TW202012680A - Substrate, selective method for accumulating film on metal surface region of substrate, accumulated film of organic matter, and organic matter - Google Patents

Substrate, selective method for accumulating film on metal surface region of substrate, accumulated film of organic matter, and organic matter Download PDF

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TW202012680A
TW202012680A TW108123239A TW108123239A TW202012680A TW 202012680 A TW202012680 A TW 202012680A TW 108123239 A TW108123239 A TW 108123239A TW 108123239 A TW108123239 A TW 108123239A TW 202012680 A TW202012680 A TW 202012680A
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film
substrate
surface area
general formula
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TWI827630B (en
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山本純基
新免益隆
增田隆司
灘野亮
宮崎達夫
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日商中央硝子股份有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
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    • C09D7/63—Additives non-macromolecular organic
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    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
    • H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

Abstract

This selective method for accumulating a film on a metal surface region of a substrate is characterized in that a film of organic matter represented by general formula (1) is selectively accumulated on a substrate having a structure in which both of a first surface region that includes metal and a second surface region that includes a non-metal inorganic material and/or a metal oxide are exposed, the film being accumulated to a greater extent in the first surface region than in the second surface region. (In general formula (1), N represents a nitrogen atom, and X represents an oxygen atom or a sulfur atom. R1 represents a C2-12 hydrocarbon group that may have a hetero atom or a halogen atom, and R2, R3, and R4 each independently represent a hydrogen atom or a C1-10 hydrocarbon group that may have a hetero atom or a halogen atom. In the case of a C3 or higher hydrocarbon group, a branched or cyclic hydrocarbon group is also included.).

Description

基板、對基板之金屬表面區域之選擇性膜堆積方法、有機物之堆積膜及有機物Substrate, selective film stacking method on metal surface area of substrate, stacked film of organic matter and organic matter

本發明係一種基板、對基板之金屬表面區域之選擇性膜堆積方法、有機物之堆積膜及有機物。The invention is a substrate, a selective film deposition method for a metal surface area of a substrate, a deposition film of organic matter and organic matter.

近年來，半導體晶片之構造益發微細化，藉由選擇性地去除構造體之一部分而進行圖案化之先前之微影法存在步驟數多或成本高等問題。認為若化學氣相沈積(CVD)法或原子層沈積(ALD)法可於基板上之所需部位選擇性地形成膜，則成為形成微細構造之最佳製程，解決該等問題。In recent years, the structure of semiconductor wafers has become increasingly miniaturized, and the previous lithography method that patterned by selectively removing a part of the structure has problems such as a large number of steps or high cost. It is considered that if the chemical vapor deposition (CVD) method or the atomic layer deposition (ALD) method can selectively form a film on a desired portion on the substrate, it becomes the optimal process for forming a fine structure to solve these problems.

但是，對於具有電極或配線所使用之金屬或絕緣膜所使用之無機介電體等材料各異之複數種表面區域之基板，於藉由CVD法或ALD法選擇性地堆積膜之情形時，必須選擇性地堆積堆積阻礙用膜，但先前之方法選擇性不足夠高。However, for a substrate having a plurality of surface areas of different materials such as metals used for electrodes or wiring, or inorganic dielectrics used for insulating films, when a film is selectively deposited by CVD or ALD, The barrier films must be selectively stacked, but the previous methods are not sufficiently selective.

關於選擇性膜之形成方法，已知於不欲形成膜之區域堆積阻礙膜之堆積之材料之方法。例如，專利文獻1中揭示有一種方法，其係藉由原子層沈積法(ALD)於基板上形成TiN、AlN或SiN等無機材料之薄膜圖案者，且包括如下步驟：於基板上使用包含氟含量為30原子%以上，具有至少1個三級碳或四級碳，且不具有酯基、羥基、羧基及醯亞胺基之含氟樹脂之原子層沈積阻礙材料，藉由網版印刷等形成原子層沈積阻礙層之圖案；其次，藉由原子層沈積法，於不存在原子層沈積阻礙層之區域形成無機材料之層。Regarding the formation method of the selective film, a method of depositing materials that hinder the accumulation of the film in a region where the film is not to be formed is known. For example, Patent Document 1 discloses a method for forming a thin film pattern of an inorganic material such as TiN, AlN, or SiN on a substrate by atomic layer deposition (ALD), and includes the following steps: using fluorine on the substrate Atomic layer deposition hindering material for fluorine-containing resins with a content of 30 atomic% or more, having at least one tertiary or quaternary carbon, and having no ester group, hydroxyl group, carboxyl group, or imide group, by screen printing, etc. The pattern of the atomic layer deposition barrier layer is formed. Secondly, by the atomic layer deposition method, a layer of inorganic material is formed in the area where the atomic layer deposition barrier layer does not exist.

又，專利文獻2中揭示有一種方法，其係於具有露出之金屬表面及露出之含矽之表面之基板上選擇性地堆積層者，且包括如下步驟：(a)於上述露出之金屬表面上沈積第1自組裝單分子膜；(b)於上述露出之含矽之表面上沈積作為有機矽烷系之第2自組裝單分子膜；(c)對上述基板進行加熱，將上述第1自組裝單分子膜自上述露出之金屬表面上去除；(d)於上述露出之金屬表面上選擇性地堆積作為低介電常數介電層或金屬層之層；以及(e)對上述基板進行加熱，將第2自組裝單分子膜自上述露出之含矽之表面上去除。In addition, Patent Document 2 discloses a method for selectively depositing layers on a substrate having an exposed metal surface and an exposed silicon-containing surface, and includes the following steps: (a) on the exposed metal surface Depositing a first self-assembled monomolecular film on top; (b) depositing a second self-assembled monomolecular film as an organic silane system on the exposed silicon-containing surface; (c) heating the above substrate and heating the first The assembled monomolecular film is removed from the exposed metal surface; (d) a layer as a low dielectric constant or metal layer is selectively deposited on the exposed metal surface; and (e) the substrate is heated , The second self-assembled monomolecular film is removed from the exposed silicon-containing surface.

根據上述方法，可對於具有包含不同材料之第1表面及第2表面之基板，利用兩者之表面狀態之差異，相較於第2表面更傾向於在第1表面選擇性地堆積膜。又，根據上述方法，可削減形成微細構造之製程之步驟數。According to the above method, for a substrate having a first surface and a second surface including different materials, the difference in the surface states of the two can be used to preferentially deposit a film on the first surface compared to the second surface. In addition, according to the above method, the number of steps in the process of forming a fine structure can be reduced.

例如，專利文獻3中揭示有如下製程：於包含作為金屬性表面之第1表面及作為介電體表面之第2表面之基板上進行包括使第1氣相前驅物質接觸之步驟及使第2氣相前驅物質接觸之步驟之堆積循環，相較於第2表面，更傾向於在第1表面上選擇性地形成有機薄膜。於專利文獻3之實施例1中記載有如下內容：將與氧化矽表面交替，具有鎢(W)特色之200 mm矽晶圓作為基板，使用1,6-二胺基己烷(DAH)及均苯四甲酸二酐(PMDA)，進行250～1000堆積循環，形成聚醯亞胺膜，金屬鎢表面上之聚醯亞胺膜之厚度厚於SiO2 表面上之聚醯亞胺膜之厚度。For example, Patent Document 3 discloses a process of performing a step including contacting a first gas-phase precursor substance and a second step on a substrate including a first surface as a metallic surface and a second surface as a dielectric surface The accumulation cycle of the step of contacting the gas-phase precursor substance is more likely to selectively form an organic thin film on the first surface than on the second surface. In Example 1 of Patent Document 3, the following content is described: a 200 mm silicon wafer with tungsten (W) characteristics alternating with the surface of silicon oxide is used as a substrate, using 1,6-diaminohexane (DAH) and Pyromellitic dianhydride (PMDA) is subjected to 250-1000 stacking cycles to form a polyimide film. The thickness of the polyimide film on the surface of metal tungsten is thicker than the thickness of the polyimide film on the surface of SiO 2 .

專利文獻4中揭示有如下方法：利用專利文獻3中記載之有機膜之選擇堆積法，於金屬製之第1表面上選擇性地形成鈍化層後，於介電體之第2表面上僅形成層X；進而利用該方法，形成積體電路之金屬化構造。Patent Document 4 discloses a method of selectively forming a passivation layer on a first surface made of metal using the selective deposition method of an organic film described in Patent Document 3, and then forming only a second surface on a dielectric body Layer X; and then use this method to form the metallization structure of the integrated circuit.

