TWI644999B - Polymer, organic layer composition, and method of forming patterns - Google Patents

Polymer, organic layer composition, and method of forming patterns Download PDF

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TWI644999B
TWI644999B TW106112724A TW106112724A TWI644999B TW I644999 B TWI644999 B TW I644999B TW 106112724 A TW106112724 A TW 106112724A TW 106112724 A TW106112724 A TW 106112724A TW I644999 B TWI644999 B TW I644999B
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金惠廷
南沇希
姜善惠
金旼秀
金瑆煥
金永珉
金有那
金眞亨
白載烈
尹星莉
鄭瑟基
崔有廷
黃善民
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三星Sdi股份有限公司
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/027Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031Organic compounds not covered by group G03F7/029
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/033Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture 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
    • 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
    • H01L21/324Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering

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Abstract

本發明揭露一種有機層組成物及使用有機層組成物形成圖案的方法,所述有機層組成物包含:聚合物,包含由化學式1表示的結構單元;單體,由化學式3表示;以及溶劑。 在化學式1及化學式3中,A、B、A0 、A1 、A2 、L1 、L2 、L3 、L4 、X1 、X2 、X3 、X4 、m及n與在說明書中所述的相同。The present invention discloses an organic layer composition and a method of forming a pattern using the organic layer composition, the organic layer composition comprising: a polymer comprising a structural unit represented by Chemical Formula 1; a monomer represented by Chemical Formula 3; and a solvent. In Chemical Formula 1 and Chemical Formula 3, A, B, A 0 , A 1 , A 2 , L 1 , L 2 , L 3 , L 4 , X 1 , X 2 , X 3 , X 4 , m and n The same as described in the manual.

Description

聚合物、有機層組成物與形成圖案之方法Polymer, organic layer composition and method of forming a pattern

本發明揭露一種有機層組成物及使用所述有機層組成物形成圖案的方法。 The present invention discloses an organic layer composition and a method of forming a pattern using the organic layer composition.

近來,根據電子裝置的小型化(微型化)及複雜度而進行的高積體設計已加速了更先進的材料及其相關製程的發展,且因此,使用傳統光阻劑的微影術亦需要新型圖案化材料及技術。 Recently, high-integration designs based on miniaturization (micro-tilization) and complexity of electronic devices have accelerated the development of more advanced materials and related processes, and therefore, lithography using conventional photoresists is also required. New patterned materials and technologies.

在圖案化製程中,可將被稱為硬罩幕層的有機層形成為硬中間層以將光阻劑的精細圖案向下轉移至基板上的足夠深度而不使其塌陷。 In a patterning process, an organic layer, referred to as a hard mask layer, can be formed as a hard interlayer to transfer the fine pattern of photoresist down to a sufficient depth on the substrate without collapse.

硬罩幕層發揮中間層的作用以藉由選擇性蝕刻製程而將光阻劑的精細圖案轉移至材料層。因此,硬罩幕層需要例如耐熱性、耐蝕刻性等特徵以便耐受多重蝕刻製程。 The hard mask layer functions as an intermediate layer to transfer the fine pattern of the photoresist to the material layer by a selective etching process. Therefore, the hard mask layer requires characteristics such as heat resistance, etching resistance, and the like in order to withstand multiple etching processes.

另一方面,近來已提議旋塗(spin-on coating)方法替代化學氣相沈積(chemical vapor deposition,CVD)方法來形成硬罩幕層。旋塗方法不僅可輕易地執行且亦可改善間隙填充特徵及平坦化特徵。 On the other hand, a spin-on coating method has recently been proposed instead of a chemical vapor deposition (CVD) method to form a hard mask layer. The spin coating method can not only be easily performed but also improve the gap filling feature and the planarization feature.

一般而言,由於耐熱性及耐蝕刻性與旋塗(spin-on)特徵具有權衡關係,因此需要一種滿足所有所述特徵的有機層材料。 In general, since heat resistance and etching resistance have a trade-off relationship with spin-on characteristics, an organic layer material satisfying all of the above characteristics is required.

本發明實施例提供一種能夠以旋塗方式進行塗佈且具有提高的耐蝕刻性的有機層組成物。 Embodiments of the present invention provide an organic layer composition that can be applied by spin coating and has improved etching resistance.

本發明另一實施例提供一種使用所述有機層組成物形成圖案的方法。 Another embodiment of the present invention provides a method of forming a pattern using the organic layer composition.

根據一個實施例,一種有機層組成物包含:聚合物,包含由化學式1表示的結構單元;單體,由化學式3表示;以及溶劑。 According to an embodiment, an organic layer composition comprises: a polymer comprising a structural unit represented by Chemical Formula 1; a monomer represented by Chemical Formula 3; and a solvent.

在化學式1中,A為經取代或未經取代的含芳族環的基、經取代或未經取代的含雜芳族環的基或其組合,B為二價有機基,且A及B中的至少一者經包含由化學式2表示的部分(moity)的官能基取代:[化學式2] In Chemical Formula 1, A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and B is a divalent organic group, and A and B At least one of them is substituted with a functional group containing a moity represented by Chemical Formula 2: [Chemical Formula 2]

其中,在化學式2中,Z為氫、羥基、經取代或未經取代的C1至C10烷基或經取代或未經取代的C6至C30芳基,且*為連接點, Wherein, in Chemical Formula 2, Z is hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and * is a point of attachment,

其中,在化學式3中,A0、A1、及A2獨立地為經取代或未經取代的含芳族環的基,A0、A1及A2中的一者或多者在結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基,L1、L2、L3及L4獨立地為單鍵、經取代或未經取代的C1至C6伸烷基、經取代或未經取代的C6至C30伸芳基或其組合,X1、X2、X3及X4獨立地為氫、羥基、經取代或未經取代的胺基、鹵素原子或其組合,其限制條件是X1與X2不同時為氫,且X3與X4不同時為氫,並且m及n獨立地為介於0至2的整數,其限制條件是m與n的 和大於或等於1,其限制條件是當m為0時,A0及A2中的至少一者在結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基,且當n為0時,A1及A0中的至少一者在結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基。 Wherein, in Chemical Formula 3, A 0 , A 1 , and A 2 are independently a substituted or unsubstituted aromatic ring-containing group, and one or more of A 0 , A 1 and A 2 are in the structure. Containing substituted or unsubstituted amino, substituted or unsubstituted vinyl, substituted or unsubstituted ethynyl, azido or nitrile, L 1 , L 2 , L 3 and L 4 Independently a single bond, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 extended aryl group, or a combination thereof, X 1 , X 2 , X 3 and X 4 independently a hydrogen, a hydroxyl group, a substituted or unsubstituted amine group, a halogen atom or a combination thereof, wherein X 1 and X 2 are not hydrogen at the same time, and X 3 and X 4 are not hydrogen at the same time, and m and n are Independently an integer between 0 and 2, with the constraint that the sum of m and n is greater than or equal to 1, with the constraint that when m is 0, at least one of A 0 and A 2 is included in the structure. a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and when n is 0, in A 1 and A 0 At least one of the packages in the structure A substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group.

包含由化學式2表示的部分的官能基可由化學式2’表示。 The functional group containing a moiety represented by Chemical Formula 2 can be represented by Chemical Formula 2'.

在化學式2’中,W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,Z為氫、羥基、經取代或未經取代的C1至C10烷基或經取代或未經取代的C6至C30芳基,a為0或1,b為介於0至10範圍內的整數,且*為連接點。 In Chemical Formula 2', W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing Or a combination thereof, Z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C30 aryl, a is 0 or 1, and b is between 0 and 10 An integer in the range, and * is the join point.

在化學式3中,A0、A1及A2可獨立地包含選自群組1的經取代或未經取代的部分。 In Chemical Formula 3, A 0 , A 1 and A 2 may independently comprise a substituted or unsubstituted moiety selected from Group 1.

在群組1中,X為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合。 In group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO 2 , CR f R g , NR h or a carbonyl group, wherein R f to R h are independently hydrogen, A substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

在化學式3中,A0、A1及A2中的至少一者可為多環環狀基。 In Chemical Formula 3, at least one of A 0 , A 1 and A 2 may be a polycyclic cyclic group.

在化學式3中,A0、A1及A2中的至少一者可在所述結構中包含由化學式4表示的官能基中的至少一者。 In Chemical Formula 3, at least one of A 0 , A 1 and A 2 may contain at least one of the functional groups represented by Chemical Formula 4 in the structure.

[化學式4] [Chemical Formula 4]

在化學式4中,W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,Y為經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基、腈基或其組合,a為0或1,b為介於0至10範圍內的整數,且*為連接點。 In Chemical Formula 4, W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, halogen-containing group Or a combination thereof, Y is a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group, a nitrile group or a combination thereof, a is 0 or 1, b is an integer ranging from 0 to 10, and * is a connection point.

當所述單體包含經取代或未經取代的乙炔基時,所述單體可由化學式3a至化學式3d中的一者表示。 When the monomer contains a substituted or unsubstituted ethynyl group, the monomer may be represented by one of Chemical Formula 3a to Chemical Formula 3d.

[化學式3b] [Chemical Formula 3b]

在化學式3a至化學式3d中,A3、A4及A5獨立地為經取代或未經取代的含芳族環的基,且W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合。 In Chemical Formula 3a to Chemical Formula 3d, A 3 , A 4 and A 5 are independently a substituted or unsubstituted aromatic ring-containing group, and W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

在化學式1中,所述A可為選自群組1及群組2的經取代或未經取代的部分。 In Chemical Formula 1, the A may be a substituted or unsubstituted moiety selected from Group 1 and Group 2.

[群組1] [Group 1]

在群組1中,X為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合。 In group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO 2 , CR f R g , NR h or a carbonyl group, wherein R f to R h are independently hydrogen, A substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

在群組2中,Z1及Z2獨立地為NRd、O、S、Te或Se,Z3至Z5為N,且Rd及Re獨立地為氫、羥基、甲氧基、乙氧基、鹵素原子、含鹵素的基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C6至C30芳基或其組合。 In group 2, Z 1 and Z 2 are independently NR d , O, S, Te or Se, Z 3 to Z 5 are N, and R d and R e are independently hydrogen, hydroxyl, methoxy, An ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

所述B可由化學式Z1至化學式Z4中的一者表示。 The B may be represented by one of the chemical formula Z1 to the chemical formula Z4.

[化學式Z3] [Chemical Formula Z3]

在化學式Z1至化學式Z4中,e及f獨立地為0或1,g為1至5的整數,Y1至Y4獨立地為選自群組3的經取代或未經取代的部分中的一者,且*為連接點:[群組3] In the chemical formula Z1 to the chemical formula Z4, e and f are independently 0 or 1, g is an integer of 1 to 5, and Y 1 to Y 4 are independently selected from the substituted or unsubstituted portion of Group 3. One, and * is the connection point: [Group 3]

在群組3中, M、M'及M"獨立地為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合, L1為經取代或未經取代的C6至C50伸芳基、經取代或未經 取代的C1至C10含環氧烷的基或其組合,r為0至10的整數,s為0至10的整數,且k為0至3的整數。 In group 3, M, M 'and M "are independently a substituted or unsubstituted C1 to C10 alkylene, O, S, SO 2, CR f R g, NR h or carbonyl, wherein R f To R h is independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing group or a combination thereof, and L 1 is a substituted or unsubstituted C6 to C50 extended aryl group, The substituted or unsubstituted C1 to C10 alkylene oxide-containing group or a combination thereof, r is an integer of 0 to 10, s is an integer of 0 to 10, and k is an integer of 0 to 3.

所述聚合物可更包含由化學式5表示的結構單元。 The polymer may further contain a structural unit represented by Chemical Formula 5.

在化學式5中,X0為經取代或未經取代的含芳族環的基、經取代或未經取代的含雜芳族環的基或其組合,L0為二價有機基,且*為連接點。 In Chemical Formula 5, X 0 is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and L 0 is a divalent organic group, and * For the connection point.

在化學式5中,X0可為選自群組1及群組2的經取代或未經取代的部分。 In Chemical Formula 5, X 0 may be a substituted or unsubstituted moiety selected from Group 1 and Group 2.

