exemplary embodiment.

[0156] Reference Figure 1 , a carrier laminate 120 including a release layer 122 and a carrier substrate 124 may be formed on the top surface of the semiconductor substrate 100. For example, the release layer 122 may be deposited on the top surface of the semiconductor substrate 100, and the carrier substrate 124 may be deposited on the top surface of the release layer 122.

[0157] The release layer 122 may include a cured product of the polyimide precursor composition as described above.

[0158] In an embodiment, the polyimide precursor composition may be coated on the top surface of the semiconductor substrate 100, and then the composition may be heated and dried to form a coating layer. Thereafter, the carrier substrate 124 may be attached to the coating layer, and the imide precursor may be imidized by thermally curing the coating layer. Therefore, the release layer 122 including polyimide may be formed on the semiconductor substrate 100.

[0159] In an embodiment, the release layer 122 may be formed by coating the above polyimide precursor composition on the bottom surface of the carrier substrate 124, and then heating and drying the composition. Thereafter, the carrier laminate 120 may be attached to the top surface of the semiconductor substrate 100 such that the release layer 122 faces the top surface of the semiconductor substrate 100.

[0160] The semiconductor substrate 100 may include a single semiconductor substrate, such as a silicon substrate, a germanium substrate, or a silicon-germanium substrate, or a composite substrate, such as a silicon-on-insulator (SOI) substrate or a germanium-on-insulator (GOI) substrate, a metal oxide polycrystalline substrate, etc.

[0161] The carrier substrate 124 can be a glass substrate or can include a semiconductor material such as single-crystalline silicon, single-crystalline germanium, or polysilicon.

[0162] In some embodiments, the circuit device 105 can be formed on the top surface of the semiconductor substrate 100. For example, the circuit device 105 can be formed on the top surface of the semiconductor substrate 100 before forming the carrier laminate 120.

[0163] For example, the circuit device 105 can include transistor elements such as a power source, a drain, a gate electrode, a capacitor electrode, a contact, a circuit pattern, a wiring, etc., or a conductive pattern such as a common electrode, a pixel electrode, and a diode element, such as an organic light-emitting layer (EL).

[0164] In an embodiment, before forming the carrier laminate 120, a pressure-sensitive adhesive layer 110 can be formed on the top surface of the semiconductor substrate 100. For example, a pressure-sensitive adhesive composition can be applied on the top surface of the semiconductor substrate 100 and then cured to form the pressure-sensitive adhesive layer 110. Thereafter, the release layer 120 can be formed on the top surface of the pressure-sensitive adhesive layer 110.

[0165] For example, the pressure-sensitive adhesive layer 110 can include a resin having low adhesion characteristics and low peel strength and can include a silicone-based resin or an acrylic resin.

[0166] Reference Figure 2 , the bottom surface of the semiconductor substrate 100 can be planarized by polishing. In an embodiment, the semiconductor substrate 100 on which the carrier laminate 120 is to be formed can be loaded into a polishing apparatus 200, and a back grinding process can be performed.

[0167] For example, the semiconductor substrate 100 can be flipped so that the carrier laminate 120 faces downward in the polishing apparatus. In this case, the bottom surface of the semiconductor substrate 100 can face the polishing pad of the polishing apparatus 200.

[0168] A polishing process can be performed such that the circuit device 105 formed on the top surface of the semiconductor substrate 100 is not exposed. While the semiconductor substrate 100 is supported by the carrier substrate 130, a polishing process can be performed such that the bottom surface of the semiconductor substrate 100 can be uniformly polished without damaging the circuit device 105. Thus, a thin-layer, light-weight, and highly integrated semiconductor device can be obtained.

[0169] In some embodiments, the polishing process can be performed by an ultra-fine grinding process or a chemical mechanical polishing (CMP) process. In an embodiment, the polishing process can be performed by a CMP process.

[0170] Reference Figure 3 and 4, light in the ultraviolet region can be irradiated onto the release layer 122. For example, a laser with a wavelength range of 290 nm to 380 nm can be irradiated.

[0171] For example, when the release layer 122 is irradiated with a laser having a wavelength within the above range, the polyimide can be carbonized, and the contact surface of the release layer 122 with the semiconductor substrate 100 or the pressure-sensitive adhesive layer 110 can be decomposed. Therefore, the release layer 122 can be delaminated from the semiconductor substrate 100 or the pressure-sensitive adhesive layer 110.

[0172] The process of detaching the carrier substrate 124 from the semiconductor substrate 100 may include a thermal debonding process in which the carrier laminate 120 is separated by heat, a mechanical debonding process in which the carrier laminate 120 is mechanically separated, or a solvent debonding process in which the carrier laminate 120 is separated by dissolving the release layer 122 in a solvent. However, the above detachment processes are carried out at high temperatures using strong mechanical forces, solvents, etc., which can cause cracking, damage, or corrosion of the semiconductor device.

