Laminate, method for manufacturing laminate, method for manufacturing element, image pickup device, method for manufacturing image pickup device, semiconductor device, and method for manufacturing semiconductor device

Abstract

The purpose of the present invention is to provide a laminate, a method for manufacturing the laminate, a method for manufacturing an element using the laminate, an imaging device provided with the laminate, a method for manufacturing the imaging device, a semiconductor device provided with the laminate, and a method for manufacturing the semiconductor device. When the laminate is laminated to form a semiconductor device, warping and cracking of elements are not liable to occur, the laminate has high moisture resistance, and excellent connection reliability can be imparted. The present invention relates to a laminate in which an organic layer is laminated on a first element and an inorganic layer is laminated on the organic layer, the organic layer having a 1% thermal weight loss temperature of 400 DEG C or more as measured in a nitrogen atmosphere at a temperature rise rate of 10 DEG C / min, the inorganic layer having a thickness of 1 nm or more and 1 [mu] m or less, the inorganic layer including a Si3N4 layer, and the thickness of the Si3N4 layer being 1 nm or more and 1 [mu] m or less. The inorganic layer has an internal stress in a compression direction.

Description

Technical Field

[0001] The present invention relates to a laminate, a method for manufacturing a laminate, a method for manufacturing a component, a photographing device, a method for manufacturing a photographing device, a semiconductor device, and a method for manufacturing a semiconductor device. Background Art

[0002] With the high performance of semiconductor devices, the three-dimensionalization of stacking multiple semiconductor chips is being promoted. In the manufacture of a semiconductor device in which multiple semiconductor chips are stacked, first, on the electrode surfaces of two elements or circuit boards (hereinafter simply referred to as elements) formed with electrodes, a bonding surface formed of a copper bonding electrode surrounded by an insulating film is formed by a damascene method. Then, the two elements are overlapped so that the bonding electrodes of the bonding surfaces face each other, and heat treatment is performed, thereby manufacturing a semiconductor device (Patent Document 1).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2006-191081 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] In the manufacture of the above semiconductor device, high-temperature treatment such as 400°C for 4 hours is performed during the bonding of the electrodes. Therefore, high heat resistance is required for the insulating layer used to form the above bonding surface. Therefore, in conventional semiconductor devices, insulating inorganic materials such as Si3N4 and SiO2 are used as the insulating layer. However, an insulating layer formed of an inorganic material easily causes warping on the substrate. If warping occurs on the substrate, the connection position of the electrodes shifts or the electrodes are broken during lamination, so that the connection reliability of the semiconductor device sometimes becomes low. In addition, in recent years, with the high performance of semiconductor devices, the substrates have become larger and thinner, so it has become easier to cause warping of the substrates. Especially when the substrate is thin, the substrate sometimes breaks.

[0008] In order to suppress warping and cracking of the substrate caused by high-temperature treatment, an organic compound having flexibility compared with an inorganic material is considered to be used as an organic layer for the insulating layer. However, an insulating layer containing an organic compound is not heat-resistant and sometimes easily causes cracking of the insulating layer due to outgassing generated by thermal decomposition. In response to this, the use of a heat-resistant resin for the insulating layer has also been studied. However, the resin easily permeates moisture, so it is not resistant to a high-humidity environment. If moisture infiltrates the electrodes in a high-humidity environment, the reliability of the semiconductor device sometimes also decreases.

[0009] As a method for eliminating such a problem of moisture resistance, an inorganic layer formed of a thin inorganic material is laminated on the organic layer. Since the inorganic material has high moisture resistance, covering the organic layer with the inorganic layer can improve the moisture resistance. In addition, by thinning the inorganic layer, the effect of the organic layer in suppressing warping and cracking of the substrate caused by high-temperature treatment is not hindered.

[0010] However, if an inorganic layer is formed on the organic layer, cracks sometimes occur in the inorganic layer during high-temperature treatment, and the reliability of the semiconductor device is reduced.

[0011] An object of the present invention is to provide a laminate, a method for manufacturing the laminate, a method for manufacturing an element using the laminate, an imaging device having the laminate, a method for manufacturing the imaging device, a semiconductor device having the laminate, and a method for manufacturing the semiconductor device, the laminate being less likely to cause warping and cracking of elements when laminated to form a semiconductor device, having high moisture resistance, and being able to impart excellent connection reliability.

[0012] Means for Solving the Problem

[0013] The present invention includes the following disclosures 1 to 19. Hereinafter, the present invention will be described in detail.

[0014] [Disclosure 1]

[0015] A laminate in which an organic layer is laminated on a first element and an inorganic layer is laminated on the organic layer.

[0016] The organic layer has a 1% thermal weight loss temperature of 400°C or higher as measured under the condition of a heating rate of 10°C / min in a nitrogen atmosphere.

[0017] The thickness of the inorganic layer is 1 nm or more and 1 μm or less.

[0018] The inorganic layer includes a Si3N4 layer.

[0019] The inorganic layer has internal stress in the compression direction.

[0020] [Disclosure 2]

[0021] The laminate according to Disclosure 1, wherein the inorganic layer includes a SiO2 layer, and the Si3N4 layer is laminated on the SiO2 layer.

[0022] [Disclosure 3]

[0023] The laminate according to Disclosure 1 or 2, wherein the organic layer is a cured product of a curable resin composition.

[0024] [Disclosure 4]

[0025] The laminate according to Disclosure 3, wherein the organic layer is a cured product of a curable resin composition containing an organosilicon compound.

[0026] [Disclosure 5]

[0027] The laminate according to Disclosure 4, wherein the organosilicon compound has a structure represented by the following general formula (1).

[0028] [Chemical formula 1]

[0029]

[0030] Here, R 0 , R 1 and R 2 each independently represent a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The aliphatic group and the aromatic group may or may not have a substituent. m and n each represent an integer of 1 or more.

[0031] [Disclosure 6]

[0032] The laminate according to Disclosure 5, wherein in the IR spectrum obtained by measuring from the surface of the inorganic layer using FT-IR, when the peak height (Si-O) at 775 cm -1 is set as P775 and the peak height (Si-H) at 2180 cm -1 is set as P2180, P2180 / P775 < 0.045.

[0033] [Disclosure 7]

[0034] The laminate according to Disclosure 5 or 6, wherein in the IR spectrum obtained by measuring from the surface of the inorganic layer using FT-IR, when the peak height (Si-O) at 775 cm -1 is set as P775 and the peak height (N-H) at 1200 cm -1 is set as P1200, P1200 / P775 < 0.300.

[0035] [Disclosure 8]

[0036] The laminate according to any one of Disclosures 1 to 7, wherein the thickness of the organic layer is 10 μm or more.

[0037] [Disclosure 9]

[0038] The laminate according to any one of Disclosures 1 to 8, wherein the first element has a first surface and a second surface, and the first surface has a plurality of chips,

[0039] and the organic layer and the inorganic layer are laminated on the first surface side.

[0040] [Publication 10]

[0041] The laminate according to any one of Publications 1 to 9, wherein a support substrate is further laminated on the inorganic layer.

[0042] [Publication 11]

[0043] An imaging device having the laminate according to any one of Publications 1 to 10.

[0044] [Publication 12]

[0045] A semiconductor device having the laminate according to any one of Publications 1 to 10.

[0046] [Publication 13]

[0047] A method for manufacturing a laminate, which is a method for manufacturing the laminate according to any one of Publications 1 to 10, and includes: a step of forming the organic layer by forming a curable resin composition on the first element; and a step of forming the inorganic layer having internal stress in the compression direction on the organic layer by chemical vapor deposition.

[0048] [Publication 14]

[0049] According to the method for manufacturing a laminate described in Publication 13, wherein the first element has a first surface and a second surface, the first surface has a plurality of chips, and in the step of forming the organic layer, the organic layer is formed on the first surface side.

[0050] [Publication 15]

[0051] According to the method for manufacturing a laminate described in Publication 13 or 14, the method includes a step of further bonding a support substrate on the inorganic layer.

[0052] [Publication 16]

[0053] A method for manufacturing an imaging device, which includes a step of manufacturing an imaging device using the laminate obtained by the manufacturing method according to any one of Publications 13 to 15.

[0054] [Publication 17]

[0055] A method for manufacturing an element, which includes:

[0056] a step of forming an organic layer by forming a curable resin composition on the surface of a substrate having an electrode and having the electrode;

[0057] a step of forming an inorganic layer having internal stress in the compression direction on the organic layer by chemical vapor deposition;

[0058] forming through holes in the organic layer and the inorganic layer;

[0059] A step of filling the through hole with a conductive material; and

[0060] A step of polishing the surface of the substrate having the electrode on the side filled with the conductive material to form a bonding electrode.

