TW201207896A - Method for manufacturing semiconductor wafer bonding product, semiconductor wafer bonding product and semiconductor device - Google Patents

Abstract

A method for manufacturing a semiconductor wafer bonding product includes a process of forming a spacer having wall portions 104' by exposing a spacer forming layer by selectively irradiating with exposing light, and then developing the spacer forming layer using a developing solution, wherein when a width of each of the wall portions 104' is defined as W ( μ m) and a height of each of the wall portions 104' is defined as H ( μ m), W and H satisfy the following relations (1) to (3). 15 ≤ W ≤ 3000 (1) 3≤ H ≤ 300 (2) 0.10 ≤ W/H ≤ 900 (3) This makes it possible to prevent or suppress suspended solid matters generated in the developing step from remaining in the semiconductor wafer bonding product as residue when the spacer to be provided between a semiconductor wafer and a transparent substrate is formed by subjecting it to the exposing and developing steps.

Description

201207896 VI. Description of the Invention: TECHNICAL FIELD The present invention relates to a method of manufacturing a semiconductor wafer bonded body, a semiconductor wafer bonded body, and a semiconductor device. [Prior Art] A semiconductor device typified by a light-receiving device such as a CMOS image sensor or a CCD image sensor has a semiconductor substrate provided with a light-receiving portion and is disposed on the side of the light-receiving portion with respect to the semiconductor substrate. Further, a spacer formed by surrounding the photosensitive portion and a plate member joined to the semi-conducting plate via the spacer (for example, refer to Lai Document 1:). For example, the method of manufacturing a semiconductor device of Patent Document 1 has a step of attaching a photosensitive adhesive film (spacer forming layer) to a semiconductor wafer provided with a plurality of photosensitive portions, and selectively interposing through the mask The step of exposing the chemical line to the adhesive film to expose the adhesive film, and performing the exposure after the exposure (4) to form a step of breaking the step of joining the transparent plate to the coffin, and separating the spacer The step of bonding the semiconductor germanium to the bonded body of the transparent substrate is performed. As described above, the exposed film of the adhesive film removes the unhardened portion of the adhesive film, which is not completely dissolved by the unsuppressed portion. In this case, a part of the front part is suspended in a solid shape, and the unhardened portion is formed. Therefore, the exposed portion of the film in which the suspended matter adheres to the film is conventionally left as the door 2 is lowered. The production rate of the flying + body device is as follows: </ RTI> after the exposure of the adhesive film into the 4/48 201207896 line, before the semiconductor wafer and the transparent substrate are bonded via the spacer, This is caused by the cleaning of the hardened portion (spacer) of the adhesive film by the cleaning liquid, but even this problem occurs. [Prior Art] [Patent Document 1] [Patent Document 1] JP-A-2008-91399 SUMMARY OF INVENTION [Problem to be Solved by the Invention] An object of the present invention is to provide a process for performing exposure processing and development. When a ϋτ material disposed between a semiconductor wafer and a transparent substrate is formed, a method of manufacturing a semiconductor wafer bonded body in which a solid-shaped suspension generated in a development process remains as a residue can be suppressed or prevented, and a reliability is provided. Jiazhi semiconductor wafer bonded body and semiconductor device. [Means for Solving the Problem] This object can be achieved by the present invention described in the following (1) to (14). (1) A method of manufacturing a semiconductor wafer bonded body, comprising: a semiconductor wafer; a transparent substrate disposed opposite to one side of the semiconductor wafer; and having a semiconductor wafer and the transparent substrate A spacer for a wall portion provided in a plurality of gap portions, wherein one of the semiconductor wafer and the transparent substrate is formed with a photosensitive resin composition. a step of forming a layer by exposing the exposure light to the spacer formation layer selectively, and performing the development by using a developer to leave the wall portion, and

5/48 S 201207896 The step of bonding the other of the semiconductor wafer and the transparent substrate to the wall portion; and setting the width of the wall portion to W [pm] and setting the height of the wall portion to Η [ In the case of μηι], the relationship of the following <1>~&lt;3> is satisfied respectively. 15^W^3000 · · · &lt;1&gt; 3SHS300 · · · &lt;2&gt; 0.10SW/HS900 · · · &lt;3&gt ; (2) The method for producing a semiconductor wafer bonded body according to the above (1), wherein the specific gravity of the developer is A, and when the specific gravity of the resin composition is B, the relationship of 0.5 SA/B$2 is satisfied. formula. (3) The method of manufacturing a semiconductor wafer bonded body according to the above aspect, wherein the wall portion is formed in a plan view when the plurality of void portions are formed in a quadrangular shape and arranged in a matrix shape. Formed. (4) The method of manufacturing a semiconductor wafer bonded body according to any one of (1) to (3), wherein the developing the semiconductor wafer or the transparent substrate on which the spacer formation layer is formed The developing solution is applied to the spacer forming layer while rotating perpendicular to the plate surface and passing through the axis near the center. (5) The method of producing a semiconductor wafer bonded body according to the above (4), wherein the developing is performed such that a surface side of the semiconductor wafer or the transparent substrate on which the spacer formation layer is provided faces upward. (6) The method of manufacturing a semiconductor wafer bonded body according to any one of (1) to (5), wherein, after the developing, and bonding the other of the semiconductor wafer and the transparent substrate to the foregoing Before the step of the wall portion, the wall portion and the 6/48 201207896 semiconductor wafer or the transparent substrate on which the wall portion is formed are washed with a cleaning liquid. (7) The method for producing a semiconductor wafer bonded body according to the above (6), wherein the specific gravity of the resin composition is B, and when the specific gravity of the cleaning liquid is C, it is 0.5 SC/BS 2 Relationship. (8) The method of manufacturing a semiconductor wafer bonded body according to the above (6) or (7), wherein the cleaning is performed by vertically surrounding the semiconductor wafer or the transparent substrate on which the wall portion is formed The plate surface is rotated by the axis near the center, and the cleaning liquid is applied to the wall portion and the semiconductor wafer or the transparent substrate on which the wall portion is formed. (9) The method of manufacturing a semiconductor wafer bonded body according to the above (8), wherein the cleaning is performed such that a surface side of the semiconductor wafer or the transparent substrate on which the wall portion is provided faces upward. (10) The method of manufacturing a semiconductor wafer bonded body according to any one of the above (6), wherein, after the cleaning, the other of the semiconductor wafer and the transparent substrate is bonded to Before the step of the wall portion, there is a step of removing the cleaning liquid. (11) The method of manufacturing a semiconductor wafer bonded body according to (10) above, wherein the step of removing the cleaning liquid is performed by causing the semiconductor wafer or the transparent substrate on which the wall portion is formed to be perpendicular to the board The surface is rotated by an axis near the center. (12) A semiconductor wafer bonded body produced by the method according to any one of (1) to (11) above. (13) A semiconductor wafer bonded body comprising: a semiconductor wafer, a transparent substrate disposed opposite to one side of the semiconductor wafer, and a region between the semiconductor wafer and the transparent substrate

7/48 S } 201207896 A conductor wafer bonded body of a spacer of a wall portion provided in a plurality of void portions, wherein: w is a width of the wall portion, and each of the above When the height of the wall portion is Η[μιη], the relationship of the following ~&lt;3> is satisfied: L, 15 ^ W^ 3000 . · . &lt;1&gt; 3 ^ 300 . . . &lt;2&gt; 0.10 SW/HS900: (3) A semiconductor device obtained by crystallizing a semiconductor wafer bonded body according to (12) or (13) above. [Embodiment] Hereinafter, embodiments of the present invention will be described based on additional drawings. &lt;Semiconductor device (image sensor)&gt;&quot; First, the semiconductor device of the present invention will be described. Fig. 1 is a cross-sectional view showing a semiconductor device according to an embodiment of the present invention. In the following description, the upper side of the drawing is referred to as "upper" and the lower side is referred to as "lower". The semiconductor device 100 shown in FIG. 1 is a photosensitive device such as a CM〇s image sensor or a CCD image sensor. As shown in FIG. 1, the semiconductor device (photosensitive device) 1 includes a base substrate 101 and a transparent substrate 102 disposed to face the base substrate 101, and includes a surface provided on the transparent substrate 102 side of the base substrate 101. The individual circuit 103 of the photosensitive portion, the spacer 104 disposed between the transparent substrate 1〇2 and the individual circuit 1〇3, and the solder bump disposed on the surface of the base substrate ι1 opposite to the individual circuit 103 Block 106. This semiconductor device 10 is obtained by subjecting the semiconductor wafer bonded body 1 of the present invention to be described later to a crystal grain 8/48 201207896. The base substrate 101 is a semiconductor substrate, and is provided with a circuit (not shown) (an individual circuit included in the semiconductor wafer). On the aspect (top surface) of the base substrate 101, the individual circuits 103 are almost entirely provided. The individual circuit 103 includes a mechanical light portion, and the wire is formed by, for example, stacking a photosensitive element and a microlens array on the base substrate 101. Examples of the photosensitive portion of the individual circuit 103 include a CCD (Charge Coupled Device) &gt; CMOS (C〇mplementary Metal Oxide Semiconductor). The individual circuits i 〇 3 having such a photosensitive element convert the light sensitized by the individual circuits 103 into electrical signals. The transparent substrate 102 is disposed on the one side of the base substrate 1〇1 and is substantially the same planar size as the planar size of the base substrate 101. Examples of the transparent substrate 102 include an acrylic resin substrate, a polyethylene terephthalate (PET) resin substrate, and a glass substrate. The spacers 104 are adhered to the individual circuits 1〇3 and the transparent substrate 〇2, respectively. Thereby, the base substrate ι 1 and the transparent substrate 102 can be joined via the spacer 104. Further, the spacer 104 is formed in a frame shape along the outer peripheral edge portions of the individual circuit 丨〇3 and the transparent substrate 1〇2. Thereby, a void portion 1〇5 is formed between the individual circuit 1〇3 and the transparent substrate 102. Here, the spacer 104' is provided so as to surround the central portion of the individual circuit 103. However, the portion of the individual circuit 103 surrounded by the spacers 〇4, that is, the portion exposed to the void portion 105, has substantial individual parts. The function of the circuit. The solder bumps 106 are electrically conductive, under the base substrate ιοί,

