Laminated body, method for manufacturing laminated body, method for manufacturing element, imaging device, method for manufacturing imaging device, semiconductor device, and method for manufacturing semiconductor device
Patent Information
- Application Number
- JP2024506204
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Filing Date
- 2024-01-31
- Publication Date
- 2025-09-30
Smart Images
Figure 2024157914000001
Abstract
Description
Stacked body, manufacturing method of stacked body, manufacturing method of element, imaging device, manufacturing method of imaging device, semiconductor device, and manufacturing method of semiconductor device
[0001] The present invention relates to a laminate, a method for manufacturing a laminate, a method for manufacturing an element, an imaging device, a method for manufacturing an imaging device, a semiconductor device, and a method for manufacturing a semiconductor device.
[0002] As semiconductor devices become more sophisticated, they are increasingly being made three-dimensional by stacking multiple semiconductor chips. In the manufacture of such semiconductor devices with multiple stacked semiconductor chips, a damascene process is first used to form a bonding surface on the electrode surface of an element or circuit board (hereinafter simply referred to as an element) on which two electrodes are formed, whereby a bonding electrode made of copper is surrounded by an insulating film. The two elements are then stacked so that the bonding electrodes on the bonding surfaces face each other, and a heat treatment is then performed to manufacture the semiconductor device (see Patent Document 1).
[0003] Japanese Patent Application Laid-Open No. 2006-191081
[0004] In the manufacturing of the semiconductor device, a high temperature treatment of 400°C for 4 hours is performed when bonding the electrodes, so the insulating layer used to form the bonding surface is required to have high heat resistance. ３ N ４ and SiO ２ Insulating inorganic materials such as the above are used. However, insulating layers made of inorganic materials are prone to warping of the substrate, and warping of the substrate can cause electrode connection positions to shift or electrodes to crack when stacked, which can reduce the connection reliability of the semiconductor device. Furthermore, in recent years, semiconductor devices have become more highly functional, and substrates have become larger and thinner, making substrate warping more likely to occur, and thin substrates in particular can crack.
[0005] To prevent warping and cracking of the substrate due to high-temperature processing, it has been considered to use an organic compound, which is more flexible than inorganic materials, as an insulating layer. However, insulating layers made of organic compounds are vulnerable to heat, and outgassing generated by thermal decomposition can easily cause cracking of the insulating layer. To address this issue, the use of heat-resistant resins as insulating layers has also been considered. However, resins are permeable to moisture and therefore vulnerable to high-humidity environments. If moisture penetrates the electrodes in a high-humidity environment, the reliability of the semiconductor device may be reduced.
[0006] As a method for solving such moisture resistance problems, it has been proposed to laminate a thin inorganic layer made of an inorganic material on an organic layer. Because inorganic materials have high moisture resistance, covering the organic layer with an inorganic layer can improve moisture resistance. Furthermore, by making the inorganic layer thin, the effect of the organic layer in suppressing warping and cracking of the substrate due to high-temperature treatment is not hindered. However, forming an inorganic layer on an organic layer can cause cracks in the inorganic layer during high-temperature treatment, which can reduce the reliability of the semiconductor device.
[0007] The present invention aims to provide a laminate that is resistant to warping or cracking of elements when stacked to form a semiconductor device, has high moisture resistance, and can provide excellent connection reliability, a method for manufacturing the laminate, a method for manufacturing elements using the laminate, an imaging device including the laminate, a method for manufacturing the imaging device, a semiconductor device including the laminate, and a method for manufacturing the semiconductor device.
[0008] The present invention includes the following Disclosures 1 to 19. The present invention will be described in detail below. [Disclosure 1] A laminate comprising an organic layer laminated on a first element and an inorganic layer laminated on the organic layer, wherein the organic layer has a 1% thermal weight loss temperature of 400°C or higher measured under conditions of a temperature rise rate of 10°C / min in a nitrogen atmosphere, the inorganic layer has a thickness of 1 nm or more and 1 μm or less, and the inorganic layer is made of Si ３ N ４ [Disclosure 2] A laminate comprising an inorganic layer having an internal stress in a compressive direction. ２ The Si ３ N ４ The layer is the SiO ２The laminate according to Disclosure 1, wherein the organic layer is laminated on a curable resin composition. [Disclosure 3] The laminate according to Disclosure 1 or 2, wherein the organic layer is a cured product of a curable resin composition containing an organosilicon compound. [Disclosure 4] The laminate according to Disclosure 3, wherein the organic layer is a cured product of a curable resin composition containing an organosilicon compound. [Disclosure 5] The laminate according to Disclosure 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 or may not have a substituent. m and n each represent an integer of 1 or more. [Disclosure 6] In an IR spectrum measured by FT-IR from the surface of the inorganic layer, －１ The peak heights (Si-O) of P775 and 2180 cm －１ [Disclosure 7] The laminate according to Disclosure 5, wherein, when the peak height (Si—H) of the inorganic layer is P2180, P2180 / P775<0.045. －１ The peak height (Si-O) was P775, 1200 cm －１The laminate according to Disclosure 5 or 6, wherein P1200 / P775<0.300, where P1200 is the peak height (N-H) of the organic layer. [Disclosure 8] The laminate according to any one of Disclosures 1 to 7, wherein the organic layer has a thickness of 10 μm or more. [Disclosure 9] The laminate according to any one of Disclosures 1 to 8, wherein the first element has a first surface and a second surface, the first surface having a plurality of chips, and the organic layer and the inorganic layer are laminated on the first surface side. [Disclosure 10] The laminate according to any one of Disclosures 1 to 9, wherein a support substrate is further laminated on the inorganic layer. [Disclosure 11] An imaging device comprising the laminate according to any one of Disclosures 1 to 10. [Disclosure 12] A semiconductor device comprising the laminate according to any one of Disclosures 1 to 10. [Disclosure 13] A method for manufacturing a laminate according to any one of Disclosures 1 to 10, comprising the steps of forming the organic layer by forming a film of a curable resin composition on the first element, and forming the inorganic layer having an internal stress in a compressive direction on the organic layer by chemical vapor deposition. [Disclosure 14] A method for manufacturing a laminate according to Disclosure 13, wherein the first element has a first surface and a second surface, the first surface has a plurality of chips, and the organic layer is formed on the first surface side in the step of forming the organic layer. [Disclosure 15] A method for manufacturing a laminate according to Disclosure 13 or 14, further comprising the step of bonding a support substrate onto the inorganic layer. [Disclosure 16] A method for manufacturing an imaging device, comprising the step of manufacturing an imaging device using a laminate obtained by the manufacturing method according to any one of Disclosures 13 to 15. [Disclosure 17] A method for manufacturing an element, comprising the steps of forming an organic layer by forming a curable resin composition on a surface of a substrate having electrodes, the surface having the electrodes, forming an inorganic layer having an 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 holes with a conductive material, and polishing the surface of the substrate having electrodes on the side filled with the conductive material to form a bonding electrode. [Disclosure 18] A method for manufacturing an imaging device, comprising the step of manufacturing an imaging device using an element obtained by the element manufacturing method described in Disclosure 17. [Disclosure 19] A method for manufacturing a semiconductor device, comprising the step of bonding two elements obtained by the element manufacturing method described in Disclosure 17 so that the connecting electrodes are bonded to each other.