[群組1] [Group 1]

在群組1中,X為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,在群組2中,Z1及Z2獨立地為NRd、O、S、Te或Se,Z3至Z5為N,且Rd及Re獨立地為氫、羥基、甲氧基、乙氧基、鹵素原子、含鹵素的基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C6至C30芳基或其組合。 In group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO 2 , CR f R g , NR h or a carbonyl group, wherein R f to R h are independently hydrogen, A substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof, in Group 2, Z 1 and Z 2 are independently NR d , O, S, Te or Se, Z 3 to Z 5 are N, and R d and R e are independently hydrogen, hydroxy, methoxy, ethoxy, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkyl group, Substituted or unsubstituted C6 to C30 aryl or a combination thereof.

所述聚合物可在所述結構單元中包含至少一個氧原子。 The polymer may comprise at least one oxygen atom in the structural unit.

所述單體可具有500至50,000的分子量。 The monomer may have a molecular weight of 500 to 50,000.

所述聚合物可具有500至200,000的重量平均分子量。 The polymer may have a weight average molecular weight of from 500 to 200,000.

所述聚合物與所述單體的重量比可為70:30至30:70。 The weight ratio of the polymer to the monomer may range from 70:30 to 30:70.

根據另一實施例,一種形成圖案之方法包括:在基板上提供材料層,將所述有機層組成物施加於所述材料層上,對所述有機層組成物進行熱處理以形成硬罩幕層,在所述硬罩幕層上形成含矽的薄層,在含矽的薄層上形成光阻劑層,對光阻劑層進行曝光及顯影以形成光阻劑圖案,使用所述光阻劑圖案來選擇性地移除所述含矽的薄層及所述硬罩幕層以暴露出所述材料層的一部分,以及對所述材料層的被暴露部分進行蝕刻。 In accordance with another embodiment, a method of forming a pattern includes: providing a layer of material on a substrate, applying the organic layer composition to the layer of material, and subjecting the organic layer composition to heat treatment to form a hard mask layer Forming a thin layer containing germanium on the hard mask layer, forming a photoresist layer on the thin layer containing germanium, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist The agent pattern selectively removes the tantalum-containing layer and the hard mask layer to expose a portion of the material layer and etch the exposed portions of the material layer.

所述有機層組成物可利用旋塗方法來施加。 The organic layer composition can be applied by a spin coating method.

所述熱處理可包括在50℃至250℃下進行第一熱處理及在所述第一熱處理之後在200℃至500℃下進行第二熱處理。 The heat treatment may include performing a first heat treatment at 50 ° C to 250 ° C and performing a second heat treatment at 200 ° C to 500 ° C after the first heat treatment.

所述方法可更包括在形成所述光阻劑層之前形成底部抗反射塗層(bottom antireflective coating,BARC)。 The method may further include forming a bottom antireflective coating (BARC) prior to forming the photoresist layer.

本發明提供一種因包含預定聚合物及預定添加劑而在以旋塗方法進行塗佈的同時具有提高的耐蝕刻性的有機層組成物。由所述有機層組成物製造的有機層具有提高的膜密度及膜平坦度。 The present invention provides an organic layer composition having improved etching resistance while being coated by a spin coating method by containing a predetermined polymer and a predetermined additive. The organic layer produced from the organic layer composition has an improved film density and film flatness.

圖1為用於闡釋一種評估平坦化特徵(階差特徵)的方法的視圖。 FIG. 1 is a view for explaining a method of evaluating a flattening feature (a step feature).

圖2為用於闡釋一種評估厚度均勻性特徵的方法的視圖。 2 is a view for explaining a method of evaluating a thickness uniformity characteristic.

本發明的示範性實施例將在以下進行詳細闡述,且可由相關技術中具有通常知識者輕易地執行。然而,本發明可實施為諸多不同形式,且不應被解釋為僅限於本文所述的示例性實施例。 Exemplary embodiments of the present invention will be explained in detail below, and can be easily performed by those having ordinary knowledge in the related art. However, the invention may be embodied in many different forms and should not be construed as being limited to the exemplary embodiments described herein.

在本說明書中,當不另外提供定義時,「經取代」指代化合物的氫被以下者置換:鹵素原子(F、Br、Cl或I)、羥基、烷氧基、硝基、氰基、胺基、疊氮基、脒基、肼基、腙基、羰基、胺甲醯基、硫醇基、酯基、羧基或其鹽、磺酸基或其鹽、磷酸或其鹽、C1至C20烷基、C2至C20烯基、C2至C20炔基、C6至 C30芳基、C7至C30芳基烷基、C1至C30烷氧基、C1至C20雜烷基、C2至C20雜芳基、C3至C20雜芳基烷基、C3至C30環烷基、C3至C15環烯基、C6至C15環炔基、C2至C30雜環烷基及其組合。 In the present specification, when no definition is provided, "substituted" means that the hydrogen of the compound is replaced by a halogen atom (F, Br, Cl or I), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, Amino, azide, sulfhydryl, fluorenyl, fluorenyl, carbonyl, amine carbhydryl, thiol, ester, carboxyl or a salt thereof, sulfonic acid or a salt thereof, phosphoric acid or a salt thereof, C1 to C20 Alkyl, C2 to C20 alkenyl, C2 to C20 alkynyl, C6 to C30 aryl, C7 to C30 arylalkyl, C1 to C30 alkoxy, C1 to C20 heteroalkyl, C2 to C20 heteroaryl, C3 to C20 heteroarylalkyl, C3 to C30 cycloalkyl, C3 To C15 cycloalkenyl, C6 to C15 cycloalkynyl, C2 to C30 heterocycloalkyl, and combinations thereof.

在本說明書中,當不另外提供定義時,「雜」指代一者包含選自B、N、O、S及P中的1至3個雜原子。 In the present specification, when a definition is not additionally provided, "hetero" refers to one containing one to three hetero atoms selected from B, N, O, S, and P.

以下,闡述根據實施例的有機層組成物。 Hereinafter, the organic layer composition according to the embodiment will be explained.

根據實施例的有機層組成物包含:聚合物,包含由化學式1表示的結構單元;單體,由化學式3表示;以及溶劑。 The organic layer composition according to the embodiment comprises: a polymer comprising a structural unit represented by Chemical Formula 1; a monomer represented by Chemical Formula 3; and a solvent.

在化學式1中,A為經取代或未經取代的含芳族環的基、經取代或未經取代的含雜芳族環的基或其組合,B為二價有機基,且A及B中的至少一者經包含由化學式2表示的部分的官能基取代:[化學式2] In Chemical Formula 1, A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and B is a divalent organic group, and A and B At least one of them is substituted with a functional group containing a moiety represented by Chemical Formula 2: [Chemical Formula 2]

其中,在化學式2中,Z為氫、羥基、經取代或未經取代的C1至C10烷基或經取代或未經取代的C6至C30芳基,且*為連接點: Wherein, in Chemical Formula 2, Z is hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and * is a point of attachment:

其中,在化學式3中,A0、A1、及A2獨立地為經取代或未經取代的含芳族環的基,A0、A1及A2中的一者或多者在所述結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基,L1、L2、L3、及L4獨立地為單鍵、經取代或未經取代的C1至C6伸烷基、經取代或未經取代的C6至C30伸芳基或其組合,X1、X2、X3及X4獨立地為氫、羥基、經取代或未經取代的胺基、鹵素原子或其組合,其限制條件是X1與X2不同時為氫,且X3與X4不同時為氫,並且m及n獨立地為介於0至2的整數,其限制條件是m與n的 和大於或等於1,其限制條件是當m為0時,A0及A2中的至少一者在所述結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基,且當n為0時,A1及A0中的至少一者在所述結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基。 Wherein, in Chemical Formula 3, A 0 , A 1 , and A 2 are independently a substituted or unsubstituted aromatic ring-containing group, and one or more of A 0 , A 1 and A 2 are in the The structure includes a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, L 1 , L 2 , L 3 , And L 4 is independently a single bond, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 extended aryl group, or a combination thereof, X 1 , X 2 , X 3 and X 4 is independently hydrogen, a hydroxyl group, a substituted or unsubstituted amine group, a halogen atom or a combination thereof, with the proviso that X 1 and X 2 are not hydrogen at the same time, and X 3 and X 4 are not hydrogen at the same time, and m and n are independently an integer between 0 and 2, with the constraint that the sum of m and n is greater than or equal to 1, with the constraint that when m is 0, at least one of A 0 and A 2 is in the The structure includes a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and when n is 0, A 1 and at least one of a 0 Comprising a substituted or unsubstituted amino group in the structure, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl, azido or nitrile group.

在本說明書中,「乙炔基」指代藉由乙炔化合物的一個氫被置換而產生的單價官能基,且「疊氮基」指代藉由疊氮化合物的一個氫被置換而產生的單價官能基。 In the present specification, "ethynyl" refers to a monovalent functional group which is produced by substitution of one hydrogen of an acetylene compound, and "azido" refers to a monovalent functional group produced by substitution of one hydrogen of an azide compound. base.

有機層組成物包含具有預定結構的聚合物及具有預定結構的單體。首先,闡述所述聚合物。 The organic layer composition contains a polymer having a predetermined structure and a monomer having a predetermined structure. First, the polymer is explained.

聚合物包含由化學式1表示的結構單元中的一者或多者,且在所述結構單元中包含由A表示的含芳族環的部分(moiety)及由B表示的連接基部分(moiety)。 The polymer contains one or more of the structural units represented by Chemical Formula 1, and includes an aromatic ring-containing moiety represented by A and a linking moiety represented by B in the structural unit. .

舉例而言,A可為經取代或未經取代的含芳族環的基,例如選自群組1的經取代或未經取代的部分(moiety),但並非僅限於此。 For example, A may be a substituted or unsubstituted aromatic ring-containing group, for example, a substituted or unsubstituted moiety selected from Group 1, but is not limited thereto.

[群組1] [Group 1]

在群組1中,X為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合。 In group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO 2 , CR f R g , NR h or a carbonyl group, wherein R f to R h are independently hydrogen, A substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

再舉例而言,所述A可為經取代或未經取代的含芳族環的基,例如選自群組2的經取代或未經取代的部分,但並非僅限於此。 By way of further example, the A may be a substituted or unsubstituted aromatic ring-containing group, such as, but not limited to, a substituted or unsubstituted moiety selected from Group 2.

[群組2] [Group 2]

在群組2中,Z1及Z2獨立地為NRd、O、S、Te或Se,Z3至Z5為N,且Rd及Re獨立地為氫、羥基、甲氧基、乙氧基、鹵素原子、含鹵素的基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C6至C30芳基或其組合。 In group 2, Z 1 and Z 2 are independently NR d , O, S, Te or Se, Z 3 to Z 5 are N, and R d and R e are independently hydrogen, hydroxyl, methoxy, An ethoxy group, a halogen atom, a halogen-containing group, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a combination thereof.

再舉例而言,A可為經取代或未經取代的含芳族環的基以及經取代或未經取代的含雜芳族環的基的組合。舉例而言,在化學式1中,A可包含二個或更多個經取代或未經取代的苯環,例如二個至六個經取代或未經取代的苯環。在本文中,苯環可經 至少一個羥基取代。 By way of further example, A can be a combination of substituted or unsubstituted aromatic ring-containing groups and substituted or unsubstituted heteroaromatic ring-containing groups. For example, in Chemical Formula 1, A may contain two or more substituted or unsubstituted benzene rings, for example, two to six substituted or unsubstituted benzene rings. In this paper, the benzene ring can be At least one hydroxyl group is substituted.

在化學式1中,由B表示的連接基可為二價有機直鏈基、二價有機環狀基或其組合。舉例而言,B可由化學式Z1至化學式Z4中的一者表示,但並非僅限於此。 In Chemical Formula 1, the linking group represented by B may be a divalent organic linear group, a divalent organic cyclic group, or a combination thereof. For example, B may be represented by one of Chemical Formula Z1 to Chemical Formula Z4, but is not limited thereto.

