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TWI610996B - Siloxane resin remover, siloxane resin removing method using the same, and manufacturing method of semiconductor substrate product and semiconductor device - Google Patents

Siloxane resin remover, siloxane resin removing method using the same, and manufacturing method of semiconductor substrate product and semiconductor device Download PDF

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TWI610996B
TWI610996B TW102145449A TW102145449A TWI610996B TW I610996 B TWI610996 B TW I610996B TW 102145449 A TW102145449 A TW 102145449A TW 102145449 A TW102145449 A TW 102145449A TW I610996 B TWI610996 B TW I610996B
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resin
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remover
mass
semiconductor substrate
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TW201431987A (en
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杉島泰雄
水谷篤史
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富士軟片股份有限公司
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    • C09J5/00Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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    • H01L21/3105After-treatment
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    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/50Additional features of adhesives in the form of films or foils characterized by process specific features
    • C09J2301/502Additional features of adhesives in the form of films or foils characterized by process specific features process for debonding adherents
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    • C09J2483/00Presence of polysiloxane
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    • H01L2221/68381Details of chemical or physical process used for separating the auxiliary support from a device or wafer
    • H01L2221/68386Separation by peeling

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Abstract

本發明的矽氧烷樹脂的去除劑是用以將附於半導體基板上的矽氧烷樹脂去除的去除劑,且含有極性非質子性溶劑及四級銨氫氧化物。 The remover of the decane resin of the present invention is a remover for removing a decane resin attached to a semiconductor substrate, and contains a polar aprotic solvent and a quaternary ammonium hydroxide.

Description

矽氧烷樹脂的去除劑、使用其的矽氧烷樹脂的去除 方法以及半導體基板製品及半導體元件的製造方法 Remover of decane resin, removal of siloxane resin using same Method and semiconductor substrate product and method of manufacturing the same

本發明是有關於一種矽氧烷樹脂的去除劑、使用其的矽氧烷樹脂的去除方法以及半導體基板製品及半導體元件的製造方法。 The present invention relates to a remover for a decane resin, a method for removing a siloxane resin using the same, and a method for producing a semiconductor substrate and a semiconductor device.

近年來,半導體基板的高性能化及積體化日益進步。隨之,半導體基板或使用其的元件的大型化或配線的微細化、多層化等進一步加速發展。另一方面,為了高密度安裝化,而封裝尺寸(package size)的小型化及薄型化成為必需。針對此種要求,提出有稱為多晶片封裝(Multi Chip Package,MCP)的技術。該技術中,於一個配線基板上以高密度安裝多個半導體元件。其中,將具有稱為矽通孔(Through Silicon Via,TSV)的貫通電極的半導體晶片積層體安裝於配線基板的一面的技術備受矚目(例如,參照專利文獻1~專利文獻3)。 In recent years, the performance and integration of semiconductor substrates have been increasing. As a result, the size of the semiconductor substrate or the element using the same, or the miniaturization and multilayering of the wiring are further accelerated. On the other hand, for high-density mounting, it is necessary to reduce the size and thickness of the package size. In response to such a request, a technique called Multi Chip Package (MCP) has been proposed. In this technique, a plurality of semiconductor elements are mounted at a high density on one wiring substrate. In particular, a technique of attaching a semiconductor wafer laminate having a through-electrode called a through-silicon via (TSV) to one surface of a wiring board has been attracting attention (see, for example, Patent Document 1 to Patent Document 3).

於利用上述TSV的半導體基板的製造中,採用縮薄矽基板(silicon substrate)的步驟,此時為了使薄的矽基板在不破損的情況下進行加工而採用接著於支持基板進行研削的加工法。該支持基板與半導體基板是經由接著層而接合,成為適於用以使基板薄化的加工的形態。因此,對該接著劑要求良好的平坦性、使兩基板接著的接著性、矽基板的背面研削時的耐研削性。進而,就生產性及製造品質的觀點而言,耐熱性、耐化學品性、剝離性等成為必需。作為此種用途中所使用的材料,專利文獻4中提出有矽酮系樹脂。 In the production of a semiconductor substrate using the TSV, a step of thinning a silicon substrate is employed. In this case, in order to process the thin tantalum substrate without damage, a processing method followed by grinding on the supporting substrate is employed. . The support substrate and the semiconductor substrate are bonded via an adhesive layer, and are formed into a form suitable for processing to thin the substrate. Therefore, the adhesive is required to have good flatness, adhesion between the two substrates, and scratch resistance when the back surface of the substrate is ground. Further, from the viewpoints of productivity and manufacturing quality, heat resistance, chemical resistance, peelability, and the like are required. Patent Document 4 proposes an anthrone-based resin as a material used in such an application.

[現有技術文獻] [Prior Art Literature]

[專利文獻] [Patent Literature]

[專利文獻1]日本專利特開2007-251145號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2007-251145

[專利文獻2]日本專利特開2012-212786號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2012-212786

[專利文獻3]日本專利特開2010-056139號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2010-056139

[專利文獻4]日本專利特開2012-004200號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2012-004200

與上述支持基板的暫時接合中所使用的接著層必須於加工後去除。就該觀點而言,理想為接著力受到抑制且分解性或溶解性高的接著層。另一方面,若無法維持充分的接著力與耐化學品性,則無法耐受研削加工等,兩者成為對立的性能項目。對此,本發明者針對上述半導體的TSV形成技術,以利用發揮出充分的性能的矽氧烷樹脂(矽酮樹脂)為前提,研究於無損其基本 性能的情況下將上述樹脂較佳地去除的技術。另一方面,於將該樹脂去除的步驟中,有已形成有利用鋁等的電極的情況。因此,探索可盡可能不損傷此種電極構件而將上述矽氧烷樹脂有效地去除的材料及其調配成分。 The adhesive layer used in the temporary bonding with the above-mentioned support substrate must be removed after processing. From this point of view, it is desirable that the adhesion layer is suppressed and the decomposition layer or the solubility is high. On the other hand, if sufficient adhesion and chemical resistance cannot be maintained, the grinding process and the like cannot be tolerated, and the two become opposite performance items. On the other hand, the inventors of the present invention have studied the TSV formation technique of the above-mentioned semiconductor, and have studied the basic characteristics of the oxime resin (an oxime resin) which exhibits sufficient performance. A technique in which the above resin is preferably removed in the case of performance. On the other hand, in the step of removing the resin, an electrode using aluminum or the like is formed. Therefore, a material which can effectively remove the above-described siloxane resin and a compounding component thereof can be explored without damaging such an electrode member as much as possible.

本發明的目的在於提供一種可將矽氧烷樹脂較佳地去除、並且視需要鋁等的電極的保護性(耐損傷性)優異的去除劑、使用其的矽氧烷樹脂的去除方法以及半導體基板製品及半導體元件的製造方法。 An object of the present invention is to provide a remover which is excellent in protective properties (damage resistance) of an electrode such as aluminum, and a method for removing a decane resin using the same, and a semiconductor A substrate product and a method of manufacturing a semiconductor element.

上述課題可藉由以下手段而解決。 The above problems can be solved by the following means.

[1]一種矽氧烷樹脂的去除劑,其是用以將附於半導體基板上的矽氧烷樹脂去除的去除劑,且含有極性非質子性溶劑及四級銨氫氧化物。 [1] A remover for a decane resin which is a remover for removing a decane resin attached to a semiconductor substrate, and which contains a polar aprotic solvent and a quaternary ammonium hydroxide.

[2]如[1]所述的去除劑,更含有醇類化合物。 [2] The remover according to [1], which further contains an alcohol compound.

[3]如[1]或[2]所述的去除劑,其中極性非質子性溶劑為二甲基亞碸(dimethyl sulfoxide,DMSO)。 [3] The remover according to [1] or [2], wherein the polar aprotic solvent is dimethyl sulfoxide (DMSO).

[4]如[1]至[3]中任一項所述的去除劑,其中上述四級銨氫氧化物為四甲基銨氫氧化物(tetramethylammonium hydroxide,TMAH)、四乙基銨氫氧化物(tetraethylammonium hydroxide,TEAH)、四丁基銨氫氧化物(tetrabutylammonium hydroxide,TBAH)、或苄基三甲基銨氫氧化物(benzyl trimethyl ammonium hydroxide)。 [4] The remover according to any one of [1] to [3] wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide Tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), or benzyl trimethyl ammonium hydroxide.

[5]如[2]至[4]中任一項所述的去除劑,其中上述醇類化合物為2-乙基己醇(2-ethylhexanol)、苯甲醇(benzyl alcohol)、或單乙醇胺(monoethanolamine)。 [5] The remover according to any one of [2] to [4] wherein the alcohol compound is 2-ethylhexanol, benzyl alcohol, or monoethanolamine ( Monoethanolamine).

[6]如[1]至[5]中任一項所述的去除劑,更含有磷酸、硼酸、有機酸、或矽化合物作為金屬腐蝕抑制劑。 [6] The remover according to any one of [1] to [5] further comprising a phosphoric acid, a boric acid, an organic acid, or a hydrazine compound as a metal corrosion inhibitor.

[7]如[1]至[6]中任一項所述的去除劑,含有40質量%~95質量%的上述極性非質子性溶劑,含有0.1質量%~10質量%的上述四級銨氫氧化物。 [7] The remover according to any one of [1] to [6], which contains 40% by mass to 95% by mass of the above polar aprotic solvent, and contains 0.1% by mass to 10% by mass of the above quaternary ammonium salt. hydroxide.

[8]如[1]至[7]中任一項所述的去除劑,含有70質量%~95質量%的上述極性非質子性溶劑,含有1質量%~8質量%的上述四級銨氫氧化物。 [8] The remover according to any one of [1] to [7], which contains 70% by mass to 95% by mass of the above polar aprotic solvent, and contains 1% by mass to 8% by mass of the above quaternary ammonium salt. hydroxide.

[9]如[2]至[8]中任一項所述的去除劑,含有1質量%~50質量%的含有醇類化合物。 [9] The remover according to any one of [2] to [8], which contains 1% by mass to 50% by mass of an alcohol-containing compound.

[10]如[2]至[9]中任一項所述的去除劑,含有0.1質量%~30質量%的金屬腐蝕抑制劑。 [10] The remover according to any one of [2] to [9], which contains 0.1% by mass to 30% by mass of a metal corrosion inhibitor.

[11]如[1]至[10]中任一項所述的去除劑,其中矽氧烷樹脂包含聚有機矽氧烷(polyorganosiloxane)。 [11] The remover according to any one of [1] to [10] wherein the decane resin comprises a polyorganosiloxane.

[12]如[1]至[10]中任一項所述的去除劑,其中矽氧烷樹脂為聚有機矽氧烷與具有環氧基(epoxy group)的樹脂的混合物,或矽酮改質環氧樹脂(silicone-modified epoxy resin)。 [12] The remover according to any one of [1] to [10] wherein the decyl alkane resin is a mixture of a polyorganosiloxane and a resin having an epoxy group, or a fluorenone modification Silicone-modified epoxy resin.

[13]如[1]至[12]中任一項所述的去除劑,其中矽氧烷樹脂為接著劑。 [13] The remover according to any one of [1] to [12] wherein the decane resin is an adhesive.

[14]如[2]至[13]中任一項所述的去除劑,其中上述醇類化合物為下述式(O-1)、下述式(A-1)或下述式(A-2)所表示的化合物,R11-(-O-R12-)n-O-H…(O-1) [14] The remover according to any one of [2] to [13] wherein the alcohol compound is represented by the following formula (O-1), the following formula (A-1) or the following formula (A) -2) the compound represented, R 11 -(-OR 12 -) n -OH...(O-1)

(R11為碳數1以上、5以下的烷基、碳數6~10的芳基、碳數7~11的芳烷基;R12為直鏈狀或分支狀的碳數1以上、4以下的伸烷基鏈;於存在多個R12時,各個R12亦可不同;n為0以上、20以下的整數) (R 11 is an alkyl group having 1 or more carbon atoms, 5 or less carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms; and R 12 is a linear or branched carbon number of 1 or more and 4 the following alkylene chain; in the presence of a plurality of R 12 when R 12 each or different; n is 0 or more and an integer of 20 or less)

NRN1 2-LN1-OH…(A-1) NR N1 2 -L N1 -OH...(A-1)

NRN2 2-(LN2-Y)m-LN3-OH…(A-2) NR N2 2 -(L N2 -Y) m -L N3 -OH...(A-2)

(RN1及RN2分別獨立地為氫原子、烷基、芳基、或芳烷基;LN1~LN3分別獨立地為伸烷基;Y為氧原子或亞胺基(imino group,-NRN-),RN與RN1相同;m為1~20的整數)。 (R N1 and R N2 are each independently a hydrogen atom, an alkyl group, an aryl group or an aralkyl group; L N1 to L N3 are each independently an alkylene group; and Y is an oxygen atom or an imine group (imino group, - NR N -), R N is the same as R N1 ; m is an integer from 1 to 20).

[15]如[6]至[14]中任一項所述的去除劑,其中上述金屬腐蝕抑制劑為下述式(S1)所表示的化合物,RS1 4Si…(S1) [15] The remover according to any one of [6] to [14] wherein the metal corrosion inhibitor is a compound represented by the following formula (S1), R S1 4 Si (S1)

(式中,RS1表示碳數1~10的烷基、碳數1~10的烷氧基、碳數6~22的芳基、或碳數6~22的芳氧基、碳數2~10的烯基、碳數1~10的醯氧基、碳數7~25的芳醯氧基、碳數2~10的肟基(oxime group)、氫原子;然而,不存在RS1全部為氫原子的情況)。 (wherein R S1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 22 carbon atoms, or an aryloxy group having 6 to 22 carbon atoms, and a carbon number of 2~ An alkenyl group of 10, a decyloxy group having 1 to 10 carbon atoms, an aryloxy group having 7 to 25 carbon atoms, an oxime group having 2 to 10 carbon atoms, and a hydrogen atom; however, none of R S1 is present The case of a hydrogen atom).