9/48 S 201207896 is electrically connected to the wiring provided on the base substrate 1G1. Thereby, the electric tfi number from the handle is transmitted to the solder bump 106 &lt;semiconductor wafer bonded body by the individual circuit 1G3. Next, the semiconductor wafer bonded body of the present invention will be described. 2 is a longitudinal view of a semiconductor wafer bonded body according to an embodiment of the present invention. FIG. 3 is a view showing a semiconductor wafer bonded body shown in FIG. 2, as shown in FIG. In the first embodiment, the semiconductor wafer 101 is laminated, and the spacer 12A and the transparent substrate are stacked. That is, the semiconductor wafer bonded body 1000 is bonded to the semiconductor wafer via the spacer 12A. And transparent substrate 102'. The semiconductor wafer 101' is a substrate of the base substrate 101 of the above-described semiconductor device 100 by performing a grain formation step which will be described later. Further, a plurality of individual circuits are not provided on the semiconductor wafer 101'. On the one hand (upper surface) of the semiconductor wafer 101', the above-described individual circuits 103 are formed corresponding to the respective individual circuits described above. The door spacer 12A is a member of the spacer 104 which becomes the upper semiconductor device 100 by performing a grain formation step which will be described later. The spacer 12A is provided so as to be spaced apart from the transparent substrate 102 by a plurality of gaps between the semiconductor wafer 101 and the transparent substrate 102. The wall portion 104' is configured to combine a plurality of ridges. In the second embodiment, as shown in Fig. 3, the wall portion 104 is formed in a plan view in which a plurality of the gap portions 1〇5 are formed in a square shape and arranged in a matrix shape in a plan view. Further, in a plan view, a plurality of individual electrodes 1〇5 corresponding portions 104 on the semiconductor wafer 10 are formed so as to surround the semiconductor wafer 101, the upper portion, and the circuit 103). ^Every individual Wei (in particular circuit, especially the '12 spacers, the wall part is \ν[μηι], the wall part 1〇4丨 (convex)), the satisfaction of the Han meet the following &lt;1&gt ;~&lt;3&gt; relationship: ...ir 15^ W^3000 . . . &lt;i&gt; 3^H^ 300 . . . &lt;2&gt; 0.10$ W/H$900 . · · &lt;3&gt;. The relationship of the above &lt;1 &gt;~&lt;3&gt; will be described in detail later. The transparent substrate 102 is bonded to the semiconductor wafer 10A via the gap #12A. The s-transparent transparent substrate 102' is a member of the transparent substrate 1A2 of the above-described semiconductor device 100 by performing a grain formation step which will be described later. By laminating such a semiconductor wafer bonded body 1 as will be described later, a plurality of semiconductor devices 1 can be obtained. &lt;Manufacturing Method of Semiconductor Device (Semiconductor Wafer Bonded Body) Next, a preferred embodiment of a method of manufacturing a semiconductor device (semiconductor wafer bonded body) of the present invention will be described. Further, the method for manufacturing a semiconductor wafer bonded body according to the invention will be described below by way of an example in which the semiconductor device 1 and the semiconductor wafer bonded body 1 are manufactured. 4 to FIG. 6 are diagrams showing an example of a method of manufacturing the semiconductor device (the semiconductor wafer bonded body shown in FIG. 2) shown in FIG. 1, and FIG. 7 is a view for explaining the method shown in FIG. 5(a). Fig. 8 is a view for explaining the action in the developing process shown in Fig. 5(a).

11/48 S 201207896 The manufacturing method of the semiconductor wafer 100 has the following steps: (4) a step of manufacturing a semiconductor package, and a step of graining a semiconductor wafer bonding group. The manufacturing method of the semiconductor wafer bonded body 1000 (the above step has the following steps: {A1> bonding the spacer forming layer 12 to the semiconductor ! ° ΐ step ' 'A2>> by exposure and development The step of selectively removing the space 12 to form the spacer 12A, &lt;A3" applies the transparent substrate spacer to the surface opposite to the semiconductor wafer, and the lower surface of the semiconductor crystal 83 1〇Γ Steps of a predetermined processing or processing. Steps Hereinafter, the steps (4) of the manufacturing method of each of the semiconductor wafer bonding bodies 1 of the semiconductor device manufacturing method will be described in detail. Conductor crystal, upper Α 1-1 First, as shown in Fig. 4 (8), prepare a film for spacer formation

This spacer forming film i has a spacer substrate 12 which supports the substrate u and the support substrate 11. The support substrate 11 has a sheet shape and has a slit spacer forming layer 12. The support substrate 11 has light transmittance. In the exposure processing of this article, the layer 12 can be formed in the state in which the support substrate u (four) is formed in the state of the branch. The material 1 is etched and cut. The constituent material of the support substrate U in the form of a spacer has a function of supporting the 12/48 201207896 spacer forming layer 12 and light transmittance as described above. For example, polyparaphenylene is exemplified. B dicarboxylic acid; 'polyethylene (IV) is not particularly limited. Among these, it is:), polypropylene (4), benzene 2 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The degree of twist is achieved, and the thickness of the intermediate portion of the spacer forming layer is uniformized. In contrast to the portion of the support substrate u, the average thickness of the support substrate u is &quot; ===, _; layer: = the degree of processing of the material forming film i is equal to the upper limit value, None::艮i support^2: Exposure light in the thickness direction -L 10〇〇/oT 0 1〇〇〇/〇&quot;T 5 4〇%&quot; π will expose the exposure light to 'can be separated by the support base Material. The material is opened 7 to form 12 and the surface of the exposed portion is surely formed and there is a lining-forming layer 12 with respect to the semiconductor wafer 1〇1, and the spacer rib can be formed into a layer 12 and a semiconductor crystal: = Shape "= two: _ light". Therefore, it is expected that the shape of the material becomes a step after the a! step: two hard: there is a thermal hardening property according to the exposure treatment even after