在化學式Z1至化學式Z4中,e及f獨立地為0或1,g為1至5的整數, Y1至Y4獨立地為選自群組3的經取代或未經取代的部分(moiety)中的一者,且*為連接點: In the chemical formula Z1 to the chemical formula Z4, e and f are independently 0 or 1, g is an integer of 1 to 5, and Y 1 to Y 4 are independently a substituted or unsubstituted moiety selected from Group 3 (moiety One of them, and * is the connection point:

在群組3中,M、M'及M"獨立地為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、 經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,L1為經取代或未經取代的C6至C50伸芳基、經取代或未經取代的C1至C10含環氧烷的基或其組合,r為0至10的整數,s為0至10的整數,且k為0至3的整數。 In group 3, M, M 'and M "are independently a substituted or unsubstituted C1 to C10 alkylene, O, S, SO 2, CR f R g, NR h or carbonyl, wherein R f To R h is independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing group or a combination thereof, and L 1 is a substituted or unsubstituted C6 to C50 extended aryl group, The substituted or unsubstituted C1 to C10 alkylene oxide-containing group or a combination thereof, r is an integer of 0 to 10, s is an integer of 0 to 10, and k is an integer of 0 to 3.

另一方面,在化學式1中,A及B中的至少一者經由化學式2表示的含乙炔的基取代。舉例而言,由A表示的含芳族環的基或含雜芳族環的基可經含乙炔的基取代,由B表示的連接基可經含乙炔的基取代,抑或A部分(moiety)及B部分(moiety)可經含乙炔的基取代。在本文中,取代的數目無特別限制。 On the other hand, in Chemical Formula 1, at least one of A and B is substituted with an acetylene-containing group represented by Chemical Formula 2. For example, the aromatic ring-containing group or the heteroaromatic ring-containing group represented by A may be substituted with an acetylene-containing group, and the linking group represented by B may be substituted with an acetylene-containing group or a moiety (moiety). And part B (moiety) may be substituted by an acetylene-containing group. Herein, the number of substitutions is not particularly limited.

舉例而言,包含由化學式2表示的部分(moiety)的官能基可由化學式2’表示,但並非僅限於此。 For example, the functional group containing a moiety represented by Chemical Formula 2 can be represented by Chemical Formula 2', but is not limited thereto.

在化學式2’中,W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,Z為氫、羥基、經取代或未經取代的C1至C10烷基或經取代或未經取代的C6至C30芳基,a為0或1,b為介於0至10範圍內的整數,且*為連接點。 In Chemical Formula 2', W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing Or a combination thereof, Z is hydrogen, hydroxy, substituted or unsubstituted C1 to C10 alkyl or substituted or unsubstituted C6 to C30 aryl, a is 0 or 1, and b is between 0 and 10 An integer in the range, and * is the join point.

舉例而言,包含由化學式2表示的部分的官能基可由化學式2”表示,但並非僅限於此。 For example, the functional group containing a moiety represented by Chemical Formula 2 may be represented by Chemical Formula 2", but is not limited thereto.

在化學式2”中,W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C20烷基、鹵素原子、含鹵素的基或其組合,a為0或1,且*為連接點。 In Chemical Formula 2", W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, substituted or unsubstituted C 1 to C 20 alkyl, halogen atom, halogen-containing Base or a combination thereof, a is 0 or 1, and * is a connection point.

舉例而言,所述聚合物可在所述結構中包含至少一個氧 原子。 For example, the polymer can comprise at least one oxygen in the structure atom.

聚合物可由於所述結構單元中的由A表示的含芳族環的基或含雜芳族環的基而確保耐蝕刻性,且可由於由B表示的有機基而確保可撓性。另外,當聚合物固化時,乙炔藉由將至少一個乙炔引入至A或B而形成環結構,且因而耐蝕刻性可被進一步提高。因此,使用所述聚合物而形成的有機層具有提高的層密度。另外,使用所述聚合物而形成的有機層可具有厚度均勻性。 The polymer can ensure etching resistance due to the aromatic ring-containing group or the heteroaromatic ring-containing group represented by A in the structural unit, and can ensure flexibility due to the organic group represented by B. In addition, when the polymer is cured, acetylene forms a ring structure by introducing at least one acetylene to A or B, and thus etching resistance can be further improved. Therefore, the organic layer formed using the polymer has an increased layer density. In addition, the organic layer formed using the polymer may have thickness uniformity.

所述聚合物可更包含例如由化學式5表示的結構單元。 The polymer may further contain, for example, a structural unit represented by Chemical Formula 5.

在化學式5中,X0為經取代或未經取代的含芳族環的基、經取代或未經取代的含雜芳族環的基或其組合,L0為二價有機基,且*為連接點。 In Chemical Formula 5, X 0 is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and L 0 is a divalent organic group, and * For the connection point.

在化學式5中,X可為選自群組1及群組2的經取代或未經取代的部分(moiety),且L0與在化學式1中作為連接基的B相同。與由化學式1表示的結構單元本質上不同,由化學式5表示的結構單元不包含乙炔官能基。 In Chemical Formula 5, X may be a substituted or unsubstituted moiety selected from Group 1 and Group 2, and L 0 is the same as B which is a linking group in Chemical Formula 1. Essentially different from the structural unit represented by Chemical Formula 1, the structural unit represented by Chemical Formula 5 does not contain an acetylene functional group.

以下,闡述有機層組成物的單體。 Hereinafter, the monomer of the organic layer composition will be described.

所述單體如上所述由化學式3表示。 The monomer is represented by Chemical Formula 3 as described above.

[化學式3] [Chemical Formula 3]

在化學式3中,A0、A1及A2獨立地為經取代或未經取代的含芳族環的基,A0、A1、及A2中的一者或多者在所述結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基,L1、L2、L3、及L4獨立地為單鍵、經取代或未經取代的C1至C6伸烷基、經取代或未經取代的C6至C30伸芳基或其組合,X1、X2、X3及X4獨立地為氫、羥基、經取代或未經取代的胺基、鹵素原子或其組合,其限制條件是X1與X2不同時為氫,且X3與X4不同時為氫,並且m及n獨立地為介於0至2的整數,其限制條件是m與n的和大於或等於1,其限制條件是當m為0時,A0及A2中的至少一者包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基,且當n為0時,A1及A0中的至少一者包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基。 In Chemical Formula 3, A 0 , A 1 and A 2 are independently a substituted or unsubstituted aromatic ring-containing group, and one or more of A 0 , A 1 , and A 2 are in the structure. Containing substituted or unsubstituted amino, substituted or unsubstituted vinyl, substituted or unsubstituted ethynyl, azido or nitrile, L 1 , L 2 , L 3 , and L 4 independently, a single bond, a substituted or unsubstituted C1 to C6 alkyl group, a substituted or unsubstituted C6 to C30 extended aryl group, or a combination thereof, X 1 , X 2 , X 3 and X 4 are independently The ground is hydrogen, a hydroxyl group, a substituted or unsubstituted amine group, a halogen atom or a combination thereof, and the limitation is that X 1 and X 2 are not hydrogen at the same time, and X 3 and X 4 are not hydrogen at the same time, and m and n is independently an integer between 0 and 2, with the constraint that the sum of m and n is greater than or equal to 1, with the proviso that when m is 0, at least one of A 0 and A 2 comprises substituted or An unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and when n is 0, at least one of A 1 and A 0 Contains replaced or not Substituted amine, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl, azido or nitrile group.

舉例而言,在化學式3中,A0、A1及A2中的一者或多者可在所述結構中包含由化學式4表示的官能基。 For example, in Chemical Formula 3, one or more of A 0 , A 1 and A 2 may include a functional group represented by Chemical Formula 4 in the structure.

在化學式4中,W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,Y為經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基、腈基或其組合,a為0或1,b為介於0至10範圍內的整數,且*為連接點。 In Chemical Formula 4, W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, halogen-containing group Or a combination thereof, Y is a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group, a nitrile group or a combination thereof, a is 0 or 1, b is an integer ranging from 0 to 10, and * is a connection point.

由化學式4表示的官能基可包括經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基。 The functional group represented by Chemical Formula 4 may include a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group.

單體可在所述結構中包含例如由化學式4表示的官能基中的一者或多者。 The monomer may contain, for example, one or more of the functional groups represented by Chemical Formula 4 in the structure.

舉例而言,在表示單體的化學式3中,A0、A1及A2獨立地為選自群組1的經取代或未經取代的部分(moiety),但並非僅限於此。 For example, in Chemical Formula 3 representing a monomer, A 0 , A 1 and A 2 are independently a substituted or unsubstituted moieties selected from Group 1, but are not limited thereto.

舉例而言,在表示單體的化學式3中,A0、A1及A2中的至少一者可為多環環狀基。 For example, in Chemical Formula 3 indicating a monomer, at least one of A 0 , A 1 and A 2 may be a polycyclic cyclic group.

舉例而言,單體可由化學式3a至化學式3d中的一者表示,但並非僅限於此。 For example, the monomer may be represented by one of Chemical Formula 3a to Chemical Formula 3d, but is not limited thereto.

[化學式3d] [Chemical Formula 3d]

在化學式3a至化學式3d中,A3、A4及A5獨立地為經取代或未經取代的含芳族環的基,且W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合。 In Chemical Formula 3a to Chemical Formula 3d, A 3 , A 4 and A 5 are independently a substituted or unsubstituted aromatic ring-containing group, and W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof.

如上所述,所述有機層組成物包含其中引入有乙炔的聚合物及作為含芳族環的化合物的單體,所述單體包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基、或腈基中的至少一者。 As described above, the organic layer composition contains a polymer in which acetylene is introduced and a monomer as an aromatic ring-containing compound containing a substituted or unsubstituted amino group, substituted or unsubstituted At least one of a substituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group, or a nitrile group.

如此,當同時使用聚合物及單體來製備有機層組成物時,被引入至聚合物中的乙炔官能基與被引入至單體中的胺、乙炔、疊氮等反應且因此形成環,並且因此有機層組成物中的碳含量可相對增加。因此,耐蝕刻性得以提高,且因此蝕刻選擇性可得以提高。因此,使用所述有機層組成物而形成的有機層可具有優異的層密度及圖案形成能力。 As such, when the polymer and the monomer are simultaneously used to prepare the organic layer composition, the acetylene functional group introduced into the polymer reacts with the amine, acetylene, azide or the like introduced into the monomer and thus forms a ring, and Therefore, the carbon content in the organic layer composition can be relatively increased. Therefore, the etching resistance is improved, and thus the etching selectivity can be improved. Therefore, the organic layer formed using the organic layer composition can have excellent layer density and pattern forming ability.

舉例而言,聚合物可具有約500至200,000的重量平均分子量。當聚合物具有處於範圍內的重量平均分子量時,可藉由調整碳含量及在溶劑中的溶解度而將包含聚合物的有機層組成物(例如,硬罩幕組成物)最佳化。另外,舉例而言,單體可具有 約500至50,000的分子量。 For example, the polymer can have a weight average molecular weight of from about 500 to 200,000. When the polymer has a weight average molecular weight in the range, the organic layer composition (for example, a hard mask composition) containing the polymer can be optimized by adjusting the carbon content and the solubility in the solvent. In addition, for example, the monomer may have A molecular weight of about 500 to 50,000.

有機層組成物的溶劑無特別限制,只要所述溶劑對於聚合物具有足夠的可溶性或可分散性,且可為例如選自以下的至少一者:丙二醇、二乙酸丙二醇酯、甲氧基丙二醇、二乙二醇、二乙二醇丁醚、三(乙二醇)單甲醚、丙二醇單甲醚、丙二醇單甲醚乙酸酯、環己酮、乳酸乙酯、γ-丁內酯、N,N-二甲基甲醯胺、N,N二甲基乙醯胺、甲基吡咯啶酮(methylpyrrolidone)、甲基吡咯酮(methylpyrrolidinone)、乙醯丙酮及3-乙氧基丙酸乙酯。 The solvent of the organic layer composition is not particularly limited as long as the solvent has sufficient solubility or dispersibility for the polymer, and may be, for example, at least one selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropylene glycol, Diethylene glycol, diethylene glycol butyl ether, tri(ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, γ-butyrolactone, N , N-dimethylformamide, N,N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, ethyl acetonide and ethyl 3-ethoxypropionate .