專利文獻5中揭示有藉由配位鍵於金屬表面形成單分子膜之方法。 [先前技術文獻] [專利文獻]Patent Document 5 discloses a method of forming a monomolecular film on a metal surface by coordination bonds. [Prior Technical Literature] [Patent Literature]

[專利文獻1]國際公開第2016/147941號 [專利文獻2]日本專利特表2018-512504號公報 [專利文獻3]日本專利特開2017-216448號公報 [專利文獻4]日本專利特開2018-137435號公報 [專利文獻5]日本專利特開平10-180929號公報[Patent Literature 1] International Publication No. 2016/147941 [Patent Document 2] Japanese Patent Special Publication No. 2018-512504 [Patent Document 3] Japanese Patent Laid-Open No. 2017-216448 [Patent Document 4] Japanese Patent Laid-Open No. 2018-137435 [Patent Document 5] Japanese Patent Laid-Open No. 10-180929

[發明所欲解決之問題][Problems to be solved by the invention]

然而，專利文獻1中並未揭示如下方法：於單一材料之基板上使用原子層沈積阻礙材料，形成特定之圖案，對於具有材料不同之複數種表面區域之基板，於所需之表面區域選擇性地形成構造。However, Patent Document 1 does not disclose the following method: using an atomic layer deposition barrier material on a single material substrate to form a specific pattern, and for a substrate having a plurality of surface areas with different materials, selectivity in a desired surface area To form a structure.

於專利文獻2中，於金屬表面上形成第1SAM(Self-Assembled Monolayer，自組裝單層)膜之步驟係將基板浸漬於含有長鏈烷基硫醇、長鏈有機膦酸、長鏈磺酸之溶液中之方法，係所謂之濕式製程。另一方面，於SAM膜之形成後進行之基板上之低介電常數介電層或金屬層所使用之ALD或CVD等製程為乾式製程，因此進行濕式製程後必須進行乾式製程，方法變得複雜，於乾式製程中期望形成堆積阻礙用膜之方法。In Patent Document 2, the step of forming the first SAM (Self-Assembled Monolayer) film on the metal surface is to immerse the substrate in a long-chain alkyl mercaptan, long-chain organic phosphonic acid, long-chain sulfonic acid The method in the solution is the so-called wet process. On the other hand, the ALD or CVD process used for the low dielectric constant dielectric layer or metal layer on the substrate after the formation of the SAM film is a dry process, so the dry process must be performed after the wet process, the method changes It is complicated, and a method of forming a barrier film is expected in the dry process.

專利文獻3及專利文獻4中記載之選擇性地形成有機薄膜之方法雖為乾式製程，但必須複數次反覆切換原料與溫度之堆積循環，有機薄膜之形成需要大量之工夫。Although the methods for selectively forming organic thin films described in Patent Document 3 and Patent Document 4 are dry processes, it is necessary to repeatedly switch the stacking cycle of the raw material and the temperature, and it takes a lot of time to form the organic thin film.

專利文獻5中雖揭示有形成單分子膜之方法，但未提及選擇性膜之形成。Although Patent Document 5 discloses a method of forming a monomolecular film, it does not mention the formation of a selective film.

本發明之目的在於鑒於上述課題，提供一種方法、藉由上述方法獲得之基板、有機物之堆積膜及有機物；上述方法係藉由簡單之操作，相較於基板上之非金屬無機材料露出之表面區域或金屬氧化物露出之表面區域，更傾向於在金屬露出之表面區域選擇性地堆積有機物之膜。 [解決問題之技術手段]The object of the present invention is to provide a method, a substrate obtained by the above method, a deposited film of organic matter, and an organic matter in view of the above problems; the above method is a simple operation, compared to the exposed surface of the non-metallic inorganic material on the substrate Areas or exposed surface areas of metal oxides are more likely to selectively deposit organic films on exposed surface areas of metals. [Technical means to solve the problem]

本發明人等進行了銳意研究，結果發現，關於下述通式(1)所表示之有機物，相較於基板上之非金屬無機材料露出之表面區域或金屬氧化物露出之表面區域，更傾向於在金屬露出之表面區域選擇性地堆積有機物之膜，從而完成了本發明。The present inventors conducted intensive research and found that the organic substance represented by the following general formula (1) is more inclined than the surface area where the non-metallic inorganic material on the substrate is exposed or the surface area where the metal oxide is exposed The present invention has been completed by selectively depositing a film of organic matter on the exposed surface area of the metal.

本發明之對基板之金屬表面區域之選擇性膜堆積方法之特徵在於：對於具有包含金屬之第一表面區域以及包含非金屬無機材料及/或金屬氧化物之第二表面區域兩者皆露出之構造之基板，相較於上述第二表面區域，更傾向於在上述第一表面區域選擇性地堆積下述通式(1)所表示之有機物之膜。 [化1]

Figure 02_image005
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 分別獨立為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)The selective film deposition method of the metal surface region of the substrate of the present invention is characterized in that both the first surface region including metal and the second surface region including non-metallic inorganic material and/or metal oxide are exposed Compared with the second surface area, the structured substrate is more likely to selectively deposit a film of an organic substance represented by the following general formula (1) on the first surface area. [Chemical 1]
Figure 02_image005
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 and R 4 are respectively (A hydrocarbon group independently a hydrogen atom or a hydrocarbon group which may have a ring or heteroatom or a halogen atom with a carbon number of 1 to 10; wherein, the hydrocarbon also includes a branched or cyclic structure when the carbon number is 3 or more)

根據上述方法，可提供如下方法：藉由使用通式(1)所表示之有機物，相較於基板上之包含非金屬無機材料露出之區域及/或金屬氧化物露出之區域之第二表面區域，更傾向於在包含金屬露出之區域之第一表面區域選擇性地堆積有機物之膜。According to the above method, the following method can be provided: By using the organic substance represented by the general formula (1), compared with the second surface area on the substrate including the exposed area of the non-metallic inorganic material and/or the exposed area of the metal oxide It is more likely to selectively deposit organic films on the first surface area containing the exposed areas of the metal.

於上述第二表面區域，可使非金屬無機材料露出，可使金屬氧化物露出，可使非金屬無機材料及金屬氧化物皆露出，亦可除金屬、非金屬無機材料及金屬氧化物以外之物質露出。即，上述第二表面區域包含非金屬無機材料及金屬氧化物中之至少1種露出之區域。上述第二表面區域可為僅非金屬無機材料及金屬氧化物中之至少1種露出之區域。上述第一表面區域可為僅金屬露出之區域。In the above-mentioned second surface area, non-metal inorganic materials can be exposed, metal oxides can be exposed, both non-metal inorganic materials and metal oxides can be exposed, except for metals, non-metal inorganic materials and metal oxides The substance is exposed. That is, the second surface region includes a region where at least one of the non-metallic inorganic material and the metal oxide is exposed. The second surface area may be an area where only at least one of the non-metallic inorganic material and the metal oxide is exposed. The first surface area may be an area where only metal is exposed.

本發明之基板之特徵在於：其係具有包含金屬之第一表面區域以及包含非金屬無機材料及/或金屬氧化物之第二表面區域兩者皆露出之構造者，且於上述第一表面區域具有下述通式(1)所表示之有機物之膜，於上述第二表面區域不具有上述有機物之膜，或者上述第二表面區域上之上述有機物之膜之厚度t2 薄於上述第一表面區域上之上述有機物之膜之厚度t1 。 [化2]

Figure 02_image007
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，上述烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)The substrate of the present invention is characterized in that it has a structure in which both a first surface area including metal and a second surface area including non-metallic inorganic material and/or metal oxide are exposed, and is on the first surface area The film having the organic substance represented by the following general formula (1) does not have the film of the organic substance in the second surface area, or the thickness t 2 of the film of the organic substance on the second surface area is thinner than the first surface The thickness t 1 of the film of the above organic substance on the area. [Chem 2]
Figure 02_image007
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are (A hydrogen atom or a hydrocarbon group which may have a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; where the above hydrocarbons also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more)

根據上述基板，可提供如下基板：藉由使用通式(1)所表示之有機物，相較於基板上之包含非金屬無機材料露出之區域及/或金屬氧化物露出之區域之第二表面區域，更傾向於在包含金屬露出之區域之第一表面區域選擇性地堆積有機物之膜。According to the above substrate, the following substrate can be provided: by using the organic substance represented by the general formula (1), compared to the second surface area on the substrate including the exposed area of the non-metallic inorganic material and/or the exposed area of the metal oxide It is more likely to selectively deposit organic films on the first surface area containing the exposed areas of the metal.