[0061] [Revelation 18]

[0062] A method for manufacturing an imaging device, comprising: a step of manufacturing the imaging device using a device obtained by the method for manufacturing a device described in Publication 17.

[0063] [Public 19]

[0064] A method for manufacturing a semiconductor device, comprising: bonding two elements obtained by the element manufacturing method described in Publication 17 so that the bonding electrodes are bonded to each other.

[0065] The laminate of the present invention is a laminate in which an organic layer is laminated on a first element, and an inorganic layer is laminated on the organic layer.

[0066] The above-mentioned organic layer and inorganic layer play the role of insulating layer between each element and substrate in a semiconductor device stacked with multiple elements and substrates. In the past, the insulating layer used hard inorganic materials to withstand high temperature treatment during manufacturing, so it is impossible to relax stress when the element is deformed, and the element is prone to warping and cracking. In the laminated body of the present invention, by using an organic compound with flexibility that can relax stress as an insulating layer, the element is not easy to warp and crack, and as a result, the offset and cracking of the electrode caused by the warping and cracking of the element can be suppressed, and the connection reliability between the elements is improved. In addition, by arranging an inorganic layer as an auxiliary insulating layer on the organic layer, the moisture in the atmosphere is more difficult to penetrate compared with a single organic layer, so that high connection reliability can be exerted even under high temperature and high humidity. It should be noted that the organic compound constituting the organic layer here also includes organic-inorganic mixed compounds such as organosilicon compounds.

[0067] The first element is not particularly limited, and a circuit substrate having elements and wiring formed thereon may be used. For example, a sensor circuit substrate having a pixel portion (pixel region), a circuit substrate having a peripheral circuit portion such as a logic circuit that performs various signal processing related to the operation of a solid-state imaging device, a circuit substrate having a peripheral circuit such as a storage circuit, etc. may be used.

[0068] The organic layer is preferably a cured product of a curable resin composition.

[0069] By using a curable resin composition as the material for the organic layer, the organic layer can be formed by coating the curable resin composition and curing it after film formation. Therefore, compared with the conventional case of using inorganic materials, the production efficiency can be improved. The curable resin constituting the curable resin composition can be thermosetting or photocurable. From the viewpoint of heat resistance, a thermosetting resin is preferred.

[0070] The organic compound constituting the organic layer is not particularly limited as long as it has heat resistance capable of withstanding high-temperature treatment at about 400 °C for 4 hours. For example, silicone compounds, polyimides, etc. can be cited. Among them, from the aspects of having excellent heat resistance and flexibility, further suppressing warping and cracking of the element and improving connection reliability, the organic layer is preferably a cured product of a curable resin composition containing a silicone compound.

[0071] The silicone compound is preferably a silsesquioxane.

[0072] Silsesquioxane has flexibility comparable to that of organic compounds and high heat resistance. Therefore, by using an organic layer mainly composed of silsesquioxane as the insulating layer of the laminate, warping and cracking of the substrate can be suppressed, and electrical connection reliability can be improved. The silsesquioxane is not particularly limited as long as it is thermosetting. From the aspect of further suppressing warping and cracking of the substrate, it preferably has structures represented by the following structural formulas (A) and (B) in one molecule.

[0073] [Chemical formula 2]

[0074]

[0075] In the structural formulas (A) and (B), R A , R B each independently represents an aliphatic group, an aromatic group, or hydrogen. j and k are repeating units, each representing an integer of 1 or more.

[0076] The silicone compound is preferably provided with a reactive site.

[0077] By using a silicone compound having a reactive site as the curable resin of the curable resin composition, warping and cracking of the element can be further suppressed. In addition, since the silicone compound has excellent heat resistance, decomposition of the organic layer caused by high-temperature treatment during the manufacture of a semiconductor device in which a plurality of laminates are stacked can be further suppressed. Examples of the reactive site include a hydroxyl group, an alkoxy group, etc.

[0078] In 100 parts by weight of the resin solid content in the above curable resin composition, the content of the above organosilicon compound having a reactive site is preferably 80 parts by weight or more, more preferably 90 parts by weight or more, and still more preferably 95 parts by weight or more. In 100 parts by weight of the resin solid content in the above curable resin composition, the content of the above organosilicon compound having a reactive site is preferably less than 100 parts by weight, and more preferably 98 parts by weight or less.

[0079] The above organosilicon compound preferably has a structure represented by the following general formula (1).

[0080] By making the organosilicon compound have the structure of the general formula (1), warpage of the element can be further suppressed. Among them, from the aspect of further improving heat resistance and further suppressing warpage and cracking of the element, the above organosilicon compound more preferably further has an aromatic ring structure.

[0081] [Chemical formula 3]

[0082]

[0083] Here, R 0 、R 1 and R 2 each independently represent a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above aliphatic group and the above aromatic group may or may not have a substituent. m and n each represent an integer of 1 or more.

[0084] In the above general formula (1), R 0 each independently represent a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above aliphatic group and the above aromatic group may or may not have a substituent. The above R 0 is preferably phenyl, an alkyl group having 1 to 20 carbon atoms or an arylalkyl group, and more preferably phenyl. By making R 0 be phenyl, an alkyl group having 1 to 20 carbon atoms or an arylalkyl group, higher heat resistance can be exhibited.

[0085] In the above general formula (1), R 1 and R 2 each independently represent a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above aliphatic group and the above aromatic group may or may not have a substituent. The above R 1 and R 2 are preferably phenyl, an alkyl group having 1 to 20 carbon atoms or an arylalkyl group, and more preferably phenyl or methyl. By making R 1 and R 2is phenyl, an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and can exhibit higher heat resistance.

[0086] In the above general formula (1), m and n are each an integer of 1 or more, representing the number of repeating units. The above m is preferably 30 or more, more preferably 50 or more, and preferably 100 or less. The above n is preferably 1 or more, more preferably 3 or more, further preferably 4 or more, preferably 8 or less, and more preferably 6 or less.

[0087] In 100% by weight of the solid content of the above curable resin composition, the content of the above silicone compound is preferably 65% by weight or more and 99% by weight or less.

[0088] By making the content of the silicone compound in the solid content of the curable resin composition within the above range, warping and cracking of the element can be suppressed, and the connection reliability between elements can be further improved. The content of the silicone compound in 100% by weight of the solid content of the above curable resin composition is more preferably 70% by weight or more, further preferably 75% by weight or more, more preferably 98% by weight or less, and further preferably 97% by weight or less.

[0089] The weight average molecular weight of the above silicone compound is not particularly limited, and is preferably 5000 or more and 150000 or less. By making the weight average molecular weight of the silicone compound within the above range, the film-forming property during coating is improved, the planarization performance is further improved, and warping and cracking of the element can be further suppressed. The weight average molecular weight of the above silicone compound is more preferably 10000 or more, further preferably 30000 or more, more preferably 100000 or less, and further preferably 70000 or less.

[0090] It should be noted that the weight average molecular weight of the above silicone compound is measured by gel permeation chromatography (GPC) in the form of polystyrene-equivalent molecular weight. The elution solvent can be set as THF, and Time-MB-M6.0×150mm (manufactured by Waters Corporation) or its equivalent can be used as the column, and it is calculated by polystyrene standard.

[0091] The above curable resin composition preferably contains a catalyst.

[0092] The above catalyst has the function of promoting the curing reaction. By making the curable resin composition have a catalyst, the curable resin composition can be cured more completely, and the decomposition of the organic layer caused by high-temperature treatment can be further suppressed.

[0093] As the above-mentioned catalyst, for example, organic tin compounds such as dibutyltin dilaurate and stannous acetate, metal carboxylates such as zinc naphthenate, acetylacetone complexes with zirconium as the central metal (Japanese original: アセチルアセトネート錯體), titanium compounds, etc. can be cited. Among them, from the aspect of being able to further promote the curing of the curable resin composition, acetylacetone complexes with zirconium as the central metal are preferred. It should be noted that the above-mentioned catalyst also exists after the curable resin composition is cured. That is, when the above-mentioned curable resin composition contains a catalyst, the obtained organic layer also contains a catalyst.

[0094] The content of the above-mentioned catalyst is not particularly limited, and is preferably 0.01 parts by weight or more and 10 parts by weight or less relative to 100 parts by weight of the curable resin in the above-mentioned curable resin composition. By setting the content of the catalyst to the above-mentioned range, the curing of the curable resin composition can be further promoted, and the decomposition of the resin cured product caused by high temperature treatment can be further suppressed. The content of the above-mentioned catalyst is more preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight or more, more preferably 7 parts by weight or less, and more preferably 5 parts by weight or less.