以有機層組成物的總量計,可包含約0.1重量%至50重量%的量的聚合物。當包含處於所述範圍內的聚合物時,可對有機層的厚度、表面粗糙度及平坦化進行控制。 The polymer may be included in an amount of from about 0.1% by weight to 50% by weight based on the total of the organic layer composition. When the polymer in the range is included, the thickness, surface roughness and planarization of the organic layer can be controlled.

以有機層組成物的總量計,可包含約0.1重量%至50重量%、例如約5重量%至50重量%的量的單體。 The monomer may be included in an amount of from about 0.1% by weight to 50% by weight, for example, from about 5% by weight to 50% by weight based on the total of the organic layer composition.

舉例而言,聚合物與單體的重量比可被控制處於70:30至30:70範圍內,但並非僅限於此。 For example, the weight ratio of polymer to monomer can be controlled in the range of 70:30 to 30:70, but is not limited thereto.

有機層組成物可更包含以下添加劑:界面活性劑、交聯劑、熱酸產生劑或塑化劑。 The organic layer composition may further comprise the following additives: a surfactant, a crosslinking agent, a thermal acid generator or a plasticizer.

界面活性劑可包括例如烷基苯磺酸鹽、烷基吡啶鎓鹽、聚乙二醇或四級銨鹽,但並非僅限於此。 The surfactant may include, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol or a quaternary ammonium salt, but is not limited thereto.

交聯劑可為例如三聚氰胺系、取代脲系或聚合物系交聯劑。較佳地,其可為具有至少兩個交聯形成取代基的交聯劑,舉例而言,例如甲氧基甲基化甘脲、丁氧基甲基化甘脲、甲氧基甲 基化三聚氰胺、丁氧基甲基化三聚氰胺、甲氧基甲基化苯並胍胺、丁氧基甲基化苯並胍胺、甲氧基甲基化脲、丁氧基甲基化脲、甲氧基甲基化硫脲或丁氧基甲基化硫脲等化合物。 The crosslinking agent may be, for example, a melamine-based, substituted urea-based or polymer-based crosslinking agent. Preferably, it may be a crosslinking agent having at least two crosslinks to form a substituent, such as, for example, methoxymethylated glycoluril, butoxymethylated glycoluril, methoxyl Melamine melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, A compound such as methoxymethylated thiourea or butoxymethylated thiourea.

交聯劑可為具有高耐熱性的交聯劑。具有高耐熱性的交聯劑可為在分子中包含含有芳族環(例如,苯環或萘環)的交聯取代基的化合物。 The crosslinking agent may be a crosslinking agent having high heat resistance. The crosslinking agent having high heat resistance may be a compound containing a crosslinking substituent containing an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule.

熱酸產生劑可為例如酸性化合物,例如對甲苯磺酸、三氟甲磺酸、吡啶鎓對甲苯磺酸、水楊酸、磺基水楊酸、檸檬酸、苯甲酸、羥基苯甲酸、萘甲酸等或/及2,4,4,6-四溴環己二烯酮、安息香甲苯磺酸酯、2-硝基苯甲基甲苯磺酸酯、其他有機磺酸烷基酯等,但並非僅限於此。 The thermal acid generator may be, for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalene. Formic acid or the like and / and 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyltosylate, other alkyl sulfonate, etc., but not Limited to this.

以100重量份的有機層組成物計,可存在約0.001重量份至40重量份的量的添加劑。在所述範圍內,可提高溶解度而有機層組成物的光學特性不會改變。 The additive may be present in an amount of from about 0.001 part by weight to 40 parts by weight based on 100 parts by weight of the organic layer composition. Within the above range, the solubility can be improved and the optical properties of the organic layer composition are not changed.

根據另一實施例,提供一種使用所述有機層組成物製造的有機層。所述有機層可例如藉由將有機層組成物塗佈於基板上並對其進行熱處理以固化而形成,且可包括例如用於電子裝置的硬罩幕層、平坦化層、犧牲層、填料等。 According to another embodiment, an organic layer fabricated using the organic layer composition is provided. The organic layer may be formed, for example, by coating an organic layer composition on a substrate and heat-treating it to cure, and may include, for example, a hard mask layer for an electronic device, a planarization layer, a sacrificial layer, a filler. Wait.

以下,闡述一種使用有機層組成物來形成圖案的方法。 Hereinafter, a method of forming a pattern using an organic layer composition will be described.

根據實施例的一種形成圖案的方法包括:在基板上提供材料層,將包含聚合物及溶劑的有機層組成物施加於材料層上,對有機層組成物進行熱處理以形成硬罩幕層,在硬罩幕層上形成 含矽的薄層,在含矽的薄層上形成光阻劑層,對光阻劑層進行曝光及顯影以形成光阻劑圖案,使用光阻劑圖案來選擇性地移除含矽的薄層及硬罩幕層以暴露出材料層的一部分,以及對材料層的被暴露部分進行蝕刻。 A method of forming a pattern according to an embodiment includes: providing a material layer on a substrate, applying an organic layer composition containing a polymer and a solvent to the material layer, and heat treating the organic layer composition to form a hard mask layer, Formed on the hard mask layer a thin layer containing germanium, forming a photoresist layer on the thin layer containing germanium, exposing and developing the photoresist layer to form a photoresist pattern, and using a photoresist pattern to selectively remove the thin layer containing germanium The layer and the hard mask layer expose a portion of the material layer and etch the exposed portions of the material layer.

基板可為例如矽晶圓、玻璃基板或聚合物基板。 The substrate can be, for example, a germanium wafer, a glass substrate, or a polymer substrate.

材料層為待最終進行圖案化的材料,舉例而言,例如鋁層及銅層等金屬層、例如矽層等半導體層或例如氧化矽層及氮化矽層等絕緣層。材料層可藉由例如化學氣相沈積(CVD)製程等方法來形成。 The material layer is a material to be finally patterned, and examples thereof include a metal layer such as an aluminum layer and a copper layer, a semiconductor layer such as a germanium layer, or an insulating layer such as a hafnium oxide layer or a tantalum nitride layer. The material layer can be formed by a method such as a chemical vapor deposition (CVD) process.

有機層組成物與上述相同,且可藉由旋塗以溶液形式施加。在本文中,有機層組成物的厚度無特別限制,但可為例如約50埃至10,000埃。 The organic layer composition is the same as described above and can be applied as a solution by spin coating. Herein, the thickness of the organic layer composition is not particularly limited, but may be, for example, about 50 angstroms to 10,000 angstroms.

可例如在約100℃至500℃下對有機層組成物執行熱處理約10秒至1小時。 The heat treatment of the organic layer composition may be performed, for example, at about 100 ° C to 500 ° C for about 10 seconds to 1 hour.

舉例而言,所述熱處理可包括在50℃至250℃下執行的第一熱處理及在所述第一熱處理之後且在200℃至500℃下執行的第二熱處理。 For example, the heat treatment may include a first heat treatment performed at 50 ° C to 250 ° C and a second heat treatment performed after the first heat treatment and at 200 ° C to 500 ° C.

含矽的薄層可由例如SiCN、SiOC、SiON、SiOCN、SiC、及/或SiN等材料形成。 The thin layer containing germanium may be formed of a material such as SiCN, SiOC, SiON, SiOCN, SiC, and/or SiN.

所述方法可更包括在形成光阻劑層之前,於含矽的薄層上形成底部抗反射塗層(BARC)。 The method can further include forming a bottom anti-reflective coating (BARC) on the tantalum-containing layer prior to forming the photoresist layer.

可使用例如ArF、KrF或EUV對光阻劑層執行曝光。在 曝光之後,可在約100℃至500℃下執行熱處理。 Exposure can be performed on the photoresist layer using, for example, ArF, KrF, or EUV. in After the exposure, the heat treatment may be performed at about 100 ° C to 500 ° C.

可藉由使用蝕刻氣體的乾式蝕刻製程對材料層的被暴露部分執行蝕刻製程,且蝕刻氣體可為例如CHF3、CF4、Cl2、BCl3及其混合氣體,但不受限制。 The etching process may be performed on the exposed portion of the material layer by a dry etching process using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 , and a mixed gas thereof, but is not limited.

經蝕刻材料層可被形成為多個圖案,且所述多個圖案可為金屬圖案、半導體圖案、絕緣圖案等,例如半導體積體電路裝置的各種各樣的圖案。 The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulating pattern, or the like, such as various patterns of the semiconductor integrated circuit device.

以下,將參考實例更詳細地說明本發明。然而,該些實例為示範性的,且本發明並非僅限於此。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the examples are exemplary and the invention is not limited thereto.

聚合物合成 Polymer synthesis

聚合例1Polymerization example 1

樹脂聚合 Resin polymerization

在燒瓶中放入了萘-1-醇(Naphthalen-1-ol)(14.2克)、聚甲醛(paraformaldehyde)(6克)、對甲苯磺酸水合物(p-toluene sulfonic acid hydrate)(1.9克)及丙二醇單甲醚乙酸酯(propylene glycol monomethyl ether acetate,PGMEA,33克),並在80℃下進行了攪拌以執行聚合反應。當藉由在反應期間以凝膠滲透層析法(gel permeation chromatography,GPC)查看分子量而重量平均分子量達到2,000至3,500時,完成了聚合反應。當聚合反應完成之後,將反應物緩慢冷卻至室溫,向其中添加了己烷(100克)以萃取丙二醇單甲醚乙酸酯,且使用蒸餾水及甲醇移除了己烷,以獲得包含由化學式1a’表示的結構單元的聚合物(重量平均分子量 (Mw)=3,000)。 Naphthalen-1-ol (14.2 g), paraformaldehyde (6 g), and p-toluene sulfonic acid hydrate (1.9 g) were placed in the flask. And propylene glycol monomethyl ether acetate (PGMEA, 33 g), and stirred at 80 ° C to carry out polymerization. When the molecular weight was observed by gel permeation chromatography (GPC) during the reaction and the weight average molecular weight reached 2,000 to 3,500, the polymerization was completed. After the completion of the polymerization, the reactant was slowly cooled to room temperature, hexane (100 g) was added thereto to extract propylene glycol monomethyl ether acetate, and hexane was removed using distilled water and methanol to obtain inclusion. Polymer of structural unit represented by Chemical Formula 1a' (weight average molecular weight) (Mw) = 3,000).

乙醯化反應 Acetylation reaction

在燒瓶中將包含由化學式1a’表示的結構單元的聚合物(10克)溶解在了N,N-二甲基甲醯胺(N,N-dimethyl formamide,DMF)(40毫升)中,且在冰水中對溶液進行了攪拌。在將其攪拌10分鐘之後,向其中緩慢地滴加了NaH(1克),在冰水中將混合物攪拌了30分鐘,且向其中滴加了炔丙基溴(propargyl bromide)(在甲苯中為80%,5.5克)。當反應完成之後,向其中添加了乙酸乙酯(ethyl acetate,EtOAc)(100毫升)以稀釋反應溶液,且用水將經稀釋反應溶液洗滌了若干次以移除N,N-二甲基甲醯胺。當將N,N-二甲基甲醯胺完全移除之後,移除了剩餘的EtOAc以獲得包含由化學式1a表示結構單元的聚合物1a。 The polymer (10 g) containing the structural unit represented by the chemical formula 1a' was dissolved in N,N-dimethylformamide (DMF) (40 ml) in a flask, and The solution was stirred in ice water. After stirring it for 10 minutes, NaH (1 g) was slowly added dropwise thereto, and the mixture was stirred in ice water for 30 minutes, and propargyl bromide was added thereto (in toluene) 80%, 5.5 grams). After the reaction was completed, ethyl acetate (ethyl acetate, EtOAc) (100 ml) was added thereto to dilute the reaction solution, and the diluted reaction solution was washed several times with water to remove N,N-dimethylformamidine. amine. After the N,N-dimethylformamide was completely removed, the remaining EtOAc was removed to obtain a polymer 1a containing the structural unit represented by Chemical Formula 1a.