本發明之有機物之堆積膜之特徵在於：其係藉由上述方法形成之有機物之膜，且 選擇性地堆積於基板上，該有機物以下述通式(1)表示。 [化3]

Figure 02_image009
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)The deposited film of an organic substance of the present invention is characterized in that it is a film of an organic substance formed by the above method and is selectively deposited on a substrate. The organic substance is represented by the following general formula (1). [Chemical 3]
Figure 02_image009
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are (A hydrogen atom or a hydrocarbon group which may have a ring of 1 to 10 carbon atoms or a heteroatom or a halogen atom; wherein the hydrocarbon group may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more)

本發明之有機物之特徵在於，用於對上述基板之金屬表面區域之選擇性膜堆積方法，且以下述通式(1)表示。 [化4]

Figure 02_image011
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)The organic substance of the present invention is characterized by a selective film deposition method for the metal surface area of the substrate, and is represented by the following general formula (1). [Chemical 4]
Figure 02_image011
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are (A hydrogen atom or a hydrocarbon group which may have a ring of 1 to 10 carbon atoms or a heteroatom or a halogen atom; wherein the hydrocarbon group may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more)

藉由使用本發明之有機物，可相較於基板上之包含非金屬無機材料露出之區域及/或金屬氧化物露出之區域之第二表面區域，更傾向於在包含金屬露出之區域之第一表面區域選擇性地堆積有機物之膜。By using the organic substance of the present invention, the first surface region including the exposed metal region can be more preferred than the second surface region including the exposed region of the non-metallic inorganic material and/or the exposed region of the metal oxide on the substrate The surface area selectively accumulates organic films.

本發明之溶液之特徵在於，含有特徵為以下述通式(1)表示之有機物及溶劑。 [化5]

Figure 02_image013
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基) [發明之效果]The solution of the present invention is characterized by containing an organic substance and a solvent characterized by the following general formula (1). [Chem 5]
Figure 02_image013
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are Hydrogen atom or a hydrocarbon group which may have a ring having 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a hydrocarbon group having a branched or cyclic structure when the carbon number is 3 or more) [Effect of the invention]

根據本發明之方法，藉由使用通式(1)所表示之有機物，可提供如下方法：相較於基板上之包含非金屬無機材料露出之區域及/或金屬氧化物露出之區域之第二表面區域，更傾向於在包含金屬露出之區域之第一表面區域選擇性地堆積有機物之膜。According to the method of the present invention, by using the organic substance represented by the general formula (1), the following method can be provided: Compared with the second on the substrate including the exposed area of the non-metallic inorganic material and/or the exposed area of the metal oxide The surface area is more likely to selectively deposit a film of organic matter on the first surface area including the exposed area of the metal.

又，根據本發明之基板，藉由使用通式(1)所表示之有機物，可提供如下基板：相較於基板上之包含非金屬無機材料露出之區域及/或金屬氧化物露出之區域之第二表面區域，更傾向於在包含金屬露出之區域之第一表面區域選擇性地堆積有機物之膜。Furthermore, according to the substrate of the present invention, by using the organic substance represented by the general formula (1), it is possible to provide the following substrate: compared to the area on the substrate including the exposed area of the non-metallic inorganic material and/or the exposed area of the metal oxide The second surface area is more likely to selectively deposit a film of organic matter on the first surface area including the exposed area of the metal.

以下，對本發明詳細地進行說明，但以下所記載之構成要件之說明為本發明之實施形態之一例，並非限定於該等具體內容。可於其主旨之範圍內進行各種變化後實施。Hereinafter, the present invention will be described in detail, but the description of the constituent elements described below is an example of an embodiment of the present invention and is not limited to these specific contents. It can be implemented after making various changes within the scope of its thrust.

本發明之實施形態之對基板之金屬表面區域之選擇性膜堆積方法之特徵在於：對於具有包含金屬之第一表面區域以及包含非金屬無機材料及/或金屬氧化物之第二表面區域兩者皆露出之構造之基板，相較於上述第二表面區域，更傾向於在上述第一表面區域選擇性地堆積通式(1)所表示之有機物之膜。The selective film deposition method for the metal surface area of the substrate according to the embodiment of the present invention is characterized by both the first surface area including metal and the second surface area including non-metallic inorganic material and/or metal oxide Compared to the second surface area, the substrates of all exposed structures are more likely to selectively deposit organic films represented by the general formula (1) on the first surface area.

於上述方法中，相較於第二表面區域，更傾向於選擇性地堆積通式(1)所表示之有機物之膜。此時，較佳為於上述基板上以如下方式進行堆積：僅於第一表面區域選擇性地堆積上述有機物之膜，於第二表面區域不堆積上述有機物之膜，或者第一表面區域上之有機物之膜之厚度t1 厚於第二表面區域上之有機物之膜之厚度t2 ，且t1 除以t2 所得之t1 /t2 之值為5以上。t1 /t2 之值較佳為10以上，更佳為100以上。再者，t1 較佳為1 nm以上，更佳為2 nm以上，較佳為200 nm以下，更佳為100 nm以下。又，t2 較佳為未達1 nm，亦可為0 nm。t1 及t2 之厚度可藉由原子力顯微鏡(AFM)進行測定。t2 為0 nm之情形意指上述條件，即上述有機物之膜僅選擇性地堆積於第一表面區域。In the above method, the film of the organic substance represented by the general formula (1) is more selectively deposited than the second surface area. At this time, it is preferable to deposit on the substrate in such a manner that the film of the organic substance is selectively deposited only on the first surface area, and the film of the organic substance is not deposited on the second surface area, or on the first surface area The thickness t 1 of the organic film is thicker than the thickness t 2 of the organic film on the second surface area, and the value of t 1 /t 2 obtained by dividing t 1 by t 2 is 5 or more. The value of t 1 /t 2 is preferably 10 or more, and more preferably 100 or more. Furthermore, t 1 is preferably 1 nm or more, more preferably 2 nm or more, preferably 200 nm or less, and more preferably 100 nm or less. In addition, t 2 is preferably less than 1 nm, and may be 0 nm. The thickness of t 1 and t 2 can be measured by an atomic force microscope (AFM). The case where t 2 is 0 nm means the above condition, that is, the film of the organic substance is selectively deposited only on the first surface area.

作為構成第一表面區域之金屬，可使用Cu、Co、Ru、Ni、Pt、Al、Ta、Ti及Hf，尤佳為使用Cu、Co及Ru。再者，構成第一表面區域之金屬亦可為上述金屬之合金。As the metal constituting the first surface region, Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf can be used, and Cu, Co, and Ru are particularly preferably used. Furthermore, the metal constituting the first surface area may also be an alloy of the aforementioned metals.

作為構成第二表面區域之上述金屬氧化物，可列舉上述金屬之氧化物。Examples of the metal oxide constituting the second surface region include oxides of the above metals.

作為構成第二表面區域之上述非金屬無機材料，可列舉：矽、矽氧化物、矽氮化物、矽氮氧化物等矽系材料及鍺、鍺氧化物、鍺氮化物、鍺氮氧化物等鍺系材料，於該等非金屬無機材料之中，較佳為矽系材料。 上述矽包含多晶矽及單晶矽兩者。矽氧化物用SiOx (x為1以上2以下)之化學式表示，通常為SiO2 。又，矽氮化物用SiNx (x為0.3以上9以下)之化學式表示，通常為Si3 N4 。矽氮氧化物用Si4 Ox Ny (x為3以上6以下，y為2以上4以下)表示，例如為Si4 O5 N3 。Examples of the non-metal inorganic material constituting the second surface area include silicon-based materials such as silicon, silicon oxide, silicon nitride, and silicon oxynitride, and germanium, germanium oxide, germanium nitride, and germanium oxynitride. Among the non-metal inorganic materials, the germanium-based materials are preferably silicon-based materials. The above silicon includes both polycrystalline silicon and single crystal silicon. Silicon oxide is represented by the chemical formula of SiO x (x is 1 or more and 2 or less), and is usually SiO 2 . The silicon nitride is represented by the chemical formula of SiN x (x is 0.3 or more and 9 or less), and is usually Si 3 N 4 . The silicon oxynitride is represented by Si 4 O x N y (x is 3 or more and 6 or less, and y is 2 or more and 4 or less), for example, Si 4 O 5 N 3 .