[0095] The curable resin composition preferably contains a cross-linking agent.

[0096] By making the curable resin composition contain a crosslinking agent, the crosslinking agent is crosslinked between the curable resins, and the crosslinking density of the cured product rises, further suppressing the decomposition in high temperature. As a result, the warping and cracking of the element can be suppressed and the connection reliability can be further improved. As the above-mentioned crosslinking agent, for example, alkoxysilane compounds such as dimethoxysilane compounds, trimethoxysilane compounds, diethoxysilane compounds, triethoxysilane compounds, or silicate oligomers obtained by condensation of tetramethoxysilane compounds and tetraethoxysilane compounds, etc. can be cited. Among them, from the viewpoint of improving the crosslinking density and improving the heat resistance, polyalkoxysilane is preferred.

[0097] The content of the crosslinking agent is not particularly limited, but is preferably 1 part by weight or more and 50 parts by weight or less relative to 100 parts by weight of the curable resin in the curable resin composition. By making the content of the crosslinking agent within the above range, the crosslinking density of the cured resin can be within a suitable range. The content of the crosslinking agent is more preferably 3 parts by weight or more, more preferably 3.2 parts by weight or more, more preferably 30 parts by weight or less, and more preferably 20 parts by weight or less.

[0098] The curable resin composition preferably contains a heat-resistant resin.

[0099] By using a heat-resistant resin in the curable resin composition, a cured film that is less likely to develop film cracking during high-temperature treatment can be produced even when an organic layer with a thickness is formed.

[0100] Examples of the above heat-resistant resins include polyimide, epoxy resin, silicone resin, benzoxazine resin, cyanate resin, phenolic resin, etc. Particularly from the viewpoint of heat resistance, polyimide is preferred.

[0101] The weight-average molecular weight of the above heat-resistant resin is not particularly limited, and is preferably 5000 or more and 150000 or less. By setting the weight-average molecular weight of the heat-resistant resin within the above range, a cured film that is less likely to develop film cracking during even higher-temperature treatment can be produced even when an organic layer with a thickness is formed. The molecular weight of the above heat-resistant resin is more preferably 10000 or more, further preferably 30000 or more, more preferably 100000 or less, and further preferably 70000 or less.

[0102] With respect to 100 parts by weight of the above silicone compound, the content of the above heat-resistant resin is preferably 0.5 part by weight or more and 50 parts by weight or less.

[0103] By setting the content of the heat-resistant resin within the above range, an organic layer that is less likely to develop film cracking during high-temperature treatment can be produced even when an organic layer with a thickness is formed.

[0104] With respect to 100 parts by weight of the silicone compound, the content of the above heat-resistant resin is more preferably 0.7 part by weight or more, further preferably 0.75 part by weight or more, particularly preferably 1 part by weight or more, more preferably 20 parts by weight or less, further preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less.

[0105] When the above heat-resistant resin is polyimide, the above polyimide preferably has a siloxane bond.

[0106] By making the above polyimide have a siloxane bond, when the curable resin composition contains a silicone compound, the compatibility with the silicone compound is improved, and thus, unevenness (surface roughness) caused by precipitation of polyimide during coating can be further suppressed.

[0107] When the above polyimide has a siloxane bond, the ratio of carbon atoms to silicon atoms C / Si in the main chain structure of the above polyimide is preferably 17 or less.

[0108] By making the ratio of carbon atoms to silicon atoms in the main chain structure of the polyimide fall within the above range, when the curable resin composition contains an organosilicon compound, the compatibility with the organosilicon compound is further improved, and thus surface roughness can be further suppressed during coating. The above C / Si is more preferably 16.5 or less, and even more preferably 16 or less. The lower limit of the above C / Si is not particularly limited, and from the viewpoints of practicality and further improving the heat resistance at 400 °C, it is preferably 4 or more. It should be noted that the ratio of carbon atoms to silicon atoms C / Si in the main chain structure of the above polyimide is the ratio of C and Si within the repeating unit, excluding C and Si at both ends. In addition, the above C / Si can be obtained by the following method: obtaining the structure of the above polyimide using 1H-NMR, 13C-NMR, and 29Si-NMR, and measuring the number of C atoms and Si atoms from the repeating unit of the main chain.

[0109] The above polyimide preferably has a plurality of aromatic rings.

[0110] By making the above polyimide have a plurality of aromatic rings, even when an organic layer with a thickness is formed, an organic layer that is not easily prone to film cracking during high-temperature treatment under various conditions can be formed.

[0111] The above polyimide preferably has an oxazine ring or an imide ring structure at at least one end, and more preferably has an oxazine ring or an imide ring structure at both ends.

[0112] By making the above polyimide have an oxazine ring or an imide ring structure at the end, surface roughness during the formation of a thick film can be further suppressed. It should be noted that the above oxazine ring and imide ring structures may have substituents.

[0113] Among them, it is further preferred that the above polyimide has any one of the following formulas (2) to (7) at at least one end, and particularly preferably has any one of the following formulas (2) to (7) at both ends. It should be noted that " " in the following formula represents the bonding site with the part other than the end of the above polyimide.

[0114] [Chemical formula 4]

[0115]

[0116] The weight average molecular weight of the above polyimide is preferably 1000 or more and 50000 or less.

[0117] By making the weight-average molecular weight of the above polyimide within the above range, when the curable resin composition contains a silicone compound, the compatibility with the silicone compound is improved, and the processability can be further improved. The weight-average molecular weight is more preferably 2,000 or more, further preferably 3,000 or more, more preferably 35,000 or less, and further preferably 30,000 or less.

[0118] It should be noted that the weight-average molecular weight of the above polyimide is measured in the form of polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). The elution solvent can be set as THF. As the column, use Time-MB-M6.0×150 mm (manufactured by Waters Corporation) or its equivalent, and calculate through polystyrene standards.

[0119] Relative to 100 parts by weight of the above silicone compound, the content of the above polyimide is preferably 0.5 parts by weight or more and 50 parts by weight or less.

[0120] By making the content of the polyimide within the above range, even when an organic layer with a thickness is formed, an organic layer that is less likely to cause film rupture during high-temperature treatment can be formed.

[0121] Relative to 100 parts by weight of the silicone compound, the content of the above polyimide is preferably 0.7 parts by weight or more, more preferably 0.75 parts by weight or more, further preferably 1 part by weight or more, preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight or less.

[0122] The above curable resin composition may contain other additives such as solvents, viscosity regulators, fillers, and adhesion promoters as needed.

[0123] The thickness of the above organic layer is preferably 10 μm or more.

[0124] By making the thickness of the organic layer within the above range, the function as an insulating layer can be exerted, and the warping and cracking of the element can be suppressed to improve the connection reliability. In addition, in a conventional laminate in which an inorganic layer is formed on an organic layer, cracks in the inorganic layer are particularly likely to occur when the organic layer is a thick film. However, in the laminate of the present invention, cracks in the inorganic layer are less likely to occur even when the organic layer is a thick film, and high moisture resistance can be exhibited. The thickness of the above organic layer is preferably 20 μm or more, more preferably 30 μm or more, preferably 200 μm or less, and more preferably 100 μm or less.

[0125] As long as the effects of the present invention are not significantly impaired, the above organic layer may contain components other than the organic compound that is the main component of the above organic layer. In this case, the content of the organic compound that is the main component in the above organic layer is preferably 90% by weight or more, more preferably 95% by weight or more, still more preferably 99% by weight or more, and generally less than 100% by weight.

[0126] The 1% thermal weight loss temperature of the above organic layer measured under the condition of a heating rate of 10 °C / min in a nitrogen atmosphere is 400 °C or higher.

[0127] By making the 1% thermal weight loss temperature of the organic layer 400 °C or higher, the decomposition of the organic layer can be suppressed even when high-temperature treatment is performed, and the generation of bubbles and cracks at the interface and the peeling at the interface can be further suppressed. In addition, the deterioration of the quality of the CVD film and the contamination of the CVD film-forming apparatus caused by the generated gas from the organic layer can be suppressed. The above 1% thermal weight loss temperature is preferably 420 °C or higher, more preferably 440 °C or higher, still more preferably 460 °C or higher. The upper limit of the above 1% thermal weight loss temperature is not particularly limited, and the higher the better, for example, it is 500 °C. The 1% thermal weight loss temperature of the above organic layer can be adjusted by the type of the organic compound that is the main component of the organic layer and the added substances incorporated, for example, the type and amount of the catalyst for promoting curing, the type and amount of the additive for suppressing thermal decomposition, etc. It should be noted that the above 1% thermal weight loss temperature can be obtained by measuring with a differential thermal-thermogravimetry simultaneous measurement device (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation or equivalent) under a nitrogen gas flow of 50 mL / min at a heating rate of 10 °C / min.