[0009] The laminate of the present invention is a laminate in which an organic layer is stacked on a first element and an inorganic layer is stacked on the organic layer. In a semiconductor device in which multiple elements and substrates are stacked, the organic layer and inorganic layer serve as insulating layers between each element and substrate. Conventional insulating layers have used hard inorganic materials to withstand high-temperature processing during manufacturing, which means that they are unable to relieve stress when the element deforms, making the element prone to warping and cracking. In the laminate of the present invention, by using an organic compound with flexibility capable of stress relief as the insulating layer, the element is less likely to warp or crack. As a result, electrode misalignment and cracking caused by element warping or cracking can be suppressed, thereby improving the connection reliability between elements. Furthermore, by providing an inorganic layer as an auxiliary insulating layer on the organic layer, moisture in the atmosphere is less likely to permeate than through an organic layer alone, thereby achieving high connection reliability even under high temperature and high humidity. The organic compound constituting the organic layer here also includes organic-inorganic hybrid compounds such as organosilicon compounds.
[0010] The first element is not particularly limited, and may be a circuit board on which elements and wiring are formed, such as a sensor circuit board provided with a pixel section (pixel region), a circuit board on which a peripheral circuit section such as a logic circuit that performs various signal processing related to the operation of the solid-state imaging device is mounted, or a circuit board on which a peripheral circuit such as a memory circuit is mounted.
[0011] The organic layer is preferably a cured product of a curable resin composition. By using a curable resin composition as a material for the organic layer, an organic layer can be formed by applying and forming a film of the curable resin composition and then curing it, thereby improving production efficiency compared to when conventional inorganic materials are used. The curable resin constituting the curable resin composition may be thermosetting or photocurable, but is preferably a thermosetting resin from the viewpoint of heat resistance.
[0012] The organic compound constituting the organic layer is not particularly limited as long as it has heat resistance sufficient to withstand high-temperature treatment at 400° C. for about 4 hours, and examples thereof include organosilicon compounds, polyimides, etc. Among these, the organic layer is preferably a cured product of a curable resin composition containing an organosilicon compound, since this has excellent heat resistance and flexibility, and can further suppress warping and cracking of the element, thereby improving connection reliability.
[0013] The organosilicon compound is preferably silsesquioxane. Silsesquioxane has high heat resistance while having flexibility comparable to that of organic compounds, so that by using an organic layer containing silsesquioxane as the insulating layer of a 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, but it is preferable that the silsesquioxane has structures represented by the following structural formulas (A) and (B) in one molecule, as this further suppresses warping and cracking of the substrate.
[0014] In 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, and each represents an integer of 1 or more.
[0015] The organosilicon compound preferably has a reactive site. By using an organosilicon 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 organosilicon compound has excellent heat resistance, decomposition of the organic layer due to high-temperature treatment performed during the manufacture of a semiconductor device in which multiple laminates are stacked can be further suppressed. Examples of the reactive site include a hydroxyl group and an alkoxy group.
[0016] The content of the organosilicon compound having a reactive site is preferably 80 parts by weight or more, more preferably 90 parts by weight or more, and even more preferably 95 parts by weight or more, per 100 parts by weight of the resin solid content in the curable resin composition. The content of the organosilicon compound having a reactive site is preferably less than 100 parts by weight, more preferably 98 parts by weight or less, per 100 parts by weight of the resin solid content in the curable resin composition.
[0017] The organosilicon compound preferably has a structure represented by the following general formula (1): When the organosilicon compound has the structure of general formula (1), warping of the element can be further suppressed. In particular, it is more preferable that the organosilicon compound further has an aromatic ring structure, since this further improves heat resistance and further suppresses warping and cracking of the element.
[0018] 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 or may not have a substituent. m and n each represent an integer of 1 or greater.
[0019] In the above general formula (1), R ０ Each of R independently represents a linear, branched, or cyclic aliphatic group, an aromatic group, or hydrogen. The aliphatic group and the aromatic group may or may not have a substituent. ０ is preferably a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, and more preferably a phenyl group. ０ When the alkyl group is a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, higher heat resistance can be exhibited.
[0020] In the above general formula (1), R １ and R ２ Each of R independently represents a linear, branched, or cyclic aliphatic group, an aromatic group, or hydrogen. The aliphatic group and the aromatic group may or may not have a substituent. １ and R ２ is preferably a phenyl group, an alkyl group or an arylalkyl group having 1 to 20 carbon atoms, and more preferably a phenyl group or a methyl group. １ and R ２ When the alkyl group is a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, higher heat resistance can be exhibited.
[0021] In the general formula (1), m and n each represent an integer of 1 or greater and represent the number of repeating units. m is preferably 30 or greater, more preferably 50 or greater, and preferably 100 or less. n is preferably 1 or greater, more preferably 3 or greater, and even more preferably 4 or greater, and is preferably 8 or less, more preferably 6 or less.
[0022] The content of the organosilicon compound is preferably 65% by weight or more and 99% by weight or less based on 100% by weight of the solid components of the curable resin composition. By having the content of the organosilicon compound in the solid components of the curable resin composition within the above range, warping and cracking of elements can be suppressed, thereby further improving the connection reliability between elements. The content of the organosilicon compound in 100% by weight of the solid components of the curable resin composition is more preferably 70% by weight or more, even more preferably 75% by weight or more, more preferably 98% by weight or less, and even more preferably 97% by weight or less.
[0023] The weight-average molecular weight of the organosilicon compound is not particularly limited, but is preferably 5,000 or more and 150,000 or less. Having the weight-average molecular weight of the organosilicon compound within this range improves film-forming properties during application, further enhancing planarization performance and further suppressing warpage and cracking of elements. The weight-average molecular weight of the organosilicon compound is more preferably 10,000 or more, even more preferably 30,000 or more, more preferably 100,000 or less, and even more preferably 70,000 or less. The weight-average molecular weight of the organosilicon compound is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Using THF as the elution solvent and a Time-MB-M 6.0 x 150 mm (manufactured by Waters Corporation) or an equivalent column, the weight-average molecular weight can be calculated using polystyrene standards.
[0024] The curable resin composition preferably contains a catalyst. The catalyst has the role of accelerating the curing reaction. By including a catalyst in the curable resin composition, the curable resin composition can be cured more completely, and decomposition of the organic layer due to high-temperature treatment can be further suppressed. Examples of the catalyst include organotin compounds such as dibutyltin dilaurate and stannous acetate, metal carboxylates such as zinc naphthenate, acetylacetonate complexes having a zirconium central metal, and titanium compounds. Among these, acetylacetonate complexes having a zirconium central metal are preferred because they can further accelerate the curing of the curable resin composition. Note that the catalyst remains even after the curable resin composition has cured. In other words, when the curable resin composition contains a catalyst, the resulting organic layer also contains the catalyst.
[0025] The content of the catalyst is not particularly limited, but is preferably 0.01 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the curable resin in the curable resin composition. By setting the content of the catalyst within this range, the curing of the curable resin composition can be further promoted and decomposition of the cured resin due to high-temperature treatment can be further suppressed. The content of the catalyst is more preferably 0.1 parts by weight or more, even more preferably 0.2 parts by weight or more, more preferably 7 parts by weight or less, and even more preferably 5 parts by weight or less.