作為獲得包含金屬之第一表面區域之方法，可列舉使用化學氣相沈積(CVD)法、物理氣相沈積(PVD)法等獲得金屬之膜之方法。例如藉由在上述非金屬無機材料或金屬氧化物之膜上，藉由上述方法形成金屬膜，藉由光微影法將金屬膜形成為特定之圖案之方法，或者於非金屬無機材料或金屬氧化物之膜上形成孔或槽，於該槽嵌入金屬之方法，可獲得包含金屬之第一表面區域以及包含非金屬無機材料及/或金屬氧化物之第二表面區域兩者皆露出之構造之基板。As a method of obtaining the first surface region containing metal, a method of obtaining a film of metal using a chemical vapor deposition (CVD) method, a physical vapor deposition (PVD) method, or the like can be mentioned. For example, by forming a metal film on the non-metal inorganic material or metal oxide film by the above method, forming the metal film into a specific pattern by photolithography, or using a non-metal inorganic material or metal A hole or groove is formed in the oxide film, and a method of embedding metal in the groove can obtain a structure in which both the first surface area including metal and the second surface area including non-metallic inorganic material and/or metal oxide are exposed Of the substrate.

例如，作為本發明之方法中使用之基板，為構造中具有金屬膜之半導體裝置之基板或者於半導體裝置之圖案化步驟中形成有金屬膜之基板等，尤其可列舉於半導體元件之絕緣膜形成具有特定圖案之金屬配線而成之基板。即，作為第一表面區域，金屬配線符合，作為第二表面區域，包含非金屬無機材料及/或金屬氧化物之絕緣膜符合。但是，本發明之對基板之金屬表面區域之選擇性膜堆積方法中使用之基板並不限定於該等構件。For example, as the substrate used in the method of the present invention, it is a substrate of a semiconductor device having a metal film in its structure or a substrate in which a metal film is formed in the patterning step of the semiconductor device, etc. In particular, it can be exemplified in the formation of an insulating film of a semiconductor element A substrate made of metal wiring with a specific pattern. That is, as the first surface area, the metal wiring conforms, and as the second surface area, the insulating film including the non-metallic inorganic material and/or the metal oxide conforms. However, the substrate used in the selective film deposition method of the metal surface area of the substrate of the present invention is not limited to these members.

使用下述通式(1)所表示之有機物作為上述有機物。 [化6]

Figure 02_image015
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 分別獨立為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)As the organic substance, an organic substance represented by the following general formula (1) is used. [化6]
Figure 02_image015
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 and R 4 are respectively (A hydrocarbon group independently a hydrogen atom or a hydrocarbon group which may have a ring or heteroatom or a halogen atom with a carbon number of 1 to 10; wherein, when the carbon number is 3 or more, the hydrocarbon group may also include a branched or cyclic structure)

作為R1 ～R4 之雜原子，可列舉：氮原子、氧原子、硫原子、磷原子。作為R1 ，可列舉：C2 H4 、C3 H6 、C4 H8 、C5 H10 、C6 H12 、苯基等，苯基之一部分可經烴基、羥基、硫醇基、胺基、鹵素等取代。 作為R2 、R3 、R4 ，可列舉氫基或CH3 、C2 H5 、C3 H7 等烴基等。構成R2 、R3 、R4 之烴基之一部分可經羥基、硫醇基、胺基、鹵素等取代。 進而，於R3 及R4 皆碳數為1以上之情形時，R3 與R4 可直接鍵結，通式(1)可採用環狀結構。R2 、R3 、R4 存在為相同取代基之情形，亦存在為不同取代基之情形。Examples of the hetero atom of R 1 to R 4 include nitrogen atom, oxygen atom, sulfur atom, and phosphorus atom. Examples of R 1 include C 2 H 4 , C 3 H 6 , C 4 H 8 , C 5 H 10 , C 6 H 12 , and phenyl. A part of the phenyl group may be hydrocarbyl, hydroxyl, thiol, Substitution with amine groups, halogens, etc. Examples of R 2 , R 3 , and R 4 include hydrogen groups and hydrocarbon groups such as CH 3 , C 2 H 5 , and C 3 H 7 . A part of the hydrocarbon group constituting R 2 , R 3 , and R 4 may be substituted with a hydroxyl group, a thiol group, an amine group, a halogen, or the like. Furthermore, when both R 3 and R 4 have a carbon number of 1 or more, R 3 and R 4 may be directly bonded, and the general formula (1) may adopt a ring structure. R 2 , R 3 , and R 4 may be the same substituent, or may be different substituents.

尤佳為作為通式(1)所表示之有機物，較佳為R2 、R3 為氫原子，上具有胺基(-NH2 )之化合物。進而較佳為R4 為氫原子，-XR4 為作為羥基(-OH)或硫醇基(-SH)之化合物。Particularly preferred is an organic substance represented by the general formula (1), preferably a compound in which R 2 and R 3 are hydrogen atoms and have an amine group (-NH 2 ). Further preferably, R 4 is a hydrogen atom, and -XR 4 is a compound as a hydroxyl group (-OH) or a thiol group (-SH).

作為通式(1)所表示之具體之化合物，例如可列舉：鄰胺基苯硫酚、2-胺基苄醇、2-胺基乙醇、2-(乙基胺基)乙醇、2-胺基乙硫醇、3-胺基-1-丙醇、鄰胺基苯酚等，於該等之中，較佳為鄰胺基苯硫酚或2-胺基苄醇。該等化合物可單獨使用或併用。Specific compounds represented by the general formula (1) include, for example, o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2-(ethylamino)ethanol, 2-amine Ethyl mercaptan, 3-amino-1-propanol, o-aminophenol, etc. Among these, o-aminothiophenol or 2-aminobenzyl alcohol is preferred. These compounds can be used alone or in combination.

作為相較於第二表面區域，更傾向於在第一表面區域選擇性地堆積通式(1)所表示之有機物之膜之具體之方法，可採用將基板暴露於含有有機物及溶劑之溶液中之方法(濕式法)以及將上述基板暴露於包含有機物之氣體之氛圍中之方法(乾式法)此二種方法。以下，對該等方法進行說明。As a specific method that prefers to selectively deposit a film of organic matter represented by the general formula (1) on the first surface area compared to the second surface area, the substrate may be exposed to a solution containing organic matter and a solvent The method (wet method) and the method of exposing the above substrate to an atmosphere containing organic matter (dry method) are two methods. Hereinafter, these methods will be described.

[濕式法] 於本發明之實施形態之濕式法中，將基板暴露於含有上述有機物及溶劑之溶液中，作為其一例，藉由將具有第一表面區域及第二表面區域之基板浸漬於含有有機物及溶劑之溶液中，可進行使上述基板之表面與上述溶液接觸，使有機物之膜選擇性地堆積於基板之第一表面區域之膜堆積步驟。作為將基板暴露於溶液中之方法，除浸漬法以外，亦可使用於將溶液滴加至基板後使之高速旋轉之旋轉塗佈法或者對基板噴霧溶液之噴塗法。[Wet method] In the wet method of the embodiment of the present invention, the substrate is exposed to a solution containing the above-mentioned organic substance and solvent. As an example, by immersing the substrate having the first surface area and the second surface area in the solution containing organic substance and solvent In the solution, a film deposition step of contacting the surface of the substrate with the solution and selectively depositing a film of organic matter on the first surface area of the substrate may be performed. As a method of exposing the substrate to the solution, in addition to the dipping method, a spin coating method for dropping the solution onto the substrate and rotating it at a high speed or a spray method for spraying the solution on the substrate can also be used.