[0128] The above inorganic layer contains a Si3N4 layer.

[0129] By using Si3N4 as the inorganic layer, the moisture resistance is improved, and the intrusion of moisture into the organic layer and the electrode can be suppressed, so the connection reliability can be improved. In a conventional semiconductor device obtained by laminating a plurality of substrates having electrodes, since only an inorganic layer is used as the insulating layer, the warpage of the element cannot be eliminated, which causes element breakage and a reduction in connection reliability. In the laminate of the present invention, most of the insulating layer is an organic layer, and the inorganic layer is set to the minimum thickness, so the warpage of the element can be eliminated and the moisture resistance can be improved. The thickness of the above Si3N4 layer is preferably 50 nm or more, more preferably 100 nm or more, preferably 500 nm or less, and more preferably 300 nm or less.

[0130] It should be noted that in this specification, the Si3N4 layer refers to a layer with a stoichiometric ratio of N / Si = about 1 to 2 (the theoretical value is N / Si = 1.33). Hereinafter, it may also be referred to as the SiN layer or the SiN film.

[0131] Preferably, the inorganic layer includes a SiO2 layer, and the Si3N4 layer is laminated on the SiO2 layer.

[0132] By further providing a SiO2 layer in the inorganic layer and laminating the Si3N4 layer on the SiO2 layer, that is, laminating in the order of the organic layer, the SiO2 layer, and the Si3N4 layer, the moisture resistance can be further improved. The thickness of the SiO2 layer is preferably 50 nm or more, more preferably 100 nm or more, preferably 500 nm or less, and more preferably 300 nm or less.

[0133] The thickness of the inorganic layer is 1 nm or more and 1 μm or less.

[0134] By making the thickness of the inorganic layer within the above range, the moisture resistance can be improved while maintaining the effect of suppressing the element warping of the organic layer. From the viewpoint of the stability of the inorganic film quality, the thickness of the inorganic layer is preferably 50 nm or more, more preferably 100 nm or more, preferably 700 nm or less, and more preferably 400 nm or less.

[0135] The inorganic layer has internal stress in the compression direction.

[0136] In the past, studies have been conducted on imparting flexibility and moisture resistance to an insulating layer by forming a thin inorganic layer on an organic layer. However, if the inorganic layer is simply disposed on the organic layer, cracks are generated in the inorganic layer, and sometimes the improvement in moisture resistance becomes insufficient. In the present invention, by forming the inorganic layer in a manner that generates internal stress in the compression direction, the difference in internal stress between the inorganic layer and the organic layer can be reduced, and sufficient moisture resistance can be imparted by suppressing the generation of cracks in the inorganic layer. In addition, the present invention has a high effect of suppressing cracks in the inorganic layer, and therefore exerts a greater effect particularly when using a thick inorganic layer that is prone to cracking. The inorganic layer having internal stress in the compression direction can be formed, for example, by a chemical vapor deposition (CVD) method and obtained by adjusting the formation conditions at this time. More specifically, in the CVD method, the following plasma CVD method can be used and the film forming temperature of the plasma, the pressure in the chamber, the applied power (Japanese original: Inka Electricity), the switching frequency of the RF frequency and other conditions can be adjusted. The plasma CVD method can form a film at a relatively low temperature, can reduce the damage to the organic layer caused by heat in the CVD process, and can form an inorganic layer on the organic layer. It should be noted that although an inorganic layer having internal stress in a compressive direction can be obtained by intentionally adjusting the above conditions, it is not easy to form, especially when there is no intention to have internal stress in a compressive direction.

[0137] Here, the internal stress with a compressive direction refers to: the inorganic layer formed on the element has a stress that wants to stretch in a direction parallel to the plane direction of the element (a direction perpendicular to the thickness direction) and in a direction from the center toward the outside at room temperature and without external force. On the contrary, when there is a stress that wants to shrink from the outside toward the center in a direction parallel to the plane direction of the element at room temperature and without external force, it is regarded as an internal stress with a tensile direction. In addition, when the above-mentioned inorganic layer is formed by multiple layers, the internal stress with a compressive direction refers to the internal stress of each layer having a compressive direction. The above-mentioned internal stress can be measured by the following method.

[0138] The warpage and radius of curvature of the untreated silicon wafer are calculated using a thin film stress measuring device (FLX2320-S, manufactured by Toho Technology or its equivalent). The radius of curvature R at this time is set to R1. Next, a 100nm inorganic film is formed on the silicon wafer with the calculated radius of curvature using PE-CVD (MPX-CVD, manufactured by Sumitomo Precision Industries, Ltd. or its equivalent). After the inorganic film is formed, the warpage and radius of curvature after the inorganic film is formed are calculated again using the thin film stress measuring device. The radius of curvature R at this time is set to R2. Based on the change in the radius of curvature before and after the inorganic film is formed, the internal stress S (Pa) of the inorganic film is calculated according to the Stoney formula shown in the following mathematical formula (A).

[0139] [Mathematical formula 1]

[0140]

[0141] It should be noted that the details of the above mathematical formula (A) are as follows.

[0142] E / (1 - v): Biaxial elastic modulus of the silicon wafer (Pa), set to 1.805×10 11 Pa.

[0143] h: Thickness of the silicon wafer (m), set to 725 μm.

[0144] t: Thickness of the inorganic film (m), set to 100 nm.

[0145] R: Radius of curvature of the substrate, obtained according to the following mathematical formula (B).

[0146] [Mathematical formula 2]

[0147]

[0148] In the above mathematical formula (A), when the internal stress S is negative, it represents an internal stress with a compressive direction, and when the internal stress S is positive, it represents an internal stress with a tensile direction. Therefore, the internal stress S of the inorganic layer of the present invention is less than 0 MPa. Considering the temperature dependence of the internal stress changing in the positive direction at high temperatures and from the perspective of preventing cracks, the above internal stress is preferably -50 MPa or less, more preferably -100 MPa or less, and further preferably -150 MPa or less. In addition, from the perspective of suppressing wrinkles caused by internal stress and improving the appearance, the above internal stress is preferably -400 Ma or more, more preferably -350 MPa or more, and further preferably -300 MPa or more.

[0149] As an example of the specific conditions of the CVD method for imparting an internal stress in the compressive direction to the above inorganic layer, for example, the plasma film formation temperature is preferably 250 °C or higher, more preferably 300 °C or higher, further preferably 350 °C or higher, preferably 500 °C or lower, more preferably 450 °C or lower, and further preferably 400 °C or lower.

[0150] Since the higher the pressure in the above chamber, the easier it is to have an internal stress in the tensile direction, the chamber pressure is preferably 50 Pa or higher, more preferably 100 Pa or higher, further preferably 130 Pa or higher, preferably 200 Pa or lower, more preferably 160 Pa or lower, and further preferably 150 Pa or lower.

[0151] The applied power and RF frequency described above are parameters for generating a plasma, which serves as a trigger for activating chemical species and causing them to react and grow on the organic film. The above RF frequency is usually mostly used alone as 13.56 MHz (HF), which is a high frequency, but sometimes it is also used in combination with 380 kHz (LF), which is a low frequency.

[0152] In the case of imparting internal stress in the compression direction to the above inorganic layer, it is preferable to apply a voltage with the above RF frequency being the low frequency, i.e., 380 kHz, alone. Additionally, in the case of using 380 kHz and 13.56 MHz in combination, regarding the application time T1 of 13.56 MHz, the relationship of the application time T2 of 380 kHz is preferably T2 > T1, more preferably T2 > 3×T1, further preferably T2 > 6×T1, preferably T2 < 20×T1, more preferably T2 < 15×T1, and further preferably T2 < 12×T1.

[0153] Regarding the above applied power, for 13.56 MHz (HF) and 380 kHz (LF), it is respectively preferably 20 W or more, more preferably 30 W or more, further preferably 50 W or more, preferably 200 W or less, more preferably 100 W or less, and further preferably 60 W or less. Additionally, HF and LF can be the same or different.

[0154] The above first element has a first surface and a second surface. The first surface may have a plurality of chips, and the above organic layer and the above inorganic layer may be laminated on the first surface side.