Adhesion formed by 13/48 C 201207896. Therefore, the spacer 12A and the transparent substrate 1〇2 are joined in the step "A3 hardening" described later. In the case of the spacer layer 12 which is formed by heat, it is not particularly limited as long as it has the above-described 丄=chemical property and thermosetting property, and it is difficult to have a hard strip and light. The poly material is hereinafter referred to as "resin composition". 々4 枓 枓 枓 枓 枓 枓 枓 枓 枓 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( _, Jiao (four) type ϋ age - ί Yue 曰, Pan class Fangyuan resin, styrene acetal resin, methyl succinate acid, etc. acrylic resin, containing secret: ^ 寻之环a hydrocarbon-based resin or a poly-based resin (specifically, a resin having at least one of an open structure, a stagnation structure, and a polyaniline structure, and having a resin in a main cooker, a base, a base, a ring, or a base) Benzene; a resin having a structure of a poly-imine precursor, a resin having a structure of a polyacrylic acid precursor, and the like, and a combination of two or more of these may be used. The spacer forming layer 12 composed of a neo-resin has an alkali-developing property with little burden on the environment. h Especially in the above-mentioned soluble resin, it is preferable to use an alkali-soluble group and a double which are beneficial for double... The resin of the bond. The cardinyl group can be exemplified by a base, a slow base, and the like. Solvent = is beneficial for the development of the test, and is beneficial to the heat hardening reaction. In addition, the alkali M raw resin 'borrows (4) has a double bond 1 to benefit the photohardening reaction. Further, a resin having such a soluble group and a double bond, for example, In the case of a curable resin which can be cured by both light and heat, for example, heat of a photoreactive group having an acrylonitrile group, a mercapto propylene group, and a vinyl machine can be mentioned. A curable resin, or a photocurable resin having a thermal reaction group such as a phenolic hydroxyl group, an alcoholic hydroxyl group, a slow group or an acid anhydride group, etc., and a curable resin capable of hardening by both light and heat is used as a base. In the case of a soluble resin, the phase hardenability of the photocurable resin and the thermosetting resin described later can be improved. As a result, the spacer forming layer 12 after curing, that is, the strength of the spacer 12A can be improved. The resin may further contain another thermal reaction group such as an epoxy group, an amine group or a cyanate group. Specific examples of the photocurable resin having such a composition include a phenol resin modified with (fluorenyl) acrylic acid and containing ( :, An acrylic polymer based on an acrylonitrile group and an acrylic acid (epoxy) ruthenium containing a carboxyl group, etc., may also be a ruthenium-like plastic resin containing a radical acrylic resin. The above-mentioned alkali-soluble group and double bond are used. A resin (a curable resin which can be cured by light and heat) is preferably made of a (Y-based) propylene-based bismuth. If a (meth)acrylic acid is used, it is desired to be modified. The resin, which is made of a curable base, is replaced with an organic solvent which is usually used in development by removing the unreacted 2%•'s (4) environment with less burden on the developing area. Furthermore, by containing The double bond causes the double-bowl to further react, and as a result, the heat of the resin composition can be improved. This: the fine resin can be reliably reduced by using an aged resin modified with (meth)acrylic acid. From the point of view, the phenolic resin modified by the use of (meth)acrylic acid. Further, for example, a phenol resin modified with propylene oxime may be exemplified by a bisphenol group and a compound having an epoxy group and a (meth) propylene group.

15/48 S 201207896 % (meth) propyl sulfhydryl-modified bisphenol resin obtained by the oxygen-based reaction. The above-mentioned chemical formula W can be exemplified by the compound of the compound which is modified by the slow (meth)acrylic acid group. [Chemical Formula 1] ch3

CH

3

CH-I , c I CH

3

HO 0 ch3 〇-CH2-CH-CH2-〇-C-C=CHj

OH

Ο H

1 I CH Guang CH—CH2-0—C~C=CH, I *

OH C-1 ! A V'xM&gt;f〇+ λγ&quot;Τ'οο-γβΚ&gt;{〇^:γύ-月匕卜,, outside, outside the tree with soluble and double bonds β'β" Λ At the end of Weishu (4), the base of the epoxy resin (in the molecular chain of the modified epoxy resin) is replaced by a base in the molecular chain of the epoxy resin. a two-70 (tetra)-carboxy bond, thereby introducing a diprotic acid-recognition compound (in addition, the epoxy repeating unit of the compound is 16/48 201207896 is 1 or more, and is introduced into the sub-chain The number of the protonic acid dibasic acid is 1 or more. Further, the compound can be obtained, for example, by first polymerizing the epichlorohydrin of the oxygen-containing resin obtained by polymerizing epichlorohydrin with a polyhydric alcohol. The reaction is carried out by reacting methyl)acrylic acid to obtain a (meth)acrylonitrile-based epoxy resin having a (mercapto)acrylonitrile group introduced at both ends of the epoxy resin, and then, The obtained hydroxyl group in the molecular chain of the (fluorenyl) propylene fluorenyl modified epoxy resin and the acid anhydride of the diprotic acid dibasic acid Thus, a carboxyl group and an ester bond of one of the dicarboxylic acid dibasic acids are formed. When a thermosetting resin having a photoreactive group is used, the rate of change (substitution ratio) of the photoreactive group is not particularly limited. Preferably, the degree of the reaction group of the resin having the soluble group and the double bond is preferably from 2 to 30%, and preferably from 30 to 70% by the mass of the photoreactive group. On the other hand, when a photocurable resin having a thermal reaction group is used, the reforming ratio (substitution ratio) of the thermal reactive group is not particularly limited, and it is preferred to have a base. The degree of the reaction group of the resin of the base and the double bond is 2 〇 to 8 〇%, particularly preferably 30 to 70%. By setting the quality of the thermal reaction group to the above-mentioned range A resin composition with excellent resolution. In addition, 'the weight average molecular weight of the resin having a soluble base and a double bond is used as the soluble solvent. The weight average molecular weight of the resin is not particularly limited, but is preferably 3 〇〇〇. 〇 below, especially preferably from 5000 to 150,000. The weight average molecular weight is in front. When the spacer forming layer 12 is formed on the support substrate 11, the film formability can be particularly good. Here, the weight average molecular weight of the soluble resin can be evaluated, for example, using PC. From the inspection line prepared by using styrene standard material in advance, the weight average molecular weight is obtained. At this time, the solvent is used in four.

17/48 S 201207896 Nitrogen 11 Fusan (THF) and measured at a temperature of 4 ° C. Further, the content of the alkali-soluble resin in the resin composition is not particularly limited, but is preferably from 15 to 5 % by weight, particularly preferably from 20 to 40 % by weight, based on the total amount of the resin composition. In addition, when the resin composition contains the filling ratio described later, the content of the alkali-soluble resin is preferably from 1 〇 to 8 〇wi% with respect to the resin component of the resin composition (excluding all the components of the filler). To the extent of 15 to 70% by weight. When the content of the alkali-soluble resin is within the above range, the productivity of the soluble resin in the spacer formation layer 12 and the thermosetting resin described later can be optimized. Therefore, the interval between the exposure and shadow processes of the step "A2" described later can be formed to form the resolution of the layer 12 pattern and the thickness of the layer 12, and the spacer is formed into the layer 12, that is, the adhesion of the spacer h UA. Achieve good. When the content of the cocoa touch is less than the lower limit value, the rear=upper limit value, the developability and the lithography technique: (=: the resolution of the pattern is lowered. _lipid, enumeration (four) class _ Resin, A (four), etc. Resin '(4) Aro, fat ^ secret type _ fat, soluble resin type epoxy, secret ring Γ F Wei, etc., epoxy resin, biphenyl "B wind resin, etc." Trisphenol methane type epoxy tree t_ 9 A generation of ethylene type epoxy resin, 9 Ί 基 改 改 改 y y y y y y y y y y y y y y 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 环氧树脂 、 、 、 、 Cyclopentyl;: bisphenol-modified phenolic type 18/48 201207896 epoxy lion's gland (urea) resin, trimeric amine resin, etc. Resin, unsaturated poly-resin resin, double horse: resin, polyurethane vinegar resin, o-dibenzoic acid di-propylene duck resin emulsion, fat, resin with benzoxazine ring, aromatic acid resin,石 The milk-modified Shi Xi Xing Xuan, etc., can be used in the type i or ^ in the above. 2禋 The above-mentioned spacers containing the thermosetting miscellaneous material are shaped I] to expose and develop It is also possible to bond by the hardening. The spacer forming layer 12 and the semiconductor wafer 1G1 are bonded and exposed, and the transparent substrate 2 can be thermocompression bonded to the spacer forming layer 12 (spacer). When the hardening resin which can be hardened by heat is used as the alkali-soluble resin, it is different from the resin. = Among the above-mentioned thermosetting resins, it is particularly preferable to use an epoxy resin. Further, the spacer forming layer 12 after the hardening is cured (the spacer 12 has heat resistance and adhesion to the transparent substrate 1〇2. Further, when an epoxy resin is used as the thermosetting resin, the tree is preferably And the epoxy tree which is solid at room temperature and the 曰 resin replaced by the 曰 resin = _ _. By this, the sub-conformity and the resolvability and the resolution are both good to form the layer 12Γ Bu, the heat hardening mm of the fascinating area towel = = r is the whole of the object, preferably the ―===: the resin content is less than the aforementioned fruit, sometimes it will drop ί ί = the heat resistance of the layered layer i2 Effect ~ ..., the content of hardening resin exceeds the aforementioned 19/48