聚合例2Polymerization example 2

樹脂聚合 Resin polymerization

以與聚合例1相同的樹脂聚合使4,4'-(9H-茀-9,9-二基)二苯酚(14克)、1,3-雙(4-(甲氧基甲基)苯(6.6克)、丙二醇單甲醚乙酸酯(propylene glycol monomethyl ether acetate,PGMEA,20克)及硫酸二乙酯(0.25克)在100℃下進行了反應,以獲得包含由化學式1b’表示的結構單元的聚合物。(重量平均分子量(Mw)=3,700)。 Polymerization of the same resin as in Polymerization Example 1 gave 4,4'-(9H-fluorene-9,9-diyl)diphenol (14 g), 1,3-bis(4-(methoxymethyl)benzene (6.6 g), propylene glycol monomethyl ether acetate (PGMEA, 20 g) and diethyl sulfate (0.25 g) were reacted at 100 ° C to obtain a formula represented by the formula 1b' Polymer of structural unit (weight average molecular weight (Mw) = 3,700).

乙醯化反應 Acetylation reaction

根據與聚合例1相同的乙醯化,使用了包含由化學式1b’表示的結構單元的聚合物(9克)、N,N-二甲基甲醯胺(45毫升)、NaH(0.9克)及炔丙基溴(在甲苯中為80%,3.5克),來獲得包含由化學式1b表示的結構單元的聚合物1b。 According to the same oximation as in Polymerization Example 1, a polymer (9 g) containing the structural unit represented by Chemical Formula 1b', N,N-dimethylformamide (45 ml), NaH (0.9 g) was used. And propargyl bromide (80% in toluene, 3.5 g) to obtain a polymer 1b containing the structural unit represented by Chemical Formula 1b.

[化學式1b] [Chemical Formula 1b]

聚合例3Polymerization example 3

樹脂聚合 Resin polymerization

根據與聚合例1相同的樹脂聚合且使用6,6'-(9H-茀-9,9-二基)二萘-2-醇(18克)、1,3-雙(甲氧基甲基)苯(6.6克)、丙二醇單甲醚乙酸酯(PGMEA,25克)及硫酸二乙酯(0.2克)在110℃下獲得了包含由化學式1c’表示的結構單元的聚合物。(重量平均分子量(Mw)=3,800)。 Polymerization according to the same resin as in Polymerization Example 1 and using 6,6'-(9H-fluorene-9,9-diyl)dinaphthyl-2-ol (18 g), 1,3-bis(methoxymethyl) Benzene (6.6 g), propylene glycol monomethyl ether acetate (PGMEA, 25 g) and diethyl sulfate (0.2 g) obtained a polymer comprising a structural unit represented by the chemical formula 1c' at 110 °C. (weight average molecular weight (Mw) = 3,800).

乙醯化反應 Acetylation reaction

根據與聚合例1相同的乙醯化,使用了包含由化學式1c’表示的結構單元的聚合物(10克)、N,N-二甲基甲醯胺(45毫升)、NaH(0.7克)及炔丙基溴(在甲苯中為80%,2.5克),來獲得包 含由化學式1c表示的結構單元的聚合物1c。 According to the same oximation as in Polymerization Example 1, a polymer (10 g) containing the structural unit represented by Chemical Formula 1c', N,N-dimethylformamide (45 ml), NaH (0.7 g) was used. And propargyl bromide (80% in toluene, 2.5 g) to obtain the package A polymer 1c containing a structural unit represented by Chemical Formula 1c.

比較聚合例1 Comparison of polymerization example 1

根據與聚合例1相同的樹脂聚合且使用萘-1-醇(14克)、1,4-雙(甲氧基甲基)苯(17克)、丙二醇單甲醚乙酸酯(PGMEA,64克)、及硫酸二乙酯(0.3克)在100℃下獲得了包含由化學式1k表示的結構單元的聚合物1k。(重量平均分子量(Mw)=3,000)。 Polymerization was carried out according to the same resin as in Polymerization Example 1 and using naphthalen-1-ol (14 g), 1,4-bis(methoxymethyl)benzene (17 g), and propylene glycol monomethyl ether acetate (PGMEA, 64)克), and diethyl sulfate (0.3 g) obtained a polymer 1k containing a structural unit represented by the chemical formula 1k at 100 °C. (weight average molecular weight (Mw) = 3,000).

單體合成 Monomer synthesis

合成例1Synthesis Example 1

在配備有機械攪拌器及冷卻管的500毫升2頸燒瓶中放入了蔻(30克,0.1莫耳)、溴萘甲醯氯(27克,0.1莫耳)及1,2-二氯乙烷(150克)並進行了充分攪拌。在15分鐘之後,向其中 緩慢添加了三氯鋁(14.67克,0.11莫耳),且使混合物在室溫下反應了1小時。當將蔻完全移除之後,將反應物添加至甲醇中,且藉由對其中的沈澱物進行過濾而移除了三氯鋁。在配備有機械攪拌器及冷卻管的500毫升2頸燒瓶中放入藉由過濾而獲得的粉末,向其中添加了1-十二硫醇(44克,0.45莫耳)、氫氧化鉀(15克,0.54莫耳)、及N,N二甲基甲醯胺(262克),且在100℃下將混合物攪拌了5小時。當反應完成之後,對反應物進行了冷卻並以7%氯化氫溶液調整為具有pH<5,且對其中的沈澱物進行了過濾。然後,在真空烘箱中對所獲得的濾液進行了乾燥以移除水分。 In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, hydrazine (30 g, 0.1 mol), bromonaphthoquinone chloride (27 g, 0.1 mol) and 1,2-dichloroethane were placed. The alkane (150 g) was thoroughly stirred. After 15 minutes, to Aluminum trichloride (14.67 g, 0.11 mol) was slowly added, and the mixture was allowed to react at room temperature for 1 hour. After the hydrazine was completely removed, the reactants were added to methanol, and trichloroaluminum was removed by filtering the precipitate therein. A powder obtained by filtration was placed in a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, and 1-dodecanethiol (44 g, 0.45 mol), potassium hydroxide (15) was added thereto. G, 0.54 mol), and N,N-dimethylformamide (262 g), and the mixture was stirred at 100 ° C for 5 hours. After the reaction was completed, the reactant was cooled and adjusted to have a pH < 5 with a 7% hydrogen chloride solution, and the precipitate was filtered. The filtrate obtained was then dried in a vacuum oven to remove moisture.

向四氫呋喃(tetrahydrofuran,THF)(160克)中添加了自其獲得的粉末以獲得溶液。然後,向溶液中緩慢添加了硼氫化鈉(8克,0.21莫耳)水溶液,且在室溫下將混合物攪拌了12小時。當反應完成之後,以7%氯化氫溶液將溶液調整為具有pH<5,並以乙酸乙酯進行了萃取,且在壓力下還原了其中的有機溶劑。 The powder obtained therefrom was added to tetrahydrofuran (THF) (160 g) to obtain a solution. Then, an aqueous solution of sodium borohydride (8 g, 0.21 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the solution was adjusted to have a pH < 5 with a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent therein was reduced under pressure.

將此所合成聚合物(10克,0.02莫耳)、二氯化雙(三苯基膦)鈀(II)(Pd(PPh3)2Cl2,0.6克,0.0008莫耳)、碘化銅(0.16克,0.0008莫耳)、三苯基膦(0.44克,0.0016莫耳)及三乙胺(36毫升)溶解在了四氫呋喃(60毫升)中。隨後,向其中添加了乙炔基三甲基矽烷(3.5克),且在80℃下將混合物攪拌了3小時。當反應完成之後,對所得物進行了過濾並使用氧化矽凝膠進行了純化。將經純化固體(12.5克,1當量)溶解在了MeOH/THF(體積比=1/2)溶液(250毫升)中,向其中添加了碳酸鉀(20克,7 當量),且在室溫下將混合物攪拌了6小時。當反應完成之後,以乙酸乙酯對所得物進行了萃取並在壓力下進行了還原以獲得由化學式3-1表示的化合物。 The synthesized polymer (10 g, 0.02 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh 3 ) 2 Cl 2 , 0.6 g, 0.0008 mol), copper iodide (0.16 g, 0.0008 mol), triphenylphosphine (0.44 g, 0.0016 mol) and triethylamine (36 ml) were dissolved in tetrahydrofuran (60 ml). Subsequently, ethynyl trimethyl decane (3.5 g) was added thereto, and the mixture was stirred at 80 ° C for 3 hours. After the reaction was completed, the resultant was filtered and purified using a cerium oxide gel. The purified solid (12.5 g, 1 eq.) was dissolved in MeOH / THF (vol. ratio = 1/2) solution (250 ml), and potassium carbonate (20 g, 7 eq.) was added thereto at room temperature. The mixture was stirred for 6 hours. After the completion of the reaction, the resultant was subjected to extraction with ethyl acetate and reduced under pressure to obtain a compound represented by Chemical Formula 3-1.

合成例2Synthesis Example 2

在配備有機械攪拌器及冷卻管的500毫升2頸燒瓶中放入了芘(10克,0.05莫耳)、溴萘甲醯氯(27克,0.1莫耳)及1,2-二氯乙烷(150克)並接著進行了充分攪拌。在15分鐘之後,向其中緩慢添加了三氯鋁(14.67克,0.11莫耳),且使所獲得的混合物在室溫下反應了1小時。當將芘全部移除之後,將反應物添加至甲醇中,且對其中的沈澱物進行了過濾以移除三氯鋁。在配備有機械攪拌器及冷卻管的500毫升2頸燒瓶中放入了藉由過濾而獲得的粉末,向其中添加了1-十二硫醇(44克,0.22莫耳)、氫氧化鉀(15克,0.25莫耳)、及N,N-二甲基甲醯胺(262克),且在100℃下將混合物攪拌了5小時。當反應完成之後,對反應物進行了冷卻並以7%氯化氫溶液調整為具有pH<5,且對其中形成的沈澱物進行了過濾。然後,在真空烘箱中對所獲得的濾液進行了乾燥以移除水分。 In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, hydrazine (10 g, 0.05 mol), bromonaphthoquinone chloride (27 g, 0.1 mol) and 1,2-dichloroethane were placed. The alkane (150 g) was then thoroughly stirred. After 15 minutes, trichloroaluminum (14.67 g, 0.11 mol) was slowly added thereto, and the obtained mixture was allowed to react at room temperature for 1 hour. After all the hydrazine was removed, the reactants were added to methanol and the precipitate was filtered to remove the aluminum trichloride. A powder obtained by filtration was placed in a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, and 1-dodecanethiol (44 g, 0.22 mol) and potassium hydroxide were added thereto. 15 g, 0.25 mol), and N,N-dimethylformamide (262 g), and the mixture was stirred at 100 ° C for 5 hours. After the reaction was completed, the reactant was cooled and adjusted to have a pH < 5 with a 7% hydrogen chloride solution, and the precipitate formed therein was filtered. The filtrate obtained was then dried in a vacuum oven to remove moisture.

然後,再次向所獲得的粉末中添加了四氫呋喃(160克)以獲得溶液。向溶液中緩慢添加了硼氫化鈉(8克,0.21莫耳)水溶液,且在室溫下將混合物攪拌了12小時。當反應完成之後,以7%氯化氫溶液將反應溶液調整為具有pH<5,並以乙酸乙酯進行了萃取,且在壓力下還原了其中的有機溶劑。 Then, tetrahydrofuran (160 g) was again added to the obtained powder to obtain a solution. An aqueous solution of sodium borohydride (8 g, 0.21 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the reaction solution was adjusted to have a pH < 5 with a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent therein was reduced under pressure.