[0026] The curable resin composition preferably contains a crosslinking agent. By including a crosslinking agent in the curable resin composition, the crosslinking agent crosslinks between the curable resins, increasing the crosslink density of the cured product and further suppressing decomposition at high temperatures. As a result, warping and cracking of the element can be suppressed, thereby further improving connection reliability. Examples of the crosslinking agent include alkoxysilane compounds such as dimethoxysilane compounds, trimethoxysilane compounds, diethoxysilane compounds, and triethoxysilane compounds, or silicate oligomers obtained by condensation of tetramethoxysilane compounds and tetraethoxysilane compounds. Among these, polyalkoxysilanes are preferred from the viewpoint of improving crosslink density and heat resistance.
[0027] 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 per 100 parts by weight of the curable resin in the curable resin composition. By setting the content of the crosslinking agent within the above range, the crosslink density of the cured resin product can be set within a suitable range. The content of the crosslinking agent is more preferably 3 parts by weight or more, even more preferably 3.2 parts by weight or more, more preferably 30 parts by weight or less, and even more preferably 20 parts by weight or less.
[0028] The curable resin composition preferably contains a heat-resistant resin. By using a heat-resistant resin in the curable resin composition, it is possible to obtain a cured film that is less likely to crack when treated at high temperatures, even when the cured film is a thick organic layer.
[0029] Examples of the heat-resistant resin include polyimide, epoxy resin, silicone resin, benzoxazine resin, cyanate resin, and phenolic resin, and polyimide is particularly preferred from the viewpoint of heat resistance.
[0030] The weight average molecular weight of the heat-resistant resin is not particularly limited, but is preferably 5,000 or more and 150,000 or less. When the weight average molecular weight of the heat-resistant resin is within the above range, even when a thick organic layer is formed, it is possible to obtain a cured film that is less likely to crack when treated at a high temperature. The molecular weight of the heat-resistant resin is more preferably 10,000 or more, even more preferably 30,000 or more, more preferably 100,000 or less, and even more preferably 70,000 or less.
[0031] The content of the heat-resistant resin is preferably 0.5 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the organosilicon compound.By making the content of the heat-resistant resin within the above range, even if the organic layer is thick, it can be made into an organic layer that is less likely to crack during high-temperature treatment.The content of the heat-resistant resin is more preferably 0.7 parts by weight or more relative to 100 parts by weight of the organosilicon compound, more preferably 0.75 parts by weight or more, particularly preferably 1 part by weight or more, more preferably 20 parts by weight or less, more preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less.
[0032] When the heat-resistant resin is a polyimide, the polyimide preferably has a siloxane bond, which enhances compatibility with an organosilicon compound when the curable resin composition contains the organosilicon compound, thereby further suppressing surface roughness caused by precipitation of the polyimide during application.
[0033] When the polyimide has a siloxane bond, the polyimide preferably has a carbon atom to silicon atom ratio (C / Si) of 17 or less in the main chain structure. When the curable resin composition contains an organosilicon compound, having a carbon atom to silicon atom ratio within the above range enhances compatibility with the organosilicon compound, thereby further reducing surface roughness during application. The C / Si ratio is more preferably 16.5 or less, and even more preferably 16 or less. While the lower limit of the C / Si ratio is not particularly limited, it is preferably 4 or more from the perspective of practical use and further improving heat resistance at 400°C. The C / Si ratio of carbon atoms to silicon atoms in the main chain structure of the polyimide refers to the ratio of C and Si atoms within the repeating unit and does not include C and Si atoms at both ends. The C / Si ratio can be determined by obtaining the structure of the 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.
[0034] The polyimide preferably has a plurality of aromatic rings, which makes it possible to form a thick organic layer that is less susceptible to film cracking during high-temperature treatment under various conditions.
[0035] The polyimide preferably has an oxazine ring or imide ring structure at at least one of its terminals, and more preferably has an oxazine ring or imide ring structure at both terminals. When the polyimide has an oxazine ring or imide ring structure at its terminal, surface roughening can be further suppressed when it is formed into a thick film. The oxazine ring and imide ring structure may have a substituent. In particular, the polyimide more preferably has any one of the structures represented by the following formulas (2) to (7) at at least one terminal, and particularly preferably has any one of the structures represented by the following formulas (2) to (7) at both terminals. In the following formulas, "*" represents the bonding site to a portion other than the terminal of the polyimide.
[0036]
[0037] The polyimide preferably has a weight-average molecular weight of 1,000 or more and 50,000 or less. When the polyimide has a weight-average molecular weight within the above range, compatibility with the organosilicon compound is improved when the curable resin composition contains the organosilicon compound, thereby further improving handleability. The weight-average molecular weight is more preferably 2,000 or more, even more preferably 3,000 or more, more preferably 35,000 or less, and even more preferably 30,000 or less. The weight-average molecular weight of the polyimide is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Using THF as the elution solvent and a Time-MB-M 6.0 x 150 mm (manufactured by Waters Corporation) or an equivalent column, the weight-average molecular weight can be calculated using polystyrene standards.
[0038] The content of the polyimide is preferably 0.5 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the organosilicon compound.By making the content of polyimide within the above range, even if the organic layer is thick, it can be made into an organic layer that is less likely to crack during high-temperature treatment.The content of the polyimide is preferably 0.7 parts by weight or more relative to 100 parts by weight of the organosilicon compound, more preferably 0.75 parts by weight or more, even more preferably 1 part by weight or more, and is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.
[0039] The curable resin composition may contain other additives such as a solvent, a viscosity modifier, a filler, and an adhesion promoter, if necessary.
[0040] The organic layer preferably has a thickness of 10 μm or more. By setting the thickness of the organic layer within the above range, it can fulfill its role as an insulating layer and suppress warping and cracking of the element, thereby improving connection reliability. Furthermore, conventional laminates in which an inorganic layer is formed on an organic layer have been particularly prone to cracking in the inorganic layer when the organic layer is made into a thick film. However, the laminate of the present invention is less likely to crack the inorganic layer even when the organic layer is made into a thick film, and can exhibit high moisture resistance. The thickness of the organic layer is preferably 20 μm or more, more preferably 30 μm or more, and preferably 200 μm or less, and more preferably 100 μm or less.
[0041] The organic layer may contain components other than the organic compound that is the main component of the organic layer, as long as the effects of the present invention are not significantly impaired. In this case, the content of the organic compound that is the main component in the organic layer is, for example, preferably 90% by weight or more, more preferably 95% by weight or more, even more preferably 99% by weight or more, and usually less than 100% by weight.
[0042] The organic layer has a 1% thermal weight loss temperature of 400°C or higher, measured under conditions of a nitrogen atmosphere and a temperature rise rate of 10°C / min. Having a 1% thermal weight loss temperature of 400°C or higher can suppress decomposition of the organic layer even when subjected to high-temperature treatment, thereby further suppressing the generation of bubbles and cracks at the interface and peeling at the interface. Furthermore, deterioration of CVD film quality due to gas generated from the organic layer and contamination of the CVD film formation equipment can be suppressed. The 1% thermal weight loss temperature is preferably 420°C or higher, more preferably 440°C or higher, and even more preferably 460°C or higher. The upper limit of the 1% thermal weight loss temperature is not particularly limited, and the higher the temperature, the better; for example, it may be 500°C. The 1% thermal weight loss temperature of the organic layer can be adjusted by the type of organic compound that is the main component of the organic layer and the additives added. Examples of the upper limit include the type and amount of a catalyst that promotes curing, and the type and amount of an additive that suppresses thermal decomposition. The 1% thermal weight loss temperature can be obtained by measuring using a thermogravimetric and differential thermal analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation or an equivalent product) under a nitrogen flow of 50 mL / min at a temperature increase rate of 10°C / min.