S 201207896 Curable resin lift spacer forming layer 12 _ Sex effect When the epoxy resin wheel curable resin, resin. The developability of the spacer forming layer 12 by adding __ resin to the bribe. Further, it is also possible to obtain (4) the thermosetting resin in the θ Γ product, which is advantageous in the strength of the spacer 104. More "formation (photopolymerization initiator) musk, benzoin isoindin, benzoin benzoic acid? vinegar = two women, fragrant (four), benzyl sulfide _ m ^ = oligo acid group _, benzene The base bismuth group is condensed, etc. &amp; * The mica, and the interlayer forming layer (1) composed of a polymerization initiator can be patterned efficiently by δ first. The content is not particularly limited, and is 3.0 wt% of the team. At least 0.5 to 5 Wt/°, especially when the value of the gate, and the content of the δ initiator is less than the aforementioned lower limit. The polymerization initiation effect may not be sufficient. When the content of the interval exceeds the above upper limit value, the reactivity of the poplar layer 12 is lowered, and the storage property or the resolution may be (photopolymerizable resin). The resin composition is in addition to the soil containing silkiness, whereby the pattern formation property of the 20/48 201207896 separator-forming layer 12 can be further improved. The photopolymerizable resin can be used as a photo-lipid as described above. In the case of an alkali-soluble resin, the curable tree photopolymerizable resin which is selected to be hardened is not particularly limited. However, it can be different from the fat. In the case of a molecule having at least one or more, for example, an acrylic monomer or oligomer having an unsaturated dilute base, etc. $ _ county or methyl propyl 7 Ah thing temple Acrylic-based person, vinyl compound of Ethylene Temple, etc., which can be used alone or in a variety of types. One type or a mixture of two-line curable resins is used as early as possible. In this way, the resin can be patterned with a relatively small amount of exposure. The "L ϊ ϊ dil acid i compound can be exemplified by acrylic acid or methyl methacrylate". Methyl) propylene glycol glycolate, di D-acrylic acid 1,6-pentanediol g, bis(indenyl)propyl-glyceride) bismuth acrylate, 1 〇-decanediol ester Generally, difunctional (methyl) acetoacetate diyl) propyl tris(tetra)ylpropanol, tris(methyl)propanyl neopentyltetramine, and bis, urenyl (meth) acrylate, tetra ( Tetrakisyl methacrylate, tetrakis(indenyl) acrylate (trimethyl propyl acrylate), tetrafunctional (fluorenyl) propylene W 曰, hexa(methyl) acrylate dipentaerythritol Alcohol vinegar single six ( Acrylic acid vinegar, etc. 1. Among these acrylic compounds, an acrylic acid-based polyfunctional monomer is preferably used, whereby the spacer material obtained from the spacer-forming layer 12 can be made 1〇4 As a result, the shape retention of the semiconductor device 1A having the material 1Q4 can be further improved. In the present specification, the acrylic polyfunctional monomer means a propylene having a difunctional or higher functionality. Mercapto or methacryl fluorenyl (mercapto) propylene 21/48

S 201207896 Monomer of ester. Further, among the acrylic polyfunctional monomers, a trifunctional (fluorenyl) acrylate or a tetrafunctional (fluorenyl) acrylate is particularly preferred. Thereby, the aforementioned effects can be made more remarkable. When an acrylic polyfunctional monomer is used as the photopolymerizable resin, it is preferred to further contain an epoxy vinyl ester resin. Thereby, since the acrylic polyfunctional monomer and the ethylene oxide resin are freely polymerized at the time of exposure of the spacer-forming layer 12, the strength of the spacer member 1〇4 formed can be more effectively improved. Further, the solubility of the unexposed portion of the spacer-forming layer 12 with respect to the enamel developing solution can be improved during development, so that the residue after development can be reduced. Examples of the epoxy vinyl ester resin include acrylic acid 2_transcarbyl-3-phenoxypropyl ester, Epolie 40E f-based acrylic acid adduct, Ep〇lite 70P pro-glycolic acid adduct, and Epolite 200P acrylic acid. Adduct, Epolite 80MF Acrylic Adduct, Epolite 3002 Mercapto Acid Additive, Ep〇Hte 3〇〇2 Acrylic Acid Additive, Epolite 1600 Acrylic Adduct, Bisphenol A Diglycidyl Ether Mercaptoacrylic acid adduct, bisphenol A diglycidyl ether acrylic acid adduct, Epolite 200E acrylic acid adduct, Ep〇lite 400E acrylic acid adduct, and the like. When the acryl-based polyfunctional monomer is contained in the photopolymerizable resin, the content of the acryl-based polyfunctional polymer in the resin composition is not particularly limited, and the total amount of the resin composition is preferably 1 to 5 Å by weight. /. The degree is particularly preferably 5% to 25 wt%. Thereby, the strength of the spacer-forming layer 12' after exposure, that is, the strength of the spacers 1〇4, can be effectively improved, and the shape retention of the semiconductor wafer 10A and the transparent substrate 102 can be effectively improved. In the photopolymerizable resin, the content of the epoxy vinyl ester resin is not particularly limited as long as the epoxy resin is contained in addition to the acrylic polyfunctional monomer, but it is preferably the entire resin composition. The domain of 3~3〇wt% 22/48 201207896 is especially good for the degree of 5%~l5wt%. Thereby, the residual rate of impurities remaining on the surface of the semiconductor wafer 101 and the transparent substrate 1 and 2, and the surface of the transparent substrate (10) can be effectively reduced. ·

Further, the photopolymerizable resin as described above is preferably liquid at normal temperature. In this case, the hardening reactivity of the spacer-forming layer 12 in accordance with the fine shot (e.g., =) can be improved. In addition, it is possible to simplify the mixing of the resin composition with other blending components (e.g., alkali-soluble resins). The photopolymerizable resin which is liquid at normal temperature may, for example, be an ultraviolet curable resin containing an acrylic compound as a main component. J. The weight average molecular weight of the photopolymerizable resin is not particularly limited, but is preferably 5,0 Torr or less, and particularly preferably 15 Å to 3 Å. The average weight of eight = f is located in the aforementioned range (four) 'the interval of the lion layered u. ς The spacer formation layer 12 also has excellent resolution. Here, the weight average molecular weight of the photopolymerizable resin can be evaluated, for example, by G.P.C., and calculated by the same method as described above. (Inorganic filler) ^ In addition, the resin composition constituting the spacer formation layer 12 is a human or machine filler. Thereby, the strength formed by the spacer forming layer 12: the spacer 104 can be further enhanced.惟 However, if the content of the inorganic filler of the resin composition towel is too large, the problem of undercutting occurs due to the adhesion of impurities of the inorganic filler to :=嶋. Therefore, the content of the heat engine filler of the resin composition is the same as the total amount of the resin composition = 〇 = / "XT, more than 4Q% by weight, and G is the following (substantially 2' contains an acrylic-based polyfunctional monomer as light. Polymeric resin when 23/48

S 201207896 The addition of the acryl-based polyfunctional monomer can sufficiently increase the strength of the spacer 12 formed of the spacer-forming layer 12, so that the addition of the inorganic filler to the resin composition can be omitted. Examples of the inorganic fillers include, for example, sulphurized fiber, glass fiber-like fibrous filler, potassium titanate, rock stone, rotten acid, needle-shaped oxidized town: needle-like filler-like filler, talc , mica, sericite, glass flaky graphite, platy calcium carbonate-like plate filler, calcium carbonate oxidized rare oxide 11, sintered clay, unsintered clay, granulated) filler zeolite, · ' General porous fillers, etc. Two = (4) "Use of seed or mixture of two or more types. Among them, special fillers are used. The average granulation of 〇.〇1~t machine filling is not particularly limited, but it is preferably Hi Γϋ曰't degree, especially preferably 0, 1 to 4 〇 _. Average particle size super-solution:: not wide, the appearance of the spacer-forming layer 12 may be abnormal or at the lower limit of the spacer material 'Don't worry about it. When 4 G2 is attached, it will be measured by the ❹ 裴 ❹ ❹ 分布 分布 此外 此外 此外 此外 此外 此外 此外 i i i i i i 夕 夕 夕 夕 夕 夕 夕 夕 夕 夕 夕In the case of the filler, the average pore diameter of the porous shell filler is preferably 2. 2 = 〜. 3 to 1 nm. The columnarity, particularly preferably the resin composition constituting the spacer forming layer 12, is not For the purpose of the present invention, the agent of the above components, the antifoaming agent, and the additive of the coupling may be used. The resin of 3 ° money, the flat material is composed of the above-mentioned mm group wire to construct the partition material Yang 12, by 24/48 201207896=The visible light of the spacer forming layer 12 can effectively prevent the warmth, the higher the degree of magic, and the higher semiconductor= The result is that the reliability can be particularly: the average thickness of the room: 20% = the thickness after bonding = no = size _ part 1G5, and the exposure step soil 11 irradiates the exposure light to the spacer to form the thickness 12 in the later-described exposure step. # Exposure processing. ^(4) When the average thickness of the spacer forming layer 12 is reduced, the spacer material 104 cannot be formed, and the spacer n is formed to form a uniform-thickness spacer. It is difficult to ensure that the exposure light of the two exposure light TM is not particularly thick, and that the exposure light is irradiated to the intermediate layer (four) forming layer 12 via the support substrate 11 without being separated. Exposure treatment is carried out. 12: In 2: Brother's book, 'The penetration rate of the so-called support substrate 11 and the spacer to form the interlayer two = the support substrate" and the secret, the penetration = this degree The peak wavelength of the exposure light in the direction (for example, the transmittance of the light supporting the substrate 11 and the spacer forming layer in the upward direction, for example, the transmittance can be measured. D 7GG () (Shimadzu Corporation) Co., Ltd., UV-160A) In addition, the flat of the film 1 for spacer formation The thickness is not particularly limited to 25/48 201207896, but is preferably 8 to 400 μm. In contrast, the 'support substrate 11' function is used when the tribute door (4) is less than 10 私 = when the thickness is more than 4 〇〇 For the spacer formation material _ i, the treatment property A1-2 !: = and a plurality of lens array laminates: half ": = Α 1-3 W (6), and the spacer layer # of the spacer forming film 1 The aforementioned aspect side of the semiconductor wafer 1G1 (layering plus "=" selectively removes the spacer forming layer 12 to form the spacer UA step A2-1, as shown in FIG. 4(d), the exposure is performed Light (ultraviolet rays) is irradiated onto the spacers &gt; layer 12 to perform exposure processing (exposure step). As shown in FIG. 4(d), the exposure light is applied to the spacer forming layer via the mask 2B having the light transmitting portion 201 formed in a plan view shape corresponding to the spacer white and the plan view. 12. The optical tooth penetration portion 201 has light penetration and is exposed through the light penetrating portion 201.