[0155] When a plurality of chips are arranged on the above first element and the conventional organic layer and inorganic layer are laminated on the surface of the first element where the chips are arranged, since unevenness is formed due to the chips, when connecting with other laminates and substrates by means of the organic layer and the inorganic layer, the connection surface of the organic layer is uneven, and the connection reliability is likely to decrease. In the laminate of the present invention, even for such an element with large unevenness, since the organic layer fills the unevenness and the connection surface becomes flat, high connection reliability can be exhibited, and warping and cracking of the above first element and the chips can be suppressed.

[0156] As the above chips, for example, memory circuit elements, logic circuit elements, etc. can be cited. Additionally, the number of the above chips is not particularly limited as long as it is 2 or more.

[0157] The laminate of the present invention may further laminate a support substrate on the above inorganic layer.

[0158] By laminating a support substrate on the inorganic layer, the fixing of electronic components including the laminate of the present invention, such as imaging devices, semiconductor devices, etc., to the housing becomes easy.

[0159] Examples of the support substrate include glass and single crystal silicon.

[0160] When the above organic layer is a cured product of a curable resin composition containing the above silsesquioxane or a silicone compound having the structure represented by the above general formula (1), for the laminate of the present invention, in the IR spectrum measured from the surface of the above inorganic layer using FT-IR, when the peak height (Si-O) at 775 cm -1 is set as P775 and the peak height (Si-H) at 2180 cm -1 is set as P2180, it is preferably P2180 / P775 < 0.045.

[0161] The peak at 775 cm -1 indicates the presence of a silicon-oxygen bond, and the peak at 2180 cm -1 indicates the presence of a silicon-hydrogen bond.

[0162] The silicon-hydrogen bond has the property of easily allowing moisture to pass through. Therefore, if the silicon-hydrogen bond is contained in a large amount, it becomes the main cause of the reduction in moisture resistance. Therefore, by making P2180 / P775 in the above range, that is, reducing the amount of the silicon-hydrogen bond compared with the silicon-oxygen bond, the moisture resistance of the inorganic layer and the laminate can be further improved. The above P2180 / P775 is more preferably less than 0.04, and further preferably less than 0.03. The lower limit of the above P2180 / P775 is not particularly limited, and the smaller the better, usually greater than 0. The above P2180 / P775 can be adjusted by the film formation conditions of the inorganic layer.

[0163] It should be noted that the reason for detecting the peak of the Si-O bond is that when measuring the IR spectrum using FT-IR, the infrared light penetrates to a depth of 2-3 μm near the surface, thereby detecting the Si-O of the underlying organic layer. On the other hand, the reason for detecting the peak of the Si-H bond is that in the reaction of forming a SiN film or SiO2 film by CVD method, it does not completely become Si3N4 or SiO2, and the Si-H bond from the raw material SiH remains.

[0164] When the above organic layer is a cured product of a curable resin composition containing the above silsesquioxane or a silicone compound having the structure represented by the above general formula (1), for the laminate of the present invention, in the IR spectrum measured from the surface of the above inorganic layer using FT-IR, when the peak height (Si-O) at 775 cm -1 is set as P775 and the peak height (N-H) at 1200 cm -1 is set as P1200, it is preferably P1200 / P775 < 0.30.

[0165] 775 cm-1 The peak at 1200 cm -1 indicates the presence of Si-O bonds, and the peak at 1200 cm

[0166] The N-H bond has the property of allowing moisture to pass through easily. Additionally, it becomes an impurity in the SiN film. Therefore, if the N-H bond is contained in a large amount, the moisture resistance decreases, which becomes the main cause of performance changes at high temperatures. Thus, by making P1200 / P775 within the above range, that is, reducing the amount of N-H bonds compared to Si-O bonds, the moisture resistance of the inorganic layer and the laminate can be further improved. The above P1200 / P775 is more preferably less than 0.28, and even more preferably less than 0.25. The lower limit of the above P1200 / P775 is not particularly limited, and the smaller the better, usually greater than 0. The above P1200 / P775 can be adjusted by the film formation conditions of the inorganic layer.

[0167] It should be noted that the reason for detecting the peak of the Si-O bond is that when measuring the IR spectrum using FT-IR, the infrared light penetrates to a depth of 2 - 3 μm near the surface, thereby detecting the Si-O of the underlying organic layer. On the other hand, the reason for detecting the peak of the N-H bond is that in the reaction of forming the SiN film by CVD method, it does not completely become Si3N4, and the N-H bond from the raw material NH3 or the raw material gas remains.

[0168] Specifically, the above P2180 / P775 and P1200 / P775 can be measured by the following method.

[0169] Measure the absorption spectrum of the element after forming the inorganic layer by the total reflection (ATR) method of Fourier transform infrared spectroscopy (FT-IR). At this time, the measurement range is set to 525 cm -1 to 4000 cm -1 , and the resolution is set to 4 cm -1 for measurement. In the obtained absorption spectrum, set the peak height (Si-O) at 775 cm -1 as P775, set the peak height (Si-H) at 2180 cm -1 as P2180, set the peak height (N-H) at 1200 cm -1 as P1200, and divide P2180 or P1200 by P775 to obtain P2180 / P775 and P1200 / P775.

[0170] Here, a schematic diagram showing an example of the laminate of the present invention is shown in Figure 1 . As shown in Figure 1As shown, the laminate of the present invention has a structure in which an organic layer 2 and an inorganic layer 3 are laminated on a first element 1, and the organic layer 2 and the inorganic layer 3 function as insulating layers when a plurality of laminates are laminated. When manufacturing a semiconductor device by laminating a plurality of conventional laminates using an organic compound for the insulating layer, although the effect of suppressing warping of the element caused by heat treatment is high, moisture in the atmosphere is easily permeated. In the laminate of the present invention, by laminating a thin inorganic layer 3 containing Si3N4 on the organic layer 2, permeation of moisture can be suppressed. Further, in the laminate of the present invention, since the inorganic layer 3 has internal stress in the compression direction, the difference in internal stress between the organic layer 2 and the inorganic layer 3 becomes small, and generation of cracks in the inorganic layer can be suppressed. As a result, moisture is less likely to permeate, and thus high connection reliability can be exhibited. It should be noted that since the thickness of the inorganic layer 3 in the laminate of the present invention is thin, it does not hinder the elimination of warping of the element in the organic layer 2. In addition, in Figure 1 the organic layer 2 and the inorganic layer 3 are single layers, but they may also be composed of a plurality of layers.

[0171] In addition, a schematic diagram showing another example of the laminate of the present invention is shown in Figure 2 , 3 . As Figure 2 shown, the laminate of the present invention may be a laminate having a plurality of chips 4 on one surface (first surface) of the first element 1 and having the organic layer 2 and the inorganic layer 3 laminated on the first surface of the first element. In addition, as Figure 3 shown, a support substrate 5 may also be laminated on the inorganic layer 3.

[0172] The manufacturing method of the laminate of the present invention is also one of the present inventions, and the manufacturing method includes: a step of forming the above-mentioned organic layer by forming a curable resin composition on the first element; and a step of forming the above-mentioned inorganic layer having internal stress in the compression direction on the above-mentioned organic layer by chemical vapor deposition.

[0173] The manufacturing method of the laminate of the present invention first performs the step of forming the above-mentioned organic layer by forming a curable resin composition on the first element.

[0174] Conventional laminates using an inorganic material for the insulating layer are manufactured by time-consuming methods such as chemical vapor deposition (CVD) and sputtering. Since the main component of the insulating layer of the laminate of the present invention is an organic compound, it can be manufactured by coating a solution and drying it, so that not only the connection reliability can be improved, but also the production efficiency can be improved. The above-mentioned first element and the curable resin composition are the same as the first element and the curable resin composition in the laminate of the present invention.

[0175] The method of the above-mentioned film formation is not particularly limited, and a conventionally known method such as a spin coating method can be used.

[0176] The solvent drying conditions are not particularly limited. From the viewpoints of reducing residual solvents and improving the heat resistance of the organic layer, it is preferable to heat at a temperature of preferably 70°C or higher, more preferably 100°C or higher, preferably 250°C or lower, and more preferably 200°C or lower for, for example, 30 minutes, and more preferably about 1 hour.

[0177] The curing conditions are not particularly limited. From the viewpoints of allowing the curing reaction to proceed sufficiently and further improving the heat resistance, it is preferable to heat at a temperature of preferably 200°C or higher, more preferably 220°C or higher, preferably 400°C or lower, and more preferably 300°C or lower for, for example, 1 hour or more, and more preferably 2 hours or more. The upper limit of the heating time is not particularly limited, and from the viewpoint of suppressing thermal decomposition of the organic layer, it is preferably 3 hours or less.