將此所合成聚合物(10克,0.018莫耳)、二氯化雙(三苯基膦)鈀(II)(Pd(PPh3)2Cl2,0.6克,0.0008莫耳)、碘化銅(0.16克,0.0008莫耳)、三苯基膦(0.44克,0.0016莫耳)及三乙胺(36毫升)溶解在了四氫呋喃(60毫升)中。然後,向其中添加了乙炔基三甲基矽烷(3.5克),且在80℃下將所獲得的混合物攪拌了3小時。當反應完成之後,對所得物進行了過濾並使用氧化矽凝膠進行了純化。將經純化固體(12.5克,1當量)溶解在了MeOH/THF(體積比=1/2)溶液(250毫升)中,向其中添加了碳酸鉀(20克,7當量),且在室溫下將混合物攪拌了6小時。當反應完成之後,以乙酸乙酯對所得物進行了萃取並在壓力下進行了還原以獲得由化學式3-2表示的化合物。 The synthesized polymer (10 g, 0.018 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh 3 ) 2 Cl 2 , 0.6 g, 0.0008 mol), copper iodide (0.16 g, 0.0008 mol), triphenylphosphine (0.44 g, 0.0016 mol) and triethylamine (36 ml) were dissolved in tetrahydrofuran (60 ml). Then, ethynyl trimethyl decane (3.5 g) was added thereto, and the obtained mixture was stirred at 80 ° C for 3 hours. After the reaction was completed, the resultant was filtered and purified using a cerium oxide gel. The purified solid (12.5 g, 1 eq.) was dissolved in MeOH / THF (vol. ratio = 1/2) (250 mL), and potassium carbonate (20 g, 7 eq. The mixture was stirred for 6 hours. After completion of the reaction, the resultant was extracted with ethyl acetate and reduced under pressure to obtain a compound represented by Chemical Formula 3-2.

合成例3Synthesis Example 3

在配備有機械攪拌器及冷卻管的500毫升2頸燒瓶中放入了芘(10克,0.05莫耳)、4-甲氧基苯甲醯氯(8.43克,0.05莫耳)及1,2-二氯乙烷(100.11克)以製備溶液。隨後,向溶液中緩慢添加了氯化鋁(6.59克,0.0494莫耳),且在室溫下將所獲得的混合物攪拌了2小時。當反應完成之後,向溶液中添加了甲醇,且對其中形成的沈澱物進行了過濾及乾燥。 In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, hydrazine (10 g, 0.05 mol), 4-methoxybenzhydryl chloride (8.43 g, 0.05 mol) and 1,2 were placed. Dichloroethane (100.11 g) was used to prepare a solution. Subsequently, aluminum chloride (6.59 g, 0.0494 mol) was slowly added to the solution, and the obtained mixture was stirred at room temperature for 2 hours. After the reaction was completed, methanol was added to the solution, and the precipitate formed therein was filtered and dried.

隨後,在燒瓶中放入了化合物(15.46克,0.0460莫耳)、1,3,5-苯三甲醯氯(4.07克,0.0153莫耳)、及1,2-二氯乙烷(102.62克)以製備溶液。隨後,向溶液中緩慢添加了氯化鋁(6.13克,0.0460莫耳),且在室溫下將所獲得的混合物攪拌了6小時。當反應完成之後,對藉由向溶液中添加甲醇而形成的沈澱物進行了過濾及乾燥。 Subsequently, a compound (15.46 g, 0.0460 mol), 1,3,5-benzenetrimethylsulfonium chloride (4.07 g, 0.0153 mol), and 1,2-dichloroethane (102.62 g) were placed in the flask. To prepare a solution. Subsequently, aluminum chloride (6.13 g, 0.0460 mol) was slowly added to the solution, and the obtained mixture was stirred at room temperature for 6 hours. After the reaction was completed, the precipitate formed by adding methanol to the solution was filtered and dried.

在燒瓶中放入了化合物(15.17克,0.0130莫耳)、1-十二硫醇(13.18克,0.0651莫耳)、氫氧化鉀(4.38克,0.0781莫耳)、及N,N-二甲基甲醯胺(76.37克),並在120℃下攪拌了3小時。隨後,對混合物進行了冷卻並以5%氯化氫溶液中和為具有pH 6至pH 7,且對其中形成的沈澱物進行了過濾及乾燥。 Compound (15.17 g, 0.0130 mol), 1-dodecanethiol (13.18 g, 0.0651 mol), potassium hydroxide (4.38 g, 0.0781 mol), and N,N-dimethyl were placed in the flask. Baseamidine (76.37 g) was stirred at 120 ° C for 3 hours. Subsequently, the mixture was cooled and neutralized with a 5% hydrogen chloride solution to have a pH of 6 to pH 7, and the precipitate formed therein was filtered and dried.

在燒瓶中放入了化合物(11.84克,0.0105莫耳)及四氫呋喃(40克)以製備溶液。隨後,向溶液中緩慢添加了硼氫化鈉(7.98克,0.2108莫耳)水溶液,且在室溫下將混合物攪拌了24 小時。當反應完成之後,以5%氯化氫溶液將所得物中和為具有pH 7,且接著以乙酸乙酯進行了萃取並進行了乾燥以獲得化合物8。 A compound (11.84 g, 0.0105 mol) and tetrahydrofuran (40 g) were placed in a flask to prepare a solution. Subsequently, an aqueous solution of sodium borohydride (7.98 g, 0.2108 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 24 times. hour. After the reaction was completed, the resultant was neutralized to have pH 7 with a 5% hydrogen chloride solution, and then extracted with ethyl acetate and dried to obtain Compound 8.

將此所合成聚合物(10克,0.012莫耳)、二氯化雙(三苯基膦)鈀(II)(Pd(PPh3)2Cl2,0.6克,0.0008莫耳)、碘化銅(0.16克,0.0008莫耳)、三苯基膦(0.44克,0.0016莫耳)及三乙胺(36毫升)溶解在了四氫呋喃(60毫升)中。然後,向其中添加了乙炔基三甲基矽烷(3.5克),且在80℃下將所獲得的混合物攪拌了3小時。當反應完成之後,對所得物進行了過濾並使用氧化矽凝膠進行了純化。將經純化固體(12.5克,1當量)溶解在了MeOH/THF(體積比=1/2)溶液(250毫升)中,向其中添加了碳酸鉀(20克,7當量),且在室溫下將混合物攪拌了6小時。當反應完成之後,以乙酸乙酯對所得物進行了萃取並在壓力下進行了還原以獲得由化學式3-3表示的化合物。 The synthesized polymer (10 g, 0.012 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh 3 ) 2 Cl 2 , 0.6 g, 0.0008 mol), copper iodide (0.16 g, 0.0008 mol), triphenylphosphine (0.44 g, 0.0016 mol) and triethylamine (36 ml) were dissolved in tetrahydrofuran (60 ml). Then, ethynyl trimethyl decane (3.5 g) was added thereto, and the obtained mixture was stirred at 80 ° C for 3 hours. After the reaction was completed, the resultant was filtered and purified using a cerium oxide gel. The purified solid (12.5 g, 1 eq.) was dissolved in MeOH / THF (vol. ratio = 1/2) (250 mL), and potassium carbonate (20 g, 7 eq. The mixture was stirred for 6 hours. After completion of the reaction, the resultant was extracted with ethyl acetate and reduced under pressure to obtain a compound represented by Chemical Formula 3-3.

合成例4Synthesis Example 4

在配備有機械攪拌器及冷卻管的500毫升2頸燒瓶中放入了甲氧基芘(40克,0.172莫耳)、對苯二甲醯氯(17.48克,0.086莫耳)及1,2-二氯乙烷(300克)並進行了充分攪拌。在15分鐘之後,向其中緩慢添加了三氯鋁(25.26克,0.189莫耳),且使所獲得的混合物在室溫下反應了5小時。當反應完成之後,在使用水移除三氯鋁後以蒸發器對所得物進行了濃縮。 In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, methoxy hydrazine (40 g, 0.172 mol), p-xylylene chloride (17.48 g, 0.086 mol) and 1, 2 were placed. Dichloroethane (300 g) was thoroughly stirred. After 15 minutes, trichloroaluminum (25.26 g, 0.189 mol) was slowly added thereto, and the obtained mixture was allowed to react at room temperature for 5 hours. After the reaction was completed, the resultant was concentrated by an evaporator after removing trichloroaluminum using water.

隨後,在燒瓶中放入了化合物(40.96克,0.068莫耳)、1-十二硫醇(41.78克,0.21莫耳)、氫氧化鉀(15.46克,0.27莫耳)及N,N-二甲基甲醯胺(230克),並在120℃下攪拌了8小時。對混合物進行了冷卻、使用5%氯化氫溶液中和為具有pH 7,且接著以乙酸乙酯進行了萃取並進行了乾燥。 Subsequently, the compound (40.96 g, 0.068 mol), 1-dodecanethiol (41.78 g, 0.21 mol), potassium hydroxide (15.46 g, 0.27 mol) and N,N-di were placed in the flask. Methylformamide (230 g) was stirred at 120 ° C for 8 hours. The mixture was cooled, neutralized with a 5% hydrogen chloride solution to have pH 7, and then extracted with ethyl acetate and dried.

然後,向化合物中添加了四氫呋喃(160克)以獲得溶液。向溶液中緩慢添加了硼氫化鈉(32克,0.84莫耳)水溶液,且在室溫下將混合物攪拌了12小時。當反應完成之後,使用7%氯化氫溶液將所得物酸化為具有pH<5,並以乙酸乙酯進行了萃取,且在壓力下還原了其中的有機溶劑。 Then, tetrahydrofuran (160 g) was added to the compound to obtain a solution. An aqueous solution of sodium borohydride (32 g, 0.84 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the resultant was acidified to have a pH < 5 using a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent therein was reduced under pressure.

將此所合成聚合物(10克,0.017莫耳)、二氯化雙(三苯基膦)鈀(II)(Pd(PPh3)2Cl2,0.6克,0.0008莫耳)、碘化銅(0.16克,0.0008莫耳)、三苯基膦(0.44克,0.0016莫耳)及三乙胺(36毫升)溶解在了四氫呋喃(60毫升)中。然後,向其中添加了乙炔基三甲基矽烷(3.5克),且在80℃下將混合物攪拌了3小時。當反應完成之後,對所得物進行了過濾並使用氧化矽凝膠進行了 純化。將經純化固體(12.5克,1當量)溶解在了MeOH/THF(體積比=1/2)溶液(250毫升)中,向其中添加了碳酸鉀(20克,7當量),且在室溫下將混合物攪拌了6小時。當反應完成之後,以乙酸乙酯對所得物進行了萃取並在壓力下進行了還原以獲得由化學式3-4表示的化合物。 The synthesized polymer (10 g, 0.017 mol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh 3 ) 2 Cl 2 , 0.6 g, 0.0008 mol), copper iodide (0.16 g, 0.0008 mol), triphenylphosphine (0.44 g, 0.0016 mol) and triethylamine (36 ml) were dissolved in tetrahydrofuran (60 ml). Then, ethynyl trimethyl decane (3.5 g) was added thereto, and the mixture was stirred at 80 ° C for 3 hours. After the reaction was completed, the resultant was filtered and purified using a cerium oxide gel. The purified solid (12.5 g, 1 eq.) was dissolved in MeOH / THF (vol. ratio = 1/2) (250 mL), and potassium carbonate (20 g, 7 eq. The mixture was stirred for 6 hours. After the completion of the reaction, the resultant was subjected to extraction with ethyl acetate and reduced under pressure to obtain a compound represented by Chemical Formula 3-4.

合成例5Synthesis Example 5

在配備有機械攪拌器及冷卻管的500毫升2頸燒瓶中放入了芘(20克,0.1莫耳)、甲氧基苯甲醯氯(34克,0.2莫耳)及1,2-二氯乙烷(312克)並進行了充分攪拌。在15分鐘之後,向其中緩慢添加了三氯鋁(29.2克,0.22莫耳),且使所述混合物在室溫下反應了3小時。當反應完成之後,向甲醇中添加了反應溶液,且對其中的沈澱物進行了過濾以移除三氯鋁。在配備有機械攪拌器及冷卻管的500毫升2頸燒瓶中放入了經過濾粉末,向其中添加了1-十二硫醇(91克,0.45莫耳)、氫氧化鉀(30克,0.54莫耳)、及N,N-二甲基甲醯胺(262克),且在100℃下將混合物攪拌了5小時。當反應完成之後,對反應物進行了冷卻並以7% 氯化氫溶液中和為具有pH<5,且對其中形成的沈澱物進行了過濾。在真空烘箱中對經過濾材料進行了乾燥以移除水分。 In a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, bismuth (20 g, 0.1 mol), methoxybenzamide chloride (34 g, 0.2 mol) and 1,2-two were placed. Ethyl chloride (312 g) was thoroughly stirred. After 15 minutes, trichloroaluminum (29.2 g, 0.22 mol) was slowly added thereto, and the mixture was allowed to react at room temperature for 3 hours. After the reaction was completed, a reaction solution was added to methanol, and the precipitate therein was filtered to remove aluminum trichloride. A filtered powder was placed in a 500 ml 2-necked flask equipped with a mechanical stirrer and a cooling tube, and 1-dodecanethiol (91 g, 0.45 m) and potassium hydroxide (30 g, 0.54) were added thereto. Mohr), and N,N-dimethylformamide (262 g), and the mixture was stirred at 100 ° C for 5 hours. After the reaction was completed, the reaction was cooled and 7% The hydrogen chloride solution was neutralized to have a pH < 5, and the precipitate formed therein was filtered. The filtered material was dried in a vacuum oven to remove moisture.