The light is irradiated on the spacer forming layer 12. Thereby, the spacer forming layer U k is exposed to light, and the portion where the exposure light is irradiated is caused to cause photo hardening. 26/48 201207896 At this time, the width and height of the official 谇β of the exposed portion, that is, the width and height of the pregnant qi, respectively, satisfy the above-mentioned σ| υ4 light treatment. &lt;3&gt; of the _ type is exposed, and the exposure process of the 'mm 彡 layer 12 行 is performed, as shown in the figure, the substrate 11 is attached to the spacer forming layer η, and the support layer is interposed. Material 11 will be exposed to 妗 ^ 12. 〗 'Nine lines are irradiated on the spacer forming layer II. When the exposure process is performed, the support substrate U has a spacer shape. = layer, which can effectively prevent impurities such as dust from adhering to the spacer and the layer 12 On the surface. In addition, it is easy to remove the impurities even if it is attached to the branch. Further, when the mask 20 is provided as described above, it is possible to reduce the rotation of the mask 2 without causing the mask 2 to be attached to the spacer forming layer u. The wire can prevent the image blur formed by the exposure light irradiated on the spacer forming layer 12 through the reticle, and the boundary between the exposed portion and the unexposed portion becomes more vivid. As a result, the layer 12 can be formed as a spacer by a j-precision wire, and the gap portion 1 () 5 of the shape and size of the design can be approximated. Thereby, the reliability of the semiconductor 100 can be improved. Further, the exposure treatment can be performed after the support substrate U is removed. In addition, after the photomask 20 is aligned, by aligning the alignment marks provided on the alignment mask 20 provided on the semiconductor wafer 101, the photomask 20 can be aligned with respect to the semiconductor wafer 10. Bit. The distance between the substrate 11 and the mask 2 is preferably 〇 2 〇〇〇 from the m spacer t is 0 to 1000 Å. Thereby, the image formed by the exposure light of the layered layer 12 is irradiated with the mask 20 interposed therebetween, and the spacer 104 is formed by the accuracy of the soil. 27/48

S 201207896 In particular, it is preferred to subject the support substrate u to the lower (four) exposure process. By this, the shape of the mask = the mask core _ the number of the mask is formed by the portion of the spacer layer which is to be exposed, so that the spacer 12A having excellent dimensional accuracy is formed therebetween. The scoop is exposed first, and more efficiently, so that 'the first time when the cut n n is in contact with the photomask 2G', by appropriately selecting the thickness of the substrate n (4) = === material_12 and the mask 2Q The distance between them. Further, the thickness of the cover 20/Pf substrate 11 can be reduced to reduce the image blur caused by the exposure light formed by the spacers 12 formed by the spacers 9 being formed by the spacers U and #12. After that, it can be heat-treated according to the temperature of (2) 1 ^ layer 12 of 40 to 8 ° °c (after the exposure, heating step _ hard 匕, bit (spacer 12A) and semiconductor wafer ι〇ι' Therefore, it is possible to effectively prevent the photo-cured portion of the spacer-forming layer 12 from being inadvertently peeled off. The temperature of the above-mentioned heat treatment may be within the above range, but it is particularly 5 〇~7〇C. In the development process described later, 'inadvertent peeling of the portion where the photo-curing of the spacer is formed can be effectively prevented. A2-2 Next, as shown in Fig. 4 (4), the support substrate 11 is removed (support base) The material removing step), that is, the k spacer material forming layer 12, peels off the branch substrate η. After the exposure is performed, 'by removing the branch substrate u before development, as described above, dust can be prevented during exposure. The impurity is adhered to the spacer formation layer 12, and the spacer formation layer 12 can be patterned. 28/48 201207896 A2-3 The receiver, as shown in Fig. 5 (8), uses the developer to 12 unhardened portions (unexposed) Part) (development processing). By this ^ ^ formation of layer U The hardened portion (that is, the wall portion 4-shaped spacer 12A and the void portion 1〇5) is formed to form a layer ===pre-displacement-shaped liquid-filled two-dip shower development method, etc. Using the development in this step, as shown in Fig. 7, in comparison with 2 = ^, in particular, the semiconductor wafer of the material forming layer 12 is formed such that the axis f near the center of the space is formed straight to the surface of the plate and through the material layer. 12 is carried out. '-Liquid L is given to the interval, 00 is the fluoroscopy liquid L is directed downwards 弋a life shadow liquid L: to the spacer forming layer 12....Baifu' will be displayed The ejection direction of B (the axial direction of the nozzle 300) The surface of the bulk wafer _ can be inclined (10) obliquely to the semiconductor day = the direction of the projection t (the direction of the nozzle axis) relative to the wafer 101, = the rotation == tilt 'The direction of the body wafer (9) which is ejected in the opposite direction (reverse flow) of the nozzle 3A can be inclined by ejecting the direction of the axis direction of the nozzle 300 in the direction of the moon 8 (flow in the forward direction) with respect to the semiconductor type. It is also possible to make the nozzle 29/48 by spraying from the semi-conductor 300 I-cansula 3. Bujing developer L

S 201207896 - In addition, the ejection enthalpy of the development ι from the nozzle 3GG is preferably 0.01 to 0.5 MPa, and more preferably 〇1 to 〇3Μρ&amp; In addition, the developing solution from the nozzle 300 is not particularly limited, but is preferably 15 to sec. (3), preferably 3, 3,600 seconds, and more preferably, from the nozzle. The ejection of the developing solution L of 300, dead or intermittent (discontinuity). The nozzle 300 can also be set in plurals in the example of the example shown in Fig. 7. When Ug ^, Wei Weiwei has a Japanese sister technique to dissolve In the developing solution 1, the "hardened portion" portion is a solid-shaped suspension. Therefore, conventionally, the suspended matter adheres to the semiconductor wafer or adheres to the hardened portion of the spacer forming layer 12 (wall). The portion lG4,) remains as a problem of the residue. The wall portion 104' is formed in a manner that the plurality of void portions 1〇5 are in a quadrangular shape and arranged in a matrix shape as described above. The wall portion 104 having such a shape is used. In the case of the spacer 12a, the above problems are particularly remarkable. Q. The inventors have carefully studied and found that the above problems can be prevented by optimizing the twist and height of the soil 卩104'. Specifically, the department found that When the width of the portion 104 is W1 &gt; m] and the height of the wall portion 104 is Η [μιη], the above-mentioned problems of &lt;1&gt;~&lt;3&gt; are respectively satisfied, and the above problems can be prevented. 15^W^3000 . · . &lt;1&gt; 3^H^300 · · . &lt;2&gt; 30/48 201207896 0.10^ W/H^900 · . · &lt;3&gt; By making wall portion 104 The width W and the height H satisfy the relationship of the above 〇&gt;~&lt;3&gt;, respectively, when the development process is performed between the exposure processing _$^12, as shown in Fig. 8, even if the shape of the money body is shown The suspended matter s, the suspended matter s also easily passes over the wall portion 1〇4. Therefore, the suspension can be efficiently removed by the flow of the selective liquid L, especially as shown in Fig. 7 The semiconductor wafer is rotated about the axis z, and when the developer L is applied to the spacer forming layer 12, the development is performed on the surface side of the semiconductor wafer 1 (1) with the spacer forming layer 12 The upper state is performed, and the solid-shaped suspension is removed by the wall portion 1〇4 by the force generated by the rotation of the semiconductor crystal hall. Therefore, the suspended object S can be prevented. As a ruin The resulting semiconductor wafer bonded body surface is obtained. As a result, the finally obtained semiconductor wafer bonded body 1 〇〇〇 has better reliability. Here, the width W of the i wall portion 1 〇 4 ′ is satisfied. The relationship between the above <丨> and &lt;3 &gt; is 彳, but preferably 5〇~2〇〇〇, especially preferably 1〇〇~2_ spleen, thereby making the suspended matter s easily cross the wall (10), and the required strength of the spacer 104 can be ensured. On the other hand, when the width w of the wall portion 104 is smaller than the lower limit value, the area of the joint surface between the wall portion 104' and the semiconductor wafer 1〇1' and the transparent substrate 1〇2 is too small, so that the resultant semiconductor can be obtained. (4) The degree of guilt of the joint body is reduced. On the other hand, the width W of the wall portion 1〇4 exceeds the above-mentioned upper limit value %· 'the solid-shaped suspension s does not easily pass over the wall portion 1 () 4 or is obtained from the semiconductor wafer bonded body circle The number of semiconductor devices (10) will be reduced. The width w of the wall portion refers to the flat portion of the wall portion.