[0043] The inorganic layer is Si ３ N ４ The inorganic layer includes a Si layer. ３ N ４ By using the above Si, moisture resistance is improved and moisture penetration into the organic layer and the electrodes is suppressed, thereby improving connection reliability. In conventional semiconductor devices in which multiple substrates having electrodes are stacked, only inorganic layers are used as insulating layers, which makes it impossible to eliminate warping of the element, causing element cracking and reduced connection reliability. In the laminate of the present invention, the majority of the insulating layer is an organic layer, and the inorganic layer is kept to a minimum thickness, so that moisture resistance can be improved while eliminating warping of the element. ３ N ４ The thickness of the layer is preferably 50 nm or more, more preferably 100 nm or more, and is preferably 500 nm or less, more preferably 300 nm or less. ３ N ４The layer refers to a layer having a stoichiometric ratio of N / Si=1 to 2 (theoretical value is N / Si=1.33), and may be referred to as a SiN layer or SiN film hereinafter.
[0044] The inorganic layer is made of SiO ２ The Si layer ３ N ４ The layer is the SiO ２ It is preferable that the inorganic layer further includes a SiO ２ The Si layer is provided. ３ N ４ The layer is made of SiO ２ Layers are stacked on top of each other, i.e., organic layers, SiO ２ layer, Si ３ N ４ By stacking the layers in this order, the moisture resistance can be further improved. ２ The thickness of the layer is preferably 50 nm or more, more preferably 100 nm or more, and is preferably 500 nm or less, more preferably 300 nm or less.
[0045] The inorganic layer has a thickness of 1 nm or more and 1 μm or less. By setting the thickness of the inorganic layer within this range, it is possible to improve moisture resistance while maintaining the effect of suppressing warpage of the organic layer element. From the viewpoint of stability of inorganic film quality, the thickness of the inorganic layer is preferably 50 nm or more, more preferably 100 nm or more, and is preferably 700 nm or less, more preferably 400 nm or less.
[0046] The inorganic layer has internal stress in the compressive direction. Forming a thin inorganic layer on an organic layer to impart flexibility and moisture resistance to an insulating layer has been studied in the past. However, simply providing an inorganic layer on an organic layer can result in cracks occurring in the inorganic layer, resulting in insufficient improvement in moisture resistance. In the present invention, by forming the inorganic layer so that internal stress occurs in the compressive 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 cracking in the inorganic layer. Furthermore, since the present invention is highly effective in suppressing cracking in the inorganic layer, it is particularly effective when using a thick inorganic layer that is prone to cracking. An inorganic layer with internal stress in the compressive direction can be obtained, for example, by forming it by chemical vapor deposition (CVD) and adjusting the formation conditions. More specifically, among CVD methods, a plasma CVD method is used, which allows film formation at a relatively low temperature and can form an inorganic layer on an organic layer while reducing damage to the organic layer due to heat during the CVD process, and can be obtained by adjusting conditions such as the plasma film formation temperature, chamber pressure, applied power, RF frequency switching frequency, etc. Note that an inorganic layer having internal stress in the compressive direction can be obtained by intentionally adjusting the above conditions, but it is difficult to form unless it is intended to have internal stress in the compressive direction.
[0047] Here, "having internal stress in the compressive direction" means that the inorganic layer formed on the element has a stress that tends to expand from the center to the outside in a direction parallel to the planar direction of the element (a direction perpendicular to the thickness direction) at room temperature and when no external force is applied. Conversely, if the inorganic layer has a stress that tends to contract from the outside to the center in a direction parallel to the planar direction of the element at room temperature and when no external force is applied, it is said to have internal stress in the tensile direction. Furthermore, when the inorganic layer is composed of multiple layers, "having internal stress in the compressive direction" means that each layer has internal stress in the compressive direction. The internal stress can be measured by the following method.
[0048] Using a thin film stress measurement device (FLX2320-S, manufactured by Toho Technology Co., Ltd. or an equivalent product), the amount of warpage and radius of curvature of the untreated silicon wafer are calculated. The radius of curvature R at this time is defined as R １ Next, a 100 nm inorganic film is formed on the silicon wafer whose radius of curvature has been calculated using PE-CVD (MPX-CVD, manufactured by Sumitomo Precision Products Co., Ltd. or an equivalent product). After the inorganic film is formed, the amount of warpage and radius of curvature after the inorganic film formation are calculated again using the thin film stress measurement device. The radius of curvature R at this time is defined as R ２ Based on the change in the radius of curvature before and after the inorganic film formation, the internal stress S (Pa) of the inorganic film is calculated from the Stoney equation expressed by the following formula (A).
[0049]
[0050] The details of the above formula (A) are as follows: E / (1-v): Biaxial elastic modulus of the silicon wafer (Pa), 1.805×10 １１ Pa. h: thickness of the silicon wafer (m), which is set to 725 μm. t: thickness of the inorganic film (m), which is set to 100 nm. R: radius of curvature of the substrate, which is obtained from the following formula (B).
[0051]
[0052] In the above formula (A), when the internal stress S is a negative value, it indicates that there is internal stress in the compressive direction, and when it is a positive value, it indicates that there is internal stress in the tensile direction. Therefore, the internal stress S of the inorganic layer of the present invention is less than 0 MPa. From the viewpoint of preventing cracks, taking into consideration the temperature dependency in which the internal stress fluctuates in the positive direction at high temperatures, the internal stress is preferably -50 MPa or less, more preferably -100 MPa or less, and even more preferably -150 MPa or less. Furthermore, from the viewpoint of suppressing wrinkles caused by the internal stress and improving the appearance, the internal stress is preferably -400 MPa or more, more preferably -350 MPa or more, and even more preferably -300 MPa or more.
[0053] Examples of specific conditions for the CVD method for imparting compressive internal stress to the inorganic layer include, for example, the plasma deposition temperature being preferably 250°C or higher, more preferably 300°C or higher, and even more preferably 350°C or higher, and preferably 500°C or lower, more preferably 450°C or lower, and even more preferably 400°C or lower.
[0054] The pressure within the chamber is preferably 50 Pa or more, more preferably 100 Pa or more, and even more preferably 130 Pa or more, and is preferably 200 Pa or less, more preferably 160 Pa or less, and even more preferably 150 Pa or less, because the higher the pressure, the more likely it is that internal stress will be in the tensile direction.
[0055] The applied power and RF frequency are parameters for generating plasma that activates chemical species and triggers their reaction and growth on the organic film. The RF frequency is usually a high frequency of 13.56 MHz (HF) alone, but may also be used in combination with a low frequency of 380 kHz (LF). When applying compressive internal stress to the inorganic layer, it is preferable to apply a voltage at a low RF frequency of 380 kHz alone. Furthermore, when using both 380 kHz and 13.56 MHz, the relationship between the application time T1 of 13.56 MHz and the application time T2 of 380 kHz is preferably T2 > T1, more preferably T2 > 3 × T1, even more preferably T2 > 6 × T1, and preferably T2 < 20 × T1 or less, more preferably T2 < 15 × T1, and even more preferably T2 < 12 × T1.