上述溶液中之有機物之濃度較佳為相對於有機物及溶劑之合計為0.1質量%以上10質量%以下，更佳為0.5質量%以上8質量%以下，尤佳為1質量%以上5質量%以下。The concentration of the organic substance in the above solution is preferably 0.1% by mass or more and 10% by mass or less relative to the total of the organic substance and the solvent, more preferably 0.5% by mass or more and 8% by mass or less, and particularly preferably 1% by mass or more and 5% by mass or less .

作為溶液中使用之溶劑，並無特別限定，較佳為使用能夠使有機物溶解之有機溶劑，例如可列舉乙醇或異丙醇(IPA)等醇等。The solvent used in the solution is not particularly limited, but it is preferable to use an organic solvent capable of dissolving organic substances, and examples thereof include alcohols such as ethanol and isopropyl alcohol (IPA).

上述濕式膜堆積步驟中之溶液之溫度較佳為0～80℃，將基板浸漬於上述溶液之時間較佳為1～1000秒。於將基板浸漬於上述溶液中時，較佳為藉由攪拌翼等攪拌溶液。The temperature of the solution in the wet film deposition step is preferably 0 to 80°C, and the time for immersing the substrate in the solution is preferably 1 to 1000 seconds. When the substrate is immersed in the above solution, the solution is preferably stirred by a stirring blade or the like.

又，於使基板浸漬於含有有機物之溶液後，較佳為進行提拉基板，藉由溶劑將基板洗淨之洗淨步驟。作為可於上述洗淨步驟中使用之溶劑，可列舉上述有機溶劑。作為洗淨之方法，較佳為於0～80℃之上述溶劑中浸漬1～1000秒。In addition, after immersing the substrate in a solution containing an organic substance, it is preferable to perform a washing step of pulling the substrate and washing the substrate with a solvent. Examples of the solvent that can be used in the washing step include the above-mentioned organic solvents. As a washing method, it is preferable to immerse in the above solvent at 0 to 80°C for 1 to 1000 seconds.

於上述洗淨步驟之後，較佳為藉由對基板吹送氮、氬等惰性氣體，使基板乾燥。吹送之惰性氣體之溫度較佳為0～80℃。After the above washing step, it is preferable to dry the substrate by blowing an inert gas such as nitrogen or argon on the substrate. The temperature of the inert gas to be blown is preferably 0 to 80°C.

[乾式法] 於本發明之實施形態之乾式法中，將上述基板暴露於含有有機物之氣體之氛圍中，具體而言，進行藉由將基板載置於腔室內，將含有有機物之氣體導入至腔室內，使含有有機物之氣體與基板之表面接觸，使有機物之膜選擇性地堆積於基板之第一表面區域之膜堆積步驟。[Dry method] In the dry method according to the embodiment of the present invention, the above substrate is exposed to an atmosphere containing an organic substance, specifically, by placing the substrate in a chamber and introducing the organic substance-containing gas into the chamber, The step of depositing the organic-containing gas in contact with the surface of the substrate to selectively deposit the organic film on the first surface area of the substrate.

作為乾式膜堆積步驟中使用之有機物，較佳為與濕式法同樣為通式(1)所表示之有機物。As the organic substance used in the dry film deposition step, the organic substance represented by the general formula (1) is preferably the same as the wet method.

含有有機物之氣體之腔室內之氛圍氣體之溫度較佳為0℃以上200℃以下，更佳為40℃以上200℃以下，尤佳為60℃以上180℃以下。The temperature of the atmosphere gas in the chamber containing the organic substance gas is preferably 0°C or more and 200°C or less, more preferably 40°C or more and 200°C or less, and particularly preferably 60°C or more and 180°C or less.

含有有機物之氣體之腔室內之氛圍氣體之壓力範圍較佳為0.1 Torr(13 Pa)以上500 Torr(67 kPa)以下，更佳為1 Torr(0.13 kPa)以上100 Torr(13 kPa)以下。The pressure range of the atmosphere gas in the chamber containing the organic substance gas is preferably 0.1 Torr (13 Pa) or more and 500 Torr (67 kPa) or less, more preferably 1 Torr (0.13 kPa) or more and 100 Torr (13 kPa) or less.

再者，為了使有機物以氣體之形式與基板接觸，腔室內之溫度與壓力必須設定為有機物為氣體狀態之條件。Furthermore, in order for organic matter to contact the substrate in the form of gas, the temperature and pressure in the chamber must be set to the condition where the organic matter is in a gaseous state.

於腔室內之氛圍氣體中，較佳為含有1體積%以上100體積%以下之有機物之氣體，更佳為含有10體積%以上100體積%以下，進而較佳為含有50體積%以上100體積%以下。In the atmosphere gas in the chamber, it is preferably a gas containing 1% by volume or more and 100% by volume or less of organic matter, more preferably 10% by volume or more and 100% by volume or less, and still more preferably 50% by volume or more and 100% by volume the following.

可藉由對液體之有機物進行減壓及/或加熱而獲得氣體之有機物，亦可藉由對液體之有機物通入惰性氣體，而獲得藉由惰性氣體稀釋而成之氣體之有機物。作為惰性氣體，可使用氮氣或氬氣、氪氣、氖氣等。Gaseous organic matter can be obtained by depressurizing and/or heating liquid organic matter, and gaseous organic matter diluted by inert gas can also be obtained by passing inert gas to the liquid organic matter. As the inert gas, nitrogen, argon, krypton, neon, etc. can be used.

於進行乾式膜堆積步驟後，可藉由將腔室內減壓至1～100 Pa，而去除多餘之有機物。於乾式法中，無需乾燥步驟。After performing the dry film deposition step, the excess organic matter can be removed by depressurizing the chamber to 1-100 Pa. In the dry method, no drying step is required.

藉由使用本發明之上述濕式法或上述乾式法，可藉由簡單之操作，相較於基板上之非金屬無機材料露出之表面區域或金屬氧化物露出之表面區域，更傾向於在金屬露出之表面區域選擇性地堆積有機物之膜。By using the above-mentioned wet method or the above-mentioned dry method of the present invention, the surface area exposed by the non-metallic inorganic material or the surface area exposed by the metal oxide on the substrate is more likely to be The exposed surface area selectively deposits organic films.

藉由進行上述濕式法或上述乾式法，選擇性地堆積於基板上之通式(1)所表示之有機物之堆積膜亦相當於本發明之有機物之堆積膜之一實施形態。By performing the above-mentioned wet method or the above-mentioned dry method, the deposited film of the organic substance represented by the general formula (1) selectively deposited on the substrate also corresponds to one embodiment of the deposited film of the organic substance of the present invention.

[選擇性堆積後之基板] 本發明之基板之特徵在於：其係具有包含金屬之第一表面區域以及包含非金屬無機材料及/或包含金屬氧化物之第二表面區域兩者皆露出之構造者，且於上述第一表面區域具有下述通式(1)所表示之有機物之膜，於上述第二表面區域不具有上述有機物之膜，或者上述第二表面區域上之上述有機物之膜之厚度t2 薄於上述第一表面區域上之上述有機物之膜之厚度t1 。 [化7]

Figure 02_image017
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，上述烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)[Substrate after selective stacking] The substrate of the present invention is characterized in that it has a structure in which both the first surface area containing metal and the second surface area containing non-metallic inorganic material and/or metal oxide are exposed And the film of the organic substance represented by the following general formula (1) in the first surface area, the film of the organic substance not in the second surface area, or the film of the organic substance on the second surface area The thickness t 2 is thinner than the thickness t 1 of the film of the organic substance on the first surface area. [化7]
Figure 02_image017
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are (A hydrogen atom or a hydrocarbon group which may have a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; where the above hydrocarbons also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more)

於本發明之基板中，如上所述，於上述第一表面區域具有下述通式(1)所表示之有機物之膜，於上述第二表面區域不具有上述有機物之膜，或者上述第二表面區域上之上述有機物之膜之厚度t2 薄於上述第一表面區域上之上述有機物之膜之厚度t1 。In the substrate of the present invention, as described above, the film of the organic substance represented by the following general formula (1) is provided in the first surface area, and the film of the organic substance is not provided in the second surface area, or the second surface The thickness t 2 of the organic film on the area is thinner than the thickness t 1 of the organic film on the first surface area.