S 201207896 Width. Further, the height Η of the wall portion 104' may satisfy the relationship of &lt;2&gt; and &lt;3=, and is preferably 5 to 25 Å, and particularly preferably 1 〇 to 2 〇〇. Thereby, the suspended material is easily passed over the wall portion, and the strength required for the spacer (10) can be ensured. Relative to this wall. When the Η1〇4' Η degree Η is less than the above lower limit value, the obtained semiconductor device 1G , cannot form a spacer of just 105 〇 1041^3⁄43 4 上 upper limit value ^, solid shape suspension It is not easy for the object s to cross the wall. Further, the ratio W/H ^ of the width w and the height H of the wall portion 104 satisfies the relationship of the above &lt;/&gt; to &lt;3&gt;, and preferably ’ is preferably 0.52 to 180. Thereby, the suspended matter can be made simple and surely ~0 part just', and the crusting can prevent the development process of the spacer forming layer 12 from being prolonged, and the above problem can be solved. In addition, the test L is determined depending on the interval of the lion layer 12, and is not particularly limited. When the specific gravity of the various developer liquids L is set to A, and the constituent wall liquid is set to B,佳系-? &lt;&lt; lining 曰 composition of the composition of the ratio, τ ^ is satisfied with the relationship 〇.5$α / β ^ 2, the formula m satisfies the relationship of 0 · 60 $ Α / Β $ 1.5, wider For the relationship of = W. Thereby, the solid-shaped suspension can be efficiently removed by the green night. When the Α/Β is smaller than the lower limit value, the solid shape s is likely to adhere to the wall portion 1〇4, and the enthalpy 、/Β Β/Β exceeds the above upper limit value. On the one hand, after the developing solution L remains on the semiconductor wafer ι〇ι, and the like, the development is also suitable for the development of the layer ～, which is difficult to obtain 32/48 201207896 to obtain the necessary characteristics. Spacer 104. Further, the spacer forming layer 12 contains the above-described tests, and the test solution can be used as a developing solution. Called the month of the month ^ 12 The pH of the test solution used is 9.5 or more, especially 〇~14.0. Thereby, the lye of the spacer formation layer can be efficiently removed, and examples thereof include an aqueous solution of Na〇H and κ〇 lion, and a “textile metal I::I; hydrogen=yi aqueous solution, Base 曱 = , Ν--Methyl E S (the amine of DMA# can be used alone or in combination. ^Looking for this A2-4 Next, as shown in Figure 5(b), use 泱, every wall has Half of the net wall section of the wealth and shape &lt;dry version of the day back to 1 〇丨丨 (washing step) 〇 (four), after the development (step _ 2_3) and before "A3"), the washing step is called (step suspension) The material s is not particularly limited by the method of imparting the SI liquid to efficiently remove the suspension by the motor 胄 of the cleaning solution. For example, the m (four) method and the shower can be used for washing. In the middle of the method, etc., the washing method is preferably a punching method, and the method of observing the above-mentioned step A2-3. In particular, washing, preferably, the side is formed with a tea photo 7), in this step The semiconductor wafer ιογ is rotated around the vertical spacer formation layer 12 (the wall portion 2 is rotated, and the plate surface is washed and passed through the shaft 101| near the center). The liquid is applied to the wall portion HH. And semiconductor wafer 33/48

S 201207896 At this point, the cleaning is the right-handed, first-handed twirling heart, and by the semiconductor wafer 101, 104 = force, the solid-shaped suspension s crosses the wall to form a liquid two, The specific gravity of each of the cleaning liquids is not particularly limited, and the specific gravity of the resin composition of c is set to B, and the relationship of the cleaning liquid (four) is __. 0.65 Zhichuanzhi;:T! relationship, better to meet the efficient flow of the surface by the surface / sundial, - C / B is less than the lower limit of the Li 'solid shape suspension (10): Λί It tends to adhere to the wall portion 1〇4, etc. On the other hand, the right upper limit is difficult to select the cleaning liquid, or it is difficult to obtain the spacer 104 having the necessary characteristics. Α 2-5 Next, as shown in Fig. 5(c), the cleaning liquid (drying step). No, the two washing steps used in the steps Α2-4 are removed. After the washing (step _2_4) and during the joining step (step "August 3"&gt;), the washing step can be prevented. It remains in the resulting semiconductor crystal splicer 1 and causes adverse effects. Further, in the manufacture of the semiconductor wafer bonded body 丨, the quality can be improved and the production efficiency can be improved. The drying step is the same as the rotation of the semiconductor wafer 10A in the developing method of the above step A2-3 (refer to the drawing). It is preferable to surround the semiconductor wafer 1G1 in which the wall portion 1 〇 4' is formed. It is perpendicular to the plane of the board and is red-turned by the axis near the center. Even after the above-mentioned washing step, the solid matter 34/48 201207896-like suspended matter s remains, and when the cleaning liquid is removed, the solid-shaped suspension S can be passed by the centrifugal force generated by the rotation of the semiconductor wafer 10Γ. The wall portion 104' is removed. "A3" is a step of bonding the transparent substrate 102' to the surface of the spacer 12A opposite to the semiconductor wafer 10A. Next, as shown in FIG. 6(a), the upper surface of the spacer 12A and the transparent substrate 102' are formed. Engagement (joining step). Thereby, the semiconductor wafer bonded body 1000 (the semiconductor wafer bonded body of the present invention) in which the semiconductor wafer 1 〇 1 and the transparent substrate 丨〇 2 ' are bonded via the spacer 12A can be obtained. The bonding of the spacer 12A and the transparent substrate 1〇2' can be carried out, for example, by laminating the upper surface of the formed spacer 12A and the transparent substrate 1〇2, followed by thermal compression bonding. The hot pressing is preferably carried out in a temperature range of 80 to 18 Torr. Thereby, while suppressing the pressing force at the time of thermocompression bonding, the "separating material 12A and the transparent substrate are combined by thermocompression bonding. Therefore, the formed spacer (10) can suppress inadvertent deformation" to achieve better dimensional accuracy. Degree. "A4" for the semiconductor crystal ® KH, the next step in the processing or processing steps, as shown in Figure 6 (b) 'semiconductor wafer 1 () 1, the opposite side of the transparent substrate (Bottom) 111 is polished (back grinding step). , +# 1N grinding is performed, and the side can be placed on the side (grinding machine). Although the field is polished by the surface U1, the semiconductor wafer can be set. The thickness is different from that of the electronic device of the semiconductor device 100, but the Tongwei break is set at the level of just ~_qing, turning over the smaller electronic machine 35/48