[0178] In the method for manufacturing a laminate of the present invention, preferably, the first element has a first surface and a second surface, the first surface has a plurality of chips, and in the step of forming the organic layer, the organic layer is formed on the first surface side.

[0179] After forming the organic layer through such a step, an inorganic layer described later is formed, whereby a laminate having Figure 2 such a structure can be manufactured.

[0180] In the method for manufacturing a laminate of the present invention, next, a step of forming the inorganic layer having internal stress in the compression direction on the organic layer by chemical vapor deposition is performed.

[0181] An inorganic layer is formed on the organic layer by chemical vapor deposition (CVD), and the conditions at this time are adjusted, whereby an inorganic layer having internal stress in the compression direction can be formed. The conditions of the inorganic layer and the CVD method are the same as the specific conditions of the inorganic layer and the CVD method in the laminate of the present invention.

[0182] The method for manufacturing a laminate of the present invention preferably includes a step of further bonding a support substrate on the inorganic layer.

[0183] By performing the step of bonding the support substrate, a laminate having Figure 3 such a structure can be manufactured.

[0184] The use of the laminate of the present invention is not particularly limited. When laminating, warping and cracking of components are less likely to occur, it has high moisture resistance, and can impart excellent connection reliability. Therefore, it is suitable for imaging devices and semiconductor devices. A method for manufacturing such an imaging device is also one aspect of the present invention, and the manufacturing method includes: a step of manufacturing an imaging device using an imaging device having the laminate of the present invention, a semiconductor device having the laminate of the present invention, and a laminate obtained by the method for manufacturing a laminate of the present invention.

[0185] The laminate of the present invention can also be used as a material for an element in which a plurality of laminates are laminated.

[0186] A method for manufacturing an element is also one of the present inventions. The manufacturing method includes: a step of forming an organic layer by forming a curable resin composition on a surface of a substrate having an electrode and having the above electrode; a step of forming an inorganic layer having an internal stress in a compression direction on the above organic layer by chemical vapor deposition; a step of forming a through hole in the above organic layer and the above inorganic layer; a step of filling the above through hole with a conductive material; and a step of polishing a surface of the above substrate having an electrode on a side filled with the above conductive material to form a bonding electrode.

[0187] The method for manufacturing an element of the present invention first performs a step of forming an organic layer by forming a curable resin composition on a surface of a substrate having an electrode and having the above electrode; and a step of forming an inorganic layer having an internal stress in a compression direction on the above organic layer by chemical vapor deposition.

[0188] The above step of forming an organic layer and the step of forming an inorganic layer are the same as the manufacturing method of the laminate of the present invention.

[0189] The above substrate having an electrode is not particularly limited, and a circuit substrate formed with elements, wirings, and electrodes can be used. For example, a sensor circuit substrate provided with a pixel portion (pixel region), a circuit substrate on which a peripheral circuit portion such as a logic circuit that performs various signal processes related to the operation of a solid-state imaging device is mounted, etc. can be used.

[0190] The material of the electrode of the above substrate having an electrode is not particularly limited, and conventionally known electrode materials such as gold, copper, and aluminum can be used.

[0191] The method for manufacturing an element of the present invention then performs a step of forming a through hole in the above organic layer and the above inorganic layer.

[0192] The organic layer and the inorganic layer on the electrode of the above substrate are removed to provide a through hole, and a conductive material is filled therein, thereby forming a bonding electrode for connecting to another substrate. The above through hole can be patterned. The method for forming the above through hole is not particularly limited, and it can be formed by laser irradiation such as CO2 laser, etching, etc. It should be noted that when other layers are formed on the electrode surface of the substrate, the above through hole is formed so as to also penetrate the above other layers to expose the electrode surface of the element.

[0193] The method for manufacturing an element of the present invention then performs a step of forming a barrier metal layer as needed.

[0194] The barrier metal layer has the function of preventing the conductive material filled in the through hole (for example, Cu atoms in the case of a Cu electrode) from diffusing into the organic layer. By providing the barrier metal layer on the surface of the through hole, the portions of the conductive material filling the through hole other than the surface in contact with the electrode are covered by the barrier metal layer, so that short circuits and conduction failures caused by the diffusion of the conductive material into the organic layer can be further suppressed. The above-mentioned barrier metal layer can be formed by sputtering, evaporation, or the like.

[0195] As the material of the above-mentioned barrier metal layer, known materials such as tantalum, tantalum nitride, titanium nitride, silicon oxide, and silicon nitride can be used.

[0196] The thickness of the above-mentioned barrier metal layer is not particularly limited. From the viewpoint of further improving the connection reliability of the laminate, it is more preferably 1 nm or more, further preferably 10 nm or more, more preferably 100 nm or less, and further preferably 50 nm or less.

[0197] Next, in the method for manufacturing the element of the present invention, a step of filling each of the above-mentioned through holes with a conductive material is performed. As a method for filling the above-mentioned conductive material, plating or the like can be used.

[0198] As the above-mentioned conductive material, the same material as the electrode of the substrate having the electrode in the laminate of the present invention can be used.

[0199] Next, in the method for manufacturing the element of the present invention, a step of grinding the surface of the substrate having the electrode on the side filled with the above-mentioned conductive material to form a bonding electrode is performed.

[0200] By grinding and removing the above-mentioned conductive material formed in the unnecessary portion, a bonding electrode connected to the electrodes of other elements is formed. Regarding the above-mentioned grinding, it is preferable to flatten and remove the layer formed of the conductive material until the above-mentioned inorganic layer is exposed.

[0201] The above-mentioned grinding method is not particularly limited. For example, a chemical mechanical polishing method or the like can be used.

[0202] The use of the element obtained by the method for manufacturing the element of the present invention is not particularly limited, and it is suitable for a photographing device having a semiconductor device in which elements are stacked. A method for manufacturing such a photographing device is also one of the present inventions, and the manufacturing method includes: a step of manufacturing a photographing device using the element obtained by the method for manufacturing the element of the present invention.

[0203] The element obtained by the method for manufacturing the element of the present invention is used for manufacturing a semiconductor device in which a plurality of elements are stacked using the bonding electrode.

[0204] A method for manufacturing such a semiconductor device is also one aspect of the present invention. The manufacturing method includes a step of bonding two or more elements obtained by the method for manufacturing an element of the present invention by bonding the bonding electrodes to each other.

[0205] As a method for connecting the bonding electrodes in the step of bonding the bonding electrodes to each other, for example, a method of melting and connecting the electrodes and the bonding electrodes by heat treatment can be cited. The above heat treatment is usually about 400 °C for 4 hours.

[0206] Here, a schematic diagram showing an example of a semiconductor device obtained by the manufacturing method of the semiconductor device of the present invention is shown in Figure 4 . As Figure 4 shown, the semiconductor device obtained by the manufacturing method of the semiconductor device of the present invention has the following structure: substrates 6 and 10 having electrodes 7 are bonded by an organic layer 2 and an inorganic layer 3, and the electrodes 7 on the substrates 6 and 10 having electrodes are electrically connected by a conductive material filled in through holes 8 provided in the organic layer 2 and the inorganic layer 3. By covering the organic layer 2 with a thin inorganic layer 3, the moisture resistance can be improved and the connection reliability can be enhanced compared with the case of the organic layer 2 alone. In addition, a barrier metal layer 9 may be provided on the surface of the through hole 8 in the semiconductor device. By forming the barrier metal layer 9 on the surface of the through hole 8, the conductive material filled in the through hole 8 is less likely to diffuse into the organic layer 2, so that short circuits and conduction failures can be further suppressed.

[0207] Advantages of the Invention

[0208] According to the present invention, it is possible to provide a laminate, a method for manufacturing the laminate, a method for manufacturing an element using the laminate, an imaging device having the laminate, a method for manufacturing the imaging device, a semiconductor device having the laminate, and a method for manufacturing the semiconductor device. When the laminate is laminated to form a semiconductor device, warping and cracking of the elements are less likely to occur, it has high moisture resistance, and excellent connection reliability can be imparted. BRIEF DESCRIPTION OF THE DRAWINGS

[0209] Figure 1 is a schematic diagram showing an example of the laminate of the present invention.

[0210] Figure 2 is a schematic diagram showing an example of the laminate of the present invention.

[0211] Figure 3 is a schematic diagram showing an example of the laminate of the present invention.

[0212] Figure 4 is a schematic diagram showing an example of a semiconductor device obtained by the manufacturing method of the semiconductor device of the present invention. Detailed implementation mode

[0213] Hereinafter, examples will be given to explain the present invention in more detail, but the present invention is not limited to these examples only.