[0056] The applied power is preferably 20 W or more, more preferably 30 W or more, and even more preferably 50 W or more, and is preferably 200 W or less, more preferably 100 W or less, and even more preferably 60 W or less, for each of 13.56 MHz (HF) and 380 kHz (LF). HF and LF may be the same or different.
[0057] The first element may have a first surface and a second surface, the first surface having a plurality of chips, and the organic layer and the inorganic layer may be laminated on the first surface side. When a plurality of chips are arranged on the first element and conventional organic and inorganic layers are laminated on the surface of the first element on which the chips are arranged, the chips form irregularities, and when connecting to other laminates or substrates via the organic and inorganic layers, the connection surface of the organic layer is not flat, and connection reliability is likely to be reduced. In the laminate of the present invention, even in elements with large irregularities, the organic layer fills the irregularities to flatten the connection surface, thereby demonstrating high connection reliability and suppressing warping and cracking of the first element and chips.
[0058] Examples of the chips include memory circuit elements, logic circuit elements, etc. The number of chips is not particularly limited as long as it is two or more.
[0059] The laminate of the present invention may further include a support substrate laminated on the inorganic layer. By laminating a support substrate on the inorganic layer, it becomes easy to fix the laminate of the present invention to the housing of an electronic component, such as an imaging device or a semiconductor device. Examples of the support substrate include glass and single crystal silicon.
[0060] When the organic layer is a cured product of a curable resin composition containing the silsesquioxane or an organosilicon compound having a structure represented by general formula (1), the laminate of the present invention has a wavelength of 775 cm in an IR spectrum measured by FT-IR from the surface of the inorganic layer. －１ The peak heights (Si-O) of P775 and 2180 cm －１ When the peak height (Si-H) of 775 cm is P2180, it is preferable that P2180 / P775<0.045. －１ The peak at 2180 cm indicates the presence of silicon-oxygen bonds. －１The peak indicates the presence of silicon-hydrogen bonds. Because silicon-hydrogen bonds have the property of easily transmitting moisture, the presence of a large number of silicon-hydrogen bonds can lead to reduced moisture resistance. Therefore, by ensuring that P2180 / P775 is within the above range, i.e., by reducing the amount of silicon-hydrogen bonds compared to silicon-oxygen bonds, the moisture resistance of the inorganic layer and laminate can be further improved. The P2180 / P775 ratio is more preferably less than 0.04, and even more preferably less than 0.03. There is no particular lower limit for the P2180 / P775 ratio; the smaller the better, but it is usually greater than 0. The P2180 / P775 ratio can be adjusted by adjusting the film formation conditions of the inorganic layer. The reason for the detection of Si-O bond peaks is that when measuring IR spectra with FT-IR, infrared light penetrates to a depth of 2-3 μm near the surface, detecting the Si-O in the underlying organic layer. On the other hand, the reason why the peak of the Si-H bond is detected is that the SiN film or SiO ２ During the film formation reaction, Si ３ N ４ or SiO ２ This is because the Si-H bond derived from the raw material SiH remains.
[0061] When the organic layer is a cured product of a curable resin composition containing the silsesquioxane or an organosilicon compound having a structure represented by general formula (1), the laminate of the present invention has a wavelength of 775 cm in an IR spectrum measured by FT-IR from the surface of the inorganic layer. －１ The peak height (Si-O) was P775, 1200 cm －１ When the peak height (N−H) of the above is P1200, it is preferable that P1200 / P775<0.30. －１ The peak at 1200 cm indicates the presence of silicon-oxygen bonds. －１The peak indicates the presence of nitrogen-hydrogen bonds. Nitrogen-hydrogen bonds have the property of easily transmitting moisture and become impurities in SiN films. Therefore, the presence of many nitrogen-hydrogen bonds reduces moisture resistance and causes performance changes at high temperatures. Therefore, by ensuring that P1200 / P775 is within the above range, i.e., by reducing the amount of nitrogen-hydrogen bonds compared to silicon-oxygen bonds, the moisture resistance of the inorganic layer and laminate can be further improved. The P1200 / P775 ratio is more preferably less than 0.28, and even more preferably less than 0.25. There is no particular lower limit for the P1200 / P775 ratio; the smaller the better, but it is usually greater than 0. The P1200 / P775 ratio can be adjusted by adjusting the film formation conditions of the inorganic layer. The reason for the detection of Si-O bond peaks is that when measuring IR spectra with FT-IR, infrared light penetrates to a depth of 2-3 μm near the surface, detecting the Si-O in the underlying organic layer. On the other hand, the reason why the N-H bond peak is detected is that Si is generated during the reaction of forming the SiN film by the CVD method. ３ N ４ The raw material NH ３ Alternatively, this is because N--H bonds derived from the source gas remain.
[0062] Specifically, the P2180 / P775 and P1200 / P775 can be measured by the following method. The absorption spectrum of the element after the inorganic layer formation is measured by the attenuated total reflection (ATR) method of Fourier transform infrared spectroscopy (FT-IR). At this time, the measurement range is 525 cm －１ From 4000 cm －１ The resolution is 4 cm －１ In the obtained absorption spectrum, －１ The peak heights (Si-O) of P775 and 2180 cm －１ The peak heights (Si-H) were P2180 and 1200 cm －１ The peak height (N−H) of the above is taken as P1200, and P2180 or P1200 is divided by P775 to obtain P2180 / P775 and P1200 / P775.
[0063] Here, a schematic diagram showing an example of the laminate of the present invention is shown in Figure 1. As shown in Figure 1, 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 act as an insulating layer when a plurality of laminates are laminated. Conventional laminates using organic compounds as insulating layers are highly effective in suppressing warpage of elements due to heat treatment when a plurality of laminates are laminated to form a semiconductor device, but are prone to permeation of moisture in the atmosphere. In the laminate of the present invention, a Si ３ N ４ By laminating a thin inorganic layer 3 containing the organic layer 2, moisture permeation can be suppressed. Furthermore, in the laminate of the present invention, since the inorganic layer 3 has internal stress in the compressive direction, the difference in internal stress between the organic layer 2 and the inorganic layer 3 is reduced, and the occurrence of cracks in the inorganic layer can be suppressed. As a result, moisture permeation is more difficult, and high connection reliability can be achieved. In addition, since the thickness of the inorganic layer 3 in the laminate of the present invention is thin, the organic layer 2 does not hinder the elimination of warpage of the element. Furthermore, although the organic layer 2 and the inorganic layer 3 are single layers in FIG. 1, they may be composed of multiple layers.
[0064] 2 and 3 are schematic diagrams showing another example of the laminate of the present invention. As shown in Fig. 2, the laminate of the present invention may be a laminate having a plurality of chips 4 on one surface (first surface) of a first element 1, and an organic layer 2 and an inorganic layer 3 laminated on the first surface of the first element. Furthermore, as shown in Fig. 3, a support substrate 5 may be laminated on the inorganic layer 3.
[0065] The present invention also provides a method for producing a laminate of the present invention, which includes the steps of forming an organic layer by depositing a curable resin composition on a first element, and forming the inorganic layer having an internal stress in a compressive direction on the organic layer by chemical vapor deposition.