[16]一種矽氧烷樹脂的去除方法,其是使如[1]至[15]中任一項所述的去除劑接觸於附於半導體基板上的矽氧烷樹脂,而將樹脂去除。 [16] A method for removing a decane resin, which is obtained by contacting the remover according to any one of [1] to [15] with a siloxane resin attached to a semiconductor substrate.

[17]一種半導體基板製品的製造方法,包括:於半導體基板上附設矽氧烷樹脂的層的步驟;使半導體基板經由矽氧烷樹脂層接著於支持基板的步驟;對半導體基板的與支持基板相反之側進行研削而使之薄化的步驟;將支持基板自經薄化的半導體基板剝離的步驟;及使如[1]至[15]中任一項所述的去除劑接觸於附著於經薄化的半導體基板的矽氧烷樹脂,而將矽氧烷樹脂去除的步驟。 [17] A method of manufacturing a semiconductor substrate product, comprising: a step of attaching a layer of a siloxane resin on a semiconductor substrate; a step of bonding the semiconductor substrate to the support substrate via a siloxane layer; and a support substrate for the semiconductor substrate a step of performing thinning on the opposite side; a step of peeling the support substrate from the thinned semiconductor substrate; and contacting the remover according to any one of [1] to [15] The step of removing the decane resin by thinning the germanium oxide resin of the semiconductor substrate.

[18]如[17]所述的半導體基板製品的製造方法,其中於矽氧烷樹脂層的與半導體基板相反之側配置剝離層,經由剝離層與支持基板接著。 [18] The method for producing a semiconductor substrate according to [17], wherein a release layer is disposed on a side opposite to the semiconductor substrate of the siloxane oxide layer, and is followed by a support layer via a release layer.

[19]一種半導體元件的製造方法,其是使用利用如[17]或[18]所述的製造方法獲得的半導體基板製品而製造半導體元件。 [19] A method of producing a semiconductor device, which is to manufacture a semiconductor device using a semiconductor substrate obtained by the method according to [17] or [18].

根據本發明,可將矽氧烷樹脂較佳地去除,並且可視需要實現對鋁等的電極的保護(損傷的抑制)。 According to the present invention, the decane resin can be preferably removed, and protection of the electrode of aluminum or the like (inhibition of damage) can be achieved as needed.

本發明的上述及其他特徵及優點根據下述的記載及隨附的圖式將變得更為明確。 The above and other features and advantages of the invention will be apparent from the description and appended claims.

1a‧‧‧半導體基板 1a‧‧‧Semiconductor substrate

1b‧‧‧半導體基板製品(矽通孔晶片) 1b‧‧‧Semiconductor substrate products (on-hole wafers)

2‧‧‧樹脂層 2‧‧‧ resin layer

3‧‧‧剝離層 3‧‧‧ peeling layer

4‧‧‧支持基板 4‧‧‧Support substrate

9a‧‧‧孔 9a‧‧‧ hole

9b‧‧‧通孔 9b‧‧‧through hole

11‧‧‧反應容器 11‧‧‧Reaction container

12‧‧‧旋轉桌台 12‧‧‧Rotating table

13‧‧‧噴出口 13‧‧‧Spray outlet

A‧‧‧供給部 A‧‧‧Supply Department

fc、fd‧‧‧流路 Fc, fd‧‧‧ flow path

M‧‧‧旋轉驅動部 M‧‧‧Rotary Drive Department

p‧‧‧被研削部 p‧‧‧The Ministry of Research

r‧‧‧方向 R‧‧‧ direction

S‧‧‧半導體基板(半導體基板1a的背面) S‧‧‧Semiconductor substrate (back side of semiconductor substrate 1a)

t‧‧‧移動軌跡線 t‧‧‧Mobile track

圖1是以示意的方式表示本發明的一實施方式中的半導體基板的製作步驟例(TSV形成)的剖面圖。 FIG. 1 is a cross-sectional view showing an example of a manufacturing process (formation of TSV) of a semiconductor substrate according to an embodiment of the present invention.

圖2是表示關於本發明的較佳實施方式的去除裝置的一部分的裝置構成圖。 Fig. 2 is a view showing a configuration of a part of a removing device according to a preferred embodiment of the present invention.

圖3是以示意的方式表示本發明的一實施方式中噴嘴相對於半導體基板的移動軌跡線的平面圖。 Fig. 3 is a plan view schematically showing a movement trajectory of a nozzle with respect to a semiconductor substrate in an embodiment of the present invention.

本發明的去除劑含有極性非質子性溶劑及四級銨氫氧化物。於說明該成分組成等的詳情之前,基於隨附的圖式對可較佳地應用該去除劑的TSV的形成步驟(實施方式)進行說明。 The remover of the present invention contains a polar aprotic solvent and a quaternary ammonium hydroxide. Before describing the details of the composition and the like, the formation step (embodiment) of the TSV to which the remover can be preferably applied will be described based on the accompanying drawings.

[TSV形成步驟] [TSV formation step]

圖1是表示對形成有TSV(矽通孔:Through Silicon Via)的半導體基板1a進行加工而製成半導體基板製品(矽通孔晶片)1b的過程的步驟說明圖。於本實施方式的製造例中,於矽晶圓(silicon wafer)上形成有孔9a(步驟a)。此時,對矽晶圓除TSV以外亦可賦予特定的電路配線或元件構造。繼而,於上述基板1a的形成有通孔的面側依序配設樹脂層2及剝離層3(步驟b、步驟c)。其後,將上述基板1a、樹脂層2、剝離層3的複合體翻轉(flip)並 經由剝離層與支持基板4接合(步驟d)。將包括該支持基板的複合體例如連接、或載置於加工裝置,自半導體基板1a的背面S側實施研削加工(步驟e)。該研削加工只要藉由旋轉研磨等常規方法進行即可,藉由該研削將被研削部p去除,孔9a成為貫通的形態的通孔(through hole)9b。繼而,使該4層的複合體翻轉(flip)(步驟f),將支持基板4剝離(步驟g)。此時,樹脂層2及剝離層3成為殘留於半導體基板製品1b側的狀態,藉由去除劑將其去除(步驟h)。本發明的去除劑於該樹脂層及剝離層的去除步驟中發揮出優異的效果。 1 is a step explanatory view showing a process of processing a semiconductor substrate 1a on which a TSV (Through Silicon Via) is formed to form a semiconductor substrate product (矽 via wafer) 1b. In the manufacturing example of the present embodiment, a hole 9a is formed in the silicon wafer (step a). In this case, a specific circuit wiring or component structure can be given to the wafer in addition to the TSV. Then, the resin layer 2 and the peeling layer 3 are sequentially disposed on the surface side of the substrate 1a on which the through holes are formed (steps b and c). Thereafter, the composite of the substrate 1a, the resin layer 2, and the release layer 3 is flipped and folded. Bonding to the support substrate 4 via the peeling layer (step d). The composite including the support substrate is, for example, connected or placed on a processing apparatus, and is subjected to grinding processing from the back surface S side of the semiconductor substrate 1a (step e). This grinding process can be performed by a conventional method such as spin polishing, and the ground portion 9a is removed by the grinding, and the hole 9a is a through hole 9b that penetrates. Then, the four-layer composite is flipped (step f), and the support substrate 4 is peeled off (step g). At this time, the resin layer 2 and the peeling layer 3 remain in the state of the semiconductor substrate product 1b side, and are removed by the removing agent (step h). The remover of the present invention exerts an excellent effect in the removal step of the resin layer and the release layer.

本發明並不受上述說明限定而解釋。例如可列舉如下形態:不使用剝離層的形態、或製成使孔中填充有金屬的孔塞(via plug)後實施研削加工的形態、於支持基板的剝離後僅樹脂層及剝離層的一部分殘留於半導體基板側的形態、於將接著層剝離的步驟中於研削面側具有切割保護膠帶(dicing tape)等支持體的形態等。 The invention is not to be construed as limited by the foregoing description. For example, a form in which a peeling layer is not used, a form in which a via plug is filled with a metal in a hole, and a grinding process are performed, and only a part of the resin layer and the peeling layer after peeling of the supporting substrate are used. The form remaining on the side of the semiconductor substrate and the step of peeling off the adhesive layer have a form of a support such as a dicing tape on the side of the grinding surface.

此外,於稱為矽基板或半導體基板、或簡稱為基板時,為不僅包含矽晶圓,而且亦包含於矽晶圓上實施有電路構造的基板構造體的含義。所謂基板的構件,是指構成上述所定義的矽基板的構件,可包含一種材料,亦可包含多種材料。有時將加工完畢的半導體基板區別稱為半導體基板製品。視需要進而對其進行加工、切割並取出,將所取出的晶片及其加工、組裝製品稱為半導體元件或半導體裝置。關於基板的定向,只要無特別說明,則就圖1而言,將與矽晶圓相反之側(剝離層側)稱為「上」或「頂」, 將支持基板側稱為「下」或「底」。 In addition, when it is called a germanium substrate or a semiconductor substrate, or simply a substrate, it is intended to include not only a germanium wafer but also a substrate structure in which a circuit structure is formed on a germanium wafer. The member of the substrate refers to a member constituting the above-described ruthenium substrate, and may include one material or a plurality of materials. The processed semiconductor substrate is sometimes referred to as a semiconductor substrate product. The wafer to be taken out and its processed and assembled product are referred to as a semiconductor element or a semiconductor device, if necessary, processed, cut, and taken out. Regarding the orientation of the substrate, unless otherwise specified, the side opposite to the ruthenium wafer (the peeling layer side) is referred to as "upper" or "top" in FIG. The side of the support substrate is referred to as "lower" or "bottom".

[去除劑] [remicide]

其次,對本發明的較佳實施方式的去除劑進行說明。 Next, the remover of the preferred embodiment of the present invention will be described.

(極性非質子性溶劑) (polar aprotic solvent)

成為去除劑的含有成分的極性非質子性溶劑可列舉:二甲基亞碸、環丁碸(sulfolane)、乙二醇二甲醚(ethylene glycol dimethyl ether)、二乙二醇二甲醚(diethylene glycol dimethyl ether)、丙二醇二甲醚(propylene glycol dimethyl ether)、丙二醇正二丁醚(propylene glycol-n-dibutyl ether)、二丙二醇二甲醚(dipropylene glycol dimethyl ether)、二丙二醇正二丁醚(dipropylene glycol-n-dibutyl ether)等,較佳為二甲基亞碸、乙二醇二甲醚、二乙二醇二甲醚、丙二醇正二丁醚,其中,尤佳為二甲基亞碸(DMSO)。 Examples of the polar aprotic solvent which is a component of the remover include dimethyl hydrazine, sulfolane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Glycol dimethyl ether), propylene glycol dimethyl ether, propylene glycol-n-dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol -n-dibutyl ether), etc., preferably dimethyl hydrazine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol n-dibutyl ether, of which dimethyl hydrazine (DMSO) is particularly preferred. .

極性非質子性溶劑相對於本實施方式的去除劑的總質量,較佳為含有40質量%以上,更佳為含有50質量%以上,進而較佳為含有60質量%以上,進而更佳為含有70質量%以上,尤佳為含有80質量%以上。上限較佳為95質量%以下,進而較佳為90質量%以下。藉由設為上述上限值以下,可抑制金屬配線(例如鋁、銅)的腐蝕,故而較佳。設為上述下限值以上時,可將矽氧烷樹脂快速地去除,故而較佳。 The polar aprotic solvent is preferably contained in an amount of 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, and even more preferably, based on the total mass of the removing agent of the present embodiment. 70% by mass or more, and particularly preferably 80% by mass or more. The upper limit is preferably 95% by mass or less, and more preferably 90% by mass or less. By setting it as the said upper limit or less, it can suppress the corrosion of metal wiring (for example, aluminum and copper), and it is preferable. When the value is at least the above lower limit value, the decane resin can be quickly removed, which is preferable.

上述極性非質子性溶劑可單獨使用一種,亦可組合使用兩種以上。 These polar aprotic solvents may be used alone or in combination of two or more.