將此所獲得的粉末溶解在了四氫呋喃(160克)中以獲得溶液。向溶液中緩慢添加了硼氫化鈉(16克,0.42莫耳)水溶液,且在室溫下將混合物攪拌了12小時。當反應完成之後,以7%氯化氫溶液將所得物酸化為具有pH<5,並以乙酸乙酯進行了萃取,且在壓力下還原了其中的有機溶劑以獲得化合物,向化合物中添加了乙腈/NMP(CH3CN/NMP=1/1,15克)以獲得溶液。然後,向溶液中添加了碳酸氫鉀(3克,0.022莫耳)及4-硝基鄰苯二甲腈(3.8克,0.022莫耳),且在85℃下將混合物攪拌了5小時。 The powder obtained was dissolved in tetrahydrofuran (160 g) to obtain a solution. An aqueous solution of sodium borohydride (16 g, 0.42 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the resultant was acidified to have a pH < 5 with a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent therein was reduced under pressure to obtain a compound, and acetonitrile was added to the compound. NMP (CH 3 CN/NMP = 1/1, 15 g) was obtained. Then, potassium hydrogencarbonate (3 g, 0.022 mol) and 4-nitrophthalonitrile (3.8 g, 0.022 mol) were added to the solution, and the mixture was stirred at 85 ° C for 5 hours.

當反應完成之後,以7%氯化氫溶液將所得物中和為具有pH<5,且對其中形成的沈澱物進行了過濾。在真空烘箱中對經過濾粉末進行了乾燥以移除水分。將所獲得的粉末再次溶解在了四氫呋喃(16克)中以獲得溶液。向溶液中緩慢添加了硼氫化鈉(0.8克,0.021莫耳)水溶液,且在室溫下將混合物攪拌了12小時。當反應完成之後,以7%氯化氫溶液將溶液酸化為具有pH<5,並以乙酸乙酯進行了萃取,且在壓力下還原了有機溶劑以獲得由化學式3-5表示的化合物。 After the reaction was completed, the resultant was neutralized to have a pH < 5 with a 7% hydrogen chloride solution, and the precipitate formed therein was filtered. The filtered powder was dried in a vacuum oven to remove moisture. The obtained powder was redissolved in tetrahydrofuran (16 g) to obtain a solution. An aqueous solution of sodium borohydride (0.8 g, 0.021 mol) was slowly added to the solution, and the mixture was stirred at room temperature for 12 hours. After the reaction was completed, the solution was acidified to have a pH < 5 with a 7% hydrogen chloride solution, and extracted with ethyl acetate, and the organic solvent was reduced under pressure to obtain a compound represented by Chemical Formula 3-5.

硬罩幕組成物的製備 Preparation of hard mask composition

實例1至實例9及比較例1 Example 1 to Example 9 and Comparative Example 1

將聚合物及單體溶解在了丙二醇單甲醚乙酸酯(PGMEA)溶劑中並進行了過濾以獲得硬罩幕組成物。 The polymer and monomer were dissolved in propylene glycol monomethyl ether acetate (PGMEA) solvent and filtered to obtain a hard mask composition.

聚合物及單體的組成物示於表1中。 The composition of the polymer and monomer is shown in Table 1.

評估1:平坦化特徵 Assessment 1 : Flattening Features

在圖案化矽晶圓(溝槽寬度:10微米,溝槽深度:100奈米)上,分別旋塗了表1中的組成物,並進行了烘烤以形成薄膜,且使用垂直掃描式電子顯微鏡(vertical scanning electron microscope,V-SEM)設備對其橫截面進行了檢查。 On the patterned tantalum wafer (groove width: 10 μm, groove depth: 100 nm), the compositions in Table 1 were spin-coated, respectively, baked to form a film, and vertical scanning electrons were used. Vertical scanning electron The microscope, V-SEM) equipment was examined for its cross section.

在首先於180℃下進行熱處理120秒及其次在400℃下進行熱處理120秒之後,對硬罩幕組成物中的固體含量進行了調整,以在裸晶圓上形成2000埃厚的薄膜。分別旋塗了各硬罩幕組成物,且隨後,將自其形成的薄膜首先在180℃下熱處理了120秒並其次在400℃下熱處理了120秒。 The solid content in the hard mask composition was adjusted to first form a 2000 angstrom thick film on the bare wafer after first heat treatment at 180 ° C for 120 seconds and then heat treatment at 400 ° C for 120 seconds. The hard mask compositions were spin-coated separately, and then the film formed therefrom was first heat treated at 180 ° C for 120 seconds and then heat treated at 400 ° C for 120 seconds.

藉由量測在抗蝕劑底層中具有孔的區與無孔的區之間的差(即,階差)而評估了薄膜的平坦化特徵。圖1是將被塗佈以塗佈液的矽晶圓中的任何圖案放大的剖視圖。在圖1中,箭頭所指的厚度為階差。 The planarization characteristics of the film were evaluated by measuring the difference (i.e., the step difference) between the region having the pores in the resist underlayer and the non-porous region. 1 is a cross-sectional view showing an enlarged view of any pattern in a germanium wafer to which a coating liquid is applied. In Fig. 1, the thickness indicated by the arrow is a step.

平坦化特徵愈優異,具有圖案的區與無圖案的區之間的差(階差)愈小,且因此,值愈小,平坦化特徵愈優異。結果示於表2中。 The more excellent the planarization feature, the smaller the difference (step difference) between the patterned region and the unpatterned region, and therefore, the smaller the value, the more excellent the planarization feature. The results are shown in Table 2.

參考表2,相較於由根據比較例1的硬罩幕組成物形成的薄膜,分別由根據實例1至實例9的硬罩幕組成物形成的薄膜顯示出了優異的平坦化特徵。 Referring to Table 2, the film formed of the hard mask compositions according to Examples 1 to 9, respectively, exhibited excellent planarization characteristics as compared with the film formed of the hard mask composition according to Comparative Example 1.

評估2:厚度均勻性 Evaluation 2 : Thickness uniformity

在12英吋矽晶圓上分別旋塗了根據實例1至實例9以及比較例1的硬罩幕組成物,且接著,將所獲得的膜首先在180℃下熱處理了120秒以及其次在400℃下熱處理了120秒。對硬罩幕組成物的固體含量進行了調整以在第二次熱處理之後形成2,000埃厚的薄膜。 The hard mask compositions according to Examples 1 to 9 and Comparative Example 1 were spin-coated on a 12-inch wafer, respectively, and then the obtained film was first heat-treated at 180 ° C for 120 seconds and then at 400. Heat treated at °C for 120 seconds. The solids content of the hard mask composition was adjusted to form a 2,000 angstrom thick film after the second heat treatment.

藉由如圖2所示採用19個點、量測19個點處的每一薄膜厚度、並使用所述薄膜厚度根據計算方程式2而評估了均勻性。使用K-MAC設備量測了薄膜的厚度。結果示於表3中。 Uniformity was evaluated according to Equation 2 by using 19 points, measuring each film thickness at 19 points as shown in FIG. 2, and using the film thickness. The thickness of the film was measured using a K-MAC device. The results are shown in Table 3.

[計算方程式2]均勻性(%)=(薄膜的19個點中的最大厚度-薄膜的19個點中的最小厚度)/(薄膜的19個點的平均厚度)×100 [Calculation Equation 2] Uniformity (%) = (Maximum thickness of 19 points of the film - Minimum thickness of 19 points of the film) / (Average thickness of 19 points of the film) × 100

參考表3,相較於由根據比較例1的硬罩幕組成物形成的薄膜,分別由根據實例1至實例9的硬罩幕組成物形成的薄膜顯示出了優異的厚度均勻性。 Referring to Table 3, the film formed of the hard mask compositions according to Examples 1 to 9, respectively, showed excellent thickness uniformity as compared with the film formed of the hard mask composition according to Comparative Example 1.

評估3:塗佈性質 Assessment 3 : Coating properties

在12英吋矽晶圓上分別旋塗了根據實例1至實例9以及比較例1的硬罩幕組成物,且接著,將所獲得的膜首先在180℃下熱處理了120秒以及其次在400℃下熱處理了120秒。對硬罩幕組成物的固體含量進行了調整以在第二次熱處理之後形成2,000埃厚的薄膜。 The hard mask compositions according to Examples 1 to 9 and Comparative Example 1 were spin-coated on a 12-inch wafer, respectively, and then the obtained film was first heat-treated at 180 ° C for 120 seconds and then at 400. Heat treated at °C for 120 seconds. The solids content of the hard mask composition was adjusted to form a 2,000 angstrom thick film after the second heat treatment.

用電子顯微鏡對薄膜的表面進行了檢查。結果示於表4中。 The surface of the film was examined with an electron microscope. The results are shown in Table 4.

[表4] [Table 4]

如表4所示,相較於由根據比較例1的硬罩幕組成物形成的薄膜,分別由根據實例1至實例9的硬罩幕組成物形成的薄膜顯示出了優異的塗佈性質。 As shown in Table 4, the films formed by the hard mask compositions according to Examples 1 to 9, respectively, exhibited excellent coating properties as compared with the film formed of the hard mask composition according to Comparative Example 1.

儘管本發明已結合目前視為實用的示例性實施例加以闡述,但應理解,本發明不限於所揭露的實施例,而是相反地意欲涵蓋包含在隨附申請專利範圍的精神及範圍內的各種潤飾及等效配置。 Although the present invention has been described in connection with the exemplary embodiments of the present invention, it is understood that the invention is not to be construed as limited Various finishes and equivalent configurations.

Claims (18)