When S 201207896, it is set to about 5〇μηη. 4-2 Next, as shown in FIG. 6(c), the surface m of the semiconductor wafer 101 is formed as a solder bump 106. In this case, although not shown in the drawing, in addition to the shape of the solder bumps 1〇6, wiring is formed on the surface 111 of the semiconductor wafer 101. y [B] Step of Graining the Semiconductor Wafer Bond 1000 Next, by crystallizing the semiconductor wafer bonded body 1000, a plurality of semiconductor wafer bonded bodies 1 can be obtained (cutting step) . At this time, the semiconductor wafer bonded body 1 is crystallized for each of the individual circuits formed in the semiconductor wafer 101', that is, for each of the gap portions 1?. Here, as described above, the wall portion 104'' is formed such that a plurality of the gap portions 1〇5 have a quadrangular shape and are arranged in a matrix. Therefore, the semiconductor wafer bonded body 1000 is cut (cut) into a checkered shape to be grained, whereby a plurality of semiconductor devices can be obtained simply and efficiently. More specifically, the semiconductor wafer bonded body 1〇〇 For example, as shown in FIG. 6(d), after the notch 21 is formed from the side of the semiconductor wafer 1〇11 along the square of the spacer 104 by the dicing blade, from the side of the transparent substrate 102', It is also caused by the cutting of the notch 21 by the cutting blade. Through the above steps, a semiconductor device can be manufactured. In this manner, the semiconductor wafer bonded body 1 is grained to obtain a plurality of semiconductor wafer bonded bodies 1 at a time, whereby the semiconductor device 100 can be mass-produced, and productivity can be improved. In particular, in the manufacture of the semiconductor wafer bonded body 1000, as described above, 36/48 201207896, the width W and the height H of the wall portion 104' satisfy the relationship of the above &lt;1 &gt;~&lt;3&gt;, respectively. A semiconductor wafer bonded body 1000 having better reliability can be obtained. Therefore, the semiconductor device 100 obtained by grain-forming the semiconductor wafer bonded body 1000 also has better reliability. Further, by using the above-described method of manufacturing the semiconductor wafer bonded body 10 (8), the semiconductor wafer bonded body 1000 and the semiconductor device 100 having high reliability can be manufactured at a high yield. The semiconductor wafer 100 thus obtained can be mounted on a substrate on which a wiring pattern is formed, for example, and electrically connected to the wiring formed on the lower surface of the base substrate 101 via the solder bumps (10). Further, the half V body device 1GG can be widely used in an electronic device such as a mobile phone, a digital camera, a video camera, or a small camera in a state of being mounted on a substrate as described above. The present invention is not limited to the above embodiments, and preferred embodiments of the present invention are set forth herein. For example, the method for producing a semiconductor wafer bonded body of the present invention may be added to one or two or more arbitrary steps. For example, a post-lamination heat treatment (PLB step) for spacer formation :: can be set between the sound and exposure steps. ^ σ ', , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , +month/ In addition, the semiconductor_joined body and the component configuration of the present invention may be replaced with any configuration that can exhibit the same work ==. In addition to the above embodiment, the substrate is transferred from the sheet-like support substrate. 37/48

S 201207896 is formed on one side of the semiconductor wafer 101' to form a spacer forming layer, but the method of forming the spacer forming layer is not limited thereto, and for example, a curable resin composition can be directly used by using various coating methods ( The resin varnish is directly formed on the one side of the semiconductor wafer 1 〇 1'. In the present embodiment, a case where a negative resin composition for removing an exposed portion by a developing solution is used as a resin composition of the spacer forming layer 12 will be described as an example. However, it is of course possible to use a developing solution. The positive resin composition of the unexposed portion is removed. [Examples] Specific examples of the invention are described below. However, the invention is not limited thereto. [1] Fabrication of semiconductor wafer bonded body (Example 1) 1. Synthesis of soluble resin (bis(A) phenolic resin modified with (fluorenyl) acrylate) Phenolic bisphenol A resin (Phenolite LF-4871) , 60% of MEK (mercaptoethyl ketone) 5 〇〇g ' of the solid ink chemistry (Dainippon Ink &amp; Chemicals Co., Ltd.) is put into a 2L flask and will be used as a catalyst. Butylamine l_5g, and hydroquinone as a polymerization inhibitor, 15 g were added thereto, and heated to 100 t; The glycidol methacrylate vinegar was added to the glycerol methacrylate in a period of 30 minutes; the mixture was stirred for 5 hours under the hydrazine to carry out a reaction, thereby obtaining a phenolic type modified by a methacryl oxime group having a solid content of 74%. Double expectant A resin MPN001 (f-based propylene sulfhydryl modification rate 50%). 2. The amount of the resin varnish constituting the resin composition of the spacer-forming layer was adjusted to be 15% by weight of trimethylolpropane trimethyl methacrylate (LightEsterTM P manufactured by Kyoeisha Chemical Co., Ltd.) and an epoxy vinyl ester resin ( A total of 38/48 201207896 Rongshe Chemical Co., Ltd., Epoxy Ester 3〇〇2M) 5 weight. /〇 as photopolymerizable resin, bisphenol A phenolic epoxy resin (made by Essence Chemical Co., Ltd., Epiclon N-865) 5% by weight, bisphenol a type epoxy resin (Japan epoxy resin (Japan) Epoxy Resin Co., Ltd., YL6810) 10% by weight, polyoxyalkylene epoxy resin (T〇ray Dow Corning Silicone Co., Ltd., Βγΐ6_115) 5 wt%, and phenols Phenolic resin (manufactured by Sumit〇m〇Bakdite Co., Ltd., PR53647) 3% by weight of an epoxy resin as a thermosetting resin, and the solid content is 55 wt% of the above]^11)] 1 as an alkali-soluble resin, 2% by weight of a photopolymerization initiator (Irgacure 651, manufactured by Chiba Spedai Chemicals Co., Ltd.), and stirred at a number of revolutions of 3000 rpm for 1 hour using a disperser. Varnish. 3. Production of a film for forming a spacer First, a polyester film ("MRX50" manufactured by Mitsubishi Plastics Co., Ltd.) having a thickness of 50 μm was prepared as a support substrate. &lt; Next, a coating film made of a resin varnish is formed by applying a varnish prepared by a (four) knife coating machine (Model No. MFG No. 194001 type 3_293) to a support substrate. 8 〇 formed in the lower shape (4) depends on the formation layer of the spacer for 2 minutes, thereby obtaining a film for forming a spacer. The obtained film for forming a spacer has an average thickness of the spacer layer of 5 〇μηι. In addition, the 'structure of the separator is formed: the specific gravity of the grease composition (after drying) is 1.2. 4. The manufacture of the joint is prepared with a diameter of almost 8 round, and the semiconductor wafer (9) is directly operated. 20.3 cm, thickness 725 μηι). Next, using a laminate laminator, the film will be laminated on the semiconductor wafer under the conditions of the roll temperature step, the reported speed 〇39/48 201207896 / shot [2.Gkgf/em, and ^^ A semiconductor wafer that forms a film. In the case where the spacer for forming the spacer is provided, and then the photomask having the light-transmitting portion formed in the same shape as the shape is formed, the film pair of the material and the spacer is formed as a 仏mm仏 handle. 'The distance between the _ 切 叙 叙 然后 然后 , , , , , , , 从 从 从 从 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切 切The way to carry out the exposure of the second--A hydroxide "ammonium hydroxide (TM butterfly aqueous solution for the miscellaneous liquid), after the exposure of the spacer material, a wall as shown in Figure 7 'system side to make the semiconductor wafer, ^ heart to The cephalometric hydraulic pressure (ejection pressure) 〇 2 MPa was carried out by forming the developing solution toward the spacer. In addition, the specific gravity of the developer is ^, 隹-=ST屯 water is used as a cleaning liquid to wash the spacer (wall portion), and then the liquid crystal is removed as shown in Fig. 7 Will wash the liquid t will be magic η. Λ Purely. In addition, the cleaning liquid is immersed in a state in which the cleaning of the cleaning liquid is stopped, as shown in Fig. 7, and the semiconductor wafer is rotated by 9 sec. 40/48 201207896 Next, a transparent substrate (quartz glass substrate, diameter 2〇.3em, thickness 725μιη) was prepared, and this was laminated to form a space using a substrate bonding apparatus (Suss Micr〇Tec, "SB8e"). A semiconductor wafer in which a semiconductor wafer and a transparent substrate are bonded via a spacer (Example 2), except that a resin varnish constituting a resin composition of the spacer forming layer is prepared in the following manner A half-wafer bonded body was produced in the same manner as in the embodiment. 'Weighing scale tridecyl acrylic acid triacetate methyl propylene vinegar (manufactured by Kyoeisha Chemical Co., Ltd., Light Ester TMP) 11% by weight and epoxy vinyl ester resin ~. Essence Chemical Co., Ltd., Ep 〇xy Ester 3〇〇2M) 4% by weight as photopolymerizable resin, bisphenol A phenolic epoxy resin (made by Dainippon Oil Co., Ltd., EPid0n N_865) 4% by weight, bisphenol A ^浐: Resin (made by Nippon Epoxy Resin Co., Ltd., YL681〇) 8 wt% „ 矽 烷 epoxy resin (poly BY16-115 manufactured by Toray Dow Corning Co., Ltd.) 4% by weight, secret resin (Sumitomo Branch company ^, company system, PR53647) 2 f amount % as a thermosetting resin ring '^ solid content of 42% by weight of the above-mentioned reward as a test soluble, 'photopolymerization initiator (steam polymerization chemistry) Product Co., Ltd., I 651) 2% by weight, 23.0% by weight of Separate Oxide (Admatechs Co., Ltd. Ul, e Admafme SE5101) as a filler, and using a fraction of 1, at a number of revolutions of 3000 rpm for 1 hour Prepare varnish. Moonlight 41/48 201207896