(四級銨氫氧化物) (Quaternary ammonium hydroxide)

四級銨氫氧化物較佳為四烷基銨氫氧化物(tetraalkyl ammonium hydroxide)(較佳為碳數4~25)。此時,於無損本發明的效果的範圍內烷基亦可經任意的取代基(例如,羥基、烯丙基(allyl group)、芳基)取代。另外,烷基可為直鏈亦可為分支,亦可為環狀。具體而言,可列舉:四甲基銨氫氧化物(TMAH)、四乙基銨氫氧化物(TEAH)、苄基三甲基銨氫氧化物、乙基三甲基銨氫氧化物(ethyl trimethyl ammonium hydroxide)、2-羥乙基三甲基銨氫氧化物(2-hydroxyethyl trimethyl ammonium hydroxide)、苄基三乙基銨氫氧化物(benzyl triethyl ammonium hydroxide)、十六烷基三甲基銨氫氧化物(hexadecyl trimethyl ammonium hydroxide)、四丁基銨氫氧化物(TBAH)、四己基銨氫氧化物(tetrahexyl ammonium ammonium hydroxide)、四丙基銨氫氧化物(tetrapropyl ammonium hydroxide)等。 The quaternary ammonium hydroxide is preferably a tetraalkyl ammonium hydroxide (preferably having a carbon number of 4 to 25). At this time, the alkyl group may be substituted with any substituent (for example, a hydroxyl group, an allyl group, an aryl group) within a range not impairing the effects of the present invention. Further, the alkyl group may be linear or branched, or may be cyclic. Specific examples thereof include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), benzyltrimethylammonium hydroxide, and ethyltrimethylammonium hydroxide (ethyl). Trimethyl ammonium hydroxide), 2-hydroxyethyl trimethyl ammonium hydroxide, benzyl triethyl ammonium hydroxide, cetyltrimethylammonium Hexadecyl trimethyl ammonium hydroxide, tetrabutylammonium hydroxide (TBAH), tetrahexyl ammonium ammonium hydroxide, tetrapropyl ammonium hydroxide, and the like.

其中,更佳為具有三個以上的甲基及/或乙基的四烷基銨氫氧化物。最佳為四甲基銨氫氧化物、或乙基三甲基銨氫氧化物。 Among them, a tetraalkylammonium hydroxide having three or more methyl groups and/or ethyl groups is more preferable. Most preferred is tetramethylammonium hydroxide or ethyltrimethylammonium hydroxide.

四級銨氫氧化物相對於本實施方式的去除劑的總質量,較佳為含有0.1質量%以上,更佳為含有0.5質量%以上,進而較佳為含有1質量%以上,進而更佳為1.5質量%以上,尤佳為含有2質量%以上。上限較佳為含有10質量%以下,更佳為9質量%以下,進而較佳為8質量%以下。藉由設為上述上限值以下,可抑制四級銨氫氧化物的析出,故而較佳。設為上述下限值以上 時,可將矽氧烷樹脂更快速地去除,故而較佳。 The quaternary ammonium hydroxide is preferably contained in an amount of 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and more preferably more preferably 1% by mass or more, based on the total mass of the removing agent of the present embodiment. 1.5% by mass or more, and particularly preferably 2% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 8% by mass or less. By setting it as the said upper limit or less, it can suppress the precipitation of a quaternary ammonium hydroxide, and it is preferable. Set to the above lower limit or higher In this case, the decane resin can be removed more quickly, so that it is preferred.

上述四級銨氫氧化物可單獨使用一種,亦可組合使用兩種以上。 These quaternary ammonium hydroxides may be used alone or in combination of two or more.

(醇類化合物) (alcohol compounds)

本發明的去除劑較佳為含有醇類化合物。醇類化合物並無特別限定,可為單元醇化合物,亦可為多元醇化合物,其中較佳為單元醇化合物。具體而言,較佳為下述的式(1)所表示的化合物。 The remover of the present invention preferably contains an alcohol compound. The alcohol compound is not particularly limited, and may be a unit alcohol compound or a polyol compound, and among them, a unit alcohol compound is preferred. Specifically, a compound represented by the following formula (1) is preferred.

R-OH…(1) R-OH...(1)

R為烷基(較佳為碳數1~10,更佳為碳數1~8,進而較佳為碳數3~8)、芳基(較佳為碳數6~22,更佳為碳數6~10)、或芳烷基(較佳為碳數7~23,更佳為碳數7~11)。上述的烷基、芳基、芳烷基亦可具有取代基,該取代基可列舉:胺基(amino group)(較佳為碳數0~6,進而較佳為碳數0~3)、烯丙基、鹵基(halogen group)、羧基、磺酸基(sulfo group)等。此時,烷基中亦可介隔存在醚鍵(-O-)、酯鍵(-COO-)、亞胺鍵(-NRN-:RN為碳數1~6的烷基或碳數6~10的芳基)。R較佳為直鏈或分支的未經取代的烷基(較佳為碳數1~10,更佳為碳數1~8,進而較佳為碳數3~8)、芳烷基(較佳為碳數7~23,更佳為碳數7~11)、或經胺基取代的烷基(較佳為碳數1~10,更佳為碳數1~6,進而較佳為碳數3~6),更佳為分支的未經取代的烷基或經 -NH2取代的烷基(較佳為碳數1~10,更佳為碳數3~8)。 R is an alkyl group (preferably having a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, more preferably a carbon number of 3 to 8), and an aryl group (preferably having a carbon number of 6 to 22, more preferably carbon). The number is 6 to 10), or an aralkyl group (preferably, the carbon number is 7 to 23, more preferably the carbon number is 7 to 11). The above alkyl group, aryl group, and aralkyl group may have a substituent, and examples of the substituent include an amino group (preferably having a carbon number of 0 to 6, more preferably a carbon number of 0 to 3). Allyl group, halogen group, carboxyl group, sulfo group, and the like. In this case, an alkyl group may also have an ether bond (-O-), an ester bond (-COO-), or an imine bond (-NR N -: R N is an alkyl group having 1 to 6 carbon atoms or a carbon number). 6~10 aryl). R is preferably a linear or branched unsubstituted alkyl group (preferably having a carbon number of 1 to 10, more preferably a carbon number of 1 to 8, more preferably a carbon number of 3 to 8) or an aralkyl group. Preferably, the carbon number is 7 to 23, more preferably the carbon number is 7 to 11), or the alkyl group is substituted with an amine group (preferably having a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, more preferably carbon). The number 3 to 6) is more preferably a branched unsubstituted alkyl group or an alkyl group substituted with -NH 2 (preferably having a carbon number of 1 to 10, more preferably a carbon number of 3 to 8).

醇類化合物進而較佳為下述式(O-1)的化合物。 The alcohol compound is more preferably a compound of the following formula (O-1).

R11-(-O-R12-)n-O-H…(O-1) R 11 -(-OR 12 -) n -OH...(O-1)

.R11 . R 11

R11為碳數1以上、5以下(較佳為1以上、3以下)的烷基、碳數6~10的芳基、碳數7~11的芳烷基。 R 11 is an alkyl group having 1 or more and 5 or less (preferably 1 or more and 3 or less), an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms.

.R12 . R 12

R12為直鏈狀或分支狀的碳數1以上、4以下的伸烷基鏈(alkylene chain)。於存在多個R12時,各個R12亦可不同。 R 12 is a linear or branched alkylene chain having 1 or more and 4 or less carbon atoms. When there are a plurality of R 12 , each R 12 may also be different.

.n . n

n為0以上、20以下的整數,較佳為0以上、10以下,更佳為0以上、5以下。 n is an integer of 0 or more and 20 or less, preferably 0 or more and 10 or less, more preferably 0 or more and 5 or less.

醇類化合物亦較佳為下述式(A-1)或下述式(A-2)所表示的化合物。 The alcohol compound is also preferably a compound represented by the following formula (A-1) or the following formula (A-2).

NRN1 2-LN1-OH…(A-1) NR N1 2 -L N1 -OH...(A-1)

NRN2 2-(LN2-Y)m-LN3-OH…(A-2) NR N2 2 -(L N2 -Y) m -L N3 -OH...(A-2)

RN1及RN2分別獨立地為氫原子或烷基(較佳為碳數1~10,更佳為碳數1~6,進而較佳為碳數1~3)、或芳基(較佳為碳數6 ~22,更佳為碳數6~10)、或芳烷基(較佳為碳數7~23,更佳為碳數7~11)。LN1~LN3為伸烷基(alkylene group)(較佳為碳數1~10,更佳為碳數1~6,進而較佳為碳數1~3)。Y為氧原子或亞胺基(-NRN-),RN與RN1相同。式(A-1)及式(A-2)中的烷基及伸烷基可為直鏈亦可為分支,亦可為環結構。m為1~20的整數,較佳為1~10的整數,更佳為1~3的整數。 R N1 and R N2 are each independently a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, more preferably a carbon number of 1 to 3), or an aryl group (preferably, The carbon number is 6 to 22, more preferably 6 to 10 carbon atoms, or aralkyl (preferably, the carbon number is 7 to 23, more preferably the carbon number is 7 to 11). L N1 ~ L N3 is an alkylene group (preferably having a carbon number of 1 to 10, more preferably a carbon number of 1 to 6, and further preferably a carbon number of 1 to 3). Y is an oxygen atom or an imino group (-NR N -), R N and R N1 same. The alkyl group and the alkylene group in the formula (A-1) and the formula (A-2) may be linear or branched, or may have a ring structure. m is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 3.

關於醇類化合物,若就閃點(flash point)而言,則較佳為50℃以上,更佳為60℃以上。上限並無特別限制,實際上為150℃以下。 The alcohol compound is preferably 50 ° C or higher, and more preferably 60 ° C or higher, in terms of a flash point. The upper limit is not particularly limited and is actually 150 ° C or less.

醇類化合物的含量並無特別限定,於去除劑中,較佳為含有1質量%以上,更佳為含有2質量%以上,尤佳為含有3質量%以上。上限並無特別限制,較佳為50質量%以下,更佳為40質量%以下,尤佳為30質量%以下。藉由設為上述上限值以下,可將矽氧烷樹脂快速地去除,故而較佳。就溶解四級銨氫氧化物的觀點而言較佳為設為上述下限值以上。 The content of the alcohol compound is not particularly limited, and is preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is not particularly limited, but is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less. It is preferable to set the above-mentioned upper limit value or less so that the decane resin can be quickly removed. From the viewpoint of dissolving the quaternary ammonium hydroxide, it is preferably at least the above lower limit value.

上述醇類化合物可單獨使用一種,亦可組合使用兩種以上。 These alcohol compounds may be used alone or in combination of two or more.

(水介質(aqueous medium)) (aqueous medium)

本發明的去除劑中亦可含有水,較佳為使用蒸餾水或離子交換水、或超純水等淨化處理水。但是,較佳為限制水的量,較佳為抑制在20質量%以下,更佳為10質量%以下,進而更佳為8質量%以下,進一步更佳為6質量%以下,尤佳為5質量%以下。下限實際上為1質量%以上。藉由設為上述上限值以下,可有效地抑 制金屬配線(例如鋁、銅)的腐蝕,故而較佳。本發明的去除劑中的水分量可利用JIS標準中所記載的卡爾費雪法(Karl Fischer's method)較佳地測定(JISK0113)。 The remover of the present invention may further contain water, and it is preferred to use purified water such as distilled water, ion-exchanged water or ultrapure water. However, it is preferable to limit the amount of water, and it is preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, still more preferably 6% by mass or less, and particularly preferably 5% by mass. Below mass%. The lower limit is actually 1% by mass or more. By setting it as the above upper limit or less, it can effectively suppress It is preferable to etch metal wiring (for example, aluminum or copper). The moisture content in the remover of the present invention can be preferably measured by the Karl Fischer's method described in JIS Standard (JISK0113).

(pH值) (pH)

於本發明中,較佳為將去除劑的pH值調整為10以上,更佳為設為12以上。就將矽氧烷樹脂快速地去除的觀點而言較佳為設為上述下限值以上。 In the present invention, the pH of the remover is preferably adjusted to 10 or more, and more preferably 12 or more. From the viewpoint of rapidly removing the siloxane oxide resin, it is preferable to set it as the above lower limit value or more.

(金屬腐蝕抑制劑) (metal corrosion inhibitor)

另外,為了防止金屬配線的進一步的腐蝕,亦可添加添加劑。具體而言,可列舉:磷酸、硼酸、有機酸(例如較佳為碳數2~8的有機酸,更佳為苯二甲酸(phthalic acid)、抗壞血酸(ascorbic acid)、己二酸(adipic acid)、蘋果酸(malic acid)、草酸(oxalic acid)、水楊酸(salicylic acid))、矽化合物。其中,可較佳地使用矽化合物作為腐蝕抑制劑,較佳為四乙氧基矽烷(tetraethoxy silane)、四甲氧基矽烷(tetramethoxy silane)、甲基三甲氧基矽烷(methyl trimethoxy silane)、甲基三乙氧基矽烷(methyl triethoxy silane)、乙基三甲氧基矽烷(ethyl trimethoxy silane)、乙基三乙氧基矽烷(ethyl triethoxy silane)、苯基三甲氧基矽烷(phenyl trimethoxy silane)、二苯基二甲氧基矽烷(diphenyl dimethoxy silane)。其中,較佳為甲基三甲氧基矽烷。 Further, in order to prevent further corrosion of the metal wiring, an additive may be added. Specific examples thereof include phosphoric acid, boric acid, and an organic acid (for example, an organic acid having 2 to 8 carbon atoms, more preferably phthalic acid, ascorbic acid, or adipic acid). ), malic acid, oxalic acid, salicylic acid, bismuth compound. Among them, a ruthenium compound can be preferably used as a corrosion inhibitor, preferably tetraethoxy silane, tetramethoxy silane, methyl trimethoxy silane, Methyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, phenyl trimethoxy silane, Diphenyl dimethoxy silane. Among them, methyltrimethoxydecane is preferred.

若進一步詳細敍述矽化合物,則較佳為下述式(S1)所表示的化合物。 When the ruthenium compound is described in more detail, the compound represented by the following formula (S1) is preferred.