於本發明之基板中，於第二表面區域上之有機物之膜之厚度t2 薄於第一表面區域上之有機物之膜之厚度t1 之情形時，較理想為t1 除以t2 所得之t1 /t2 之值為5以上。t1 /t2 之值較佳為10以上，更佳為100以上。再者，t1 較佳為1 nm以上，更佳為2 nm以上，較佳為200 nm以下，更佳為100 nm以下。又，t2 較佳為未達1 nm，亦可為0 nm。t1 及t2 之厚度可藉由原子力顯微鏡(AFM)進行測定。於t2 為0 nm之情形時，為上述條件，即上述有機物之膜僅選擇性地堆積於第一表面區域。In the substrate of the present invention, when the thickness t 2 of the organic film on the second surface area is thinner than the thickness t 1 of the organic film on the first surface area, it is more preferably obtained by dividing t 1 by t 2 The value of t 1 /t 2 is 5 or more. The value of t 1 /t 2 is preferably 10 or more, and more preferably 100 or more. Furthermore, t 1 is preferably 1 nm or more, more preferably 2 nm or more, preferably 200 nm or less, and more preferably 100 nm or less. In addition, t 2 is preferably less than 1 nm, and may be 0 nm. The thickness of t 1 and t 2 can be measured by an atomic force microscope (AFM). When t 2 is 0 nm, it is the above-mentioned condition, that is, the film of the organic substance is selectively deposited only on the first surface area.

於本發明之基板中，關於包含金屬之第一表面區域、包含非金屬無機材料及/或金屬氧化物之第二表面區域、通式(1)所表示之有機物等，於上述本發明之對基板之金屬表面區域之選擇性膜堆積方法中進行了說明，因此此處省略詳細說明。In the substrate of the present invention, regarding the first surface area containing metal, the second surface area containing non-metallic inorganic material and/or metal oxide, the organic matter represented by the general formula (1), etc. The selective film deposition method of the metal surface area of the substrate is described, so detailed description is omitted here.

認為上述有機物之膜係上述有機物之分子中之具有氮原子、氧原子或硫原子之基與第一表面區域之金屬相互作用而形成。 [實施例]It is considered that the film of the above-mentioned organic substance is formed by interaction between a group having a nitrogen atom, an oxygen atom or a sulfur atom in the molecule of the above-mentioned organic substance and the metal in the first surface region. [Example]

以下，藉由下述實驗確認可於金屬露出之表面區域藉由有機物選擇性地堆積膜。Hereinafter, it was confirmed by the following experiment that a film can be selectively deposited by an organic substance on the surface area where the metal is exposed.

[實驗例1-1] 於異丙醇(以下稱為IPA)中使1%之鄰胺基苯硫酚溶解，製備含有作為有機物之鄰胺基苯硫酚及溶劑之溶液。 其次，使含有Cu表面之基板浸漬於該溶液60秒，使有機物之膜堆積。溶液之溫度為20～25℃。其後，於20～25℃之IPA液中浸漬60秒，實施2次，進行多餘之有機物之去除，繼而，吹送20～25℃之氮氣60秒，使基板乾燥。 藉由原子力顯微鏡(AFM)測定形成於基板上之有機物之膜厚，結果為48 nm。又，藉由X射線光電子光譜法(XPS)分析元素組成，結果確認到氮與硫之強尖峰。[Experiment Example 1-1] Dissolve 1% of o-aminothiophenol in isopropanol (hereinafter referred to as IPA) to prepare a solution containing o-aminothiothiol as an organic substance and a solvent. Next, the substrate containing the Cu surface was immersed in this solution for 60 seconds to deposit the organic film. The temperature of the solution is 20-25°C. After that, it was immersed in an IPA solution at 20 to 25°C for 60 seconds and performed twice to remove excess organic matter, followed by blowing nitrogen at 20 to 25°C for 60 seconds to dry the substrate. The thickness of the organic substance formed on the substrate was measured by an atomic force microscope (AFM). The result was 48 nm. Furthermore, the elemental composition was analyzed by X-ray photoelectron spectroscopy (XPS), and as a result, strong spikes of nitrogen and sulfur were confirmed.

[實驗例1-2～1-24] 將基板表面之金屬、有機物之種類、溶劑之種類、溶液濃度等變更為如表1所示，除此以外，與實驗例1-1同樣地實施，進行評估。將其結果示於表1。[Experiment example 1-2～1-24] Except that the type of metal, organic substance, type of solvent, solution concentration, etc. on the surface of the substrate were changed as shown in Table 1, the evaluation was carried out in the same manner as in Experimental Example 1-1. The results are shown in Table 1.

[實驗例2-1] 於IPA中使5%之鄰胺基苯硫酚溶解，製備含有作為有機物之鄰胺基苯硫酚及溶劑之溶液。 其次，將含有Si表面之基板浸漬於該溶液60秒，使有機物之膜堆積。溶液之溫度為20～25℃。其後，於20～25℃之IPA液中浸漬60秒，實施2次，進行多餘之有機物之去除，吹送20～25℃之氮氣60秒，使基板乾燥。 藉由AFM測定形成於基板上之有機物之膜厚，結果為0 nm。又，藉由XPS分析元素組成，結果無法確認到氮與硫之尖峰。[Experimental Example 2-1] Dissolve 5% o-aminothiophenol in IPA to prepare a solution containing o-aminothiothiol as an organic substance and a solvent. Next, the substrate containing the Si surface was immersed in this solution for 60 seconds to deposit a film of organic matter. The temperature of the solution is 20-25°C. After that, it was immersed in an IPA liquid at 20 to 25°C for 60 seconds and performed twice to remove excess organic matter, and nitrogen gas at 20 to 25°C was blown for 60 seconds to dry the substrate. The film thickness of the organic substance formed on the substrate was measured by AFM, and the result was 0 nm. Furthermore, the elemental composition was analyzed by XPS, and as a result, peaks of nitrogen and sulfur could not be confirmed.

[實驗例2-2～2-10] 將基板表面之金屬、有機物之種類、溶劑之種類、溶液濃度等變更為如表2所示，除此以外，與實驗例2-1同樣地實施，進行評估。將其結果示於表2。[Experiment Example 2-2～2-10] Except that the type of metal, organic substance, type of solvent, solution concentration, etc. on the surface of the substrate were changed as shown in Table 2, the evaluation was carried out in the same manner as in Experimental Example 2-1. The results are shown in Table 2.

[實驗例3-1] 於能夠進行真空處理之腔室內設置含有Cu表面之基板，將腔室壓力設定為1 Torr(0.13 kPa，絕對壓力)。其次，將與腔室連接之鄰胺基苯硫酚之汽缸加熱至80℃，開放閥，將鄰胺基苯硫酚之氣體供給至腔室內，於含有Cu之基板上使有機物之膜堆積。再者，腔室之溫度設為與汽缸之溫度相同，鄰胺基苯硫酚之氣體之溫度設為於與基板接觸為止保持成與將汽缸保溫之溫度相同。於有機物之膜堆積後，將腔室內減壓至0.1 Torr(13 Pa)，去除多餘之有機物。 藉由AFM測定形成於基板上之有機物之膜厚，結果為10 nm。又，藉由XPS分析元素組成，結果確認到氮與硫之強尖峰。[Experiment Example 3-1] A substrate containing a Cu surface was installed in a chamber capable of vacuum processing, and the chamber pressure was set to 1 Torr (0.13 kPa, absolute pressure). Next, the cylinder of o-aminothiophenol that was connected to the chamber was heated to 80°C, the valve was opened, and the gas of o-aminothiophenol was fed into the chamber to deposit organic films on the substrate containing Cu. Furthermore, the temperature of the chamber is set to be the same as the temperature of the cylinder, and the temperature of the gas of o-aminothiophenol is kept to be the same as the temperature of keeping the cylinder warm until it contacts the substrate. After the organic matter is deposited on the film, the chamber is decompressed to 0.1 Torr (13 Pa) to remove excess organic matter. The film thickness of the organic substance formed on the substrate was measured by AFM, and the result was 10 nm. Furthermore, the elemental composition was analyzed by XPS, and as a result, strong spikes of nitrogen and sulfur were confirmed.