[0066] The method for producing a laminate of the present invention first involves forming a film of a curable resin composition on a first element to form the organic layer. Conventional laminates using inorganic materials for the insulating layer have been produced by time-consuming methods such as chemical vapor deposition (CVD) or sputtering. Because the insulating layer of the laminate of the present invention is primarily composed of an organic compound, it can be produced by applying and drying a solution, thereby improving not only connection reliability but also production efficiency. The first element and curable resin composition are the same as the first element and curable resin composition in the laminate of the present invention.
[0067] The film formation method is not particularly limited, and conventionally known methods such as spin coating can be used. The solvent drying conditions are not particularly limited. However, from the viewpoint of reducing residual solvent 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 example, for 30 minutes, more preferably 1 hour. The curing conditions are not particularly limited. However, from the viewpoint of sufficiently progressing the curing reaction and further improving 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 example, for 1 hour or more, more preferably 2 hours or more. The upper limit of the heating time is not particularly limited. However, from the viewpoint of suppressing thermal decomposition of the organic layer, 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 example, for 1 hour or more, more preferably 2 hours or more.
[0068] In the method for producing a laminate of the present invention, it is preferable that the first element has a first surface and a second surface, the first surface has a plurality of chips, and the organic layer is formed on the first surface in the step of forming the organic layer. After forming the organic layer in such a step, an inorganic layer, which will be described later, is formed, thereby producing a laminate having a structure as shown in FIG.
[0069] The method for producing a laminate of the present invention then involves forming the inorganic layer having a compressive internal stress on the organic layer by chemical vapor deposition (CVD). The inorganic layer can be formed on the organic layer by chemical vapor deposition (CVD), and the conditions for this process can be adjusted to produce an inorganic layer having a compressive internal stress. The conditions for the inorganic layer and the CVD process are the same as those for the inorganic layer and the CVD process in the laminate of the present invention.
[0070] The method for producing a laminate of the present invention preferably further comprises a step of laminating a support substrate onto the inorganic layer. By performing the step of laminating the support substrate, a laminate having a structure as shown in FIG. 3 can be produced.
[0071] The use of the laminate of the present invention is not particularly limited, but since the laminate is less likely to warp or crack when laminated, has high moisture resistance, and can impart excellent connection reliability, it is suitable for image pickup devices and semiconductor devices. Such an image pickup device having the laminate of the present invention, a semiconductor device having the laminate of the present invention, and a method for manufacturing an image pickup device comprising a step of manufacturing an image pickup device using a laminate obtained by the method for manufacturing a laminate of the present invention also constitute one aspect of the present invention.
[0072] The laminate of the present invention is also used as a material for an element in which a plurality of laminates are stacked. The present invention also includes a method for manufacturing an element, the method comprising the steps of: forming an organic layer by depositing a curable resin composition on a surface of a substrate having electrodes, the surface having the electrodes, and the inorganic layer having a compressive internal stress by chemical vapor deposition; forming through holes in the organic layer and the inorganic layer; filling the through holes with a conductive material; and polishing the surface of the substrate having electrodes on the side filled with the conductive material to form a bonding electrode.
[0073] The method for producing an element of the present invention first involves the steps of forming an organic layer by depositing a curable resin composition on the electrode-bearing surface of a substrate, and then forming an inorganic layer having a compressive internal stress on the organic layer by chemical vapor deposition. The steps of forming the organic layer and the inorganic layer are the same as those in the method for producing a laminate of the present invention.
[0074] The substrate having the electrodes is not particularly limited, and may be a circuit substrate on which elements, wiring, and electrodes are formed, such as a sensor circuit substrate provided with a pixel section (pixel region), or a circuit substrate on which peripheral circuit sections such as logic circuits that perform various signal processing related to the operation of the solid-state imaging device are mounted.
[0075] The material of the electrodes of the electrode-bearing substrate is not particularly limited, and conventionally known electrode materials such as gold, copper, and aluminum can be used.
[0076] The method for manufacturing an element of the present invention then involves a step of forming through-holes in the organic layer and the inorganic layer. The organic layer and the inorganic layer on the electrode of the substrate are removed to provide through-holes, which are then filled with a conductive material to form connection electrodes for connecting to other substrates. The through-holes may be patterned. The method for forming the through-holes is not particularly limited, and may be carried out by CO ２ They can be formed by laser irradiation such as laser or etching, etc. When other layers are formed on the electrode surface of the substrate, the through holes are formed so as to penetrate the other layers as well and expose the electrode surface of the element.
[0077] The method for manufacturing an element of the present invention then optionally includes a step of forming a barrier metal layer. The barrier metal layer serves to prevent the conductive material (e.g., Cu atoms in the case of a Cu electrode) filled in the through-hole from diffusing into the organic layer. By providing a barrier metal layer on the surface of the through-hole, the conductive material filling the through-hole is covered with the barrier metal layer except for the surface that contacts the electrode, thereby further suppressing short circuits and poor conduction due to the diffusion of the conductive material into the organic layer. The barrier metal layer can be formed by sputtering, vapor deposition, or the like.
[0078] The barrier metal layer may be made of known materials such as tantalum, tantalum nitride, titanium nitride, silicon oxide, and silicon nitride.
[0079] The thickness of the barrier metal layer is not particularly limited, but from the viewpoint of further improving the connection reliability of the laminate, it is preferably 1 nm or more, even more preferably 10 nm or more, more preferably 100 nm or less, and even more preferably 50 nm or less.
[0080] The method for manufacturing an element of the present invention then includes a step of filling each of the through holes with a conductive material. The conductive material may be filled by plating or the like. The conductive material may be the same as the material of the electrodes of the electrode-bearing substrate of the laminate of the present invention.
[0081] The method for manufacturing an element of the present invention then includes a step of polishing the surface of the electrode-bearing substrate on the side filled with the conductive material to form a bonding electrode. The conductive material formed in the unnecessary portion is removed by grinding, thereby forming a bonding electrode that connects to an electrode of another element. The polishing preferably involves planarizing and removing the layer formed of the conductive material until the inorganic layer is exposed. The polishing method is not particularly limited, and for example, chemical mechanical polishing or the like can be used.
[0082] The use of the element obtained by the element manufacturing method of the present invention is not particularly limited, but it is suitable for an imaging device having a semiconductor device in which elements are stacked. Such a manufacturing method of an imaging device, which includes a step of manufacturing an imaging device using the element obtained by the element manufacturing method of the present invention, also constitutes one aspect of the present invention.
[0083] The element obtained by the element manufacturing method of the present invention is used for manufacturing a semiconductor device in which a plurality of elements are stacked with bonding electrodes. A method for manufacturing a semiconductor device, which includes a step of bonding two such elements obtained by the element manufacturing method of the present invention so that the connection electrodes are bonded to each other, also constitutes one aspect of the present invention.
[0084] In the step of bonding the connection electrodes together, the connection electrodes can be connected by a method of melting and connecting the electrodes by heat treatment, etc. The heat treatment is usually performed at 400° C. for about 4 hours.