RS1 4Si…(S1) R S1 4 Si...(S1)

式中,RS1表示碳數1~10(較佳為1~3)的烷基、碳數1~10(較佳為1~3)的烷氧基、碳數6~22(較佳為6~10)的芳基、或碳數6~22(較佳為6~10)的芳氧基、碳數2~10(較佳為2~4)的烯基(較佳為乙烯基、烯丙基)、碳數1~10(較佳為1~3)的醯氧基、碳數7~25(較佳為7~11)的芳醯氧基、碳數2~10(較佳為2~4)的肟基、氫原子。然而,不存在RS1全部為氫原子的情況。 In the formula, R S1 represents an alkyl group having 1 to 10 carbon atoms (preferably 1 to 3), an alkoxy group having 1 to 10 carbon atoms (preferably 1 to 3), and a carbon number of 6 to 22 (preferably 6 to 10) an aryl group, or an aryloxy group having 6 to 22 carbon atoms (preferably 6 to 10), an alkenyl group having 2 to 10 carbon atoms (preferably 2 to 4) (preferably a vinyl group, Allyl), a decyloxy group having 1 to 10 carbon atoms (preferably 1 to 3), an aryloxy group having 7 to 25 carbon atoms (preferably 7 to 11), and a carbon number of 2 to 10 (preferably It is a thiol group and a hydrogen atom of 2 to 4). However, there is no case where all of R S1 is a hydrogen atom.

上述RS1亦可更具有取代基,該取代基較佳為胺基(較佳為碳數為0的胺基、碳數為1~10的烷胺基(alkylamino group)、碳數為6~18的芳胺基(arylamino group))、羥基、羧基、縮水甘油基(glycidyl group)、氧雜環丁烷基(oxetane group)等。該些取代基亦可介隔存在後述任意的連結基L而連結。 The above R S1 may further have a substituent, and the substituent is preferably an amine group (preferably an amine group having a carbon number of 0, an alkylamino group having a carbon number of 1 to 10, and a carbon number of 6~). An arylamino group of 18, a hydroxyl group, a carboxyl group, a glycidyl group, an oxetane group, or the like. These substituents may be bonded to each other via any of the linking groups L described later.

此外,如此般亦可更具有取代基的情況於後述RS2~RS3中亦相同,其範圍亦相同。進而,該些取代基的烷基、烯基可為直鏈亦可為分支、或亦可為環狀。 Further, the case where the substituent is more likely to be the same is also the same in R S2 to R S3 described later, and the range is also the same. Further, the alkyl group or the alkenyl group of the substituent may be linear or branched, or may be cyclic.

.烷氧基矽烷(alkoxysilane) . Alkoxysilane

其中,有機矽化合物較佳為烷基(單、二、三)烷氧基矽烷或四烷氧基矽烷(以下,稱為特定烷氧基矽烷類)。特定烷氧基矽烷類較佳為下述的式(S2)所表示者。 Among them, the organic ruthenium compound is preferably an alkyl (mono, di, or tri) alkoxy decane or a tetraalkoxy decane (hereinafter referred to as a specific alkoxy decane). The specific alkoxydecane is preferably represented by the following formula (S2).

RS2 m1Si(ORS3)m2…(S2) R S2 m1 Si(OR S3 ) m2 ...(S2)

RS2表示碳數1~10(較佳為1~3)的烷基、碳數2~10(較佳為2~4)的烯基、碳數6~22(較佳為6~10)的芳基。RS2於存在多個時,可相互相同亦可不同。其中,較佳為烷基,具體而言,可列舉:甲基、乙基、丙基、異丙基等。另外,其中較佳為甲基或乙基,尤佳為甲基。 R S2 represents an alkyl group having 1 to 10 carbon atoms (preferably 1 to 3), an alkenyl group having 2 to 10 carbon atoms (preferably 2 to 4), and a carbon number of 6 to 22 (preferably 6 to 10). Aryl. When there are a plurality of R S2 , they may be the same or different from each other. Among them, an alkyl group is preferred, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Further, among them, a methyl group or an ethyl group is preferred, and a methyl group is preferred.

RS3表示碳數1~10的烷基或碳數6~22(較佳為6~10)的芳基。RS3於存在多個時,可相互相同亦可不同。其中,更佳為碳數1~4(更佳為1~3)的烷基。 R S3 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 22 carbon atoms (preferably 6 to 10 carbon atoms). When there are a plurality of R S3 , they may be the same or different from each other. Among them, an alkyl group having a carbon number of 1 to 4 (more preferably 1 to 3) is more preferred.

m1、m2為1~3的整數,且m1+m2為4。其中,較佳為m1=1、m2=3的三烷氧基矽烷化合物。 M1 and m2 are integers of 1 to 3, and m1+m2 is 4. Among them, a trialkoxy decane compound having m1 = 1 and m2 = 3 is preferred.

金屬腐蝕抑制劑於去除劑中,較佳為含有0.1質量%以上,更佳為含有0.5質量%以上,尤佳為含有1質量%以上。上限並無特別限制,較佳為30質量%以下,更佳為20質量%以下,尤佳為10質量%以下。藉由設為上述上限值以下,而不會使樹脂的去除性過度降低,故而較佳。設為上述下限值以上時,可獲得良好的金屬電極的防蝕性,故而較佳。 The metal corrosion inhibitor is preferably contained in an amount of 0.1% by mass or more, more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. It is preferable to set it as the said upper limit or less, and the resin removal property may not fall too much. When the value is equal to or higher than the above lower limit value, good corrosion resistance of the metal electrode can be obtained, which is preferable.

本發明的去除劑對矽氧烷樹脂發揮出良好的去除性的理由包含尚不明確的方面,但可認為如下所述。即,由四級銨氫氧化物所供給的氫氧化物離子(OH-)作用於矽氧烷樹脂的Si-O 鍵,此處可理解為使樹脂化合物分解。關於該分解物的溶解等,推測其反應區間中極性非質子性溶劑較佳地發揮作用。進而於本發明的較佳實施方式中,可認為醇類化合物更有效地促進上述分解物的溶解等,呈現出高的去除作用。另外,作為另一較佳實施方式,可認為藉由含有上述金屬腐蝕抑制劑,而使其作為保護劑對金屬電極發揮作用,維持對矽氧烷樹脂的充分的去除性,並且提高金屬電極的耐損傷性。 The reason why the remover of the present invention exhibits good removability to the decane resin includes an unclear aspect, but it can be considered as follows. That is, the hydroxide ion (OH - ) supplied from the quaternary ammonium hydroxide acts on the Si-O bond of the siloxane resin, and it can be understood that the resin compound is decomposed. Regarding the dissolution or the like of the decomposition product, it is presumed that the polar aprotic solvent in the reaction zone preferably functions. Further, in the preferred embodiment of the present invention, it is considered that the alcohol compound promotes the dissolution of the above-mentioned decomposition product more effectively, and exhibits a high removal action. Further, as another preferred embodiment, it is considered that the metal corrosion inhibitor is contained as a protective agent to act on the metal electrode, to maintain sufficient removal of the siloxane resin, and to improve the metal electrode. Damage resistance.

上述金屬腐蝕抑制劑可單獨使用一種,亦可組合使用兩種以上。 The metal corrosion inhibitor may be used singly or in combination of two or more.

(界面活性劑) (surfactant)

本發明中的去除劑中亦可含有界面活性劑。界面活性劑有陰離子界面活性劑、陽離子界面活性劑、非離子界面活性劑等,並無特別限定。 The remover in the present invention may also contain a surfactant. The surfactant is not particularly limited as long as it is an anionic surfactant, a cationic surfactant, a nonionic surfactant, or the like.

所謂陰離子界面活性劑,並無特別限定,典型而言,意指分子內具有親水基與親油基,親水基的部分於水溶液中發生解離而成為陰離子、或帶有陰離子性的化合物。此處,陰離子界面活性劑可以伴有氫原子的酸的形式存在,亦可為其發生解離而成的陰離子,亦可為其鹽。若帶有陰離子性,則亦可為非解離性的陰離子界面活性劑,亦包含酸酯(acid ester)等。 The anionic surfactant is not particularly limited, and typically means a compound having a hydrophilic group and an oleophilic group in the molecule, and a hydrophilic group is dissociated in an aqueous solution to become an anion or an anionic compound. Here, the anionic surfactant may be present in the form of an acid accompanied by a hydrogen atom, an anion formed by dissociation thereof, or a salt thereof. If it is anionic, it may be a non-dissociable anionic surfactant, and may also contain an acid ester or the like.

上述陰離子界面活性劑較佳為碳數3以上,更佳為碳數5以上,尤佳為碳數10以上的陰離子界面活性劑。上限並無特別限制,實際上為碳數40以下。 The anionic surfactant is preferably an anionic surfactant having a carbon number of 3 or more, more preferably a carbon number of 5 or more, and particularly preferably a carbon number of 10 or more. The upper limit is not particularly limited, and is actually 40 or less carbon atoms.

碳數10以上、40以下的陰離子界面活性劑的具體例可列舉:碳數10以上、40以下的羧酸化合物、碳數10以上、40以下的膦酸化合物、碳數10以上、40以下的磺酸化合物。其中,較佳為烷基磺酸(alkyl sulfonic acid)、烷基苯磺酸(alkylbenzene sulfonic acid)、烷基萘磺酸(alkyl naphthalene sulfonic acid)、烷基二苯醚磺酸(alkyl diphenyl ether sulfonic acid)(較佳為單磺酸(monosulfonic acid)或二磺酸(disulfonic acid))、脂肪醯胺磺酸(fatty acid amide sulfonic acid)、聚氧乙烯烷基醚羧酸(polyoxyethylene alkyl ether carboxylic acid)、聚氧乙烯烷基醚乙酸(polyoxyethylene alkyl ether acetic acid)、聚氧乙烯烷基醚丙酸(polyoxyethylene alkyl ether propionic acid)、烷基膦酸(alkylphosphonic acid)、脂肪酸(fatty acid)及該些的鹽。其中,較佳為烷基二苯醚單磺酸(alkyl diphenyl ether monosulfonic acid)、烷基二苯醚二磺酸(alkyl diphenyl ether disulfonic acid)或其鹽或該些的混合物。上述「鹽」可列舉:銨鹽、鈉鹽、鉀鹽、四甲基銨鹽。 Specific examples of the anionic surfactant having a carbon number of 10 or more and 40 or less include a carboxylic acid compound having 10 or more carbon atoms and 40 or less carbon atoms, a phosphonic acid compound having 10 or more carbon atoms and 40 or less carbon atoms, and a carbon number of 10 or more and 40 or less. Sulfonic acid compound. Among them, preferred is alkyl sulfonic acid, alkylbenzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether sulfonic acid (alkyl diphenyl ether sulfonic acid) Acid) (preferably monosulfonic acid or disulfonic acid), fatty acid amide sulfonic acid, polyoxyethylene alkyl ether carboxylic acid ), polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl ether propionic acid, alkylphosphonic acid, fatty acid, and the like Salt. Among them, an alkyl diphenyl ether monosulfonic acid, an alkyl diphenyl ether disulfonic acid or a salt thereof or a mixture thereof is preferred. Examples of the "salt" include an ammonium salt, a sodium salt, a potassium salt, and a tetramethylammonium salt.

陽離子性界面活性劑可列舉氯化十六烷基吡啶(cetyl pyridinium chloride)等烷基吡啶系界面活性劑。 The cationic surfactant may, for example, be an alkylpyridine-based surfactant such as cetyl pyridinium chloride.

非離子界面活性劑具有碳數為8以上的疏水性基與一個以上的親水性基。疏水性基較佳為分別選自碳數14以上的烷基、烯基、炔基、環烷基、芳基、雜環基、及組合兩個以上該些基團而成的基團中的基團。親水性基較佳為包含一個以上的O原子、 N原子、S原子的基團。進而較佳的親水性基可列舉具有環氧乙烷基(ethylene oxide group)或環氧丙烷基(propylene oxide group)的基團,可列舉具有親水性基的非離子性界面活性劑,上述親水性基具有合計為6個以上的(較佳為6個以上、100個以下)包含上述兩基的重複單元。此時,疏水性基的碳數較佳為14~50,更佳為16~30。環氧乙烷基或環氧丙烷基的碳數的合計較佳為12~1000的整數,更佳為12~200的整數。 The nonionic surfactant has a hydrophobic group having 8 or more carbon atoms and one or more hydrophilic groups. The hydrophobic group is preferably selected from the group consisting of an alkyl group having at least 14 carbon atoms, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and a group in which two or more of these groups are combined. Group. The hydrophilic group preferably contains more than one O atom, A group of N atoms and S atoms. Further, preferred examples of the hydrophilic group include a group having an ethylene oxide group or a propylene oxide group, and examples thereof include a nonionic surfactant having a hydrophilic group, and the above hydrophilic group. The compound has a total of 6 or more (preferably 6 or more, 100 or less) repeating units containing the above two groups. In this case, the carbon number of the hydrophobic group is preferably from 14 to 50, more preferably from 16 to 30. The total number of carbon atoms of the oxiranyl group or the propylene oxide group is preferably an integer of from 12 to 1,000, more preferably an integer of from 12 to 200.

界面活性劑亦較佳為下述通式所表示的界面活性劑。 The surfactant is also preferably a surfactant represented by the following formula.

式(A)R-(CH2CH2O)nH Formula (A) R-(CH 2 CH 2 O) n H

式(B)R-(CH2CH2CH2O)mH Formula (B) R-(CH 2 CH 2 CH 2 O) m H

式(C)R-(CH2CH2O)n(CH2CH2CH2O)mH Formula (C) R-(CH 2 CH 2 O) n (CH 2 CH 2 CH 2 O) m H

R表示碳數10以上、50以下的直鏈或具有分支的烴基,n、m表示1以上、100以下的整數。 R represents a linear or branched hydrocarbon group having 10 or more and 50 or less carbon atoms, and n and m represent an integer of 1 or more and 100 or less.