[0173] In the method of manufacturing a semiconductor device according to an exemplary embodiment, the release layer 122 contains polyimide formed from the above-mentioned imide precursor, and a laser lift-off (LLO) process can be performed. Therefore, the release layer 122 can be delaminated by a relatively small force generated by laser irradiation.

[0174] For example, the polyimide can have strong absorption characteristics for light in the ultraviolet region (e.g., a wavelength of 308 nm) due to the imide structure included in the main chain. Therefore, energy can be concentrated in the region of laser irradiation, and high heat can be generated in this region. In this case, the polyimide can be decomposed due to the heat energy generated in the release layer 122, or the chemical bond between the surface of the pressure-sensitive adhesive layer 110 and the polyimide can be decomposed, so that the release layer 122 can be delaminated from the pressure-sensitive adhesive layer.

[0175] Therefore, since the release layer 122 has high absorption characteristics for light with a wavelength range of 290 nm to 380 nm, the laser energy density (E / D) required for the laser lift-off process can be reduced. In this case, the detachment time can be shortened, the processability can be improved, and damage to the semiconductor substrate 100 caused by the irradiated laser can be prevented.

[0176] The release layer 122 and the carrier substrate 124 can be separated from the semiconductor substrate 100, so that a semiconductor device including the semiconductor substrate 100 on which the circuit device 105 is formed can be provided.

[0177] For example, when one end of the release layer 122 is fixed, a force can be vertically applied to the top surface of the carrier substrate 124 so that the carrier laminate 120 is separated from the semiconductor substrate 100 or the pressure-sensitive adhesive layer 110.

[0178] In some embodiments, the adhesive layer 110 may also be included between the semiconductor substrate 100 and the release layer 122. In this case, the adhesive layer 110 may be separated from the semiconductor substrate 100 to provide a semiconductor device. The pressure-sensitive adhesive layer 110 may have a low adhesive strength so that it can be easily peeled off without damaging the circuit device 105 even with a low peeling force.

[0179] In an embodiment, the bottom surface of the semiconductor substrate 100 may be attached to the dicing tape 300, and then the release layer 120 is separated from the semiconductor substrate 100. The semiconductor substrate 100 may be fixed to the dicing tape 300 such that the release layer 122 and the carrier substrate 124 can be easily separated from the semiconductor substrate 100.

[0180] Preferred embodiments are presented below to describe the present invention more specifically. However, the following examples are given only to illustrate the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. Such changes and modifications should be appropriately included in the appended claims.

[0181] Examples

[0182] In a four-neck round-bottom flask, γ-butyrolactone (GBL) was added as a solvent, and 2,2-bis(trifluoromethyl)benzidine (TFMB) and 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) were added in a molar ratio of 1:1 so that the solid content was 20 wt% and they were reacted with each other at 10 °C for 24 hours. Thereafter, water was added in an amount of 0.1 mol based on 1 mol of the dianhydride monomer, and the reaction was carried out at 50 °C for 24 hours. Thereafter, glycidyl isopropyl ether was added in an amount of 0.1 mol relative to 1 mol of the dianhydride monomer, and the reaction was carried out at 50 °C for 48 hours to prepare an imide precursor composition having a viscosity of 40 cps.

[0183] Examples 2 to 20

[0184] The imide precursor composition was prepared in the same manner as in Example 1, except that the reactive monomers were mixed in the components, and the corresponding molar ratios are shown in Table 1 below.

[0185] Comparative Example 1

[0186] In a four-necked round-bottom flask, γ-butyrolactone (GBL) was added as a solvent, and 2,2-bis(trifluoromethyl)benzidine (TFMB) and 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) were added in a molar ratio of 1:1 so that the solid content was 20 wt%, and the reaction was carried out at 10 °C for 24 hours. Thereafter, water was added in an amount of 0.1 mol relative to 1 mol of the dianhydride monomer, and the reaction was carried out at 50 °C for 24 hours to prepare an imide precursor composition having a viscosity of 39 cps.

[0187] Comparative Examples 2 to 4

[0188] The imide precursor composition was prepared in the same manner as in Comparative Example 1, except that the reactive monomers were mixed with the components, and the molar ratios were as shown in Table 1.

[0189] [Table 1]

[0190]

[0191]

[0192] The specific components listed in Table 1 are as follows.