[0085] FIG. 4 is a schematic diagram illustrating an example of a semiconductor device obtained by the semiconductor device manufacturing method of the present invention. As shown in FIG. 4 , the semiconductor device obtained by the semiconductor device manufacturing method of the present invention has a structure in which substrates 6 and 10 each having an electrode 7 are bonded via an organic layer 2 and an inorganic layer 3, and the electrode 7 on the substrate 6 and 10 each having an electrode is electrically connected through a conductive material filled in a through-hole 8 provided in the organic layer 2 and the inorganic layer 3. By covering the organic layer 2 with the thin inorganic layer 3, moisture resistance can be improved compared to when the organic layer 2 is used alone, and connection reliability can be enhanced. The semiconductor device may also have a barrier metal layer 9 on the surface of the through-hole 8. 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, thereby further reducing short circuits and poor electrical continuity.
[0086] According to the present invention, it is possible to provide a laminate that is less likely to warp or crack elements when stacked to form a semiconductor device, has high moisture resistance, and can impart excellent connection reliability, a method for manufacturing the laminate, a method for manufacturing elements 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.
[0087] It is a schematic diagram showing an example of a laminate of the present invention. It is a schematic diagram showing an example of a laminate of the present invention. It is a schematic diagram showing an example of a laminate of the present invention. It is a schematic diagram showing an example of a semiconductor device obtained by the manufacturing method of a semiconductor device of the present invention.
[0088] The following examples will further illustrate the present invention, but the present invention is not limited to these examples.
[0089] Example 1 (1) Production of Organosilicon Compound A 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. Heating was initiated with stirring under a nitrogen stream. Stirring was continued for 6 hours from the start of reflux and then the mixture was allowed to stand overnight at room temperature. The reaction mixture was then transferred to a filter and filtered under pressure with nitrogen gas. The resulting solid was washed once with 2-propyl alcohol, filtered, and then dried under reduced pressure at 80°C to obtain 33.0 g of a colorless solid (DD-ONa).
[0090] A 300 ml three-neck flask equipped with a dropping funnel, reflux condenser, and thermometer was charged with 11.6 g of compound (DD-ONs), 100 g of tetrahydrofuran, and 3.0 g of triethylamine, and the flask was sealed with dry nitrogen. While stirring with a magnetic stirrer, 4.5 g (30 mmol) of methyltrichlorosilane was added dropwise at room temperature. Stirring was then continued at room temperature for 3 hours. 50 g of water was added to the reaction solution to dissolve the generated sodium chloride and hydrolyze unreacted methyltrichlorosilane. The reaction mixture thus obtained was separated, and the organic layer was washed once with 1 N hydrochloric acid, once with a saturated aqueous sodium bicarbonate solution, and then three times with ion-exchanged water. 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).
[0091] A 100 mL flask was equipped with a condenser, mechanical stirrer, Dean-Stark tube, oil bath, and thermometer protection tube, and the interior of the flask was purged with nitrogen. 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 placed in 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 layer was washed with water, aqueous sodium bicarbonate, and saturated saline, and then dried over anhydrous sodium sulfate. This solution was concentrated under reduced pressure, and the residue was reprecipitated in a solution of 2-propanol:ethyl acetate = 50:7 (weight ratio), purified, and dried to obtain organosilicon compound A (weight average molecular weight: 36,000) having the structure of the following formula (8), in which m is 27 and n is an average of 4.
[0092]
[0093] (2) Preparation of Additive A A 100 mL flask was equipped with a condenser, mechanical stirrer, Dean-Stark tube, oil bath, and thermometer protection tube. 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 added to the flask and stirred. The flask was heated at 100°C for 1 hour and then refluxed in a 170°C oil bath for 1 hour. The solution was cooled to room temperature, and 1.3 g of citraconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 120°C for 10 minutes and then refluxed in a 170°C oil bath for 1 hour to obtain Additive A (weight average molecular weight: 9900) having the structure of the following formula (9). Note that 1 in the following formula (9) represents the number of repeating units.
[0094]
[0095] (3) Production of Curable Resin Composition A curable resin composition was obtained by adding 100 parts by weight of the obtained organosilicon compound, 0.2 parts by weight of a catalyst (ZC-162, an acetylacetonate complex having a zirconium 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 to a solvent (cyclopentanone, manufactured by Tokyo Chemical Industry Co., Ltd.) so that the content was 65% by weight and mixing them.
[0096] (4) Production of Laminate 15 g of the obtained curable resin composition was dispensed onto the center of an 8-inch silicon wafer (surface roughness <0.1 μm). Then, using a spin coater (ACT-400II; manufactured by ACTIVE Corporation), spin coating was performed at 500 rpm for 12 seconds, and the wafer was solvent dried in a 125°C oven for 10 minutes to obtain an 85 μm resin film. This resin film was heat-treated at 300°C for 1 hour to obtain an organic layer. The obtained silicon wafer with the organic layer was heat-treated at 400°C for 1 hour in a nitrogen atmosphere using a vacuum process high-speed heating furnace (VPO-650, manufactured by Unitemp Corporation). Next, inorganic film formation was performed by CVD for a predetermined time under the conditions shown in Table 3 using a PE-CVD (product number MPX-CVD, manufactured by Sumitomo Precision Products Co., Ltd.), and a 400 nm thick SiN layer (inorganic layer) was formed on the organic layer to obtain a laminate. In Table 3, "HF" in "Upper RF Power" indicates the power during film formation at 13.56 MHz, and "LF" indicates the power during film formation at 380 kHz. Furthermore, "First" in "Switching mode" indicates that 13.56 MHz and 380 kHz are applied first when they are applied alternately, and "End" indicates that they are applied last. Furthermore, "Compressive" in "Film stress" indicates a force in the compressive direction, and "Tensile" indicates a force in the tensile direction.
[0097] (5) Measurement of 1% Thermal Weight Loss Temperature: Each organic monolayer was prepared by the above method. The obtained monolayer was heated at a temperature increase rate of 10°C / min under a nitrogen flow of 50 mL / min using a thermogravimetric and differential thermal analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation), and the temperature at which the weight loss rate reached 1% was measured. The results are shown in Table 1.
[0098] (6) Measurement of Internal Stress Using a thin film stress measurement device (FLX2320-S, manufactured by Toho Technology Co., Ltd.), the amount of warpage and radius of curvature of the untreated silicon wafer were calculated. The radius of curvature R at this time was defined as R １ Next, on the silicon wafer whose radius of curvature was calculated, a 100 nm inorganic film was formed using PE-CVD (product number MPX-CVD, manufactured by Sumitomo Precision Products Co., Ltd.) under the conditions shown in Table 2. After the inorganic film was formed, the amount of warpage and radius of curvature after the inorganic film formation were calculated again using the thin film stress measurement device. The radius of curvature R at this time was defined as R ２ The inorganic film stress S (Pa) was calculated from the change in the radius of curvature before and after inorganic film formation using Stoney's equation, which is expressed by the following formula (A). The results are shown in Table 1. In the table, negative values for the film stress indicate that there is internal stress in the compressive direction, and positive values indicate that there is internal stress in the tensile direction.
[0099]
[0100] In the formula (A), E / (1-v) is the biaxial elastic modulus of the silicon wafer (Pa), which is 1.805×10 １１ Pa. h: thickness of the silicon wafer (m), which was set to 725 μm. t: thickness of the inorganic film (m), which was set to 100 nm. R: radius of curvature of the substrate, which is obtained from the following formula (B).