R可列舉:直鏈、分支鏈、或環式的經取代或未經取代的烷基、烯基、炔基、環烷基、芳基、雜環基、或組合兩個以上該些基團而成的基團,尤佳為直鏈及分支烷基。此外,於本說明書中,關於取代基,於末尾附隨「基」這一用語來稱謂時,意味著該基團亦可具有任意的取代基。 R may be a linear, branched, or cyclic substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclic group, or a combination of two or more of these groups. The group formed is preferably a straight chain and a branched alkyl group. Further, in the present specification, the term "substituent" as used in the term "base" as used in the term means that the group may have any substituent.

n較佳為6~500的整數,更佳為6~100的整數。 n is preferably an integer of 6 to 500, more preferably an integer of 6 to 100.

m較佳為6~500的整數,更佳為6~100的整數。 m is preferably an integer of 6 to 500, more preferably an integer of 6 to 100.

界面活性劑於金屬腐蝕抑制劑中的含量並無特別限定,相對於金屬腐蝕抑制劑的總質量,較佳為於0.001質量%~5質量%的範圍內含有,更佳為含有0.01質量%~3質量%,進而較佳為含有0.05質量%~1質量%。 The content of the surfactant in the metal corrosion inhibitor is not particularly limited, and is preferably contained in the range of 0.001% by mass to 5% by mass, and more preferably 0.01% by mass based on the total mass of the metal corrosion inhibitor. 3 mass%, further preferably contains 0.05 mass% to 1 mass%.

上述界面活性劑可單獨使用一種,亦可組合使用兩種以上。 The above surfactants may be used alone or in combination of two or more.

於本說明書中,包括化合物的取代基或連結基的選擇、溫度、厚度等各技術事項,其所列項(list)可分別獨立地記載,亦可相互組合。 In the present specification, each of the technical matters including the selection of a substituent or a linking group of a compound, temperature, thickness, and the like may be independently described or combined with each other.

(容器) (container)

本發明的去除劑只要抗腐蝕性等不成為問題,則可填充於任意的容器中進行保管、搬運,然後使用。另外,在半導體用途時,較佳為容器的潔淨度(cleanliness)高、雜質的溶出少的容器。可使用的容器可列舉愛賽璐化學股份有限公司(AICELLO CHEMICAL Co.,Ltd.)製造的「Clean Bottle」系列(series)、兒玉樹脂工業股份有限公司(KODAMA PLASTICS Co.,Ltd.)製造的「Pure Bottle」等,但並不限定於該些。 The remover of the present invention can be stored in a container, stored, transported, and used as long as it does not cause problems such as corrosion resistance. Further, in the case of semiconductor use, it is preferred that the container has a high cleanliness and a small amount of elution of impurities. The container which can be used is exemplified by "Clean Bottle" series (series) manufactured by AICELLO CHEMICAL Co., Ltd., and KODAMA PLASTICS Co., Ltd. "Pure Bottle", etc., but not limited to these.

關於本發明的去除劑,鑒於其使用用途,較佳為液中的雜質、例如金屬成分等少。 Regarding the remover of the present invention, in view of its use, it is preferred that impurities such as a metal component in the liquid are small.

[處理條件] [Processing conditions]

於本實施方式中,進行去除處理的條件並無特別限定,可為單片式的處理,亦可為浸漬式(批次式(batch))的處理。於單片式的處理中,使半導體基板沿特定的方向搬送或旋轉,對其空間 賦予(噴射、流入、滴加等)去除劑而接觸於上述半導體基板。另一方面,於批次式的處理中,於包含去除劑的液浴中浸漬半導體基板,於上述液浴內與半導體基板接觸。該些方式只要根據基板的構造或所去除的樹脂材料等而適當區分使用即可。 In the present embodiment, the conditions for performing the removal treatment are not particularly limited, and may be a one-piece treatment or a immersion (batch) treatment. In a monolithic process, the semiconductor substrate is transported or rotated in a specific direction to the space thereof. A remover is applied (sprayed, inflowed, dropped, etc.) to contact the semiconductor substrate. On the other hand, in the batch type processing, the semiconductor substrate is immersed in a liquid bath containing a remover, and is brought into contact with the semiconductor substrate in the liquid bath. These methods may be appropriately used depending on the structure of the substrate, the resin material to be removed, and the like.

圖2是表示可較佳地用於本發明的單片式裝置的例子的裝置構成圖。關於本實施方式的去除處理,若使用該圖進行說明,則自供給部A供給所製備的去除劑(溶液組成物),其後經由流路(flow path)fc移行至噴出口13。其後,去除劑自噴出口13噴射,應用於反應容器11內的半導體基板S的上表面。流路fd表示用以再利用化學溶液的返迴(return)路徑。於本實施方式中,半導體基板S位於旋轉桌台12上,藉由旋轉驅動部M與旋轉桌台一併旋轉。 Fig. 2 is a view showing a configuration of a device which can be preferably used in the example of the one-chip device of the present invention. When the removal process of the present embodiment is described using the figure, the prepared remover (solution composition) is supplied from the supply unit A, and then moved to the discharge port 13 via the flow path fc. Thereafter, the removing agent is ejected from the ejection port 13 and applied to the upper surface of the semiconductor substrate S in the reaction container 11. The flow path fd represents a return path for reusing the chemical solution. In the present embodiment, the semiconductor substrate S is placed on the rotary table 12, and the rotary drive unit M rotates together with the rotary table.

進行處理的環境溫度較佳為40℃以上,更佳為50℃以上,尤佳為60℃以上。上限較佳為100℃以下,更佳為90℃以下。藉由設為上述上限值以下,使化學溶液起火的可能性降低而可安全地使用,故而較佳。就將矽氧烷樹脂快速地去除的觀點而言,較佳為設為上述下限值以上。 The ambient temperature to be treated is preferably 40 ° C or higher, more preferably 50 ° C or higher, and particularly preferably 60 ° C or higher. The upper limit is preferably 100 ° C or lower, more preferably 90 ° C or lower. It is preferable to set it as the said upper limit or less, and it is easy to use by the chemical solution, and it can use it safely. From the viewpoint of rapidly removing the siloxane oxide resin, it is preferably at least the above lower limit value.

去除劑的供給速度並無特別限定,較佳為設為0.5L/min~3L/min,更佳為設為1L/min~2L/min。藉由設為上述上限值以下,可減少化學溶液的使用量,故而較佳。就提高面內的處理均勻性的觀點而言,較佳為設為上述下限值以上。於使半導體基板旋轉時,亦取決於其大小等,但就與上述相同的觀點而言,較佳為以 50rpm~500rpm旋轉。 The supply rate of the remover is not particularly limited, but is preferably 0.5 L/min to 3 L/min, and more preferably 1 L/min to 2 L/min. By setting it as the said upper limit or less, the usage amount of a chemical solution can be reduced, and it is preferable. From the viewpoint of improving the uniformity of processing in the plane, it is preferably at least the above lower limit value. When the semiconductor substrate is rotated, it depends on its size, etc., but from the same viewpoint as described above, it is preferable to Rotate from 50rpm to 500rpm.

在批次式的情況下,根據與上述相同的理由,亦較佳為將液浴設為上述溫度範圍。半導體基板的浸漬時間並無特別限定,較佳為設為0.5分鐘~30分鐘,更佳為設為1分鐘~10分鐘。 In the case of the batch type, it is also preferred to set the liquid bath to the above temperature range for the same reason as described above. The immersion time of the semiconductor substrate is not particularly limited, but is preferably 0.5 minutes to 30 minutes, more preferably 1 minute to 10 minutes.

於本發明的較佳實施方式的單片式的處理中,較佳為使半導體基板沿特定的方向搬送或旋轉,對其空間噴射去除劑而使上述去除劑接觸於上述半導體基板。關於去除劑的供給速度或基板的旋轉速度,與已敍述者相同。 In the monolithic process according to the preferred embodiment of the present invention, it is preferable that the semiconductor substrate is transferred or rotated in a specific direction, and a removing agent is sprayed into the space to bring the removing agent into contact with the semiconductor substrate. The supply rate of the remover or the rotational speed of the substrate is the same as that described above.

於本發明的較佳實施方式的單片式的裝置構成中,較佳為如圖3所示般,一面使噴出口(噴嘴(nozzle))移動,一面賦予去除劑。具體而言,於本實施方式中,在對半導體基板S應用去除劑時,基板沿r方向旋轉。另一方面,使噴出口沿著自該半導體基板的中心部分向端部分延伸的移動軌跡線t移動。如此,於本實施方式中,將基板的旋轉方向與噴出口的移動方向設定為不同的方向,藉此使兩者相互進行相對運動。其結果,可對半導體基板的整個表面無遺漏地賦予去除劑,成為可較佳地確保處理的均勻性的構成。 In the monolithic device configuration of the preferred embodiment of the present invention, it is preferable to apply a remover while moving the discharge port (nozzle) as shown in Fig. 3 . Specifically, in the present embodiment, when the remover is applied to the semiconductor substrate S, the substrate rotates in the r direction. On the other hand, the discharge port is moved along a movement trajectory t extending from the central portion of the semiconductor substrate toward the end portion. As described above, in the present embodiment, the rotation direction of the substrate and the movement direction of the discharge port are set to different directions, thereby causing the two to move relative to each other. As a result, the remover can be applied to the entire surface of the semiconductor substrate without any omission, and the uniformity of the treatment can be preferably ensured.

噴出口(噴嘴)的移動速度並無特別限定,較佳為0.1cm/s以上,更佳為1cm/s以上。另一方面,其上限較佳為30cm/s以下,更佳為15cm/s以下。移動軌跡線可為直線亦可為曲線(例如圓弧狀)。任一情況下,移動速度均可根據實際的軌跡線的距離與該移動所花費的時間而算出。 The moving speed of the discharge port (nozzle) is not particularly limited, but is preferably 0.1 cm/s or more, and more preferably 1 cm/s or more. On the other hand, the upper limit is preferably 30 cm/s or less, more preferably 15 cm/s or less. The moving trajectory can be a straight line or a curved line (for example, an arc shape). In either case, the speed of movement can be calculated from the distance of the actual trajectory line and the time taken for the movement.

[矽氧烷樹脂] [矽 烷 树脂 resin]

藉由應用本實施方式的去除劑而去除的材料只要為矽氧烷樹脂則可為任意的矽氧烷樹脂,但較佳為包含聚有機矽氧烷(polyorganosiloxane),較佳為矽酮改質環氧樹脂或具有環氧基的樹脂與聚有機矽氧烷(不含環氧基的矽酮樹脂)的混合物。 The material to be removed by applying the remover of the present embodiment may be any siloxane oxide as long as it is a siloxane oxide, but preferably contains a polyorganosiloxane, preferably an oxime oxime. A mixture of an epoxy resin or a resin having an epoxy group and a polyorganosiloxane (an epoxy group-free fluorenone resin).

矽酮樹脂較佳為含有由下述式(1)所表示的矽氧烷單元。 The fluorenone resin preferably contains a siloxane unit represented by the following formula (1).

-Si(R1)2O-…(1) -Si(R 1 ) 2 O-...(1)

R1相互獨立地為碳數1~10的一價烴基,例如可列舉:甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、戊基、新戊基、己基、環己基、辛基、癸基等烷基,乙烯基、烯丙基、丙烯基(propenyl group)、丁烯基等烯基,苯基、甲苯基等芳基,苄基、苯基乙基等芳烷基,該些烴基的氫原子的一部分或全部經鹵素原子等取代而成的鹵代一價烴基。較佳為甲基或苯基。亦可使R1的一部分成為-O-連結基而形成樹脂基質(matrix)。 R 1 is independently a monovalent hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, and pentyl group. An alkyl group such as neopentyl, hexyl, cyclohexyl, octyl or decyl, an alkenyl group such as a vinyl group, an allyl group, a propenyl group or a butenyl group; an aryl group such as a phenyl group or a tolyl group; An aralkyl group such as a phenylethyl group, or a halogenated monovalent hydrocarbon group in which a part or all of a hydrogen atom of the hydrocarbon group is substituted with a halogen atom or the like. It is preferably a methyl group or a phenyl group. A part of R 1 may be made into a -O-linking group to form a resin matrix.

矽酮改質環氧樹脂較佳為包含使芳香族聚合物與有機氫(organohydrogen)聚矽氧烷進行加成反應而獲得的矽酮改質環氧樹脂的矽酮改質環氧樹脂。 The anthrone-modified epoxy resin is preferably an anthrone-modified epoxy resin comprising an anthrone-modified epoxy resin obtained by an addition reaction of an aromatic polymer with an organohydrogen polyoxyalkylene.

該芳香族聚合物可列舉下述式(2)所表示的含烯基的化合物。 The aromatic polymer may, for example, be an alkenyl group-containing compound represented by the following formula (2).

Figure TWI610996BD00001
Figure TWI610996BD00001

R2為含縮水甘油基的基團(較佳為碳數2~10)。R3為末端含乙烯基的伸烷氧基(較佳為碳數2~10)。X為鹵素原子(溴原子等)。m為0~3的整數。 R 2 is a glycidyl group-containing group (preferably, carbon number 2 to 10). R 3 is a vinyl group-containing alkoxy group (preferably having a carbon number of 2 to 10). X is a halogen atom (such as a bromine atom). m is an integer from 0 to 3.