[Table 1] Wall (spacer) Developer solution evaluation width W ίμΐΏ] 13⁄4 degree Η "μηι] W/H Specific gravity B Specific gravity AA/B Specific gravity CC/B With or without residue Example 1 600 50 12 1.2 1.0 0.83 1.0 0.83 ◎ Example 2 600 50 12 1.5 1.0 0.67 1.0 0.67 ◎ Comparative Example 4000 50 80 1.2 1.0 0.83 1.0 0.83 X (Comparative Example) The width and height of the wall portion were changed to those shown in Table 1. A semiconductor wafer bonded body was produced in the same manner as in the above-described first embodiment. [2] The spacers and the void portions of the semiconductor wafer bonded bodies of the respective examples and comparative examples were observed by a stereoscopic microscope (x500 times), and the following were followed. The evaluation criteria were used to evaluate the presence or absence of residue. ◎: The residue was not confirmed at all, and there was no problem in practical use. 〇: Although some residue was confirmed, it was a practically problem-free grade. △: Relatively large residue was observed, non-utility grade X: A number of residues were confirmed, and the results were as shown in Table 1. From the first table, it was found that the semiconductor wafer bonded body of the example of the present invention was not confirmed to be completely broken. Further, a plurality of semiconductor devices are obtained by dicing a semiconductor wafer bonded body according to an embodiment of the present invention, and most of the plurality of semiconductor devices have a desired characteristic for a long period of time, and are preferably provided. In contrast, in the semiconductor wafer bonded body of the comparative example, a large amount of residue was observed. Further, a plurality of semiconductor devices were obtained by dicing a semiconductor wafer bonded body of a comparative example, and the plurality of semiconductor devices were obtained. Most of the semiconductor devices of the semi-conductive 42/48 201207896 cannot exhibit the desired characteristics, and the reliability thereof is inferior to that of the semiconductor device of the embodiment. INDUSTRIAL APPLICABILITY According to the present invention, the spacer material after the exposure treatment is formed. When the layer is subjected to the development treatment, even if a solid-shaped suspension is generated, the suspended matter easily passes over the wall portion, so that the suspended matter can be efficiently removed by the flow of the developer. Therefore, the suspended matter can be prevented from remaining as a residue. The obtained semiconductor wafer bonded body has a result that the obtained semiconductor wafer bonded body has better reliability. In addition, the semiconductor device obtained by grain-forming the semiconductor wafer bonded body has better reliability. Further, by using the method for manufacturing a semiconductor wafer bonded body of the present invention, it can be manufactured at a high yield. A semiconductor wafer bonded body and a semiconductor device having a high reliability are known. From the above, it is understood that the present invention has industrial applicability. [Simplified Schematic] FIG. 1 shows an embodiment of the present invention. Cross-sectional view of a semiconductor device FIG. 2 is a longitudinal cross-sectional view showing a semiconductor wafer bonded body according to an embodiment of the present invention. 3 is a plan view showing the semiconductor wafer bonded body shown in FIG. 2. Fig. 4 is a view showing an example of a method of manufacturing the semiconductor device (the semiconductor wafer bonded body shown in Fig. 2) shown in Fig. 1. Fig. 5 is a view showing an example of a method of manufacturing the semiconductor device (the semiconductor wafer bonded body shown in Fig. 2) shown in Fig. 1.

43/48 S 201207896 Fig. 6 is a view showing an example of a method of manufacturing the semiconductor device (the semiconductor wafer bonded body shown in Fig. 2) shown in Fig. 1. Fig. 7 is a view for explaining the development processing shown in Fig. 5 (a). Fig. 8 is a view for explaining the action in the developing process shown in Fig. 5 (a). [Description of main component symbols] 1 spacer film forming film 11 supporting substrate 12 spacer forming layer 12A, 104 spacer 20 mask 21 notch 100 semiconductor device (photosensitive device) 101 base substrate 10 semiconductor wafer 102, 102' transparent Substrate 103 individual circuit 104 spacer 104' wall portion 105 void portion 106 solder bump 111 surface 201 light penetrating portion 300 nozzle 1000 semiconductor wafer bonding body Η height L developing solution 44/48 201207896 s suspension w width z axis

Claims (1)

201207896 VII. Patent application scope: L A method for manufacturing a semiconductor wafer bonded body, comprising: a semiconductor wafer, a transparent substrate disposed opposite to one side of the semiconductor wafer, and having a semiconductor crystal in the foregoing A spacer for a wall portion provided between a circle and the transparent substrate, which is formed by a plurality of void portions, is characterized in that: one of the semiconductor wafer and the transparent substrate is formed to have a photosensitive resin a spacer forming layer formed of the composition, a second step of performing the exposure by selectively irradiating the exposure light to the spacer, and performing development by using a developing solution And a step of joining the other of the semiconductor wafer and the transparent substrate to the wall portion; and the width of the wall portion is W [pm], and the width of the wall portion is [μηι] , respectively, satisfy the relationship of the following &lt; i &gt; ~ <3 &gt; 1 sigh... 15^ W^3〇〇〇. · . &lt;1&gt; 3^H^300 · · · &lt;2&gt; 0, 10$ W/HS900 . . . &lt;3 &gt;. 2. The method for producing a semiconductor wafer bonded body according to the scope of the invention, wherein the specific gravity of the developing solution is A, and the specific gravity of the resin is (4), which satisfies the relationship of 〇.5 formula. 3. If you apply for a patent scope! Or a semiconductor wafer bonded body of two or more, wherein the "wall portion" is formed in a plan view so that the plurality of portions are formed in a quadrangular shape and arranged in a matrix shape. The method of manufacturing a semiconductor wafer according to any one of the preceding claims, wherein the developing is performed by vertically forming the semiconductor wafer or the transparent substrate on which the spacer formation layer is formed. The surface of the semiconductor wafer bonding body of the fourth aspect of the invention is applied to the surface of the board and rotated by the axis of the middle (four), and the developer is applied to the spacer layer. In order to allow the surface of the semiconductor wafer or the transparent substrate on which the spacer layer is formed to face upward, it is possible to enter the body of the 谇 谇 、, 苻 苻 α 〜 肢 肢 肢 肢 肢 肢 肢 肢 肢 : : : : : : : : After the development of the core, the other portion of the semiconductor and the transparent substrate are joined to the wall portion to clean the wall portion and the wall portion is formed. Conductor wafer 7. The transparent substrate. 7. The method for manufacturing a semiconductor wafer bonded body according to item 6, wherein the specific gravity of the heavy product is set to 6, and the cleaning liquid s is directly and upwardly satisfying the relationship of 0.5 SC/BS2. The method of manufacturing the semiconductor wafer bonded body of the method or the item: the semiconductor is formed by the side of the transparent portion, and the transparent substrate is washed perpendicularly to the wall portion and thoroughly (four) to the front plate. In the case of the semiconductor wafer or the transparent substrate of the above-mentioned fourth embodiment, the surface of the semiconductor wafer bonded body of the eighth aspect of the invention is carried out with the surface side facing upward. The manufacturing method of the semiconductor wafer bonding 47/48 S 201207896, wherein the step of removing the cleaning liquid before the semiconductor is further performed on the wafer and the transparent substrate Steps / (4) Steps of the wall section 11. If you apply for the stipulation of the 10th item of the patent scope, 1 defer, f... the first half of the manufacturing side of the ® ® 接合 ; ; ; ; ; ; ; ; ; By forming the aforementioned wall 丨aa® to describe the transparent surface and passing the axis near the center of the heart Rotating to perform. Straight to the board 12. A semiconductor (four) bonded body, which is characterized by the method of any one of the items 1 to 11, which is made of a semiconductor wafer bonded body, which has Semiconductors = a transparent substrate 3 on the side of the circle - and a spacer of a wall spacer provided with a plurality of gaps between the 逑 + conductor wafer and the transparent substrate, and characterized in that: On the next day, the width of the wall portion is set to w[_], and when the above-mentioned each is Η[(4), the following 15>WS&lt;3&gt; are respectively satisfied. 15SWS3000 · . . &lt;1&gt; 3^Η^ 300 · . . &lt;2&gt; 0.10$ W/HS900 ... &lt;3&gt; 0 14_ A semiconductor device characterized by crystallizing a semiconductor wafer bonded body according to claim 12 or 13 It is obtained by granulation. 48/48