[0101]
[0102] (7) Measurement of P2180 / P775 and P1200 / P775 The absorption spectrum of the substrate after inorganic film formation was measured by the attenuated total reflection (ATR) method of Fourier transform infrared spectroscopy (FT-IR). At this time, the measurement range was 525 cm －１ From 4000 cm －１ The resolution is 4 cm －１ In the obtained absorption spectrum, －１ The peak heights (Si-O) of P775 and 2180 cm －１ The peak height (Si-H) of P2180 was taken as P2180, and P2180 was divided by P775 to obtain P2180 / P775. －１The peak height (N−H) was taken as P1200 and divided by P775 to obtain P1200 / P775.
[0103] (Examples 2 to 19, Comparative Examples 1 to 6) Laminates were obtained under the same conditions as in Example 1, except that the organic and inorganic layer configurations and film-forming conditions were as shown in Tables 1 to 3. The 1% thermal weight loss temperature, internal stress, and P2180 / P775 and P1200 / P775 were measured. For Comparative Example 6, dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the catalyst. For Examples 16, 18, and 19, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.) was used as the crosslinking agent. Resin B and additives B to D were resins, additives, or commercially available products obtained by the following methods. Furthermore, for film-forming conditions 10 to 12, a PD-220NL (manufactured by Samco) was used as the film-forming apparatus.
[0104] (Production of Resin B) A 100 mL flask was equipped with a condenser, mechanical stirrer, Dean-Stark tube, oil bath, and thermometer protection tube, and the interior 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 placed in 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 layer was washed with water, aqueous sodium bicarbonate, and saturated saline, and then dried over anhydrous sodium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by reprecipitation in a solution of 2-propanol:ethyl acetate = 50:7 (weight ratio), followed by drying to obtain an organosilicon compound (Resin B, weight average molecular weight 46,000) having the structure of the above formula (8), in which m is 36 and n (number of DMS chains) is an average of 3.
[0105] (Production of Additive B) A 100 mL flask was equipped with a condenser, a mechanical stirrer, a Dean-Stark tube, an oil bath, and a thermometer protection tube. 3.9 g of bisaminopropyltetramethyldisiloxane (PAM-E, manufactured by Shin-Etsu Silicones Co., Ltd.), 36.3 g of anisole, and 3.53 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the flask and stirred. The mixture was refluxed in a 170°C oil bath for 2 hours, and the resulting synthetic liquid was cooled to room temperature and then 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.
[0106]
[0107] (Additives C and D) The following additives were used as additives C and D. Additive C: TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.) Additive D: BYK-320 (manufactured by BYK Corporation)
[0108] <Evaluation> The laminates obtained in the examples and comparative examples were evaluated as follows. The results are shown in Tables 1 and 2. Note that the amount of thermal decomposition of the resin film was large in Comparative Example 6, and CVD film formation was not possible, so evaluation was not performed.
[0109] (Evaluation of cracks during film formation) In the production of the laminate, the inorganic layer formed was visually observed and evaluated for cracks during film formation according to the following criteria: ◯: No cracks ×: Cracks present
[0110] (Evaluation of heat resistance) The laminate was heat-treated in a nitrogen atmosphere at 400°C for 3 hours using a vacuum process high-speed heating furnace (VPO-650, manufactured by Unitemp). After the heat treatment, the laminate was evaluated for film cracking in the thick film according to the following criteria: ○: No cracking after heat treatment △: Cracks of about 2 mm occurred at the edge after heat treatment ×: Cracks occurred after heat treatment
[0111] (Evaluation of moisture resistance) The laminate was left to stand for 500 hours in an environment of a temperature of 85°C and a humidity of 85%. Thereafter, the laminate was visually observed, and the moisture resistance was evaluated according to the following criteria: ⊚: No trace of water penetration from the edge was observed; ◯: Trace of water penetration from the edge was less than 2 mm; △: Trace of water penetration from the edge was 2 mm or more but less than 4 mm; ×: Trace of water penetration from the edge was 4 mm or more.
[0112]
[0113]
[0114]
[0115] According to the present invention, it is possible to provide a laminate that is less likely to warp or crack elements when stacked to form a semiconductor device, has high moisture resistance, and can impart excellent connection reliability, a method for manufacturing the laminate, a method for manufacturing elements 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.
[0116] REFERENCE SIGNS LIST 1 First element 2 Organic layer 3 Inorganic layer 4 Chip 5 Support substrate 6 Substrate having electrode 7 Electrode 8 Through hole 9 Barrier metal layer 10 Substrate having electrode
Claims
1. 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 has a 1% thermal weight loss temperature of 400°C or higher, measured under a nitrogen atmosphere at a temperature increase rate of 10°C / min; the inorganic layer has a thickness of 1 nm or more and 1 μm or less, The inorganic layer is Si ３ N ４ layer, The inorganic layer is a laminate having an internal stress in a compressive direction.
2. The inorganic layer is made of SiO ２ The Si layer ３ N ４ The layer is the SiO ２ The laminate of claim 1 , laminated on a 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 organosilicon compound.
5. 5. The laminate according to claim 4, wherein the organosilicon compound has a structure represented by the following general formula (1): 【Chemical 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 or may not have a substituent. m and n each represent an integer of 1 or more.
6. In the IR spectrum measured by FT-IR from the surface of the inorganic layer, －１ The peak heights (Si-O) of P775 and 2180 cm －１ The laminate according to claim 5, wherein P2180 / P775<0.045 when the peak height (Si-H) of
7. In the IR spectrum measured by FT-IR from the surface of the inorganic layer, －１ The peak height (Si-O) was P775, 1200 cm －１ The laminate according to claim 5, wherein P1200 / P775<0.300, where P1200 is the peak height (N-H) of the above-mentioned compound.
8. The laminate according to claim 1 or 2, wherein the organic layer has a thickness of 10 μm or more.
9. the first element has a first surface and a second surface, the first surface having a plurality of chips; The laminate according to claim 1 or 2, wherein the organic layer and the inorganic layer are laminated on the first surface side.
10. The laminate according to claim 1 or 2, further comprising a supporting substrate laminated on the inorganic layer.
11. An imaging device having the laminate described in claim 1 or 2.
12. A semiconductor device having a laminate according to claim 1 or 2.
13. A method for manufacturing a laminate as described in claim 1 or 2, comprising the steps of forming the organic layer by depositing a curable resin composition on the first element, and forming the inorganic layer having an internal stress in the compressive direction on the organic layer by chemical vapor deposition.
14. The method for manufacturing 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 the organic layer is formed on the first surface side in the step of forming the organic layer.
15. The method for producing a laminate according to claim 13 , further comprising the step of laminating a support substrate onto the inorganic layer.
16. A method for manufacturing an imaging device, comprising a step of manufacturing an imaging device using a laminate obtained by the manufacturing method described in claim 13.
17. forming an organic layer by depositing a curable resin composition on a surface of a substrate having electrodes, the surface having the electrodes; forming an inorganic layer having an 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 holes with a conductive material; and polishing the surface of the substrate having the electrode on the side where the conductive material is filled to form a bonding electrode.
18. A method for manufacturing an imaging device, comprising the step of manufacturing an imaging device using an element obtained by the method for manufacturing an element according to claim 17.
19. A method for manufacturing a semiconductor device, comprising the step of bonding two elements obtained by the method for manufacturing an element according to claim 17 together so that the connection electrodes are joined to each other.