上述有機氫聚矽氧烷較佳為下述式(3)所表示的化合物。 The above organohydrogenpolysiloxane is preferably a compound represented by the following formula (3).

HSi(R1)2-O-[Si(R1)2O]n-Si(R1)2H…(3) HSi(R 1 ) 2 -O-[Si(R 1 ) 2 O] n -Si(R 1 ) 2 H...(3)

R1與上述式(1)含義相同。n為0~200的整數,較佳為5~100。 R 1 has the same meaning as the above formula (1). n is an integer from 0 to 200, preferably from 5 to 100.

矽氧烷樹脂亦可製成另外含有硬化劑或其他有機聚矽氧烷等的樹脂組成物。關於該矽氧烷樹脂或樹脂組成物,例如可參照日本專利特開2011-132337號公報、日本專利特開2012-004200號公報等。此外,於本說明書中,稱為「樹脂」時,是用於除特定的樹脂與其他用劑的組成物以外,亦包含該樹脂與其他樹脂的混合物的含義。 The decane resin may also be formed into a resin composition containing a curing agent or other organic polysiloxane. For example, JP-A-2011-132337, JP-A-2012-004200, and the like can be referred to. In addition, in the present specification, the term "resin" is used to mean a mixture of a specific resin and another agent, and a mixture of the resin and another resin.

矽氧烷樹脂的組成物較佳為含有硬化劑,無特別限定,可使用公知的硬化劑。具體而言,可列舉酚樹脂系硬化劑、胺系硬化劑、酸酐系硬化劑等,其中可較佳地使用酚樹脂系硬化劑。 The composition of the decane resin preferably contains a curing agent, and is not particularly limited, and a known curing agent can be used. Specific examples thereof include a phenol resin-based curing agent, an amine-based curing agent, and an acid anhydride-based curing agent. Among them, a phenol resin-based curing agent can be preferably used.

酚樹脂系硬化劑可使用一分子中具有至少兩個以上的酚性羥基的酚樹脂。具體而言,此種硬化劑可例示:苯酚酚醛清漆樹脂(phenol novolac resin)、甲酚酚醛清漆樹脂(cresol novolac resin)等酚醛清漆型酚樹脂,對二甲苯改質酚醛清漆樹脂、間二甲苯改質酚醛清漆樹脂、鄰二甲苯改質酚醛清漆樹脂,雙酚A(bisphenol-A)、雙酚F(bisphenol-F)等雙酚型樹脂,聯苯型酚樹脂、可溶酚醛型酚樹脂、苯酚芳烷基樹脂、含聯苯骨架的芳烷基型酚樹脂、三苯酚烷烴型樹脂及其聚合物等酚樹脂,含萘環的酚樹脂、二環戊二烯改質酚樹脂、脂環式酚樹脂、雜環型酚樹脂等,該些可單獨使用一種,亦可組合使用兩種以上。 As the phenol resin-based curing agent, a phenol resin having at least two or more phenolic hydroxyl groups in one molecule can be used. Specifically, such a curing agent can be exemplified by a phenol novolac resin such as a phenol novolac resin or a cresol novolac resin, a para-xylene-modified novolac resin, and a meta-xylene. Modified novolac resin, o-xylene modified novolak resin, bisphenol-A, bisphenol-F bisphenol type resin, biphenyl type phenol resin, resol type phenolic resin a phenol resin such as a phenol aralkyl resin, an aralkyl type phenol resin containing a biphenyl skeleton, a triphenyl alkane type resin, and a polymer thereof, a naphthalene ring-containing phenol resin, a dicyclopentadiene-modified phenol resin, and a fat The cyclic phenol resin, the heterocyclic phenol resin, and the like may be used alone or in combination of two or more.

上述酚樹脂系硬化劑的軟化點較佳為60℃~150℃,尤佳為70℃~130℃。另外,羥基當量較佳為90~250。另外,酚樹脂系硬化劑較佳為使用其精製過程中殘存的鈉、鉀為10ppm(質量基準)以下的酚樹脂。在使用其精製過程中殘存的鈉、鉀超過10ppm的酚樹脂密封半導體裝置,並將半導體裝置長時間放置於高溫高濕下的情況下,有促進耐濕性的劣化的情況。 The softening point of the phenol resin-based curing agent is preferably from 60 ° C to 150 ° C, particularly preferably from 70 ° C to 130 ° C. Further, the hydroxyl equivalent is preferably from 90 to 250. Further, the phenol resin-based curing agent is preferably a phenol resin having a sodium or potassium content of 10 ppm (mass-based or less) remaining in the purification process. When the semiconductor device is sealed with a phenol resin having a sodium or potassium content of more than 10 ppm remaining in the purification process, and the semiconductor device is placed under high temperature and high humidity for a long period of time, deterioration of moisture resistance may be promoted.

關於硬化劑的調配量,在使用環氧樹脂的情況下,只要為硬化的有效量即可,並無特別限制,較佳為相對於環氧樹脂中所含的環氧基1莫耳,與硬化劑中所含的反應性官能基(例如酚 性羥基)的莫耳比較佳為0.4~2.0,尤佳為0.6~1.8。 The amount of the curing agent to be used is not particularly limited as long as it is an effective amount of curing, and is preferably 1 mol per epoxy group contained in the epoxy resin. Reactive functional groups (such as phenols) contained in the hardener The molarity of the hydroxyl group is preferably from 0.4 to 2.0, and more preferably from 0.6 to 1.8.

矽氧烷樹脂的分子量較佳為5,000~200,000,更佳為8,000~100,000。若分子量為上述下限值以上,則所獲得的被膜的強度變高,故而較佳。另一方面,分子量為上述上限值以下的矽氧烷樹脂有富有對溶劑的溶解性,而容易操作的情況。此外,於本說明書中,矽氧烷樹脂的分子量只要無特別說明則為數量平均分子量,是指利用凝膠滲透層析法(gel permeation chromatography,GPC)獲得的聚苯乙烯換算的數量平均分子量。載體(carrier)只要使用可溶解測定對象樹脂的任意的載體即可,例如可較佳地使用THF(tetrahydrofuran,四氫呋喃)。 The molecular weight of the siloxane resin is preferably from 5,000 to 200,000, more preferably from 8,000 to 100,000. When the molecular weight is at least the above lower limit value, the strength of the obtained film becomes high, which is preferable. On the other hand, a decane resin having a molecular weight of at most the above upper limit value is rich in solubility in a solvent and is easy to handle. In the present specification, the molecular weight of the decane resin is a number average molecular weight unless otherwise specified, and refers to a polystyrene-equivalent number average molecular weight obtained by gel permeation chromatography (GPC). As the carrier, any carrier that can dissolve the resin to be measured can be used. For example, THF (tetrahydrofuran) can be preferably used.

於本發明中,矽氧烷樹脂亦較佳為使用與具有環氧基的樹脂(環氧樹脂)的混合物。矽氧烷樹脂可列舉具有上述式(1)的樹脂。環氧樹脂可較佳地使用抗蝕劑(resist)用途等中所應用的通常的樹脂。矽氧烷樹脂與環氧樹脂的混合比並無特別限定。 In the present invention, the siloxane resin is also preferably used in a mixture with a resin (epoxy resin) having an epoxy group. The rhodium oxide resin may, for example, be a resin having the above formula (1). As the epoxy resin, a usual resin to be used in a resist application or the like can be preferably used. The mixing ratio of the decane resin to the epoxy resin is not particularly limited.

環氧樹脂並無特別限定,可使用先前公知的各種環氧樹脂,較佳為一分子中具有至少兩個環氧基的環氧樹脂。 The epoxy resin is not particularly limited, and various conventionally known epoxy resins can be used, and an epoxy resin having at least two epoxy groups in one molecule is preferable.

環氧樹脂可列舉:雙(4-羥基苯基)甲烷(bis(4-hydroxyphenyl)methane)、2,2'-雙(4-羥基苯基)丙烷(2,2'-bis(4-hydroxyphenyl)propane)或該些的鹵化物的二縮水甘油醚(diglycidyl ether)及該些的縮聚物(所謂的雙酚F型環氧樹脂、雙酚A型環氧樹脂等);丁二烯二環氧化物(butadiene diepoxide);乙烯環己烯二氧化物(vinylcyclohexene dioxide);1,2-二羥基苯(1,2-dihydroxybenzene) 的二縮水甘油醚、間苯二酚(resorcinol)的二縮水甘油醚、1,4-雙(2,3-環氧丙氧基)苯(1,4-bis(2,3-epoxypropoxy)benzene)、4,4'-雙(2,3-環氧丙氧基)二苯醚(4,4'-bis(2,3-epoxypropoxy)diphenyl ether)、1,4-雙(2,3-環氧丙氧基)環己烯(1,4-bis(2,3-epoxypropoxy)cyclohexene)等的二縮水甘油醚;己二酸雙(3,4-環氧-6-甲基環己基甲基)酯(bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate);使多元酚或多元醇與表氯醇(epichlorohydrin)縮合而獲得的聚縮水甘油醚;使苯酚酚醛清漆、甲酚酚醛清漆等酚醛清漆型酚樹脂或鹵化酚醛清漆型酚樹脂與表氯醇縮合而獲得的環氧酚醛清漆(即,苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂);藉由過氧化法而進行環氧化的環氧化聚烯烴(polyolefin)或環氧化聚丁二烯(polybutadiene);含萘環的環氧樹脂;聯苯型環氧樹脂;苯酚芳烷基型環氧樹脂;聯苯芳烷基型環氧樹脂;二環戊二烯(dicyclopentadiene)型環氧樹脂(即,具有二環戊二烯骨架的環氧樹脂)等。 Epoxy resins include bis(4-hydroxyphenyl)methane and 2,2'-bis(4-hydroxyphenyl)propane (2,2'-bis(4-hydroxyphenyl) Propane) or diglycidyl ether of such halides and polycondensates (so-called bisphenol F type epoxy resin, bisphenol A type epoxy resin, etc.); butadiene ring Butadiene diepoxide; vinylcyclohexene dioxide; 1,2-dihydroxybenzene Diglycidyl ether, diglycidyl ether of resorcinol, 1,4-bis(2,3-epoxypropoxy)benzene (1,4-bis(2,3-epoxypropoxy)benzene) , 4,4'-bis(2,3-epoxypropoxy)diphenyl ether, 1,4-bis(2,3- Diglycidyl ether of 1,4-bis(2,3-epoxypropoxycyclohexene); bis(3,4-epoxy-6-methylcyclohexyl) Bis (3,4-epoxy-6-methylcyclohexylmethyl)adipate; polyglycidyl ether obtained by condensation of polyphenol or polyol with epichlorohydrin; phenol novolac, cresol novolac An epoxy novolac obtained by condensation of a novolac type phenol resin or a halogenated novolac type phenol resin with epichlorohydrin (that is, a novolak type epoxy resin such as a phenol novolak type epoxy resin or a cresol novolak type epoxy resin) Resin); epoxidized olefin or polybutadiene epoxidized by peroxidation; naphthalene ring-containing epoxy resin; biphenyl type epoxy resin; phenol aralkyl group Epoxy resin; biphenyl aralkyl type epoxy Fats; dicyclopentadiene (dicyclopentadiene) epoxy resin (i.e., an epoxy resin having a dicyclopentadiene skeleton) and the like.

上述樹脂層2及剝離層3(圖1)較佳為使用上述的矽氧烷樹脂或其組成物。於本說明書中,將包含上述矽氧烷樹脂的層、包含含有上述矽氧烷樹脂的樹脂組成物的層、該些的硬化物的層統稱為矽氧烷樹脂層。進一步考慮到耐化學品性、接著性、耐破壞性(耐研削性),樹脂層2較佳為使用矽酮改質環氧樹脂或矽氧烷樹脂與環氧樹脂的混合物。剝離層3可列舉更優先考慮剝 離性而使用未導入環氧基的矽酮樹脂的例子。樹脂層2的厚度並無特別限定,較佳為10μm~200μm。剝離層的厚度較佳為1μm~50μm。 The resin layer 2 and the release layer 3 (Fig. 1) preferably use the above-described decane resin or a composition thereof. In the present specification, a layer containing the above-described siloxane oxide resin, a layer containing a resin composition containing the above siloxane oxide resin, and a layer of the cured product are collectively referred to as a siloxane oxide resin layer. Further, in consideration of chemical resistance, adhesion, and chipping resistance (drilling resistance), the resin layer 2 is preferably a mixture of an anthrone-modified epoxy resin or a siloxane resin and an epoxy resin. Peel layer 3 can be cited as a priority An example of an anthrone resin which does not introduce an epoxy group is used as an excipient. The thickness of the resin layer 2 is not particularly limited, but is preferably 10 μm to 200 μm. The thickness of the release layer is preferably from 1 μm to 50 μm.