[0193] Diamine monomer (A)

[0194] A-1: 2,2-bis(trifluoromethyl)benzidine (TFMB) A-2: 4,4-methylenedianiline (MDA)

[0195] A-3: 4,4-oxydiphenylether (ODA)

[0196] Dianhydride monomer (B)

[0197] B-1: 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)

[0198] B-2: 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA)

[0199] B-3: 3,3',4',4'-benzophenonetetracarboxylic dianhydride (BTDA)

[0200] B-4: 4,4'-oxybisphthalic anhydride (ODPA)

[0201] Monomer (C) containing a cyclic ether group

[0202] C-1: Glycidyl isopropyl ether

[0203] C-2: tert-Butyl glycidyl ether

[0204] C-3: Ethyl glycidyl ether

[0205] Experimental Examples

[0206] (1) Evaluate time-dependent stability: Measure the viscosity change ratio

[0207] The initial viscosities of the polyimide precursor compositions of the examples and comparative examples were measured using a viscometer (DV3T, manufactured by Brookfield) at a temperature of 25 °C and a rotational speed of 10 rpm to 60 rpm. Thereafter, after being placed at a temperature of 40 °C for 4 weeks, the viscosity was measured at a temperature of 25 °C and a rotational speed of 10 rpm to 60 rpm.

[0208] The viscosity change ratio was measured by calculating the change value of the viscosity after storage relative to the initial viscosity as a percentage.

[0209] (2) Measure the change ratio of the coating film thickness

[0210] The polyimide precursor compositions according to each of the examples and comparative examples were spin-coated on a glass substrate at a rotational speed of 1500 rpm. Thereafter, heat treatment was carried out at a temperature of 280 °C under vacuum using a vacuum oven for 1 hour to prepare a coating film having a thickness of the coating film.

[0211] The initial thicknesses of the coating films according to each of the examples and comparative examples were measured. Thereafter, the coating films were placed at a temperature of 40 °C for 4 weeks, and then the thickness was measured after storage, and the thickness change ratio was measured by calculating the change value of the thickness relative to the initial thickness as a percentage.

[0212] [Table 2]

[0213]

[0214] Referring to Tables 1 and 2, in the imide precursor compositions according to the examples, even when placed at a high temperature for a long time, the change ratio of the viscosity decreased. Furthermore, in the coating films thus formed, the change ratio of the thickness was relatively reduced.

[0215] However, in the imide precursor compositions according to the comparative examples, the viscosity changed greatly, and the change ratio of the thickness of the coating film increased.

[0216] Therefore, it was confirmed that the imide precursor having a structure derived from an epoxy compound has high time-dependent stability, and the change ratios of the viscosity and the coating film thickness are small even when stored under harsh conditions for a long time.

[0217] Manufacture a polyimide film

[0218] The polyimide precursor compositions according to the examples and comparative examples were spin-coated on a glass substrate at a rotational speed of 1500 rpm. Thereafter, a coating film was formed by heating and drying in a vacuum oven at a temperature of 120 °C for 1 hour under vacuum. The prepared coating film was heat-treated at a temperature of 280 °C for 1 hour in a vacuum state to prepare a polyimide film having a thickness of of

[0219] (3) Measurement of thermal decomposition temperature (Td)

[0220] The decomposition temperature (Td) of the polyimide films according to each of the examples and comparative examples was measured using a thermogravimetric analyzer (TGA Q500, TA Instruments). Specifically, the thermal decomposition temperature (Td) was measured by measuring the temperature at which the initial weight of the polyimide film decreased by 1% while increasing the temperature from 0 °C to 600 °C at a heating rate of 10 °C / min.

[0221] (4) Measurement of coefficient of thermal expansion (CTE)

[0222] The coefficient of thermal expansion (CTE) of the polyimide films according to each of the examples and comparative examples was measured using a thermomechanical analyzer (TMA 2940, TA Instruments) in the temperature range of 50 °C to 150 °C under the conditions of a heating rate of 10 °C / min and a load of 5 g.

[0223] (5) Measurement of glass transition temperature (Tg)

[0224] The glass transition temperature (Tg) of the polyimide films according to each of the examples and comparative examples was measured using a differential scanning calorimeter (DSC 200F3, Netzsch). Specifically, the glass transition temperature (Tg) was measured by increasing the temperature from 25 °C to 400 °C at a heating rate of 10 °C / min.

[0225] (6) Evaluation of laser detachability

[0226] The polyimide films according to the examples and comparative examples were irradiated with light having a wavelength of 308 nm using a laser oscillator (XeCl excimer pm848, Light Machinery). Specifically, the energy density of the laser irradiation was 200 mJ / cm 2 , and the laser overlap was 50%.

[0227] Thereafter, a force was applied perpendicularly to one end of the polyimide film to separate the polyimide film from the glass substrate. The laser detachability was evaluated by observing the residue of the polyimide film on the glass substrate. The evaluation criteria are as follows.