[0214] (Example 1)

[0215] (1) Production of organosilicon compound A

[0216] 65.4 g of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 198.29), 8.8 g of sodium hydroxide, 6.6 g of water, and 263 mL of 2-propanol were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel. While stirring, heating was started under a nitrogen stream. After continuing stirring for 6 hours from the start of reflux, it was left standing overnight at room temperature. Then, the reaction mixture was transferred to a filter and filtered under pressure with nitrogen. The obtained solid was washed once with 2-propanol, filtered, and dried under reduced pressure at 80°C to obtain 33.0 g of a colorless solid (DD-ONa).

[0217] 11.6 g of compound (DD-ONs), 100 g of tetrahydrofuran, and 3.0 g of triethylamine were put into a 300-ml three-necked flask equipped with a dropping funnel, a reflux condenser, and a thermometer, and sealed with dry nitrogen. While stirring with a magnetic stirrer, 4.5 g: 30 mmol of methyltrichlorosilane was added dropwise at room temperature. Then, it was stirred at room temperature for 3 hours. 50 g of water was added to the reaction solution to dissolve the generated sodium chloride and hydrolyze the unreacted methyltrichlorosilane. The reaction mixture thus obtained was separated by liquid separation, and the organic layer was washed once with 1N hydrochloric acid, once with a saturated aqueous sodium bicarbonate solution, and further washed repeatedly with ion-exchanged water 3 times. The washed organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure using a rotary evaporator to obtain 7.1 g of a white powdery solid (DD(Me)-OH).

[0218] A cooling tube, a mechanical stirrer, a Dean-Stark tube, an oil bath, and a thermometer protection tube were installed on a 100 mL flask, and nitrogen replacement was performed inside the flask. 5.0 g of DD(Me)-OH, 11.6 g of octamethylcyclotetrasiloxane (D4), 3.9 g of sulfuric acid, 52 g of toluene, and 13 g of 4-methyltetrahydropyran were added to the flask. After stirring at 100 °C for 5 hours, water was poured into the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, an aqueous sodium bicarbonate solution, and saturated brine, and then dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure, and the residue was reprecipitated and purified in a solution mixed at a ratio of 2-propanol:ethyl acetate = 50:7 (weight ratio), and then dried, whereby an organosilicon compound A having the structure of the following formula (8), m = 27, and an average n = 4 (weight average molecular weight: 36,000) was obtained.

[0219] [Chemical formula 5]

[0220]

[0221] (2) Production of additive A

[0222] A cooling tube, a mechanical stirrer, a Dean-Stark tube, an oil bath, and a thermometer protection tube were installed on a 100 mL flask. 11.1 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) (manufactured by Daikin Industries, Ltd.), 7.8 g of bisaminopropyltetramethyldisiloxane (PAM-E, manufactured by Shin-Etsu Silicones Co., Ltd.), and 92.1 g of anisole were put into the flask and stirred. After heating the flask at 100 °C for 1 hour, it was refluxed in an oil bath at 170 °C for 1 hour. The solution was cooled to room temperature, 1.3 g of citraconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and after stirring at 120 °C for 10 minutes, it was refluxed in an oil bath at 170 °C for 1 hour to obtain additive A having the structure of the following formula (9) (weight average molecular weight: 9,900). It should be noted that l in the following formula (9) represents the number of repeating units.

[0223] [Chemical formula 6]

[0224]

[0225] (3) Production of curable resin composition

[0226] To 100 parts by weight of the obtained silicone compound, 0.2 part by weight of a catalyst (ZC-162, an acetylacetone complex with zirconium as the central metal, manufactured by Matsumoto Fine Chemical Co., Ltd.), 3.2 parts by weight of a crosslinking agent (methyl silicate 51, manufactured by COLCOAT Co., Ltd.), and 1 part by weight of additive A, a solvent (cyclopentanone, manufactured by Tokyo Chemical Industry Co., Ltd.) was added in such a manner that the content became 65% by weight and mixed, whereby a curable resin composition was obtained.

[0227] (4) Manufacture of the laminate

[0228] 15 g of the obtained curable resin composition was ejected onto the center of an 8-inch silicon wafer (surface roughness < 0.1 μm). Then, using a spin coater (ACT-400II; manufactured by ACTIVE Co., Ltd.), spin coating was performed at a rotational speed of 500 rpm for 12 seconds, and solvent drying was carried out in an oven at 125°C for 10 minutes, whereby an 85-μm resin film was obtained. The resin film was heat-treated at 300°C for 1 hour to obtain an organic layer. The silicon wafer with the organic layer was heat-treated in a nitrogen atmosphere at 400°C for 1 hour using a vacuum process high-speed heating furnace (VPO-650, manufactured by UniTemp Co., Ltd.). Next, using PE-CVD (product number MPX-CVD, manufactured by Sumitomo Precision Co., Ltd.), a CVD-based inorganic film formation was carried out for a specified time under the conditions shown in Table 3 to form a 400-nm-thick SiN layer (inorganic layer) on the organic layer, whereby a laminate was obtained. It should be noted that in Table 3, "HF" in "Upper RF Power (upper radio frequency power)" represents the power during film formation at 13.56 MHz, and "LF" represents the power during film formation at 380 kHz. In addition, "First" in "Switching mode" means that when alternating between 13.56 MHz and 380 kHz, it is applied first, and "End" means it is applied later. Furthermore, "Compressive" in "Film stress" represents the force in the compressive direction, and "Tensile" represents the force in the tensile direction.

[0229] (5) Measurement of the 1% thermal weight loss temperature

[0230] Monolithic bodies of the organic layer were produced respectively by the above method. For the obtained monolithic bodies, using a differential thermal-thermogravimetric simultaneous measurement device (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Co., Ltd.), heating was carried out at a heating rate of 10°C / min under a nitrogen gas flow of 50 mL / min, and the temperature at which the weight reduction rate reached 1% was measured. The results are shown in Table 1.

[0231] (6) Measurement of the internal stress

[0232] Using a thin film stress measurement device (FLX2320-S, manufactured by Toho Technology Co., Ltd.), the warpage amount and radius of curvature of the untreated silicon wafer were calculated. Let the radius of curvature R at this time be R1. Next, on the silicon wafer for which the radius of curvature had been calculated, using PE-CVD (product number MPX-CVD, manufactured by Sumitomo Precision Co., Ltd.), an inorganic film with a thickness of 100 nm was formed under the conditions shown in Table 2. After forming the inorganic film, the warpage amount and radius of curvature after inorganic film formation were again calculated using the thin film stress measurement device. Let the radius of curvature R at this time be R2. Based on the change in the radius of curvature before and after inorganic film formation, the inorganic film stress S (Pa) was calculated according to the Stoney formula represented by the following mathematical formula (A). The results are shown in Table 1. It should be noted that in the table, when the value of the film stress is negative, it indicates an internal stress in the compressive direction, and when the value of the film stress is positive, it indicates an internal stress in the tensile direction.

[0233] [Mathematical formula 3]

[0234]

[0235] It should be noted that in mathematical formula (A),

[0236] E / (1 - v): Biaxial elastic modulus of the silicon wafer (Pa), set to 1.805×10 11 Pa.

[0237] h: Thickness of the silicon wafer (m), set to 725 μm.

[0238] t: Thickness of the inorganic film (m), set to 100 nm.

[0239] R: Radius of curvature of the substrate, obtained according to the following mathematical formula (B).

[0240] [Mathematical formula 4]

[0241]

[0242] (7) Measurement of P2180 / P775 and P1200 / P775

[0243] The absorption spectrum of the substrate after inorganic film formation was measured by the total reflection (ATR) method of Fourier transform infrared spectroscopy (FT-IR). At this time, the measurement range was set to 525 cm -1 to 4000 cm -1 , and the resolution was set to 4 cm -1 for measurement. In the obtained absorption spectrum, the peak height (Si - O) at 775 cm -1 was set to P775, and the peak height at 2180 cm -1The peak height of (Si-H) was set as P2180, and P2180 was divided by P775 to obtain P2180 / P775. Similarly, the peak height of (N-H) at 1200 cm -1 was set as P1200, and it was divided by P775 to obtain P1200 / P775.