[電極] [electrode]

電極中所使用的材料並無特別限定,若列舉近來的製程(process)中所應用的材料,則可列舉:鋁(Al)、銅(Cu)、鎢(W)、鎳(Ni)、錫銀合金(Sn/Ag)、鈦(Ti)、鉛(Pb)、多晶矽(polysilicon)等。其中,就較佳地表現出本發明的去除劑的效果的觀點而言,較佳為使用鋁、鎢、多晶矽。另外,電極的材料亦可為合金,例如可列舉鋁與銅的合金。電極的露出面的相當於圓的直徑(相當於圖1的通孔9b的寬度)實際上為2μm~100μm左右。 The material used in the electrode is not particularly limited, and examples of the materials used in recent processes include aluminum (Al), copper (Cu), tungsten (W), nickel (Ni), and tin. Silver alloy (Sn/Ag), titanium (Ti), lead (Pb), polysilicon, and the like. Among them, aluminum, tungsten, and polycrystalline germanium are preferably used from the viewpoint of preferably exhibiting the effect of the remover of the present invention. Further, the material of the electrode may be an alloy, and examples thereof include an alloy of aluminum and copper. The diameter of the circle corresponding to the exposed surface of the electrode (corresponding to the width of the through hole 9b in Fig. 1) is actually about 2 μm to 100 μm.

[半導體基板製品的製造] [Manufacture of semiconductor substrate products]

於本實施方式中,較佳為製造於矽晶圓內具有通孔9b或形成於其中的電極的半導體基板製品,及使用其的半導體元件或半導體製品。具體而言,可列舉包括如下步驟的製造過程:(1)於半導體基板上附設矽氧烷樹脂層的步驟;(2)使上述半導體基板經由上述矽氧烷樹脂層而接著於支持基板的步驟;(3)對上述半導體基板的與上述支持基板相反之側進行研磨而使之薄化的步驟;(4)將上述支持基板自上述經薄化的半導體基板剝離的步驟;及(5)使上述去除劑接觸於附著於上述經薄化的半導體基板的上述矽氧烷樹脂,而將該矽氧烷樹脂層去除的步驟。此時,亦較佳為 於上述矽氧烷樹脂層的與上述半導體基板相反之側配置剝離層,經由該剝離層與上述支持基板接合。此外,上述各步驟的順序並無特別限定,亦可於發揮出所需的效果的範圍內適當地變更步驟順序,或於步驟間介隔存在其他步驟。例如,上述步驟(4)與步驟(5)可同時進行,亦可將支持基板與接著劑一併去除。 In the present embodiment, a semiconductor substrate product having a via hole 9b or an electrode formed therein in a germanium wafer, and a semiconductor element or a semiconductor article using the same are preferably used. Specifically, a manufacturing process including the steps of: (1) a step of disposing a siloxane chain on the semiconductor substrate; and (2) a step of attaching the semiconductor substrate to the support substrate via the siloxane chain. (3) a step of polishing and thinning the side of the semiconductor substrate opposite to the support substrate; (4) a step of peeling the support substrate from the thinned semiconductor substrate; and (5) The removing agent is in contact with the above-described decane resin adhered to the thinned semiconductor substrate to remove the siloxane oxide resin layer. At this time, it is also preferred A release layer is disposed on a side opposite to the semiconductor substrate of the siloxane oxide layer, and is bonded to the support substrate via the release layer. Further, the order of the above steps is not particularly limited, and the order of the steps may be appropriately changed within a range in which the desired effect is exerted, or there may be other steps interposed between the steps. For example, the above steps (4) and (5) may be performed simultaneously, and the support substrate may be removed together with the adhesive.

[實施例] [Examples]

以下,對本發明的實施例進行詳細說明,但本發明並不受該些實施例限定而解釋。此外,實施例中所示的量或比率的規定只要無特別說明則為質量基準。 Hereinafter, the embodiments of the present invention will be described in detail, but the present invention is not limited by the embodiments. Further, the specification of the amount or ratio shown in the examples is a mass basis unless otherwise specified.

矽氧烷樹脂是使用將聚二甲基矽氧烷(polydimethylsiloxane)(Mw.10000)與雙酚A二縮水甘油醚混合而成的樹脂作為矽氧烷樹脂A,使用聚二甲基矽氧烷(Mw.40000)作為矽氧烷樹脂B。將矽氧烷樹脂A、矽氧烷樹脂B分別旋轉塗佈於12英吋(inch)晶圓(wafer),利用加熱板(hot plate)於200℃下加熱30分鐘,藉此獲得矽氧烷層A(圖1的樹脂層2)及矽氧烷層B(圖1的剝離層3)。將上述晶圓及Al的毯覆式晶圓(blanket wafer)切割成1cm×2cm而獲得試驗晶圓(test wafer)。 The decyl alkane resin is a resin obtained by mixing polydimethylsiloxane (Mw. 10000) and bisphenol A diglycidyl ether as a decyl alkane resin A, and polydimethyl methoxy oxane is used. (Mw. 40000) as a decane resin B. The decane resin A and the decane resin B were spin-coated on a 12 inch wafer, and heated at 200 ° C for 30 minutes using a hot plate to obtain a decane. Layer A (resin layer 2 of Fig. 1) and a buffer layer B (peeling layer 3 of Fig. 1). A test wafer was obtained by cutting the above wafer and Al blanket wafer into 1 cm × 2 cm.

製成下述組成的化學溶液,於燒杯(beaker)中加溫至70℃之後,浸漬上述試驗晶圓,算出蝕刻速率(etching rate)。此外,膜厚的測定中,矽氧烷層A是使用觸針型膜厚測定計(優貝克股份有限公司(ULVAC,Inc.)製造,商品名Dektak),矽氧烷層B是使用光學式膜厚計(Filmetrics公司製造,商品名F-20)、 Al是使用四端子型電流計(國際電氣阿爾法(KOKUSAI DENKI ALPHA)公司製造,商品名VR200)。此外,Al是根據電流值而算出膜厚。 A chemical solution having the following composition was prepared, and after heating to a beaker for 70 ° C, the test wafer was immersed to calculate an etching rate. Further, in the measurement of the film thickness, the siloxane layer A is a stylus type film thickness meter (manufactured by ULVAC, Inc., trade name: Dektak), and the siloxane layer B is optical. Film thickness meter (manufactured by Filmetrics, trade name F-20), Al is a four-terminal type ammeter (manufactured by KOKUSAI DENKI ALPHA, trade name VR200). Further, Al is a film thickness calculated from the current value.

Figure TWI610996BD00002
Figure TWI610996BD00002

成分的調配量的單位是(質量%) The unit of the amount of the ingredients is (% by mass)

DMSO:二甲基亞碸 DMSO: dimethyl hydrazine

TMAH:四甲基銨氫氧化物 TMAH: tetramethylammonium hydroxide

ER:蝕刻速率(etching rate) ER: etching rate (etching rate)

1Å=0.1nm 1Å=0.1nm

開頭為C者為比較例 The first one is C, which is a comparative example.

Figure TWI610996BD00003
Figure TWI610996BD00003

Figure TWI610996BD00004
Figure TWI610996BD00004

Figure TWI610996BD00005
Figure TWI610996BD00005

Figure TWI610996BD00006
Figure TWI610996BD00006

如上所述,根據本發明的去除劑,可將矽氧烷樹脂較佳地去除。另外,可知於其較佳實施方式中對鋁電極的保護性(耐蝕刻性)優異。 As described above, the deuterium resin can be preferably removed according to the remover of the present invention. Further, it is understood that the aluminum electrode is excellent in protection (etching resistance) in the preferred embodiment.

上文對本發明與其實施方式一併進行了說明,但我等認為,只要未特別指定,則於說明的任何細節均未欲限定我等的發明,應於不違背隨附的申請專利範圍所示的發明的精神與範圍的情況下進行廣泛的解釋。 The invention has been described above in connection with its embodiments, but it is to be understood that the invention is not intended to limit the details of the invention, and is not intended to be The spirit of the invention and the scope of the scope are extensively explained.

本申請案主張基於2012年12月11日在日本提出專利申請的日本專利特願2012-270787、及2013年2月4日在日本提出專利申請的日本專利特願2013-019764的優先權,並參照該些申請案將其內容作為本說明書的記載的一部分而併入本文中。 The priority of Japanese Patent Application No. 2012-270787, which is filed on the Japanese Patent Application No. 2012-270787, and the Japanese Patent Application No. 2013-019764, filed on Jan. The contents of these applications are hereby incorporated by reference in their entirety in their entireties in their entireties.

1a‧‧‧半導體基板 1a‧‧‧Semiconductor substrate

1b‧‧‧半導體基板製品(矽通孔晶片) 1b‧‧‧Semiconductor substrate products (on-hole wafers)

2‧‧‧樹脂層 2‧‧‧ resin layer

3‧‧‧剝離層 3‧‧‧ peeling layer

4‧‧‧支持基板 4‧‧‧Support substrate

9a‧‧‧孔 9a‧‧‧ hole

9b‧‧‧通孔 9b‧‧‧through hole

p‧‧‧被研削部 p‧‧‧The Ministry of Research

S‧‧‧半導體基板(半導體基板1a的背面) S‧‧‧Semiconductor substrate (back side of semiconductor substrate 1a)

Claims (17)