[0228] <Evaluation criteria>

[0229] ○: No polyimide film residue was observed on the glass substrate.

[0230] ×: Polyimide film residue was observed on the glass substrate.

[0231] (7) Measure the light transmittance

[0232] The light transmittance of the polyimide film for each of the examples and comparative examples at a wavelength of 308 nm was measured using an ultraviolet spectrometer (UV-3600, Shimadzu).

[0233] [Table 3]

[0234]

[0235]

[0236] Referring to Tables 1 and 3, the polyimide film according to the example has high absorbance at 308 nm, while maintaining high heat resistance, and the debonding characteristics obtained by laser irradiation are improved.

[0237] However, the polyimide film according to the comparative example has low absorbance at a wavelength of 308 nm, and laser irradiation deteriorates the detachability.

[0238] Therefore, it was confirmed that the structure derived from the epoxy compound increases the absorbance at wavelengths in the ultraviolet region (e.g., a wavelength of 308 nm), thereby further improving the laser debonding characteristics.

Claims

1. A polyimide precursor composition comprising an imide precursor represented by Chemical Formula 1 or Chemical Formula 2: [Chemical Formula 1] [Chemical Formula 2] Among them, In Chemical Formulas 1 and 2, X is a divalent aliphatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms, Y is a tetravalent aliphatic hydrocarbon group having 4 to 30 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms, Z is a moiety derived from a compound containing a cyclic ether group having 4 to 30 carbon atoms, wherein the compound containing a cyclic ether group includes at least one selected from the group consisting of tert-butyl glycidyl ether, glycidyl isopropyl ether, and ethyl glycidyl ether, and n and m are each an integer from 5 to 100.

2. The polyimide precursor composition according to claim 1, wherein The imide precursor is a product of a monomer blend including a diamine compound, a dianhydride compound, and a compound containing a cyclic ether group.

3. The polyimide precursor composition according to claim 2, wherein, The diamine compound includes a compound represented by Chemical Formula 3: [Chemical Formula 3] H2N-X-NH2 Wherein, in Chemical Formula 3, X is a divalent aliphatic hydrocarbon group having 6 to 30 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

4. The polyimide precursor composition according to claim 3, wherein The diamine compound includes at least one of the compounds represented by Chemical Formulas 5 to 9: [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] [Chemical Formula 9] 5. The polyimide precursor composition according to claim 2, wherein The dianhydride compound includes a compound represented by Chemical Formula 4: [Chemical Formula 4] Wherein, in Chemical Formula 4, Y is a tetravalent aliphatic hydrocarbon group having 4 to 30 carbon atoms or a tetravalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

6. The polyimide precursor composition according to claim 5, wherein The dianhydride compound includes at least one of the compounds represented by Chemical Formulas 10 to 14: [Chemical Formula 10] [Chemical Formula 11] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] 7. The polyimide precursor composition according to claim 2, wherein The content of the compound containing a cyclic ether group in the monomer blend is in the range of 10 moles to 150 moles based on 100 moles of the dianhydride compound.

8. The polyimide precursor composition according to claim 2, wherein, The content of the diamine compound in the monomer blend is in the range of 80 moles to 120 moles based on 100 moles of the dianhydride compound.

9. A polyimide film comprising a cured product of the polyimide precursor composition according to claim 1.

10. The polyimide film according to claim 9, wherein, The polyimide film is used as a release layer for laser lift-off (LLO).

11. The polyimide film according to claim 9, wherein, The light transmittance at a wavelength of 308 nm measured at a thickness of is 25% or less.

12. A method of manufacturing a semiconductor device, comprising: Forming a carrier laminate on the top surface of a semiconductor substrate, the carrier laminate including a carrier substrate and a release layer formed from the polyimide precursor composition according to claim 1; Polishing the bottom surface of the semiconductor substrate; And Removing the carrier laminate from the semiconductor substrate.

13. The method according to claim 12, wherein, Removing the carrier laminate from the semiconductor substrate includes: Irradiating the release layer with a laser; and Detaching the release layer from the semiconductor substrate.

14. The method according to claim 12, further comprising forming a circuit device on the top surface of the semiconductor substrate before forming the carrier laminate on the top surface of the semiconductor substrate, Among them, Polishing the bottom surface of the semiconductor substrate includes flipping the semiconductor substrate so that the carrier laminate faces down.

15. The method according to claim 12 further includes forming a pressure-sensitive adhesive layer on the top surface of the semiconductor substrate before forming the carrier laminate on the top surface of the semiconductor substrate; and after removing the carrier laminate from the semiconductor substrate, removing the pressure-sensitive adhesive layer from the semiconductor substrate.

Images