[實驗例3-2～3-12] 將基板上之金屬、有機物之種類、將汽缸保溫之溫度(有機物加熱溫度)、腔室壓力等變更為如表3所示，除此以外，與實驗例3-1同樣地實施，進行評估。將其結果示於表3。[Experiment Example 3-2～3-12] Except that the types of metals and organic substances on the substrate, the temperature of the cylinder holding temperature (organic substance heating temperature), the chamber pressure, and the like were changed as shown in Table 3, the evaluation was carried out in the same manner as in Experimental Example 3-1. The results are shown in Table 3.

[實驗例4-1] 於能夠進行真空處理之腔室內設置含有Si表面之基板，將腔室壓力設定為10 Torr。其次，將與腔室連接之鄰胺基苯硫酚之汽缸加熱至120℃，開放閥，將鄰胺基苯硫酚之氣體供給至腔室內，於含有Si表面之基板上使有機物之膜堆積。於有機物之膜堆積後，將腔室內減壓至0.1 Torr，去除多餘之有機物。 藉由AFM測定形成於基板上之有機物之膜厚，結果為0 nm。又，藉由XPS分析元素組成，結果無法確認到氮與硫之尖峰。[Experiment Example 4-1] A substrate containing a Si surface was placed in a chamber capable of vacuum processing, and the chamber pressure was set to 10 Torr. Next, the cylinder of o-aminothiophenol connected to the chamber is heated to 120°C, the valve is opened, the gas of o-aminothiophenol is supplied into the chamber, and the organic film is deposited on the substrate containing the Si surface . After the organic matter is deposited on the film, the chamber is decompressed to 0.1 Torr to remove excess organic matter. The film thickness of the organic substance formed on the substrate was measured by AFM, and the result was 0 nm. Furthermore, the elemental composition was analyzed by XPS, and as a result, peaks of nitrogen and sulfur could not be confirmed.

[實驗例4-2～4-10] 將基板上之金屬、有機物之種類、將汽缸保溫之溫度、腔室壓力等變更為如表4所示，除此以外，與實驗例4-1同樣地實施，進行評估。將其結果示於表4。[Experiment Example 4-2～4-10] Except for changing the types of metals and organic substances on the substrate, the temperature for holding the cylinder, the chamber pressure, etc., as shown in Table 4, the evaluation was carried out in the same manner as in Experimental Example 4-1. The results are shown in Table 4.

再者，於上述實驗例中，含有Cu表面之基板藉由如下方式進行製作：藉由蒸鍍於矽基板上以厚度約100 nm之方式成膜銅膜後，去除表面自然氧化膜。 含有Co表面之基板藉由如下方式進行製作：藉由蒸鍍於矽基板上以厚度約100 nm之方式成膜鈷膜後，去除表面自然氧化膜。 含有Ru表面之基板藉由如下方式進行製作：藉由蒸鍍於矽基板上以厚度約100 nm之方式成膜釕膜後，去除表面自然氧化膜。In addition, in the above-mentioned experimental example, the substrate containing the Cu surface was prepared by depositing a copper film with a thickness of about 100 nm on a silicon substrate by vapor deposition, and then removing the natural oxide film on the surface. The substrate containing the Co surface is produced by: depositing a cobalt film with a thickness of about 100 nm on a silicon substrate by evaporation, and then removing the natural oxide film on the surface. The substrate containing the Ru surface is produced by the following method: after depositing a ruthenium film with a thickness of about 100 nm on a silicon substrate by evaporation, the natural oxide film on the surface is removed.

又，含有Si表面之基板藉由去除矽基板之自然氧化膜而進行製作。 含有SiO2 表面之基板藉由利用化學氣相沈積法於矽基板上以厚度約30 nm之方式成膜二氧化矽膜而進行製作。 含有SiN表面之基板藉由利用化學氣相沈積法於矽基板上以厚度約30 nm之方式成膜Si3 N4 之化學式所表示之氮化矽膜而進行製作。 含有SiON表面之基板藉由如下方式進行製作：藉由化學氣相沈積法於矽基板上形成SiN表面後進行氧化，以厚度約10 nm之方式成膜Si4 Ox Ny (x為3以上6以下，y為2以上4以下)之化學式所表示之氮氧化矽膜。 含有CuO表面之基板藉由利用蒸鍍於矽基板上以厚度約100 nm之方式成膜氧化銅膜而進行製作。 含有CoO表面之基板藉由利用蒸鍍於矽基板上以厚度約100 nm之方式成膜氧化鈷膜而進行製作。In addition, the substrate containing the Si surface is produced by removing the natural oxide film of the silicon substrate. The substrate containing the SiO 2 surface is produced by forming a silicon dioxide film on the silicon substrate with a thickness of about 30 nm by chemical vapor deposition. The substrate containing the SiN surface is produced by forming a silicon nitride film represented by the chemical formula of Si 3 N 4 on the silicon substrate with a thickness of about 30 nm using a chemical vapor deposition method. The substrate containing the SiON surface is produced by: forming a SiN surface on a silicon substrate by chemical vapor deposition and then oxidizing it to form a film of Si 4 O x N y (x is 3 or more) with a thickness of about 10 nm 6 or less, y is 2 or more and 4 or less) the silicon oxynitride film represented by the chemical formula. A substrate containing a CuO surface is produced by depositing a copper oxide film with a thickness of about 100 nm on a silicon substrate by evaporation. The substrate containing the CoO surface is produced by depositing a cobalt oxide film with a thickness of about 100 nm on a silicon substrate by evaporation.

將以上結果總結於下述表1～表4。The above results are summarized in Tables 1 to 4 below.

[表1]

Figure 108123239-A0304-0001
[Table 1]
Figure 108123239-A0304-0001

[表2]

Figure 108123239-A0304-0002
[Table 2]
Figure 108123239-A0304-0002

[表3]

Figure 108123239-A0304-0003
[table 3]
Figure 108123239-A0304-0003

[表4]

Figure 108123239-A0304-0004
[Table 4]
Figure 108123239-A0304-0004

根據表1～表4所示之結果可知，於上述實驗例中，有機物於Cu、Co、Ru等金屬上堆積膜，但於Si、SiO2 、SiN、SiON等非金屬無機材料上或CuO、CoO等金屬氧化物上不堆積膜。因此，於使用具有金屬露出之表面區域以及非金屬無機材料露出之表面區域或金屬氧化物露出之表面區域之基板之情形時，藉由使用表1～表4所示之有機物，可僅於金屬露出之表面區域選擇性地堆積膜。From the results shown in Tables 1 to 4, it can be seen that in the above experimental examples, organic materials deposited films on metals such as Cu, Co, Ru, but on non-metallic inorganic materials such as Si, SiO 2 , SiN, SiON, or CuO, No film is deposited on metal oxides such as CoO. Therefore, in the case of using a substrate having a surface area exposed by a metal and a surface area exposed by a non-metallic inorganic material or a surface area exposed by a metal oxide, by using the organic substances shown in Tables 1 to 4, it is possible to use only organic materials The exposed surface area selectively deposits a film.

再者，通式(1)所表示之有機物除Co、Cu、Ru以外，於作為半導體裝置等之配線材料或者適合作為電極材料之導電材料之Ni、Pt、Al、Ta、Ti、Hf等金屬上亦可使膜堆積。In addition, the organic substance represented by the general formula (1) is not only Co, Cu, Ru, but also metals such as Ni, Pt, Al, Ta, Ti, Hf, etc., which are wiring materials for semiconductor devices, etc. or conductive materials suitable for electrode materials. The film can also be deposited on top.