一種矽氧烷樹脂的去除劑,其是用以將附於半導體基板上的矽氧烷樹脂去除的去除劑,且含有80質量%~95質量%的極性非質子性溶劑、1質量%~8質量%的四級銨氫氧化物。 A remover for a decane resin, which is a remover for removing a decane resin attached to a semiconductor substrate, and contains 80% by mass to 95% by mass of a polar aprotic solvent, 1% by mass to 8 Mass% of quaternary ammonium hydroxide. 一種矽氧烷樹脂的去除劑,其是用以將附於半導體基板上的矽氧烷樹脂去除的去除劑,且含有40質量%~95質量%的極性非質子性溶劑、0.1質量%~10質量%的四級銨氫氧化物及1質量%~50質量%的醇類化合物。 A remover for a decane resin, which is a remover for removing a decane resin attached to a semiconductor substrate, and contains 40% by mass to 95% by mass of a polar aprotic solvent, 0.1% by mass to 10% 5% by mass of quaternary ammonium hydroxide and 1% by mass to 50% by mass of an alcohol compound. 如申請專利範圍第1項或第2項所述的矽氧烷樹脂的去除劑,其中上述極性非質子性溶劑為二甲基亞碸(DMSO)。 The remover of a decyl alkane resin according to claim 1 or 2, wherein the polar aprotic solvent is dimethyl sulfoxide (DMSO). 如申請專利範圍第1項或第2項所述的矽氧烷樹脂的去除劑,其中上述四級銨氫氧化物為四甲基銨氫氧化物(TMAH)、四乙基銨氫氧化物(TEAH)、四丁基銨氫氧化物(TBAH)、或苄基三甲基銨氫氧化物。 The remover of a decyl alkane resin according to claim 1 or 2, wherein the quaternary ammonium hydroxide is tetramethylammonium hydroxide (TMAH) or tetraethylammonium hydroxide ( TEAH), tetrabutylammonium hydroxide (TBAH), or benzyltrimethylammonium hydroxide. 如申請專利範圍第2項所述的矽氧烷樹脂的去除劑,其中上述醇類化合物為2-乙基己醇、苯甲醇、或單乙醇胺。 The remover of a decyl alkane resin according to claim 2, wherein the alcohol compound is 2-ethylhexyl alcohol, benzyl alcohol, or monoethanolamine. 如申請專利範圍第1項或第2項所述的矽氧烷樹脂的去除劑,更含有磷酸、硼酸、有機酸、或矽化合物作為金屬腐蝕抑制劑。 The remover of the decane resin as described in claim 1 or 2 further contains phosphoric acid, boric acid, an organic acid, or a ruthenium compound as a metal corrosion inhibitor. 如申請專利範圍第2項所述的矽氧烷樹脂的去除劑,含有70質量%~95質量%的上述極性非質子性溶劑,含有1質量%~8質量%的上述四級銨氫氧化物。 The deodorant for a decyl alkoxide resin according to claim 2, which contains 70% by mass to 95% by mass of the above polar aprotic solvent, and contains 1% by mass to 8% by mass of the above quaternary ammonium hydroxide. . 如申請專利範圍第6項所述的矽氧烷樹脂的去除劑,含有0.1質量%~30質量%的上述金屬腐蝕抑制劑。 The remover of the decane resin described in claim 6 contains 0.1% by mass to 30% by mass of the above metal corrosion inhibitor. 如申請專利範圍第1項或第2項所述的矽氧烷樹脂的去除劑,其中上述矽氧烷樹脂包含聚有機矽氧烷。 The remover of a decyl alkane resin according to claim 1 or 2, wherein the above siloxane oxide resin comprises a polyorganosiloxane. 如申請專利範圍第1項或第2項所述的矽氧烷樹脂的去除劑,其中上述矽氧烷樹脂為聚有機矽氧烷與具有環氧基的樹脂的混合物,或矽酮改質環氧樹脂。 The remover of a decyl alkane resin according to claim 1 or 2, wherein the above siloxane oxide resin is a mixture of a polyorganosiloxane and a resin having an epoxy group, or an oxime oxime modification ring. Oxygen resin. 如申請專利範圍第1項或第2項所述的矽氧烷樹脂的去除劑,其中上述矽氧烷樹脂為接著劑。 The remover of a decyl alkane resin according to the first or second aspect of the invention, wherein the above siloxane oxide resin is an adhesive. 如申請專利範圍第2項所述的矽氧烷樹脂的去除劑,其中上述醇類化合物為下述式(O-1)、下述式(A-1)或下述式(A-2)所表示的化合物,R11-(-O-R12-)n-O-H…(O-1)(R11為碳數1以上、5以下的烷基、碳數6~10的芳基、碳數7~11的芳烷基;R12為直鏈狀或分支狀的碳數1以上、4以下的伸烷基鏈;於存在多個R12時,各個R12亦可不同;n為0以上、20以下的整數)NRN1 2-LN1-OH…(A-1) NRN2 2-(LN2-Y)m-LN3-OH…(A-2) (RN1及RN2分別獨立地為氫原子、烷基、芳基、或芳烷基;LN1~LN3分別獨立地為伸烷基;Y為氧原子或亞胺基(-NRN-),RN與RN1相同;m為1~20的整數)。 The remover of a decane resin according to the second aspect of the invention, wherein the alcohol compound is represented by the following formula (O-1), the following formula (A-1) or the following formula (A-2) The compound represented by R 11 -(-OR 12 -) n -OH (O-1) (R 11 is an alkyl group having 1 or more and 5 or less carbon atoms, an aryl group having 6 to 10 carbon atoms, and 7 carbon atoms; ~ 11 aralkyl; R 12 is a linear or branched carbon number of 1 or more and 4 or less chain alkylene group; in the presence of a plurality of R 12 when R 12 each or different; n is 0 or more, An integer of 20 or less) NR N1 2 -L N1 -OH...(A-1) NR N2 2 -(L N2 -Y) m -L N3 -OH...(A-2) (R N1 and R N2 are independently is a hydrogen atom, an alkyl group, an aryl group, or aralkyl; L N1 ~ L N3 are each independently an alkylene group; an oxygen atom or an imino group (-NR N -) Y is, R N and R N1 same; m is an integer from 1 to 20). 如申請專利範圍第6項所述的矽氧烷樹脂的去除劑,其中上述金屬腐蝕抑制劑為下述式(S1)所表示的化合物,RS1 4Si…(S1)(式中,RS1表示碳數1~10的烷基、碳數1~10的烷氧基、碳數6~22的芳基、或碳數6~22的芳氧基、碳數2~10的烯基、碳數1~10的醯氧基、碳數7~25的芳醯氧基、碳數2~10的肟基、氫原子;然而,不存在RS1全部為氫原子的情況)。 The remover of a decane resin according to claim 6, wherein the metal corrosion inhibitor is a compound represented by the following formula (S1), R S1 4 Si (S1) (wherein, R S1 An alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 22 carbon atoms, an aryloxy group having 6 to 22 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and carbon The number of decyloxy groups of 1 to 10, the aryloxy group having 7 to 25 carbon atoms, the fluorenyl group having 2 to 10 carbon atoms, and a hydrogen atom; however, there is no case where all of R S1 is a hydrogen atom). 一種矽氧烷樹脂的去除方法,其是使如申請專利範圍第1項至第13項中任一項所述的矽氧烷樹脂的去除劑接觸於附於半導體基板上的矽氧烷樹脂,而將上述矽氧烷樹脂去除。 A method for removing a decane resin, which is obtained by contacting a remover of a decane resin according to any one of claims 1 to 13 to a siloxane resin attached to a semiconductor substrate, The above siloxane resin was removed. 一種半導體基板製品的製造方法,包括:於半導體基板上附設矽氧烷樹脂層的步驟;使上述半導體基板經由上述矽氧烷樹脂層接著於支持基板的步驟;對上述半導體基板的與上述支持基板相反之側進行研削而使之薄化的步驟;將上述支持基板自上述經薄化的半導體基板剝離的步驟;及使如申請專利範圍第1項至第13項中任一項所述的矽氧烷樹脂的去除劑接觸於附著於上述經 薄化的半導體基板上的上述矽氧烷樹脂,而將上述矽氧烷樹脂去除的步驟。 A method for producing a semiconductor substrate product, comprising: a step of attaching a siloxane chain on a semiconductor substrate; a step of bonding the semiconductor substrate to the support substrate via the siloxane resin layer; and the support substrate of the semiconductor substrate a step of performing thinning on the opposite side; a step of peeling the support substrate from the thinned semiconductor substrate; and a crucible according to any one of claims 1 to 13 The remover of the oxyalkylene resin is in contact with the above-mentioned a step of removing the above-described decane resin by thinning the above-described decane resin on the semiconductor substrate. 如申請專利範圍第15項所述的半導體基板製品的製造方法,其中於上述矽氧烷樹脂層的與上述半導體基板相反之側配置剝離層,經由上述剝離層與上述支持基板接著。 The method for producing a semiconductor substrate according to claim 15, wherein a release layer is disposed on a side opposite to the semiconductor substrate of the siloxane oxide layer, and the release layer is followed by the support layer. 一種半導體元件的製造方法,其是使用利用如申請專利範圍第15項或第16項所述的半導體基板製品的製造方法獲得的半導體基板製品而製造半導體元件。 A method of producing a semiconductor device, which is a semiconductor device manufactured by using the method for producing a semiconductor substrate according to the fifteenth or sixteenth aspect of the invention.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI856294B (en) * 2021-03-12 2024-09-21 李長榮化學工業股份有限公司 Composition of etchant, method for forming semiconductor device using the same, and semiconductor device

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6165665B2 (en) 2013-05-30 2017-07-19 信越化学工業株式会社 Substrate cleaning method
JP6329889B2 (en) * 2014-12-11 2018-05-23 信越化学工業株式会社 Cleaning liquid and coating film forming apparatus piping cleaning method
FR3030880B1 (en) * 2014-12-19 2018-05-11 Commissariat Energie Atomique METHOD FOR TRANSFORMING AN ELECTRONIC DEVICE
JP6193425B2 (en) * 2016-03-04 2017-09-06 株式会社トウペ Water-based paint remover
JP6536464B2 (en) * 2016-04-26 2019-07-03 信越化学工業株式会社 Cleaner composition and method for manufacturing thin substrate
TWI732005B (en) * 2016-07-29 2021-07-01 日商富士軟片股份有限公司 Manufacturing method of set, detergent composition and semiconductor element
KR102680736B1 (en) 2016-12-14 2024-07-03 삼성전자주식회사 Method for processing substrate and cleaner composition for adhension layer
TW201831667A (en) * 2017-01-13 2018-09-01 日商富士軟片股份有限公司 Kit, method for producing semiconductor element, and method for cleaning substrate of semiconductor element
JP7405100B2 (en) * 2019-01-15 2023-12-26 株式会社レゾナック Disassembly cleaning composition, adhesive polymer cleaning method, and device wafer manufacturing method
WO2020166704A1 (en) 2019-02-15 2020-08-20 日産化学株式会社 Cleaning agent composition and cleaning method
JP7219423B2 (en) 2019-02-15 2023-02-08 日産化学株式会社 Cleaning composition and cleaning method
JP7530048B2 (en) 2019-02-15 2024-08-07 日産化学株式会社 Cleaning composition and cleaning method
CN113544247B (en) * 2019-03-05 2024-04-30 日产化学株式会社 Cleaning agent composition and cleaning method
JP7323870B2 (en) 2019-03-14 2023-08-09 日産化学株式会社 Cleaning composition and cleaning method
KR20220011151A (en) * 2019-05-22 2022-01-27 신에쓰 가가꾸 고교 가부시끼가이샤 Cleaning composition, method of cleaning substrate and method of cleaning support or substrate
JP7220119B2 (en) 2019-05-22 2023-02-09 信越化学工業株式会社 Cleaning liquid for temporary adhesive for substrate, method for cleaning substrate, and method for cleaning support or substrate
WO2021033654A1 (en) * 2019-08-19 2021-02-25 富士フイルム株式会社 Cleaning composition, rinsing liquid, cleaning kit, cleaning object production method and semiconductor element production method
WO2021039274A1 (en) * 2019-08-27 2021-03-04 昭和電工株式会社 Composition, and method for cleaning adhesive polymer
WO2021100651A1 (en) 2019-11-20 2021-05-27 日産化学株式会社 Cleaning agent composition and cleaning method
KR20220158244A (en) 2020-03-23 2022-11-30 닛산 가가쿠 가부시키가이샤 Cleaning method of semiconductor substrate, manufacturing method of processed semiconductor substrate, and composition for stripping
KR20220158246A (en) 2020-03-23 2022-11-30 닛산 가가쿠 가부시키가이샤 Cleaning method of semiconductor substrate, manufacturing method of processed semiconductor substrate, and composition for stripping
JP7530035B2 (en) 2020-03-23 2024-08-07 日産化学株式会社 Method for cleaning semiconductor substrate with bumps
JP7640940B2 (en) 2020-03-23 2025-03-06 日産化学株式会社 Method for cleaning semiconductor substrates, method for producing processed semiconductor substrates, and stripping composition
US20230151307A1 (en) 2020-03-23 2023-05-18 Nissan Chemical Corporation Method for manufacturing semiconductor substrate, method for manufacturing processed semiconductor substrate, and release composition
CN115315788A (en) 2020-03-23 2022-11-08 日产化学株式会社 Method for cleaning semiconductor substrate, method for producing processed semiconductor substrate, and composition for peeling off
EP4131344A4 (en) 2020-03-23 2024-04-10 Nissan Chemical Corporation Semiconductor substrate cleaning method, processed semiconductor substrate manufacturing method, and composition for peeling
KR20220162139A (en) 2020-03-31 2022-12-07 닛산 가가쿠 가부시키가이샤 Method for manufacturing detergent composition and processed semiconductor substrate
JP7498427B2 (en) 2020-03-31 2024-06-12 日産化学株式会社 Cleaning composition and method for producing processed semiconductor substrate
US20230039366A1 (en) 2020-04-09 2023-02-09 Showa Denko K.K. Composition, and method for cleaning adhesive polymer
CN120199681A (en) 2021-09-16 2025-06-24 日产化学株式会社 Method for cleaning semiconductor substrate, method for producing processed semiconductor substrate, and composition for stripping and dissolving
CN117981055A (en) 2021-09-16 2024-05-03 日产化学株式会社 Semiconductor substrate cleaning method, method for producing processed semiconductor substrate, and stripping and dissolving composition
JP7353439B1 (en) 2022-08-03 2023-09-29 信越化学工業株式会社 Silicone resin dissolving agent and method for separating silicone coating and base fabric
EP4571819A1 (en) 2022-09-13 2025-06-18 Nissan Chemical Corporation Method for cleaning semiconductor substrate, method for producing processed semiconductor substrate, and peeling and dissolving composition
KR20250068635A (en) 2022-09-13 2025-05-16 닛산 가가쿠 가부시키가이샤 Method for cleaning a semiconductor substrate, method for manufacturing a processed semiconductor substrate, and composition for peeling and dissolving

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004177669A (en) * 2002-11-27 2004-06-24 Tokyo Ohka Kogyo Co Ltd Method for stripping and removing silicon-containing double layer resist and washing liquid used therefor
TW200829696A (en) * 2006-09-25 2008-07-16 Advanced Tech Materials Compositions and methods for the removal of photoresist for a wafer rework application
JP2012004200A (en) * 2010-06-15 2012-01-05 Shin Etsu Chem Co Ltd Thin wafer manufacturing method

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3302120B2 (en) * 1993-07-08 2002-07-15 関東化学株式会社 Stripper for resist
JP3410369B2 (en) * 1998-04-28 2003-05-26 花王株式会社 Release agent composition
DE60108286T2 (en) * 2000-03-27 2005-12-29 Shipley Co., L.L.C., Marlborough Removal agent for polymer
JP3792620B2 (en) * 2001-08-03 2006-07-05 日本電気株式会社 Release agent composition
JP5040252B2 (en) * 2006-10-13 2012-10-03 東レ株式会社 Adhesive composition for semiconductor, semiconductor device using the same, and method for producing semiconductor device
JP5238927B2 (en) * 2007-03-14 2013-07-17 セミコンダクター・コンポーネンツ・インダストリーズ・リミテッド・ライアビリティ・カンパニー Manufacturing method of semiconductor device
JP2009094205A (en) * 2007-10-05 2009-04-30 Renesas Technology Corp Polishing pad and polishing device for device wafer
JP2009094335A (en) * 2007-10-10 2009-04-30 Nec Electronics Corp Semiconductor device and its manufacturing method
JP5546134B2 (en) * 2009-01-27 2014-07-09 古河電気工業株式会社 Adhesive tape for surface protection
JP5320619B2 (en) * 2009-09-08 2013-10-23 三菱電機株式会社 Manufacturing method of semiconductor device
JP5601922B2 (en) * 2010-07-29 2014-10-08 富士フイルム株式会社 Polishing liquid and polishing method
JP2012060050A (en) * 2010-09-13 2012-03-22 Fujifilm Corp Cleaning composition, cleaning method using the same, and method of manufacturing semiconductor element
JP5735774B2 (en) * 2010-09-30 2015-06-17 芝浦メカトロニクス株式会社 Protective body, substrate laminate, bonding apparatus, peeling apparatus, and substrate manufacturing method
WO2012066894A1 (en) * 2010-11-19 2012-05-24 三菱瓦斯化学株式会社 Liquid composition for cleaning semiconductor substrate and method for cleaning semiconductor substrate using same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004177669A (en) * 2002-11-27 2004-06-24 Tokyo Ohka Kogyo Co Ltd Method for stripping and removing silicon-containing double layer resist and washing liquid used therefor
TW200829696A (en) * 2006-09-25 2008-07-16 Advanced Tech Materials Compositions and methods for the removal of photoresist for a wafer rework application
JP2012004200A (en) * 2010-06-15 2012-01-05 Shin Etsu Chem Co Ltd Thin wafer manufacturing method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI856294B (en) * 2021-03-12 2024-09-21 李長榮化學工業股份有限公司 Composition of etchant, method for forming semiconductor device using the same, and semiconductor device

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