[0244] (Examples 2 to 19, Comparative Examples 1 to 6)

[0245] Except that the compositions and film-forming conditions of the organic layer and the inorganic layer were set as shown in Tables 1 to 3, laminates were obtained under the same conditions as in Example 1, and the 1% thermal weight loss temperature, internal stress, P2180 / P775, and P1200 / P775 were measured. It should be noted that for Comparative Example 6, dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the catalyst. In addition, in Examples 16, 18, and 19, ethyl silicate 48 (manufactured by COLCOAT Co., Ltd.) was used as the crosslinking agent. Regarding Resin B and Additives B to D, resins, additives, or commercially available products obtained by the following methods were used. In addition, under film-forming conditions 10 to 12, PD-220NL (manufactured by Samco Co., Ltd.) was used as the film-forming apparatus.

[0246] (Manufacture of Resin B)

[0247] A 100 mL flask was equipped with a condenser, a mechanical stirrer, a Dean-Stark tube, an oil bath, and a thermometer protection tube, and the inside of the flask was purged with nitrogen. 5.0 g of DD(Me)-OH, 11.2 g of octamethylcyclotetrasiloxane (D4), 3.9 g of sulfuric acid, 52.0 g of toluene, and 13.0 g of 4-methyltetrahydropyran were added to the flask. After stirring at 100 °C for 5 hours, water was poured into the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layers were washed with water, an aqueous sodium bicarbonate solution, and saturated brine, and then dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure, and the residue was reprecipitated and purified in a solution mixed at a ratio of 2-propanol:ethyl acetate = 50:7 (weight ratio) and dried to obtain a silicone compound (Resin B, weight average molecular weight 46000) having the structure of the above formula (8), where m is 36 and the average number of DMS chains (n) is 3.

[0248] (Manufacture of Additive B)

[0249] A condenser, a mechanical stirrer, a Dean-Stark tube, an oil bath, and a thermometer protection tube were installed on a 100 mL flask. 3.9 g of bis(aminopropyl)tetramethyldisiloxane (PAM-E, manufactured by Shin-Etsu Silicones), 36.3 g of anisole, and 3.53 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were put into the flask and stirred. The mixture was refluxed in an oil bath at 170 °C for 2 hours. After the resulting synthesis solution was cooled to room temperature, it was filtered using a membrane filter (product number: ADVANTEC T080A075C, manufactured by Toyo Roshi Kaisha, Ltd.) to obtain Additive B having the structure of the following formula (10) as a precipitate.

[0250] [Chemical formula 7]

[0251]

[0252] (Additives C, D)

[0253] The following additives were used as Additives C and D, respectively.

[0254] Additive C: TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.)

[0255] Additive D: BYK-320 (manufactured by BYK)

[0256] <Evaluation>

[0257] The following evaluations were performed on the laminates obtained in the examples and comparative examples. The results are shown in Tables 1 and 2. Note that for Comparative Example 6, since the amount of thermal decomposition of the resin film was large and CVD film formation could not be performed, no evaluation was carried out.

[0258] (Evaluation of cracks during film formation)

[0259] In the manufacture of the above laminate, the cracks during film formation were evaluated according to the following criteria by visually observing the formed inorganic layer.

[0260] ○: No cracks

[0261] ×: Cracks

[0262] (Evaluation of heat resistance)

[0263] Using a vacuum process high-speed heating furnace (VPO-650, manufactured by UniTemp), the laminate was heat-treated at 400 °C for 3 hours in a nitrogen atmosphere. Regarding the laminate after heat treatment, the film rupture in the thick film was evaluated according to the following criteria.

[0264] ○: No rupture after heat treatment

[0265] △: Cracks of about 2 mm occurred at the ends after heat treatment

[0266] ×: Breakage occurred after heat treatment

[0267] (Evaluation of moisture resistance)

[0268] The laminate was left standing for 500 hours in an environment of temperature 85°C and humidity 85%. Then, the laminate was visually observed, and the moisture resistance was evaluated according to the following criteria.

[0269] ◎: No trace of water intrusion from the ends was observed

[0270] 〇: The trace of water intrusion from the ends was less than 2 mm

[0271] △: The trace of water intrusion from the ends was 2 mm or more and less than 4 mm

[0272] ×: The trace of water intrusion from the ends was 4 mm or more

[0273] [Table 1]

[0274]

[0275] [Table 2]

[0276]

[0277] [Table 3]

[0278]

[0279] Industrial applicability

[0280] According to the present invention, it is possible to provide a laminate, a method for manufacturing the laminate, a method for manufacturing a component using the laminate, an imaging device having the laminate, a method for manufacturing the imaging device, a semiconductor device having the laminate, and a method for manufacturing the semiconductor device. When the laminate is laminated to form a semiconductor device, warping and breakage of the component are less likely to occur, the laminate has high moisture resistance, and excellent connection reliability can be imparted.

[0281] Explanation of reference numerals

[0282] 1 First component

[0283] 2 Organic layer

[0284] 3 Inorganic layer

[0285] 4 Chip

[0286] 5 Support substrate

[0287] 6 Substrate with electrodes

[0288] 7 Electrode

[0289] 8 Through-hole

[0290] 9 Barrier metal layer

[0291] 10 Substrate with electrode

Claims

1. A laminate comprising an organic layer laminated on a first element, and an inorganic layer laminated on the organic layer, The 1% thermal weight loss temperature of the organic layer measured under a nitrogen atmosphere at a heating rate of 10°C / min is above 400°C, The thickness of the inorganic layer is greater than or equal to 1 nm and less than or equal to 1 μm. The inorganic layer comprises a Si3N4 layer, The inorganic layer has internal stress in a compressive direction.

2. The laminate according to claim 1, wherein The inorganic layer includes a SiO2 layer, and the Si3N4 layer is stacked on the SiO2 layer.

3. The laminate according to claim 1 or 2, wherein: The organic layer is a cured product of a curable resin composition.

4. The laminate according to claim 3, wherein: The organic layer is a cured product of a curable resin composition containing an organic silicon compound.

5. The laminate according to claim 4, wherein The organosilicon compound has a structure represented by the following general formula (1): Here, R 0 , R 1 and R 2 Each independently represents a linear, branched or cyclic aliphatic group, an aromatic group or hydrogen; the aliphatic group and the aromatic group may have a substituent; and m and n each represent an integer greater than 1.

6. The laminate according to claim 5, wherein In the IR spectrum measured from the surface of the inorganic layer by FT-IR, at 775 cm -1 The peak height of Si-O is set as P775, and the peak height of 2180cm -1 When the peak height, that is, the Si-H peak height, is set to P2180, P2180 / P775<0.

045.

7. The laminate according to claim 5 or 6, wherein: In the IR spectrum measured from the surface of the inorganic layer by FT-IR, at 775 cm -1 The peak height of Si-O is set to P775, and the peak height of 1200cm -1 When the peak height, that is, the NH peak height, is set to P1200, P1200 / P775<0.

300.

8. The laminate according to any one of claims 1 to 7, wherein The thickness of the organic layer is greater than 10 μm.

9. The laminate according to any one of claims 1 to 8, wherein The first element has a first surface and a second surface, the first surface has a plurality of chips, The organic layer and the inorganic layer are stacked on the first surface side.

10. The laminate according to any one of claims 1 to 9, wherein A supporting substrate is further stacked on the inorganic layer. 11 . An imaging device comprising the laminate according to claim 1 . 12 . A semiconductor device comprising the laminate according to claim 1 .

13. A method for manufacturing a laminate, which is the method for manufacturing a laminate as described in any one of claims 1 to 10, comprising: a step of forming a film of a curable resin composition on the first element to form the organic layer; and a step of forming the inorganic layer having internal stress in a compressive direction on the organic layer by chemical vapor deposition.

14. The method for producing a laminate according to claim 13, wherein: The first element has a first surface and a second surface, the first surface has a plurality of chips, and in the step of forming the organic layer, the organic layer is formed on the first surface side. 15 . The method for producing a laminate according to claim 13 or 14 , further comprising the step of bonding a supporting substrate onto the inorganic layer. 16 . A method for producing an imaging device, comprising the step of producing the imaging device using the laminated body obtained by the production method according to claim 13 .

17. A method for manufacturing a component, comprising: A step of forming an organic layer by forming a film of a curable resin composition on a surface of a substrate having an electrode and having the electrode; forming an inorganic layer having internal stress in a compressive direction on the organic layer by chemical vapor deposition; forming through holes in the organic layer and the inorganic layer; filling the through hole with a conductive material; as well as The step of forming a bonding electrode by polishing the surface of the substrate having the electrode on the side filled with the conductive material. 18 . A method for manufacturing an imaging device, comprising: a step of manufacturing the imaging device using a device obtained by the method for manufacturing a device according to claim 17 . 19 . A method for manufacturing a semiconductor device, comprising: bonding two elements obtained by the method for manufacturing an element according to claim 17 together so that the bonding electrodes are bonded to each other.

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