一種有機層組成物,包含:聚合物,包含由化學式1表示的結構單元;單體,由化學式3表示;以及溶劑, 其中,在化學式1中,A為經取代或未經取代的含芳族環的基、經取代或未經取代的含雜芳族環的基或其組合,B為二價有機基,且A及B中的至少一者經包含由化學式2表示的部分(moity)的官能基取代, 其中,在化學式2中,Z為氫、羥基、經取代或未經取代的C1至C10烷基或經取代或未經取代的C6至C30芳基,且*為連接點, 其中,在化學式3中,A0、A1及A2獨立地為經取代或未經取代的含芳族環的基,A0、A1及A2中的一者或多者在結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基,L1、L2、L3及L4獨立地為單鍵、經取代或未經取代的C1至C6伸烷基、經取代或未經取代的C6至C30伸芳基或其組合,X1、X2、X3、及X4獨立地為氫、羥基、經取代或未經取代的胺基、鹵素原子或其組合,其限制條件是X1與X2不同時為氫,且X3與X4不同時為氫,並且m及n獨立地為介於0至2的整數,其限制條件是m與n的和大於或等於1,其限制條件是當m為0時,A0及A2中的至少一者在所述結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基,且當n為0時,A1及A0中的至少一者在所述結構中包含經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基或腈基。 An organic layer composition comprising: a polymer comprising a structural unit represented by Chemical Formula 1; a monomer represented by Chemical Formula 3; and a solvent, Wherein, in Chemical Formula 1, A is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and B is a divalent organic group, and A And at least one of B and B is substituted with a functional group containing a moity represented by Chemical Formula 2, Wherein, in Chemical Formula 2, Z is hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, and * is a point of attachment, Wherein, in Chemical Formula 3, A 0 , A 1 and A 2 are independently a substituted or unsubstituted aromatic ring-containing group, and one or more of A 0 , A 1 and A 2 are in the structure. A substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and L 1 , L 2 , L 3 and L 4 are independently Is a single bond, a substituted or unsubstituted C1 to C6 alkylene group, a substituted or unsubstituted C6 to C30 extended aryl group, or a combination thereof, X 1 , X 2 , X 3 , and X 4 independently a hydrogen, a hydroxyl group, a substituted or unsubstituted amine group, a halogen atom or a combination thereof, wherein X 1 and X 2 are not hydrogen at the same time, and X 3 and X 4 are not hydrogen at the same time, and m and n are Independently an integer between 0 and 2, with the constraint that the sum of m and n is greater than or equal to 1, with the constraint that when m is 0, at least one of A 0 and A 2 is in the structure A substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group, and when n is 0, A 1 and A 0 At least one of the The structure includes a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group or a nitrile group. 如申請專利範圍第1項所述的有機層組成物,其中包含由化學式2表示的所述部分的所述官能基由化學式2’表示, 其中,在化學式2’中,W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,Z為氫、羥基、經取代或未經取代的C1至C10烷基或經取代或未經取代的C6至C30芳基,a為0或1,b為介於0至10範圍內的整數,且*為連接點。 The organic layer composition according to claim 1, wherein the functional group including the moiety represented by Chemical Formula 2 is represented by Chemical Formula 2', Wherein, in the chemical formula 2', W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, A halogen group or a combination thereof, Z is hydrogen, a hydroxyl group, a substituted or unsubstituted C1 to C10 alkyl group or a substituted or unsubstituted C6 to C30 aryl group, a is 0 or 1, and b is 0. An integer up to the range of 10, and * is the join point. 如申請專利範圍第1項所述的有機層組成物,其中在化學式3中,A0、A1及A2獨立地包含選自群組1的經取代或未經取代的部分:[群組1] 其中,在群組1中,X為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合。 The organic layer composition according to claim 1, wherein in Chemical Formula 3, A 0 , A 1 and A 2 independently comprise a substituted or unsubstituted portion selected from Group 1: [Group 1] Wherein, in group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO 2 , CR f R g , NR h or a carbonyl group, wherein R f to R h are independently Hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen containing group or a combination thereof. 如申請專利範圍第1項所述的有機層組成物,其中在化學式3中,A0、A1及A2中的至少一者為多環環狀基。 The organic layer composition according to claim 1, wherein in Chemical Formula 3, at least one of A 0 , A 1 and A 2 is a polycyclic cyclic group. 如申請專利範圍第1項所述的有機層組成物,其中在化學式3中,A0、A1、及A2中的至少一者在所述結構中包含由化學式4表示的官能基中的至少一者:[化學式4] 其中,在化學式4中,W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,Y為經取代或未經取代的胺基、經取代或未經取代的乙烯基、經取代或未經取代的乙炔基、疊氮基、腈基或其組合,a為0或1,b為介於0至10範圍內的整數,且*為連接點。 The organic layer composition according to claim 1, wherein in Chemical Formula 3, at least one of A 0 , A 1 , and A 2 contains the functional group represented by Chemical Formula 4 in the structure. At least one: [Chemical Formula 4] Wherein, in Chemical Formula 4, W is O, S, NR a or CR b R c , wherein R a to R c are independently hydrogen, substituted or unsubstituted C 1 to C 10 alkyl, halogen atom, halogen-containing Or a combination thereof, Y is a substituted or unsubstituted amino group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted ethynyl group, an azide group, a nitrile group or a combination thereof, a is 0 or 1, b is an integer ranging from 0 to 10, and * is a connection point. 如申請專利範圍第1項所述的有機層組成物,其中當所述單體包含經取代或未經取代的乙炔基時,所述單體是由化學式3a至化學式3d中的一者表示: [化學式3b] 其中,在化學式3a至化學式3d中,A3、A4、及A5獨立地為經取代或未經取代的含芳族環的基,且W為O、S、NRa或CRbRc,其中Ra至Rc獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合。 The organic layer composition according to claim 1, wherein when the monomer comprises a substituted or unsubstituted ethynyl group, the monomer is represented by one of Chemical Formula 3a to Chemical Formula 3d: [Chemical Formula 3b] Wherein, in Chemical Formula 3a to Chemical Formula 3d, A 3 , A 4 , and A 5 are independently a substituted or unsubstituted aromatic ring-containing group, and W is O, S, NR a or CR b R c Wherein R a to R c are independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing group or a combination thereof. 如申請專利範圍第1項所述的有機層組成物,其中在化學式1中,A為選自群組1及群組2的經取代或未經取代的部分(moiety),[群組1] [群組2] 其中,在群組1中,X為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,其中,在群組2中,Z1及Z2獨立地為NRd、O、S、Te或Se,Z3至Z5為N,且Rd及Re獨立地為氫、羥基、甲氧基、乙氧基、鹵素原子、含鹵素的基、經取代或未經取代的C1至C30烷基、經取代或未經取 代的C6至C30芳基或其組合。 The organic layer composition according to claim 1, wherein in Chemical Formula 1, A is a substituted or unsubstituted moiety selected from Group 1 and Group 2, [Group 1] [Group 2] Wherein, in group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO 2 , CR f R g , NR h or a carbonyl group, wherein R f to R h are independently a hydrogen, substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof, wherein, in Group 2, Z 1 and Z 2 are independently NR d , O, S, Te Or Se, Z 3 to Z 5 are N, and R d and R e are independently hydrogen, hydroxy, methoxy, ethoxy, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 Alkyl, substituted or unsubstituted C6 to C30 aryl or a combination thereof. 如申請專利範圍第1項所述的有機層組成物,其中B由化學式Z1至化學式Z4中的一者表示: 其中,在化學式Z1至化學式Z4中,e及f獨立地為0或1,g為1至5的整數,Y1至Y4獨立地為選自群組3的經取代或未經取代的部分 (moiety)中的一者,且*為連接點, 其中在群組3中,M、M'及M"獨立地為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其 組合,L1為經取代或未經取代的C6至C50伸芳基、經取代或未經取代的C1至C10含環氧烷的基或其組合,r為0至10的整數,s為0至10的整數,且k為0至3的整數。 The organic layer composition as described in claim 1, wherein B is represented by one of chemical formula Z1 to chemical formula Z4: Wherein, in the chemical formula Z1 to the chemical formula Z4, e and f are independently 0 or 1, g is an integer of 1 to 5, and Y 1 to Y 4 are independently a substituted or unsubstituted portion selected from the group 3 One of (moiety), and * is the connection point, Wherein in the group 3, M, M 'and M "are independently a substituted or unsubstituted C1 to C10 alkylene, O, S, SO 2, CR f R g, NR h or a carbonyl group, wherein R f to R h are independently hydrogen, substituted or unsubstituted C1 to C10 alkyl, halogen atom, halogen-containing group or a combination thereof, and L 1 is a substituted or unsubstituted C6 to C50 extended aryl group, The substituted or unsubstituted C1 to C10 alkylene oxide-containing group or a combination thereof, r is an integer of 0 to 10, s is an integer of 0 to 10, and k is an integer of 0 to 3. 如申請專利範圍第1項所述的有機層組成物,其中所述聚合物更包含由化學式5表示的結構單元: 其中在化學式5中,X0為經取代或未經取代的含芳族環的基、經取代或未經取代的含雜芳族環的基或其組合,L0為二價有機基,且*為連接點。 The organic layer composition according to claim 1, wherein the polymer further comprises a structural unit represented by Chemical Formula 5: Wherein in Chemical Formula 5, X 0 is a substituted or unsubstituted aromatic ring-containing group, a substituted or unsubstituted heteroaromatic ring-containing group, or a combination thereof, and L 0 is a divalent organic group, and * is the connection point. 如申請專利範圍第9項所述的有機層組成物,其中在化學式5中,X0為選自群組1及群組2的經取代或未經取代的部分,[群組1] 其中在群組1中,X為經取代或未經取代的C1至C10伸烷基、O、S、SO2、CRfRg、NRh或羰基,其中Rf至Rh獨立地為氫、經取代或未經取代的C1至C10烷基、鹵素原子、含鹵素的基或其組合,其中在群組2中,Z1及Z2獨立地為NRd、O、S、Te或Se,Z3至Z5為N,且Rd及Re獨立地為氫、羥基、甲氧基、乙氧基、鹵素原子、含鹵素的基、經取代或未經取代的C1至C30烷基、經取代或未經取代的C6至C30芳基或其組合。 The organic layer composition according to claim 9, wherein in Chemical Formula 5, X 0 is a substituted or unsubstituted portion selected from Group 1 and Group 2, [Group 1] Wherein in group 1, X is a substituted or unsubstituted C1 to C10 alkyl group, O, S, SO 2 , CR f R g , NR h or a carbonyl group, wherein R f to R h are independently hydrogen a substituted or unsubstituted C1 to C10 alkyl group, a halogen atom, a halogen-containing group or a combination thereof, wherein in Group 2, Z 1 and Z 2 are independently NR d , O, S, Te or Se Z 3 to Z 5 are N, and R d and R e are independently hydrogen, hydroxy, methoxy, ethoxy, halogen atom, halogen-containing group, substituted or unsubstituted C1 to C30 alkyl group A substituted or unsubstituted C6 to C30 aryl group or a combination thereof. 如申請專利範圍第1項所述的有機層組成物,其中所述聚合物在所述結構單元中包含至少一個氧原子。 The organic layer composition of claim 1, wherein the polymer comprises at least one oxygen atom in the structural unit. 如申請專利範圍第1項所述的有機層組成物,其中所述單體具有500至50,000的分子量。 The organic layer composition according to claim 1, wherein the monomer has a molecular weight of 500 to 50,000. 如申請專利範圍第1項所述的有機層組成物,其中所述聚合物具有500至200,000的重量平均分子量。 The organic layer composition of claim 1, wherein the polymer has a weight average molecular weight of 500 to 200,000. 如申請專利範圍第1項所述的有機層組成物,其中所述聚合物與所述單體的重量比為70:3至30:70。 The organic layer composition of claim 1, wherein the weight ratio of the polymer to the monomer is from 70:3 to 30:70. 一種形成圖案之方法,包括在基板上提供材料層,將如申請專利範圍第1項至第14項中任一項所述的有機層組 成物施加於所述材料層上,對所述有機層組成物進行熱處理以形成硬罩幕層,在所述硬罩幕層上形成含矽的薄層,在所述含矽的薄層上形成光阻劑層,對所述光阻劑層進行曝光及顯影以形成光阻劑圖案,使用所述光阻劑圖案來選擇性地移除所述含矽的薄層及所述硬罩幕層以暴露出所述材料層的一部分,以及對所述材料層的被暴露部分進行蝕刻。 A method of forming a pattern, comprising providing a material layer on a substrate, the organic layer group according to any one of claims 1 to 14. An object is applied to the layer of material, the organic layer composition is heat treated to form a hard mask layer, and a thin layer containing germanium is formed on the hard mask layer, on the thin layer containing germanium Forming a photoresist layer, exposing and developing the photoresist layer to form a photoresist pattern, using the photoresist pattern to selectively remove the germanium-containing thin layer and the hard mask The layer exposes a portion of the layer of material and etches the exposed portion of the layer of material. 如申請專利範圍第15項所述的形成圖案之方法,其中所述有機層組成物是利用旋塗方法來施加。 The method of forming a pattern according to claim 15, wherein the organic layer composition is applied by a spin coating method. 如申請專利範圍第15項所述的形成圖案之方法,其中所述熱處理包括在50℃至250℃下進行第一熱處理及在所述第一熱處理之後在200℃至500℃下進行第二熱處理。 The method of forming a pattern according to claim 15, wherein the heat treatment comprises performing a first heat treatment at 50 ° C to 250 ° C and performing a second heat treatment at 200 ° C to 500 ° C after the first heat treatment. . 如申請專利範圍第15項所述的形成圖案之方法,其中所述形成圖案之方法更包括在形成所述光阻劑層之前形成底部抗反射塗層(BARC)。 The method of forming a pattern according to claim 15, wherein the method of forming a pattern further comprises forming a bottom anti-reflective coating (BARC) prior to forming the photoresist layer.
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