Figure 108123239-A0101-11-0002-2
Figure 108123239-A0101-11-0002-2

Claims (18)

一種方法，其特徵在於對於具有包含金屬之第一表面區域以及包含非金屬無機材料及/或金屬氧化物之第二表面區域兩者皆露出之構造之基板， 相較於上述第二表面區域，更傾向於在上述第一表面區域選擇性地堆積下述通式(1)所表示之有機物之膜； [化1]
Figure 03_image019
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 及R4 分別獨立為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時，亦包含支鏈或者環狀結構之烴基)。A method characterized in that, for a substrate having a structure in which both a first surface area containing a metal and a second surface area containing a non-metallic inorganic material and/or a metal oxide are exposed, compared to the second surface area, It is more likely to selectively deposit organic films represented by the following general formula (1) on the first surface area;
Figure 03_image019
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom having 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 and R 4 are respectively A hydrocarbon group independently a hydrogen atom or a hydrocarbon group that may have a ring or heteroatom or a halogen atom with a carbon number of 1 to 10; where the hydrocarbon is based on a carbon number of 3 or more, it also includes a branched or cyclic hydrocarbon group). 如請求項1之方法，其中上述金屬為選自由Cu、Co、Ru、Ni、Pt、Al、Ta、Ti及Hf所組成之群中之至少一種。The method of claim 1, wherein the metal is at least one selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf. 如請求項1或2之方法，其中上述非金屬無機材料為選自由矽、矽氧化物、矽氮化物及矽氮氧化物所組成之群中之至少一種。The method according to claim 1 or 2, wherein the non-metallic inorganic material is at least one selected from the group consisting of silicon, silicon oxide, silicon nitride, and silicon oxynitride. 如請求項1至3中任一項之方法，其中上述金屬氧化物為選自由Cu、Co、Ru、Ni、Pt、Al、Ta、Ti及Hf所組成之群中之至少一種金屬之氧化物。The method according to any one of claims 1 to 3, wherein the metal oxide is an oxide of at least one metal selected from the group consisting of Cu, Co, Ru, Ni, Pt, Al, Ta, Ti, and Hf . 如請求項1至4中任一項之方法，其中於上述通式(1)中，R2 、R3 及R4 為氫原子。The method according to any one of claims 1 to 4, wherein in the above general formula (1), R 2 , R 3 and R 4 are hydrogen atoms. 如請求項1之方法，其中上述有機物為選自由鄰胺基苯硫酚、2-胺基苄醇、2-胺基乙醇、2-(乙基胺基)乙醇、2-胺基乙硫醇、3-胺基-1-丙醇及鄰胺基苯酚所組成之群中之至少一種。The method according to claim 1, wherein the organic substance is selected from the group consisting of o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2-(ethylamino)ethanol, 2-aminoethylthiol At least one of the group consisting of 3-amino-1-propanol and o-aminophenol. 如請求項1至6中任一項之方法，其中相較於上述第二表面區域，更傾向於在上述第一表面區域選擇性地堆積有機物之膜之步驟係將上述基板暴露於含有上述有機物及溶劑之溶液中之步驟。The method according to any one of claims 1 to 6, wherein the step of preferentially depositing a film of organic matter on the first surface area compared to the second surface area is to expose the substrate to the organic matter And the steps in the solution of the solvent. 如請求項7之方法，其中上述溶液相對於有機物及溶劑之合計，含有0.1質量%以上10質量%以下之上述通式(1)所表示之有機物。The method according to claim 7, wherein the solution contains the organic substance represented by the above general formula (1) in an amount of 0.1% by mass or more and 10% by mass or less with respect to the total of the organic substance and the solvent. 如請求項7或8之方法，其中對於上述基板選擇性地堆積上述通式(1)所表示之有機物之膜後，藉由溶劑將上述基板洗淨。The method according to claim 7 or 8, wherein after selectively depositing a film of the organic substance represented by the general formula (1) on the substrate, the substrate is washed with a solvent. 如請求項1至6中任一項之方法，其中相較於上述第二表面區域，更傾向於在上述第一表面區域選擇性地堆積上述通式(1)所表示之有機物之膜之步驟係將上述基板暴露於含有上述有機物之氣體之氛圍中之步驟。The method according to any one of claims 1 to 6, wherein the step of selectively depositing a film of an organic substance represented by the general formula (1) on the first surface area is more preferred than the second surface area It is a step of exposing the substrate to an atmosphere containing a gas of the organic substance. 如請求項10之方法，其中上述氛圍之溫度範圍為0℃以上200℃以下。The method according to claim 10, wherein the temperature range of the atmosphere is 0°C or more and 200°C or less. 如請求項10或11之方法，其中上述氛圍之壓力範圍為13 Pa以上67 kPa以下。The method of claim 10 or 11, wherein the pressure range of the above atmosphere is 13 Pa or more and 67 kPa or less. 如請求項1至12中任一項之方法，其中上述第一表面區域上之有機物之膜之厚度t1 與前期第二表面區域上之有機物之膜之厚度t2 之比(t1 /t2 )為5以上。The method according to any one of claims 1 to 12, wherein the ratio of the thickness t 1 of the organic film on the first surface area to the thickness t 2 of the organic film on the second surface area (t 1 /t 2 ) 5 or more. 一種基板，其特徵在於其係具有包含金屬之第一表面區域以及包含非金屬無機材料及/或金屬氧化物之第二表面區域兩者皆露出之構造者，且 於上述第一表面區域具有下述通式(1)所表示之有機物之膜， 於上述第二表面區域不具有上述有機物之膜，或者上述第二表面區域上之上述有機物之膜之厚度t2 薄於上述第一表面區域上之上述有機物之膜之厚度t1 ； [化2]
Figure 03_image021
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)。A substrate characterized in that it has a structure in which both a first surface area containing metal and a second surface area containing non-metallic inorganic material and/or metal oxide are exposed, and has a lower surface in the first surface area The film of the organic substance represented by the general formula (1) does not have the film of the organic substance in the second surface area, or the thickness t 2 of the film of the organic substance on the second surface area is thinner than the first surface area The thickness t 1 of the film of the above organic matter; [Chem 2]
Figure 03_image021
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are The hydrogen atom may be a hydrocarbon group having a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more). 一種有機物之堆積膜，其特徵在於其係藉由如請求項1至13中任一項之方法形成之有機物之膜，且 選擇性地堆積於基板上，該有機物以下述通式(1)表示； [化3]
Figure 03_image023
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)。A deposited film of organic matter, characterized in that it is a film of organic matter formed by the method as claimed in any one of claims 1 to 13, and is selectively deposited on a substrate, the organic matter is represented by the following general formula (1) ; [化3]
Figure 03_image023
(In general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are The hydrogen atom may be a hydrocarbon group having a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more). 一種有機物，其特徵在於用於如請求項1至13中任一項之方法，且以下述通式(1)表示； [化4]
Figure 03_image025
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)。An organic substance characterized by the method used in any one of claims 1 to 13 and represented by the following general formula (1);
Figure 03_image025
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are The hydrogen atom may be a hydrocarbon group having a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more). 一種溶液，其特徵在於含有特徵為以下述通式(1)表示之有機物及溶劑； [化5]
Figure 03_image027
(於通式(1)中，N為氮原子，X為氧原子或硫原子； R1 為可具有碳數2～12之雜原子或鹵素原子之烴基，R2 、R3 、R4 為氫原子或者可具有碳數1～10之環或雜原子或鹵素原子之烴基；其中，該烴基於碳數為3以上之情形時亦包含支鏈或者環狀結構之烴基)。A solution characterized by containing an organic substance and a solvent characterized by the following general formula (1); [化5]
Figure 03_image027
(In the general formula (1), N is a nitrogen atom, X is an oxygen atom or a sulfur atom; R 1 is a hydrocarbon group which may have a hetero atom of 2 to 12 carbon atoms or a halogen atom, and R 2 , R 3 , and R 4 are The hydrogen atom may be a hydrocarbon group having a ring of 1 to 10 carbon atoms or a hetero atom or a halogen atom; wherein the hydrocarbon may also include a branched or cyclic hydrocarbon group when the carbon number is 3 or more). 如請求項17之溶液，其中上述有機物為選自由鄰胺基苯硫酚、2-胺基苄醇、2-胺基乙醇、2-(乙基胺基)乙醇、2-胺基乙硫醇、3-胺基-1-丙醇及鄰胺基苯酚所組成之群中之至少一種， 上述溶劑為選自由乙醇及異丙醇所組成之群中之至少一種， 上述溶液含有相對於有機物及溶劑之合計0.1質量%以上10質量%以下之上述通式(1)所表示之有機物。The solution according to claim 17, wherein the organic substance is selected from the group consisting of o-aminothiophenol, 2-aminobenzyl alcohol, 2-aminoethanol, 2-(ethylamino)ethanol, 2-aminoethylthiol , At least one of the group consisting of 3-amino-1-propanol and o-aminophenol, The above solvent is at least one selected from the group consisting of ethanol and isopropanol, The said solution contains the organic substance represented by the said general formula (1) with respect to the total of organic substance and solvent 0.1 mass% or more and 10 mass% or less.
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